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TREATISE ON

GENERAL AND INDUSTRIAL

ORGANIC CHEMISTRY
6Y

DR.

ETTORE MOLINARI

PROFESSOR OF INDUSTRIAL CHEMISTRY AT THE ROYAL MILAN POLYTECHNIC AND AT THE LUIGI BOCCONI COMMERCIAL UNIVERSITY

SECOND ENGLISH EDITION

TRANSLATED FROM THE THIRD ENLARGED AND REVISED ITALIAN

EDITION BY

THOMAS

H. POPE,

B.Sc.,

A.C.G.L, F.I.C.

PART
WITH
303

II

ILLUSTRATIONS

LONDON
J.
7

&

A.

CHURCHILL
1923

GREAT MARLBOROUGH STREET

Printed in Great Britain.

CONTENTS
PAGE

VIIT.

ESTERS

(Oils, Fats, Waxes, Candles, Soaps)

;

457
;

Preparation

theory of formation^; fruit essences

various esters
. .

457

GLYCERIDES, OILS, FATS

.*.,.
;
;

.460

Reichcrt-Meissl-Wollny number, 461 ; ccrotic acid, 462 ; lecithin, 4o2 ; drying oils, varnishes, 462 ; Soxhlet extraction apparatus, 462 ; rancidity of oils, 463 refractive index, butyro-refractometer, 463 blown oils, ozone number, Maumene number, Tortelli thermo-oleometer, 464.
Tripalmitin, tristearin, tri61ein, 460
;

WAXES
of

wax

.............
:

beeswax, virgin wax, white wax, carnauba wax, Japanese wax, uses

465

Table of physical and chemical constants of

soaps, 467

fats, oils
;

and fatty

acids, 466.

SAPONIFICATION OF FATS AND WAXES, 467

;

hydrolysis of

ammonia
468
;

saponification number, 468.

ANIMAL OILS AND FATS

butter, Tallow, 468 oleomargarine and margarine (artificial butter), 470 milk and cheese, 474 casein, 474 analysis of milk, 475 renovated butter, whale oil, cod-liver oil, spermaceti, 477 ; bone fat, 477 lard, 478 fish oils 478 degras, 478 wool fat, 479 chrysalis oil, 480.
;

INDUSTRIAL HARDENING OF OILS BY MEANS OF HYDROGEN

480
482

VEGETABLE

OILS

Table, 482 ; extraction by pressure, hydraulic presses, 483 ; extraction by solvents, Florentine receiver, 486 ; refining, deodorising and bleaching, 488. Olive oil, 490 ; sulphocarbon oil, 491 ; adulterations, 492. Castor oil, 493 ;
riciiioleic acid,

sulphoricinate, 494.

Linseed
496.

oil,

494
pil,

and
oil,

lacs, copal, 495.

oil,

Walnut

oil,

Palm

496.

drying power, oil varnishes Palm-kernel oil, 497.

Coconut
499.

Maize
oil,

copra, 498. Vegetable tallow, 499. Cottonseed oil, 499. Sesame oil, 500. Arachis oil, 500. Colza oil, 499.
502.

Kapok
oil,

501.

Sqga bean

Grapeseed

oil,

502.

Tomatoseed

oil,

502.

Wood
.

oil,
.

503.

TREATMENT OF FATS FOR MAKING CANDLES AND SOAPS

Saponification with lime, 503.

.503

Solid fatty acids, 504. Krebitz process, 505. Hydrolysis with sulphuric acid, 506. Distilled oleine and stearine, 506. Hydroxystearic acid, 506. Transformation of oleic acid into solid fatty acids, 506.
507.

Hydrolysis by hot water under pressure, 507. TwitchelTs Catalytic process, 508.

Biological or

Enzymic

process,

MANUFACTURE OF CANDLES
MANUFACTURE OF
513.

510
History, 513.

SOAP,

513.

Theory of action of soap,

Soft

Oleine soap, 517.

Mottled soap, 519.

Transparent soaps, 520.

soaps, 520.

Analysis of soap, 522.

GG.

ALDEHYDIC OR KETONIC POLYHYDRIC ALCOHOLS

523
general

CARBOHYDRATES
A.
,

MONOSES, 524;

methods of formation,

525.

Formation

of

carbohydrates in plants, 525. Tetroses, pentoses, pentosans, and their estima^fcn, 525 ; furfuroids, 628. Hexoses, 529 ; d-glueose, 531 ; invert sugar, 531 ; Caramel, 533 ; fructose, 533 ; mannose, 534 ; galactose, 534 ; glucosides, 534.

vi
B.

CONTENTS
PAGE

HEXABIOSES,
;

535.

Maltose, lactose, 536.

;

Saccharose, 538
;

beet-sugar, 539

maple sugar, 540

;

sugar-cane, 540

development

history of of the beet;

Extraction of sugar from beet, 545 ; extraction by diffusion, sugar industry, 545. 548 ; Steffen process, 553 Claassen process, 554 ; defecation with lime, 555 ; filtration under pressure, 556 ; concentration of the juice, 559 ; vacuum concentration,

559

massecuite, 565

boiling of the concentrated juice, 564 ; centrifugation of the ; refining, 567 ; revivification of the animal charcoal, 568 ; cube

Molasses and its utilisation by the osmosis, lime, sugar, 570 ; pile sugar, 570. Yield of sugar, cost of production, statistics, strontia and baryta processes, 570.
fiscal

regulations,

etc.,

574.

chemical determination, 582.

C.

Estimation of sugar, 577 ; polarimetry, 579 Purification of waste- waters from sugar- works

584

TRIOSES,

584.

Raffinose, 584.

D. TETROSES, 585.

Mannotetrosc, 585.
585.

K
596.

HIGHER POLYOSES,
CSums,
598.

Starch, 585

soluble starch, 596.

Dextrin,

CUycogen, 598. Cellulose, 598. Cellulose acetate, 599. Artificial parchment, 600. Paper industry, 602 treatment of rags, 603 mechanical wood-pulp, 605 chemical wood-pulp, 607. Cork, 615.
; ;

PART
T.

III.

CYCLIC COMPOUNDS
616
BenIso-

A A. ISOCYCLIC COMPOUNDS
Cyclofiaraffin* and cyclo-ohfinw or 'polt/Mt>thylene compounds, 616. II. zene derivative* or aromatic compounds : the formula of benzene, 618.

merism

in

benzene derivatives, 620.

General character and formation of

benzene derivatives, 621, 622.

A.

AROMATIC HYDROCARBONS

622

Coal and other tars, 623. Table, 623. Lampblack, 624. Distillation of tar, Tar oils, 628. Preservation of wood, 629. Benzene, 633. Toluene and 625. Hydrocarbons with unsaturated side-chains, 634. xylencs, 633.
B.

HALOGEN SUBSTITUTION DERIVATIVES OF BENZENE

SULPHONIC ACIDS

634

Table, 636.
C.

636

Benzenesulphonic acid, 637.

D.

PHENOLS

637

Table, 639. Carbolic acid, 638 ; synthesis, 640. (a) Monohydric phenols, 638. Baekelite, 641. Homologues of phenol, 643. (6) Dihydric Antiseptics, 640.
phenols
644. 645.
K.

pyrocatechol, resoreinol, hydroquinone. orcinol, eugeiiol, isoeugenol, Trihydric phenols : pyro^allol, hydroxyhydroquinone, phloroglucinol, 646. (d) Polyhydric phenols : hexahydroxy benzene, quercitol, inositol,
:

(c)

F.

QUINONES NITRO-DERIVATIVES OF AROMATIC HYDROCARBONS

Nitrobenzene, dinitrobciizenes,

647
. .

.648

Table, 650.

trinitrobenzenes, nitrotoluenes,

trinitrotoluenes, phenylnitrometharie, pseudo-acids, 648-654.

G.

AMINO-DERIVATIVES OF AROMATIC HYDROCARBONS

of
;

.654

Table
triamines 9

Aromatic
(3)

Amines,
Aniline,

655:
;

(1)

primary

tnonamines
bases
;

(2)
(5)

monamines

tertiary

monamines

(4)

quaternary

secondary diamines,

telramines.

nitraniline,

phenylsulphaminic acid, acetanilidc, etc. xylidines, benzylamine, phenylenediamine, 654-663.

11.

methylanilines, diphenylamine, Monologues of aniline : toluidines,

NITROPHENOLS, AMINOPHENOLS, AND THIOPHENOLS

picric acid,

663

Nitrophenol, 663-667.

aminophenols, phenacetin, salvarsan, thiophenols,

CONTENTS
I.

vii
PAGE

AZO- DIAZO- AND DIAZOAMINO-COMPOUNDS AND HYDRAZINES

Azo-derivativcs
;

667

(1)

(2)

diazo-derivatives

(3)

diazoamino-derivatives

(4) hydrazines,

667-674.
. .

J.

AROMATIC ALCOHOLS, ALDEHYDES, AND KETONES

.674

Benzyl alcohol, benzaldehyde and its homologues, cinnamaldehyde, 674-675. Aromatic ketones, 675. Aromatic oximes, 676. Beckmann rearrangement, 676.

K.

HYDROXY-ALCpHOLS, ALCOHOLS
. .

HYDROXY- ALDEHYDES,
'

AND

KETONIC
677

Salicylaldchyde, anisaldehydc, hydroxy-aldehydes, 677.

L.

vanillin,

coniferin,

677-678.

Aromatic

AROMATIC ACIDS
(a)

67S

General methods of preparation and properties, 670-680.

MONOBASIC AROMATIC ACIDS,

680.

Table,

681.

Benzoic

anhydride, hetizoyl chloride, bcnzamide, hippurk- acid, chlorobenzoic acid, m -nitrobenzoic aeid, azobenzoic aeids, aminobenzoie acids (anthranilic acid), diazobenzoic acids, anthranil, sulphobenzoic ncids, saccharin, toluic acids,
phenylacetic acid, xylic acids, cumiiiic acid, citmamic acid, phenylpropiolic aeid/ 680-684.
(l>)

DIBASIC

AND POLYBASIC AROMATIC

ACIDS,

684.

Fhthalic

acid, phthaleins, phthalide, phthalo])henone, phenolphthalcin, fluorescein, eosin, phthalimide, isophthalie acid, tercphthalic acid ; poll/basic acids :

mellitic acid, 684-686.

()
aeids.

HYDROXY-ACIDS OR PHENOLIC ACIDS,

acids, gallic acid, ink,

w- and p-hydroxy benzole

M. NITRO-DER1VATIVES
N.

686; salicylic aeid, coumaric and inandelic

Tannin, tanning of skins, commercial data, 686-701.

OF BENZOIC ACIDS
acid.

701

HYDROGENATED BENZENE COMPOUNDS

Terpenes, cinene,

701

Naphthenes, naphthenic acids, hexamethylene, quinic

carvene, Mimoncne, sylvestrene, terpinolene, terpinene, dihydrocymene, phellanComplex Terpenes, pinenr, oil of turpendrene, menthene, meiithane, 701 706.
tine,

colophony, campheiie, fenchene, camphane ; rubber, guttapercha, ebonite, artificial musk ; camphors, synthetic rubber, rubber substitutes, isoprcne, ionone, carvone, menthol, terj)in, cineol ; camphor, terpineol, terpenol, pulegone, terpane, celluloid, artificial leather, artificial camphor, 706-718.
O.
1

CONDENSED BENZENE NUCLEI

Diphenyl and
its

718

diphenyl, bcnzidine, carbazole, dihydroxy( ) derivatives : tetramethyl base, phenyl, etc., 718. (2) Diphenylmethane and its ketone), dihydroxybenzophenone, (Michler's tetrainethyldiamiiiobenzophenone its derivatives : paradiphenylethane, fluorene, 719. (3) Triphenylmethane and
derivatives
:

rosaniline, rosaniline, rosolic acid, aurin, phthalophenone, hexa- and penta-phenylethanes, 720. (4) Dibenzyl and its derivatives : stilbene, tolane, p-diaminostil-

bene, diaminostilbenedisulphonic aeid, benzoin, hydrobenzoin, benzil, desoxybenzoin, hexabenzylethane,

thalene,
lenes,

722.

(5)

Naphthalene and
di-,

its derivatives
tri-,

naph-

u-chloronaphthalene,

a-nitronaphthalene,

and

tetra-nitro-

naphthalenes, a- and /?-naphthylamines, a- and /3-iiaphthols, dihydroxynaphthaaminonaphthols, 723. Sulphonic derivatives of naphthalene, na])hthols and naphthylamines, a-, /3-, and 2 6-naphthaquinones, 728. Additive products of naphthalene, 730. (6) Anthracene group : anthracene, anthraquinoiie, alizarin, phenanthrene, other condensed nuclei, 731.
:

BB. HETEROCYCLIC COMPOUNDS

Furfuran, furfural, thiophen, pyrrole, pyrazole, pyramidone, Pyrinazole, lysidine, oxazolc, osotriazole, triazole, tetrazole, azoxazole, 736. dine and its derivatives picoline, lutidines, collidines, pyridones, pyridine:

736
thiazole, imi-

viii

CONTENTS
PAQE

carboxylic acids, hydropyridines, piperidine, 740. Alkaloids : Separation and tests, synthesis of alkaloids and medicine, table, anaesthetics, adrenaline, coniine, nicotine (tobacco), atropine, morphine, cocaine, narcotine, strychnine,
quinine, 743.

Quinoline and

its

derivatives

quinaldine, isoquinoline, chromone,

flavone, coumarone, isatin, indoxyl, skatole, indole, indazole, indigo (natural artificial), 753.

and

CO.

COLOURING MATTERS
Witt's theory, chromophores, chromogens, auxochromes, 764. Rosaniline, fulvene derivatives, conjugated double linkings, basic, acid and neutral colouring

764

behaviour of colouring matters towards fibres and mordants, 765. Ostwald's new theory of colours and their Physiological action of dyestuffs, 772. numerical definition, 773. RosenstiehTs colour system, 774. Manufacture of
matters,

colouring matters, 776.

matters, 778.
II.

Classification of colouring matters

I.

Nitro- colouring-

Azo- colouring-matters, 778.

III. Derivatives of

hydrazones

and pyrazolones, 782. IV Hydroxyquinones and quinoneoximes, 783. V. Diphenyl- and triphenyl-methane colouring-matters, 783. VI. Derivatives of quinonimide, 785. VII. Aniline black, 786. VIII. Quinoline and acridine IX. Thiazole colouring-matters, X. Oxyketones, 787. 787. derivatives, xanthones, flavones, and coumarins, 787. XI. Indigo and similar and other
indanthrene group, 789. XII. Sulphur colour; ing-matters, 790. Dyewoods, cochineal, chlorophyll, 791. Testing of colouringmatters, 795. Recognition of the principal colouring matters on dyed fibres, 803.
natural colouring-matters, 788

TEXTILE FIBRES
Wool, 804. Cotton, 807. Kapok, 810. Flax, 810. Hemp, 812. Jute, 812. Sea silk, 820. Artificial silk, 821. Chemical tests for the recognition Silk, 813.
of different textile fibres, 827. 828.

804

Quantitative analysis of mixtures of textile

fibres,

Dyeing and printing tests on fibres, 830. Fastness tests, 831. dyeing, 832. Machinery used in dyeing and finishing textiles, 835.

Theory of

DD. PROTEINS
General characters, reactions, hydrolysis and synthesis, polypeptides, 857. I. Natural proteins : (1) Albumins, lecithin, egg industry, 859. (2) Globulins. (5) Histones. (6) Pro(4) Fibrinogen, rnyosin. (3) Nucleo-albumins, 861. tamines, 862. II. Modified proteins: (1) Albumoses and peptones. (2) Salts
of proteins,
862.
III.
(3) Nucleo-proteins. (3) Collagen,* 863. (2) Keratin.
(2) Conjugated proteins (proteids) (1) Haemoglobin. 862. IV. Albuminoids: (I) Elastin. Glucoproteins,
:

857

V. Various proteins, 865.

GLUCOSIDES AND OTHER SUBSTANCES OF UNCERTAIN OR UNKNOWN COMPOSITION Amygdalin saponin digitalin salicin sesculin populin
:

hesperidin ; phloretin ; iridin ; arbutin ; coniferin ; sinigrin ; santonin ; aloin ; lecithin ; cerebrin ; iodolrtiyrin ; taurocholic, glycocholic, and cholic acids ; biliverdin, bilifuchsin,

and

bilirubin

cantharidin

chitin

cholesterol, vitamins, 865.

INDEX

868

ESTERS

457

PART
VIII.
(Oils,

II

ESTERS

Fats,

Waxes, Candles, Soaps)

formed by alcohols with inorganic acids have already been studied (see pp. 234 et, seq.), and we shall now consider the esters resulting from the substitution of the typical hydrogen of organic acids by alkyl radicals. Various isomerides exist with these compounds, e.g., methyl butyrate
esters

The compounds or

formate with propyl acetate. Attention however, be paid more especially to the esters of glycerine (glycerides), since on these are based the fat, oil, soap, and candle industries. PREPARATION. These esters may be obtained by the general methods already described (loo. eit.), e.g., by the action of the acid chlorides or anhydrides on the alcohols or sodium alkoxidcs
is

iflomeric with ethyl propionate, butyl

will,

C 2H5 CO

Cl

C 2H5 Oil

= HC1 + C H
2

COOG 2II5

They arc formed also by the interaction of the silver salt of the acid and the alkyl iodide, and by the action of gaseous hydrogen chloride on a hot alcoholic solution of the nitrile of the acid. Further, the alcohols and acids themselves react, slowly in the cold and more rapidly although not completely in the hot, with formation of esters
:

C 2IT5

OH + CII 3 C0 2H - CH 3 C0 2C 2H5 + H 20.

:

In practice the preparation is carried out as follows the dry organic acid is mixed with an excess of absolute alcohol and the mixture saturated with dry hydrogen chloride gas, left for some time in a moderately warm place and then poured into water the ester separates in an insoluble form after neutrali;

sation of the aqueous liquid with alkali in the cold. In this reaction the acid chloride is probably formed as an intermediate HC1 CO 2 product 3 2 CH, CO Cl the latter -which with water might give the reverse reaction being in presence of excess of the
:

CH

H+

-H

Esterification is, however, alcohol, forms the ester (equation given above). never complete, as the reaction is a reversible one, the hydrochloric acid and also other inorganic acids such as sulphuric acid, even in the dilute state, behaving as true moitf catalysts (Berthelot, 1879 V. Meyer, Fischer and Speier, 1895 Senderens and Aboulenc, Sabatier and Mailhe, 1909-1913)
;

C, H
t

2 ,,

+ 1

OH + C.11,.0,

II 2

+ CJI^A C, H
-

ia

After a certain time a system is obtained which contains given quantities of alcohol (), acid (b), water and ester (z). The same equilibrium is attained by mixing 1 mol. of ester and 1 mol. of water as by mixing 1 mol. of acid and 1 mol. of alcohol, and this equilibrium is represented by the following equation for bimolecular reactions (see Vol. 1., p. 69) : z k(a z)(b z) I\z 9 where a and b represent the respective initial concentrations of alcohol and ester and z that of the ester and water when equilibrium is reached, all expressed in itwls. (gram-molecules) ; k and k L are constants depending on the nature of the reaction
and, according to a definite law, slightly on the temperature.
If,

for convenience, -y

is

made equal
VOL.
ii.

to

K, the equation becomes

(a

z)(b

z)

Kz\
30

458

ORGANIC CHEMISTRY
K=
-

With 46 grams of alcohol and 60 grams of acetic acid (gram-molecules), it is found 0-25, and, as a and fo-both assume the, value 1, 1 mol. of each experimentally that 1 0-25 z 3 i.e., \-z~- 0-5 z or z :. reacting, the equation becomes (1 This z} means that when a state of equilibrium is reached, the system contains \ mol. of acetic acid f- i mol of alcohol 4 * mol. of ester {mol. of water. Every substance partici paling in the equilibrium acts in proportion to its mass. If the above equation is given

the form

=
A'^

it

becomes evident that, in order to displace the equilibrium

so as to have a greater value of z (i.e., of esterilication), the value of a must be increased and that of b decreased, esterification being complete when </ The same final result oo is obtained when b is much greater than n, esterilication when b co
.

again being complete In practice, almost complete esterification is attained when I mol. .of acid is employed per 10 mols. of alcohol or rice versa. That the same result is obtained with excess of alcohol as with excess of acid is shown by the above equation, since, if instead of mols. of both acid and alcohol, n times as many molecules of acid are taken, the equation becomes :
.

/w

A
2
ti

11

ttl

whilst

if

n times as

many molecules of alcohol

are taken,

it

becomes

in

z
r

^~__

"V
-

l'hese

two equations are

identical, multiplication of the

terms of

the former by

giving the latter.

The limit of esterification is modified but slightly by change of temperature, and in the case of acetic acid, to 62-2 per cent, at 10 and to fifi-5 per cent, at 220",

amounts,

Rabatier and Mailhe (1909 1913) have shown that in many cases esters are obtained with dry catalysts, especially thorium oxide or, better, titanium oxide at about 300 over these is passed the mixed acid and alcohol vapours in suitable proportions, i.e., with excess of one or the other component. Wlien, however, a certain temperature, varying with the nature of the catalysing oxide, is exceeded the reaction becomes reversible and more or less decomposition
;

occurs.

and monobasic fatty acids are neutral than water (0-8 to 0-0) and pleasant smelling (some forming artificial fruit essences) they are slightly soluble in water (the first members more soluble than the higher ones) and they boil undecomposed.
esters of moiiohydric alcohols

The

liquids lighter

By means
The

of Grignard's reaction (see p. 243) they yield tertiary alcohols.

components when heated with alkali, mineral acid, or aluminium chloride, or superheated with water. The mineral acid has a purely catalytic accelerating action on the following reaction due to the water, which is very slow in its action
esters are hydrolysed into their
:

OH 3 C0 2 2H 5
-

+H

-.=

H OH + CH 3 CO
5
:

H.

With

bases, the hydrolysis

is

expressed by the equation

2

CH 3 C0 8
disscciation, i.e., far more slowly

C H + NaOII = H5 OH
2 6

f GH 3 CO 2Na.

The hydrolysing on

velocity of acids and bases depends on their degrees of their strengths, so that feeble acids and bases hydrolyse than the strong ones. In the case of acids, the hydrolysis is

by the hydrogen ions, and in that of bases by the hydroxyl ions. In the latter instance, however, the velocity of hydrolysis is greater than with for dccinormal potassium fc'cids, and with methyl acetate, tin value of hydroxide is 1350 times that for decinormal hydrcchloric acid. In the hydrolysis of fats, the acids of which are feeble and the resultant salts therefore hydrolytically dissociated to a marked extent (i.e., even with excess of fatty acid, there always remains free base or hydroxyl ions), complete hydrolysis is obtained industrially with a quantity of base (e.g., lime) much less than that
caused

required theoretically.

FRUIT ESSENCES
with suitable admixtures as
artificial fruit evssences. 1
,

459

As has been already mentioned, the esters of the first monobasic acids and monohydric alcohols are, in general, substances of pleasing odour and are used

ETHYL FORMATE, H COOC 2 H 5

rum
to or arrack.

boils at

55

and

is

used for

artificial

METHYL ACETATE, sp. gr. 0-9577, b.-pt, 57-5, is used to dissolve cellulose make the varnish ( u dope ") for aeroplanes in its manufacture from acetates,
;

sulphuric acid and methyl alcohol, the plant is rapidly attacked, even if enamelled. Duchemin obtains the ester directly from pyroligneous acetic acid and methyl alcohol by means of a catalyst (the nature of which is not dihcloRcd), a yield of 95 p^r cent, being thus obtained and the intermediate the resulting ester is -then rectified preparation of calcium acetate avoided r/feo Ger. Pats. 232,8JS, 277,1 JJ, 277,187, (,sr*, 277,188,~285,990, and 286,812). ETHYL ACETATE or Acetic Ester, CH 3 COOC 2H 5 is used in medicine and for the preparation of ethyl acetoacetatc, which is of considerable importance in organic syntheses. It is prepared by heating alcohol with acetic and sulphuric acids under the conditions given above. It boils at 77 and has the sp. gr. 0-9238 at 0.
; ,

sp. gr. 0-8702 at 15 and b.-pt, to 139, and forms a colourless, fairly mobile inflammable liquid, of neutral reaction and with the odour of pears it is very highly soluble in alcohol or ether and slightly so in water, and burns with a luminous flame. It is used as a solvent for cellulose acetate and celluloid in the preparation of varnishes, " " to some extent it serves for making alcoholic especially aeropkne dope solutions of artificial fruit (pear) essences.

AMYL ACETATE, CH 3 COOC 5 H 11? has the

;

138

The crude impure product is prepared directly from fusel oil (see p. 105) and acetic and sulphuric; acids (calcium acetate is also used). The pure ester is obtained by heating 100 parts of pure amyl alcohol, 100 of glacial acetic acid, and 50 of concentrated sulphuric acid for two to three hours at 100 in a
copper vessel fitted with a reflux condenser. It is then distilled in a current of steam, the vapours being rectified slightly by means of a short column. The distillate is washed with a little sodium bicarbonate solution and twice with a little water, and is then dried by means of fused calcium chloride. The final product contains 85 to 95 per cent, of amyl acetate, the rest being amyl alcohol. The yield is about 95 per Cc nt., the loss of sulphuric rcid amounting to per cent. A second rectification yields a purer product, Amyl acetate may be obtained also by passing amyl alcohol and acetic acid vapours over a catalyst, #.</., dry titanium oxide at 280 to 290 (or oxide of thorium or glucinum). Prior to the war the commercial product cost 5 to i>er cwt., and the pure ester about double as much.
j

Commercial fruit essences arc prepared from the following mixtures

cost from 2s.

of esters,

and formerly

-f- 135 grams amyl valerate + 5 grams ehlorofonn -|- 5 grams aldehyde + 850 grams alcohol. Essence of apples : 50 grams ethyl nitrite -}- 50 grams ethyl acetate -f 100 grams amyl valerate -|- 40 grams glycerol -f 7-5 grams aldehyde 7-5 grams chloroform 745 grams

to 5s. per kilo : Essence of pineapple : 25 grams ethyl butyrate

tid.

alcohol.
nitrite
: 200 grams amyl acetate \- 50 grams ethyl acetate -| 100 grams ethyl 20 grams glycerol -f- 630 grams alcohol. Essence of apricots : 45 grams benzaldehyde -f- 190 grams amyl butyrate -f- 10 grams chloroform 705 grams alcohol. Essence of strawberries : 27 grams amyl acetate -f 18 grams amyl valerate + 9 grams amyl butyrate + 9 grams amyl formate + 15 grams ethyl acetate -f 7 grams essence of violets -\- 915

Essence of i#ars

grams

alcohol.

Essence of peaches : 100 grams ainyl valerate -f- 100 grams amyl butyrate -{- 20 grams ethyl acetate -f- 10 grams benzaldehyde -f 770 grams alcohol. The natural essences of the citrus fruits were given on p. 415 The amounts of different volatile oils and essences imported into France were (tons) : 845 in 1913, 612 in 1914, and 759 in 1915.

460
of pineapple

ORGANIC CHEMISTRY
,

ETHYL BUTYRATE, C 3H 7 COOC 2H5

and
in ruin.

boijs at 121

and

is

used as essence

ISOAMYL ISOVALERATE, C 4 ' COOC rfL ll9 boils at 194 and is used in essence of apples. The higher otter* form constituents of waxes (Cetyl Palmitate, C lfiI[ sl 2C 16 33 ; Melissyl Palmitate, Ceryl Cerotate, C 26 r>1 2 26 II5 3, etc,'). 81 O a (1 ao ir6l lfl
ft

These higher esters distil unchanged only in a vacuum ; under ordinary pressure they decompose into olefines and fatty acids. Esters of Polybasic Acids are prepared by the. general methods described acid esters are obtainable if one or more of the carboxyl groups are above
;

not

esterilied.

The esters of oxalic j:eid are obtained, for instance, by heating anhydrous oxalic acid \\ith alcohols, the normal ester being separated from tin acid ester by fractional distillation.
1
,

The impoitaucc
illustrated

on pp.

3(58 ef w//.

of Malonic Esters in organic syntheses has already been and tins ; the normal inethvl ester boils at 181 also be repaired
:

The two hydrogen atoms united with the by alkyl groups. Thus, for example, may Ethyl Dimethylmalonate, (r 2 H- V())., f-((. H.,) 2 is obtained from the sodium derivative by treatment with methyl iodide. These compounds, when heated, lose C0 3 and yield alkylacetic derivatives. Similar relations are found with
ethyl at 198
(sp. gr. MJfiH at 18").

middle carbon atom

the alkyl derivatives of succinic acid or esters. The preparation of Ethyl Acetoacetate and its importance in organic syntheses have been dealt with on p. 396. ( O 2 OH,, The Normal Methyl Ester of sumnic acid, CII 3 CO 2 CH 2 2 melts at 19 and boils at 8') under 10 mm. pressure the el In/I e^ler boils at-

CH

216.

GLYCERIDES, OTLS, FATS

(Jlycerol being a trihydrie alcohol, its three alcoholic groups may be partially It suffices, indeed, to heat glycerol or wholly esterified by acid residues. with fatty acids to obtain mono-, di-, and tri-glyeerides. These glyrerides are also formed by the action of the tissues of the pancreas on a mixture of oleic acid and giyrerol, a still better method for synthesising fats being the treatment of the sulphuric ethers of glycerol with fatty aeids dissolved in concentrated sulphuric acid. Most fats and oils are formed of triglycerides, which, according to the nature of the fatty acid saturating the. three alcoholic groups of the glyeerol, are termed Tripalmitin (melts at 60'"'), Tristearin (melts first at 55 and, after resolidificiition, at 71-6), and Triolein (liquid, solidifying

at about 0).
Triolein,

of olive

oil, is

which is the principal component of liquid fats and especially formed bv the estcri (i cat ion of the glycerol molecule with 3 mols.
:

of oleic acid (ace p. 358)

cn

o o (iu
-

cn 2 o o tyi 33
-

Mono- and di-glycerides arc not found in the fats (only ravison oil contains a diglyceride. dimtein ; *ee aho esters of polyhydrii* alcohols and glyeerol with mineral acids, pp. 350, 381 el set].). Certain fats (butter, cocoa-butter) contain mixed triglyrerides, i.e., with different aeid radicles, some of them being of aeids of low molecular weights, soluble in water. 1 A. (.{run (1906 1909) synthesised mixed glycerides conThe number of c.e. of dccinormal potassium hydroxide Vohttik fatly acids whittle in wattr. Holution required to neutralise the volatile fatty tic-ids soluble in water from 5 grms. of the fat
1

R El

CHERT AND HEHNER NUMBERS

,

461

1 The most simple glyceride is Tritainiug three acid residues, all .different. formin, C 31I5 (()0 2H) 3 which w*i& obtained crystalline by P. van Romburgh it (1910) by protracted healing of glycerol with 100 per cent., formic acid (7(52 mm. pressure), crystallises with difficulty, melts at 18", boils at 20(5 and at 210, under ordinary pressure, decomposes. It is Imlrolysed slowly by
;

cold, rapidly

by hot water.
number, and serves to ascertain the purity

constitutes the so-called Reichert-Meissl-Wollny

of certain fats, especially ot butter. The dcterniinntioii is made as iollows : exactly 5 grins. ot the fat (melted at a low temperature and rapidly Hltered) is healed in a llask of about 3f>0 e.c.

capacity with 10 e.c. of alcoholic potash (20 grins, ot K<>H in 100 c.c. 70 per cent, alcohol) on a water-bath with frequent shaking until almost all the alcohol is evaporated ; the remainder of the alcohol is completely expelled by shaking the Jlask aud introducing a current of air every half-minute. After about twenty minutes, when the smell of alcohol is no longer detectable, 100 c.c. of distilled water is added, the heating being continued until a clear Mention is obtained (if the liquid does not become clear the test must be commenced anew, hydrolysis being incomplete). To the tepid solution are then added 10 c.c. of the dilute sulphuric acid (1 vol. cone. HgKO, {- 10 vols. water) and a lew Iragments of pumice, the tlask being then placed on a double wire-gauze and the liquid distilled, the dimensions of the apparatus
In about half an hour, exactly 110 e.c. being shown in mm. in Fig. 2.54. of liquid distils over; this is mixed and filtered through a dry tilter, MM) c.c. of the filtrate being titrated with dec norm a I KOII solution in presence of phenolphthalein. The volume ot the alkali used is incicased bv one-tenth of its value (the \olmnc of the distillate being 1 H) c.c.) and diminished by the number of c.c. of the alkali obtained from a control experiment made without
i

The result is the I'eichert on the reagents employed At the present time many laboratories employ the LeiTmann-Bcam-1'olenske method, which eileets more rapid hydrolysis For butter the limits for this number allowed by law are (JWT laltr. Butter). 2(> to 31-5 (Municipal Laboratory of Milan), the butter being suspected if it gives u value of 22 to 2(i, althouuh the butter of certain districts and from certain animals may, in exceptional cases, give a number as low as 21. The value for rancid butter, even two months old, is only slightly lo\\er (by about 2) than the normal. luttoluhh fully at itfu. The quantity ol fatty acid insoluble in water obtainable from 100 parts of fat is called the Hehner number, and is determined as iollows into a ilask of about 2lM) c.c. capacity is dropped, from a weighed vessel containing the dry filtered fat, to 4 grins, of the substance, the vessel being then reweighed exactly. After addition of fill c.c. ot alcohol and 1 to 2 grrns. of KOli, the flask is heated on a water-bath lor five minutes, Km. 254. a clear solution being obtained. It the addition of a drop of water pro duces turbidity, saponification is incomplete, and the heating is continued for a further period of five minutes, the liquid being then tested as before, Evaporation is then continued until there remains a dense mass, which is taken up in 100 to 150 c.c. of water, acidified with dilute sulphuric acid, and heated until the clear fatty acids float on the surface. The liquid is then poured on a dry, tared filter (about 12 cm. in diameter and in a funnel either without a neck or viitli a verj short one), previously half filled with hot water. The, acids are u ashed with boiling water until the washing water ceases to show an acid reaction (as much as 2 litres of water is sometimes required). The filter is then cooled in a beaker of water so that the fatty acids solidify. The filter is then detached from the tilter and introduced, with the acids, into a tared beaker, which is heated in an oven at 100 to 102" until its weight remains almost constant (difference between two weighings less than I mgrm.). The weight of fatty aeifls, referred to 100 parts of fat, represents the Hehner number. Unadulterated fats generally have Hehner numbers ot (15 to 97 (for butter it is K7-5 ; for coconut oil, 85 to 92 ; for palm -kernel oil, 91). 1 The synthesis of t Hole in has been applied practically by (i. (Jianoli (1S91) to diminish the rancidity of oils, especially of olfw oil obtained from the* pressed residue by means ot carbon This oil contains 20 to 30 per cent., or even more, of oleie acid, and is heated in an disulphide. autoclave with the corresponding quantity of glycerol (or even a slight excess) at 250" in a slow stream of (*O at or in a vacuum with a trace of oxalic acid to facilitate mix-in? of the liquids and avoid blackening of the mass owing to the presence of hydroxy-acids; the distillation of the. water formed in the reaction is hastened by adding fragments of tin to the mass. This procedure yields a neutral or almost neutral oil with an iodine number less than 75 and a marked viscosity, so that it may be used even for mixing with lubricating oils. Bellticci (1911) also achiever) an almost quantitative synthesis by heating together the theoretical proportions of ulycerol and hours a vacuum, so as to expel the acid to 2<K)^ for two in (1 mol.) (3 mols.) at ISO fatty water formed, which would otherwise produce the reverse reaction iti a current of (_'Oj, the same reaction takes place at the ordinary pressure. \. Walter (1911) obtained a mixture of tri- and di-oleins by treating glycerol and acetic acid in presence of th enzymes of castor oil seeds, which aet as catalysts. Indeed, ratal'//*/* cause reversible reactions, and whiln in presence of water the enzymes of 'castor oil seeds hydrolyse fats (we laltt\ Biological Saponification) with formation of glycerol and fatty acids, if water 'is CA eluded as much as 35 per cent, of the fatty acids may be converted into glyeerides.
fat as

a cheek

MeissMVolluy number.

.'$

'

462
Oils

ORGANIC CHEMISTRY
and
fats

expansion greater than those of other becomes 101 -6 at 20). Fats and, still more, waxes contain also non-glyceride components, e.g. Cetyl Alcohol, C^H^O, which, as such or as palmitic ester, forms one of the principal constituents of spermaceti fat. Cerotic Acid, C 27 52 2 and its ester occur in large proportions in wax. Non-hydrolysable substances (cholesterol, phytosterol, isocholesterol, aromatic alcohols, etc.) are always found in small -75 per cent. ravison oil, 1 per cent. quantities in fats (olive oil, about cottonseed oil, 1-6 per cent. cod liver oil, 0-5 to 3 per lard, 0-25 per cent. cent. bone fat, 04 to 24 per cent. tallow, 0*02 to 0-6 per cent. wool fat more than 7 per cent.). The oils of cereals and of Leguminosece contain abundant amounts of LECITHIN, C42H86 9NP, which is decomposed by the enzyme of the pancreas or castor oil seed, but not by that of the blood (serum lipase).
coefficients of

have

liquids (100 litres of olein at

fat of peas contains 1-17 per cent, of phosphorus or 304 per cent, of and that of wheat, 0-25 per cent, of phosphorus or 6-5 of lecithin. Lecithin abounds in the brain, nerves, blood corpuscles, and egg-yolk ; for its The amount of lecithin is obtained by constitution, see chapter on Proteins. multiplying that of phosphorus by 26. Fresh fats and oils contain minimum proportions of free acids than 1
lecithin,

The

fatty

(less

per cent.), these increasing with lapse of time, especially if the fats are not melted. This rancidity is facilitated by sunlight and also by the protein substances of unrefined fats and oils. Coconut oil does not readily turn rancid, but with olive oil the proportion of free oleic acid reaches 25 per cent., and with palm oil as much as 70 per cent, of free acids may be formed. The taste and smell of fats depend, not on the glycerides, but on other substances. The specific gravity of oils and fats varies from 0-875 to 0-970 (see Table given later) and is determined by means of an aerometer or Westphal balance (see Vol. I., p. 76). They are almost completely insoluble in water, acetone, or cold alcohol (this dissolves a certain amount of castor oil and of olive-kernel oil).

The solubility increases markedly in boiling alcohol and is complete in ether, chloroform, carbon disulphide or tetrachloride, petroleum or petroleum ether (in the last two, castor oil is slightly soluble, while ether dissolves .a little pure tristearin). 1

When

heated on a spatula held some distance above a flame,

fats give greenish flames, owing to the presence of carbon monoxide and sodium ; also all fats are blackened osmium
all

by

tetroxide (sensitive reaction). Oils dissolve small quantities of sulphur or phosphorus and larger quantities of soaps even when they are dissolved in ether or

petroleum ether.
it is

walnut, hempseed, poppyseed, etc.), which are thus transformed into varnishes, this occurrirg more readily if the oils are boiled with oxide of lead
or of marganese.

The oxygen of the air fixed by the drying

exerts a

marked and rapid

influence, as

oils (linseed,

To determine the quantity of fat contained in any solid substance, a weighed portion of the latter in a finely divided, dry state (5 to 15 grms. is taken and, if pasty, mixed with fragments of pumice) is introduced into a filter-paper cartridge situate in a tioxhlet apparatus (Fig. 255). The Soxhlet apparatus is connected at the bottom with a tared flask resting on a water-bath, and at the top with a reflux condenser. From 100 to 160 c.c. of petroleum ether or ether is then added and extraction continued for 2 to 4 hours in such a way that the solvent siphons over 16 or 20 times calcium per hour. FIG. 265. chloride tube may be attached to the extremity of the condenser to prevent access of moisture from the air. The solvent is afterwards evaporated from the flask and the residual fat dried at 100 to 102 until almost constant in weight. The difference between the weight of fat and 'that of the original substance gives the solids
1

not fat.

IODINE NUMBER REFRACTIVE INDEX

;

463

With the other non-dryicg oils, the air (together with light) gradually causes rancidity, which, however, some attribute to the action of bacteria, Or rather to hydrolysing and oxidising enzymes however this may be, the acidity increases owing to formation of butyric, caproic, oleic, etc., acids, but the rancid taste and smell are due more especially to the formation of aldehydic, ketonic, and ethereal substances, hydroxy-acids, and volatile acids which can be eliminated by repeated washing with dilute solution of alkali and subsequently of bisulphite
Butter).
(for

the aldehydes and ketones, see

later,

Eenovated

turn rancid, the iodine number 1 is lowered and the index of the refraction? dropping or melting-point (see pp. 5 and 6), and the acetyl
fats

When

The Iodine Number is characteristic of a fat (see Table, p. 466), and expresses the percentage by the fat (i.e., by its unsaturated components, e.g., oleic acid or the corresponding glycerides, two atoms of iodine being fixed for each double linking, see, p. 107). This determination requires (1) An iodine solution obtained by mixing, 48 hours before using, equal volumes of the two following solutions (a) 25 grins, of iodine in 500 c.c. of pure 95 per .cent. alcoholj and (b) 30 grms. of mercuric chloride in 500 c.c. of pure 95 per cent, alcohol (2) a sodium thiosulphate solution, prepared by dissolving 24 grms. of the pure salt in a litre of water, the
1

of iodine absorbed

titre in iodine
is

3-8657 grms. of pure, dry potassium dichromate being ascertained as follows dissolved in water at 15 and the solution made up to a litre ; exactly 20 c.c. of this solution is introduced into a flask with a ground stopper, about 15 c.c. of a 10 per cent, potassium iodide solution (free from hydroxide) being added and then 5 c.c. of concentrated hydrochloric acid. This procedure results in the liberation of exactly 0-2 The thiosulphate solution is then run grrn. of iodine. in from a burette until the solution is only faintly A few drops of fresh starch-paste a\e then yellow. added and addition of the thiosulphate continued until the blue colour disappears. It is thus found how much iodine corresponds with 1 c.c. of thiosulphate solution, the strength of which remains constant for several months. The iodine number is determined by dissolving a known weight of the fat or oil (0-2 to 0-5 grm. or, for drying-oils, 0-1 to 0-12 grm.), in a 500 to 800 c.c. flask with a ground stopper, in 15 c.c. of pure chloroform and adding 25 c.c. of the iodine solution (prepared 48 hours previously, as stated above) ; if, after two hours, the liquid is no longer very brown, a further measured volume of iodine solution is added and the whole left in the dark. After six hours the excess of iodine left unabsorbed by the fat is determined by adding 20 c.c. of 10 per cent. Kl solution, diluting with 150 c.c. of water, and adding more Kl if the reddish brown solution is not clear. The excess of iodine is then titrated with the thiosulphate solution in the manner already described. Immediately afterwards, 25 c.c. of the iodine solution employed is titrated. The difference between the two values thus obtained, expressed as grams of iodine per FIG. 256. 100 grms. of the fat, represents the iodine number. 2 The index of refraction is measured in the Zeiss Buty ro -re flactometer (Fig. 256), by observing the total reflection of a very thin layer of oil or fat situate between two prisms, '/>, mounted in the two chambers, A and (the latter rotates on the hinge, C, so as to squeeze uniformly the film of oil smeared in p : the screw. F, fixes B against A). Indirect light from the sun or from a powerful sodium lamp is passed through the prisms by means of the mirror, J, and the limit between the light and dark portions of a scale reading from to 100 is read through the eye-piece, K. thermometer, M, indicates the temperature at which the observation is made, and this temperature may be regulated (SD as to melt solid fats) by passing water, at a higher or lower temperature, in at E and through the rubber tube, D, to the outflow, , The refraction is usually stated in the centesimal degrees of the Zeiss scale, the temperature being indicated. Values obtained at other temperatures may be referred to normally 25 the normal temperature by adding or subtracting 0-55 for each degree above or below 25 (the number 0-55 is accurate for butter, but slightly inexact for other fats). The index of refraction is obtained from the reading on the Zeiss scale by adding to the value 1-4220 as many ten-thousandths as are obtained by multiplying the scale degrees by 7-8 when the reading is between and 30 ; 7-5 if between 30 and 50 ; 7-3 if between 50 and 70 ; and 7-0 if between 70 and 100. (This procedure, too, gives accurate values for butter, but slightly inaccurate ones for other fats). Thus, 30 on the ZMss scale would correspond with a refractive
:

index of 1-4220 -f 30

14*220 -f 0-0234

14454, which agrees almost exactly with

464
number

ORGANIC CHEMISTRY

In butter rancidity is facilitated by the presence of (see p. 224) rise. the casein and milk-sugar, which give rise to other decompositions. Although hot rigorously exact, the degree of rancidity is expressed by the number of c.c. of normal potash necessary to neutralise 100 grms. of the fat. A butter with 10 of rancidity should be rejected. The free fatty acids in fats and oils are usually determined with a decinormal alkali solution, 5 to 10 grms. of the fat being dissolved in 50 to 60 c.c. of a perfectly neutral mixture of alcohol and ether (1:2) and phenolphthalein being used as indicator. The acid number gives the number of mgrms. of necessary to neutralise 1 grm.

KOH

of fat.

By passing a current of air through oils heated to 70 to 120, the so-called blown or oxidised oils, rich in triglycerides of hydroxy-acids, are obtained. These are dark in colour and have the density of castor oil (but are soluble " " in petroleum ether), but if blown in the cold for a longer time, they are obtained almost colourless. Blown oils are valued as lubricants. If the blowing is continued, yellow or brown gelatinous masses are obtained. With the exception of the iodine number and the Hehner number which are lowered the chemical and physical constants of blown oils (thickened oils, etc.) are higher than those of the original oils. Oils also fix ozone in proportion to the unsaturated fatty acids they contain, and at the same time become denser (see olive oil has the ozone number 15-8 (grms. of ozone fixed per 100 grms. p. 359) of oil maize oil, 21 linseed oil, 33 and castor oil, 16. Also Fenaroli, 1906) sulphur is dissolved and combined in aliiount increabirg with the proportion of glycerides of unsaturated acids present, giving very viscous, brown liquids, sometimes almost solid and gummy.
;
: ; ;
;

Chlorine acts on fats, partly replacing hydrogen and partly combining

directly.
is added slowly, but the addition becomes rapid in alcoholic solution in presence of mercuric chloride (Hiibl). Addition of concentrated sulphuric acid to oils results in the development

Iodine

and

of heat and the evolution of sulphur dioxide in the cold, sulphuric ethers of the triglycerides are formed. 1 Dilute nitric acid, in the hot, slowly oxidises fats, while the concentrated acid attacks them with evolution of red vapours. Nitrous Acid renders non-drying oils denser and solidifies them, the triolein the drying oils remain liquid, being* converted into trielaidin (see p. 359)
; ;

although their specific gravity, viscosity, and saponification number increase, ~ and the iodine number and Hehner number (per cent, of
insoluble fatty acids) diminish. When burnt, fats give the characteristic odour of acrole'in,

which

is

derived from the glycerol.

similarly,

*7o

the true index of refraction (14452)

refractive index of 1-4220 -f 60

60 on the scale means

-

Inversely, the scale -TQQQO reading is obtained by subtracting 1-4220 from the refractive index and dividing the remainder by 7-8, 7-5, 7-3, or 7-0. The colour of the line of demarcation on the scale sometimes gives an indication of impurity in the fat, being colourless for pure butter, blue if margarine is present, and orange with admixtures of certain other fats. 1 Maumen6 found that the rise of temperature produced by suphuric acid of definite concentration serves to distinguish different fats (see Table FIG. 257. given later). This constant (Maumend number) is nowadays determined by means of the Tortelli thermo-oleometer (1905). 20 c.c. of the oil is poured into the glass receiver, A (Fig. 257), the jacket of which has been evacuated. The oil is stirred for one minute with the thermometer, J5, fitted with platinum vanes, and the initial 5 c.c. of concentrated sulphuric acid (sp. gr. 1-8413 or 66 Be\) is then temperature read. added from a pipette in 30 seconds, the liquid being kept stirred as long as the temperature rises. The rise of temperature is the Maumend nuiriber. If the sulphuric acid has not the density given above, but is allowed to absorb even traces of moisture, discordant results are obtained.

1>4658

WAXES
On
(different

465

paper, fats and oils produce a translucent spot, insoluble in water

from

glycerol).

All these reactions serve as qualitative the purity of fatty substances (see later).

and quantitative

tests to establish

WAXES. Unlike fats, waxes are usually composed, not of triglycerides, but of esters derived from the higher monohydric alcohols (e.g., cetyl, myricyl, and ceryl alcohols, cholesterol, etc.), and sometimes dihydric alcohols also. They contain, in addition, the high acids (e.g., palmitic, stearic, cerotic, oleic, etc.) and alcohols in the free state. Further, beeswax contains as^much as 15 per cent, of high melting-point hydrocarbons.
They form homogeneous mixtures in all proportions when fused with fats and give also a greasy spot on paper, but they yield no odour of acrole'm when burned (unlike fats) and do not become rancid when exposed to the air.

The commonest waxes are beeswax, Japanese wax, spermaceti wax (from whales), and carnauba wax (from the leaves of certain palms). Beeswax forms the hexagonal cells of beehives. After the honey has been expressed, the mass is melted with water to remove impurities ; on cooling, a solid layer of crude wax separates at the surface, and this, after being melted and cast into blocks, forms virgin or yellow wax. This is placed on the market in various qualities and colours, some of them being olive-brown they bear the name of the place of origin and can be bleached with
;

varying

facility.

The European waxes have the

following physical

and chemical constants, which allow

of the detection of the frequent adulteration to which they are subjected : melting-point, 62 to 64; solidification point, 60 ; specific gravity at 98 to 100, 0-822-0-847 ; saponification number, 95 to 97 (rarely 88 to 105) ; acid number, 19 to 22 ; difference between

saponification number and acid number (ester number), 74 to 76 ; iodine number, 8 to 11 ; degrees on the Zeiss butyro-rcfractometer at 40, 44 to 45-5 (rarely 42). Foreign waxes

have somewhat

different constants.

of the wax is effected by melting it several times with slightly acidified water, allowing it to cool slowly so as to separate the impurities more thoroughly and then causing it to solidify in thin layers on a cylinder half immersed in water and exposing these to the sun and air for five to six weeks. A more expeditious method of bleaching consists in treatment with hydrogen peroxide or other oxidising agent (dichromate and

The bleaching

dilute sulphuric acid), or with animal charcoal.

The

white

wax thus obtained

often

improved in appearance by the addition of 4 to 5 per cent, of tallow presents almost the same physical and chemical constants as the virgin wax, the iodine number alone
being lowered by
1

to

7.

insoluble or only slightly soluble in cold alcohol or ether, but dissolves in the boiling solvents. It dissolves in the cold in chloroform, oil of turpentine, carbon It resists dilute caustic alkalis and concentrated alkali cardisulphide, or fatty oils.
is

The wax

bonates.

It is

used^for making candles,

waxed

cloth

and paper, mastics,

artificial fruit

and

flowers, etc.

Carnauba wax is exuded from the leaves of certain palms (Corypha cerifera) of Brazil In the crude state, it is hard and brittle, and of a yellowish green colour it melts at 83 to 88, has the acid number 4 to 8, the saponification number 80 to 95, the ester number 75 to 76, and the iodine number 7 to 13, and contains more than 50 per cent, of non-hydrolysable substances. It is used for the manufacture of candles and, mixed with potash (soft) soap, forms the encaustic with which pavements are cleaned. Japanese wax is the fat extracted from the fruit of certain Japanese and Chinese trees

and Venezuela.

(Rhus succedanea, R. vernicifera, and R. sylvestris). It differs number of about 200 and a saponification number of about 220. It is completely hydrolysable, since it consists of glycerides of palmitic, stearic, and arachic acids, and contains also 9 to 13 per cent, of free palmitic acid. Uses. Wax was formerly used mostly for making the wax candles prescribed for religious ceremonies in Roman Catholic churches, and about the beginning of the present century the Holy Synod of the Orthodox Russian Church rendered obligatory the use of candles of beeswax. Admixture with beeswax of stearin, paraffin wax, and various other

of the order Terebinthaceae

from beeswax in having an

ester

substances is, however, not easy to detect by analysis. Before the European War, yellow beeswax cost up to

150 per ton and the bleached

wax

170.

466

ORGANIC CHEMISTRY
i!
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SAPONIFICATION

467

Hydrolysis (Saponification) of fats and waxes. The term saponification is applied to the decomposition of fats into the alcohols and acids composing them with simultaneous addition of a molecule of water (hydrolysis), by heating with water under pressure at 200 or by the action of acid or alkali (see
p. 458) ; when alkali is used, the alkali salt (soap) of the fatty acid free acid itself is obtained
:

and not the

C 3H5 (0

OC 18H 35 ) 3
Tristearin

+ 3KOH = C 3H5 (OH) + aC^H^K.

3
Glycerine

Potassium stearate

gradually, (bimolecular reaction) (see Vol. L, p. 69) and di- and monoglycerides being formed as intermediate products, whilst, according to others, saponification was a single (tetramolecular) reaction. Only since the investi-

troversy.

The mechanism of the saponificatiou Some regarded it as occurring

1 of alkali

of fats

was

for long a matter of conmol. of fat first reacting

with

gations of Geitel (1897), Lewkowitsch (1898-1901) and, more especially, Kremann (1906), does it appaar to be established with certainty that saponification is gradual, consisting of successive bimolecular reactions. Contrary to the view of Fortini (1912), J. Meyer (1913) showed that the various glycerides, glycerol, and soap occur together in an equilibrated mixture, the equilibrium

undergoirg gradual displacement towards complete saponification, as was by the results of Kellner (1909) and of Kremann (1905-1908). Saponification with lime, baryta, or lead oxide is never so complete as wi';h caustic potash or soda in the hot, while with an alcoholic solution of caustic potash or soda it is complete and rapid, formation of the ethyl ester of the fatty acids and liberation of glycerine first occurring and then complete hydrolysis of the ethyl ester. The latter may be obtained directly from fats by heating them with slightly acidified alcohol. Sodium and potassium carbonates do not attack fats. Fats may be saponified by treatment with a small propo\cion of aqueous ammonia in an autoclave, but the early attempts to render this process practicable on an industrial scale were unsuccessful. The reaction was, however, investigated systematically by Garelli, Barbe and De Paoli, who obtain complete saponification by heating the fat for seven to eight hours in a lead-lined autoclave under a pressure of 6 atmos. with a minimum amount of ammonia (0-6 per cent.), which acts catalytically and liberates the fatty acids. This process is undoubtedly an improvement on the lime, magnesia and zinc oxide processes, but since the ammonia cannot be recovered, it cannot compete with the enzymic decomposition of fats in open wooden vats at comparatively low The use of 6 to 7 per cent, of ammonia, as proposed temperatures (see later). by Buisine (1883), or even of 2 to 3 per cent., in an autoclave leads to serious difficulty owing to the formation of a completely emulsified mass of ammonia soaps which do not allow the glycerine solution to separate, and to the trouble and expense of treating the ammonia soaps with steam to separate the fatty acids. Garelli, Barb6 and De Paoli (Ger. Pat. 209,537, 1906) transform the ammonia soaps directly into soda soaps by simple treatment with sodium the recovery of the chloride, just as in the Solvay soda process (Vol. I., p. 596) ammonia is, however, difficult and the loss exceeds 8 per cent.
indicated
;

A process patented some years ago for saponifying fats by means of sulphur dioxide or bisulphite in autoclaves at 10 to 15 atmos. offers no promise of
practical epplication.

No matter how difficult the saponification of a fat, it may be rendered complete even in the cold by the Henriques process, which consists in dissolving, say, 3 to 4 grms. of the fat in 25 c.c. of p3troleum ether and 25 c.c. of normal alcoholic potash, the mixture being shaken from time to time during a on heating, waxes are also dissolved in this manner. period of twelve hours
;

468
of alkali

ORGANIC CHEMISTRY
of alkali fixed (saponification number), 1 the excess
is

To determine the quantity

titrated with

normal acid solution. Dilution of the saponified waxes with a considerable amount of water results in the separation of the higher alcohols, which can be extracted with
ether.

are

Spermaceti contains 40 to 60 per cent, of these insoluble alcohols (which industrially as non-sap onifiable substances), beeswax 53 per cent., and carnauba wax 55 per cent.

known

ANIMAL OILS AND FATS

not possible 'heje to study in detail all fats, so that only the more important ones, the processes of treating which are partially applicable to the others, will be considered. Classification of fats into those of animal and those of vegetable origin or into solids (tallow, lard, sheep's tallow, goose grease, and coconut butter) and liquids (oils) is of no practical value, but it is necessary, with the liquid vegeIt
is

table fats, to distinguish between those which have drying (linseed, walnut, poppyseed) and those with non-drying properties (olive, colza, arachis, castor,

cottonseed, maize, etc.). Animal fats are usually melted (by direct-fire heat or by steam) or compressed either hot or cold, although sometimes they are extracted with solvents. Vegetable oils are extracted from the disintegrated seeds by pressing them hot or by treatment with suitable solvents. In both cases they are refined by a series of mechanical and chemical operations which will be described more
particularly in dealing with tallow, butter, and olive
oil.

etc., but not hog's fat) melts at 35 to 37, contains 75 per and palmitin (in equal parts) arid 25 per cent, of olcin. In the crude state, as it comes from the slaughterhouse, it is incorporated in a cellular tissue and contains various impurities, such as blood, skin, etc., which gradually putrefy, giving a bad odour to the tallow. To prepare the real fat from the crude tallow, the latter is cut up in suitable machines fitted with knives and is then melted in open iron or copper boilers provided with stirrers and heated either wholly by direct-fire heat or partly in this way (Fig. 258) and the tube, D. The partly by injecting direct steam, superheated to 180 to 200 through burned. strongly smelling gases evolved are led by the pipe, a, under the hearth and there

TALLOW

(ox fat, sheep fat,

cent, of stearin

or KotMorf number, indicates the number of milligrams is made necessary to saponify 1 grm. of fat or wax completely. The determination 1-5 to 2-2 grm. of the filtered fat is weighed into a 150 to 200 c.c. wide-necked flask, as follows solution prepared with 90 per cent, to which is then added 25 c.c. of seminormal alcoholic The mixture is then heated for 15 to 20 minutes alcohol and also 25 c.c. of neutralised alcohol. in a reflux apparatus on a water-bath previously heated to boiling, and, while still tepid, is 2 SO 4 ), titrated with seminormal hydrochloric acid (not sulphuric acid, which would precipitate c.c. of seminormal using phenolphthalein as indicator. Multiplication of the number of solution actually consumed in the saponification by 0-0301 gives the number of mgrms. of KOH, which is calculated for 1 grm. of the fat. can be detected Non-saponifiabh substances (mineral oils, etc.) added to fats as adulterants for one by the following qualitative test devised by Holde two drops of the oil are boiled minute with a solution of a piece of caustic potash the size of a pea in 5 c.c. of boiling absolute in presence of as little as alcohol, 3 to 4 c.c. of water being afterwards added to the liquid Also a benzene solution 1 per cent, of non-saponifiable compounds, a turbidity is produced. of picric acid gives a red coloration with fat containing 1 per cent, of mineral oil.
1

of

KOH

The Saponification number,

:

KOH

KOH

test is

Turbidity of the liquid indicates the presence of much however, the liquid remains clear, cold methyl alcohol is poured carefully on to its surface ; a turbid ring is formed between the two layers of liquid in presence even of traces of neutral fats (this test doss not answer with palm oil). The addition of resin to fat is discovered by the Liebermann-Storch-Morawski test applied to the fatty acids obtained in determining the Hehner number (see p. 461 ): a few drops of cold acid of 50 Be. are added to a well-cooled solution of 1 to 2 grms. of the fatty acids
in 15 c.c. of hot alcohol.
If,

For detecting traces of neutral fats (non-saponified) in pure fatty acids of commerce, OeiteTs of the fatty acids employed 15 c.c. of ammonia solution is added to a solution of 2 grms.
:

neutral fat.

sulphuric are resin (pine or colophony) (which contain the resins) in 1 c.c. of acetic acid. If traces of forms immediately and rapidly gives way to a brown present, an intense red or violet coloration fluorescence (presence of cholesterol or wool-fat produces a reddish brown coloration, which changes to blue and then to green).

TALLOW
The

469

clear, molten fat, after a long rest, is discharged through the tap, E, and filtered and other impurities being through a bag, the solid fragments of cellular membranes retained by a perforated double bottom. 1 These impurities, while still hot, are squeezed in a press such as that made by C. E. Rost, of Dresden (Fig. 259), being placed inside the the jacket, h, and closed by the cover, 6, perforated cylinder, a, which is'surrounded by

FIQ. 258.

FIG. 259.

improves

N the pressure is exerted underneath on a plate raised by means of The pressed residue is then either treated with carbon disulphide to recover amount of fat still retained, or used directly as cattle-food. A powerful press, which is largely used, is shown in Fig. 260. 'Fusion of Tallow with Acid (d'Arcet method). This method increases the yield and the flavour of the tallow. It is carried out in the Fouche apparatus (Fig. 261),

fixed

by the
e.

screws, d

the lever, the small

can be heated both consisting of a closed boiler, which

by

indirect

steam circulating through

FIG. 260.

FIG. 261.

through be used for feeding cattle. Fusion with Alkali. Evrard heats the tallow with a very dilute solution of sodium

a coil on the bottom and by direct steam issuing from a perforated pipe passing also to the bottom. 100 kilos of tallow are mixed with 50 kilos of water containing 1 kilo of sulphuric acid of 66 Be., the whole being heated for two hours at 105 to 110. The clear, fused fat floats on the surface of the acid solution, which is replaced by pure water, the tallow being after some time, the washed heated and mixed with the latter by means of direct steam tallow is discharged from a lateral tube which, inside the vessel, is free and floatsa cloth bag. When this acid process is used, the solid fragments separated cannot
;

470

ORGANIC CHEMISTRY
and does not diminish the amount
of

carbonate, while Rorard treats 1000 kilos of the tallow with 200 of water containing a kilo of caustic soda, the mixture being then melted at 100 in the Fouche apparatus. The
alkaline process gives a diminished yield

pungent

gases evolved. If the fusion, especially Refining.

when acid is used, has been successfully carried It is, however, required when the tallow is to be out, refining is usually unnecessary. used for food or for fine soaps ; that employed for candles is sometimes bleached. In
general, it is heated and stirred with water for a long time in suitable vats. It is then left at rest until it separates from the water and is filtered through a cloth bag and collected in a tank, heated outside in order to retard solidification and give time for any further

impurities present to deposit. If the fused tallow is allowed to cool slowly at a temperature above 28, it sets to a granular mass, as crystals of stearin and palmitin first separate ; from this mass the olein
easily removed by subsequent compression. different processes have been suggested for the bleaching of tallow, but the only ones deserving of mention here are those consisting in heating with animal charcoal, boneis

more

Many

black, and fuller's earth (magnesium hydrosilicate, see pp. 80, 89, and Vol. L, p. 738), and then filtering, and those in w hich, say, 1000 kilos of tallow is heated with a solution containc ing 20 kilos of water, 10 of oncentrated sulphuric acid, and 5 of potassium dichromate (or 60 kilos of concentrated hydrochloric acid and 15 of permanganate at 40) after stirring, the mixture is left for a time and then washed several times with hot water. In some cases, the tallow is stirred and heated to 40 with 25 kilos of an aqueous solution containing 250 grms. of potassium permanganate, and 250 gms. of concentrated sulphuric acid, and well washed with hot water, a little sodium bisulphite being finally added. Chlorine, which is sometimes used for vegetable oils, is harmful to animal fats. Excellent results have been obtained recently by bleaching with sodium hydrosulphite (Vol. I., p. 586). Certain fats can be well bleached at 80 to 100 with 1 to 2 per cent, of barium peroxide, which is added gradually and with continual stirring. Fats and fatty acids are sometimes deodcrised by treating with 20 per cent, of concentrated sulphuric acid at 30 to 40, and then distilling the fatty acids under reduced pressure. The purity of tallow is determined by the analytical methods already given (see also Table on p. 466), and for industrial purposes the solidification temperature of the fatty acids obtained by the Hehner method (see p. 461) is measured by introducing them in the fused
;

and

state into a double-walled test-tut e (best, that of the Tortelli thermo-oleometer, p. 464) stirring with a thermometer until they begin to turn turbid. The temperature then
fall and at a certain moment rises (the heat of solidification being developed) and remains constant until the whole mass has solidified this constant temperature is that of solidification and, for good tallow, should be at least 43. Adulteration with cottonseed oil is detected by Halpherfs reaction : a mixture of 20 c.c. of the fat, 20 c.c. of amyl alcohol, and 2 c.c. of a 1 per cent, solution of sulphur in carbon disulphide is boiled in a test-tube after about ten minutes' heating, a dark orange or red coloration will appear if even as little If no coloration is evident after 'the lapse of as 5 per cent, of cottonseed oil be present. ten minutes, a little more carbon disulphide may be added and the heating continued ten minutes longer. If the suspected tallow or the cottonseed oil before addition to the tallow were heated to 200 to 250, Halphen's reaction would not be given. The greater part of the tallow made is used in the manufacture of soap and candles, but an appreciable proportion is employed in margarine factories (see below). A wellfattened ox may give as much as 100 kilos of crude tallow.

ceases to

Continental Europe imports large quantities of tallow from America, Australia, and 56 per ton, in 1884 The price varies somewhat, and, while in 1870 it was 40 in 1906 it was 33, in 1885 28, in 1886 22, in 1888 27, in 1892 24, and in 1893 27 the price on the Italian markets varied from 28 to 31, in 1907 from 32 to 36, and in

England.

1903 from 30 to 33. France imported 16,500 tons of tallow in 1913, 17,190 tons in 1914, and 10,180 in
,1915.

later,

tons of tallow in 1888 and almost 11,000 tons in 1891 (see Importation of melted tallow for oleomargarine). In 1909 England imported 110,000 tons of tallow and stearin, and in 1910 123.150 tons, while the United States exported 8500 tons in 1910 and 22,000 tons in 1911. OLEOMARGARINE and MARGARINE (Artificial Butter). The oleomargarine obtained

Germany imported 6226

MARGARINE
emulsifiers.

471

from tallow serves to prepare margarine or artificial butter by churning it up with milk. It is also used to some extent for making the so-called margarine-cheese from separated milk, the butter being replaced by oleomargarine, which is incorporated by means of
It was Napoleon III, who, on account of the rise in price of provisions and more especially of butter, offered in 1870 a prize for the discovery of a cheap fat to replace butter, and placed at the disposal of "the inventor a large works at Poissy, near Paris, adapted to the

development of the industry. The prize was awarded in 1871 to the Mege Mouries process for the manufacture of oleomargarine from tallow by a method which is almost identical with that used at the present day (the addition of sheep's stomach to render soluble the cellular membranes enveloping the fat has now, however, been abandoned). As early as 1873 30 tons of margarine was consumed in Paris.
oleomargarine factories are situated close to the slaughterhouses, so that the be obtained fresh from the animals. The tallow is cooled immediately by washing it in a current of cold water, which removes the blood and other impurities, and if it cannot be worked at once is hung in separate pieces in a cold chamber. The tallow is then cut up and introduced, with one-fourth of its weight of water at 55, into a vat similar to that used for the melting of tallow (see p. 468), but nowadays the heating and melting are effected by the circulation of hot water at 60 to 70 instead of steam, so as to avoid scalding the mass. The latter is kept slowly stirred and a couple of hours is sufficient time to melt 2000 kilos of tallow, which floats on the water, whilst the bits and membranes are deposited on the bottom this separation is facilitated by the addition of
rule,

As a

tallow

may

2 per cent, of salt, previously dissolved in water. After the mass has remained at rest for some time, all the impurities settle and the molten fat is removed by a tap connecting inside the vat with a free, floating tube which gradually falls as the layer of fat diminishes the latter is collected in tinned, double-walled
;

tanks surrounded by hot water, so that further clarification may result on long standing. The fat then bears the name premier -jus and is mixed in small proportion into margarine, while the remainder is poured into flat, tinned moulds holding about 20 kilos and allowed to solidify in a chamber kept at a temperature of about 30. The semi-solid mass thus formed is placed in cloths and squeezed not too strongly in hydraulic presses (similar to those used in making stearic acid for candles, see later) in a room at about 25. This procedure yields about 45 per cent, of a solid residue of stearin (for candles) mixed with a little olein, and a liquid product (55 to CO per cent.) composed of
is

triolein, 35 per cent, of tripalmitin, and 10 to 15 per cent, of tristearin this oleomargarine, which assumes an almost pasty consistency at ordinary temperatures and has a yellow colour and a pleasant odour similar to that of butter.

55 per cent, of

It is

used in some cases as fat for cooking, but usually

sp. gr.

it is

converted into

artificial

butter.

Oleomargarine has the

0-859 to 0-860 at 100, melts at 33-7, has the Hehner

461) 95-5, the Reichert-Meissl-Wollny the iodine number (see p. 463) 44 to 55.
(see p.

number

number

(see p.

461) 0-4 to 0-9, and

*

prepared from oleomargarine, from one-tenth to one-fifth of sesame or arachis or even cottonseed oil being added for the lower qualities (in America maize oil is used). In some countries no milk is now used, attempts being made to flavour the oleomargarine directly with certain strongly flavoured cheeses prepared for this express purpose, or with butyric acid or its homologues, or with a special flavouring placed on the market under the name of margol. It is necessary that artificial butter, when fried, should give the same smell as natural

MARQARINE

(or Artificial Butter) is

butter, and this result is attained partly by adding a little cholesterol (Ger. Pat. 127,376) to the milk used to render the oleomargarine pasty. Margarine is also required to brown and froth like natural butter when fried, and this is attained by adding about 2 per cent,
of egg-yolk (Ger. Pat. 97,057) or 0-2 per cent, of lecithin (a constituent of yolk of egg Pat. 142,397) and a small quantity of glucose, while it has also been proposed to
little
;

Ger.

add a

casein, egg-yolk and pasteurised milk-cream (Ger. Pat. 170,163). colour of commercial, natural butter is imitated by the addition of a little in sesame or cottonseed oil (placed on butyroflavine (dimethylaminoazobenzene) dissolved the market by the Societ6 Fab. de Produits Chimiques de Thann et de Mulhouse). In the manufacture of first-quality margarine, the fats to be mixed (e.g., for summer 30 kilos of premier- jus (see above), and 60 kilos of margarine, 600 kilos of oleomargarine,

powdered

The yellow

472
sesame" oil

ORGANIC CHEMISTRY
for winter margarine, the premier- jus is ; replaced by a similar quantity of For inferior margarines, less oleooil) are first melted separately at 40 to 45.

sesam6

margarine, more premier- jus, and a certain amount of cottonseed oil are used. Half of the molten, homogeneous fat is introduced into a churn (that of H. Grasso, of Hertogenbosch, Holland, Fig. 262, gives good results) containing 300 litres of milk * previously churned to the clotting point and mixed with 50 grms. of colouring solution 0-1 per cent. of glycerine is sometimes added to render the mixing more complete. The churn has a closely fitting lid and is jacketed so that it can be surrounded with water at 35 to 45 it is fitted with stirrers (120 revs, per minute) and the inner surface is thickly tinned.
;

of the milk

After 10 to 15 minutes' churning the remaining half and molten fat is introduced, the churning being continued for a further period of 20 to 25 minutes. When the mass has reached a temperature of 30 to
(better quality but diminished yield is obtained at it is allowed to flow into a shallow double-walled

45

30),

vessel cooled

by the

circulation of water at

to

2,

washed with a powerful jet of water at 2 and is constantly mixed with wooden blades. The wash-water is then run off and the hardened, disintegrated mass left overnight so that
and, as
it

flows, it

is

the wash-water may separate better. A homogenising FIG/ 262. machine of the Schroeder type has been introduced recently, and this allows of continuous working and effects a far more perfect mixing of the fats and milk, while it yields a more aromatic and stable product.

To complete the separation of the whey and washing-water, and to obtain a homogeneous pasty mass, the cold mixture is introduced gradually into an ordinary butter kneader (Fig. 263) with rotating base, this being situate in a cold chamber. After passing under the grooved cone eight or ten times, the mass is collected in blocks, which are left for 24 hours. If it is desired to mix a little cream or the allowed quantity of water (10 to 12 per
cent. ) into the mass, the latter
is introduced into the Werner-Pfleiderer kneader (similar to that used for kneading bread), which can easily be reversed so as to expel the excess of liquid and

finally the paste itself (Fig. 264).

into cakes

The margarine thus obtained is made up by means of suitable moulds bearing the trade mark and is then wrapped in parchment-paper previously disinfected in brine. In some countries this paper is marked with

FIG. 263.

coloured stripes to allow the public readily to

distinguish margarine from butter, and in all obligatory to exhibit margarine for sale in shops with a placard which distinguishes it from butter. In Germany and Austria the law requires margarine to be prepared with at least 10 per cent, of sesame oil and not more than 10 per cent, of butter ;

countries

it

is

by

this

means, the detection of butter adulterated with margarine

oil

is facilitated, as,

to the sesame
1

present,

it

gives the

Baudouin

reaction for furfural. 2

If

owing more than

finer margarines, cream is used, but for ordinary varieties skim-milk from the employed. In all cases, in order to obtain a margarine which will keep, even in summer, the milk is pasteurised at 55 to 60 and then subjected to slight acid fermentation with pure cultures of bacteria, which are sold by butter manufacturers. The cooled milk is kept in clean, closed vessels in a cool place, and is consumed as soon as It may be centrifuged after pasteurising and cooling. possible so as to avoid contamination. If it is not rendered acid, the milk, and also the butter obtained therefrom, keep badly and do not incorporate well with the other fats. 2 10 c.c. of margarine, filtered into a separating funnel, is shaken for half a minute with 10 c.c. of HC1 (sp. gr. 1*125). If the acid is coloured red, it is decanted off and the residue shaken with a fresh quantity of the acid. After removal of the acid, 5 c.c. of the fat is poured into a graduated cylinder with a ground stopper, where it is shaker} with 10 c,c, of HC1 (sp. gr. 1-19}

For the
is

separators

MARGARINE
10 per cent, of butter exceeds 2-5.
is

478

added to margarine the Reichert-Meissl-Wollny number (see p. 461)

Normal margarine contains 8 to 9 per cent, of water and 1 to 2 per cent, of NaCl, and has the saponification number 193 to 203 (coconut fat raises this number to 220 and the Wollny number to 5) and the iodine number 52 to 60. The experiments of Ltihrig (1900) have shown with certainty that margarine is digested by man as well as butter. In 1911 many cases of fatal poisoning occurred in Germany owing to the use in margarine of cardamom oil (or Marotti fat) which may contain the poisonous chaulmoogric acid, C 18 32 O 2 m.-pt. 69, and possibly also hydnocarpic acid, C 16 H 28 O 2> m.-pt. 60-4,

which

is

The

likewise poisonous. consumption of margarine,

which costs

little

more than

half as

much

as butter,

is

continually increasing in

possessed 55 factories in 1886 and 83, employing 1555 workmen in 1895 ; and in 1899 produced 91,000 tons (worth more than 3,800,000) of first- and second-quality margarines, 55,000 tons of animal fats, ^3,000 of
all countries.

Germany

>

vegetable fats and oils, 53,000 of skim-milk, and 4800 of salt being employed. Germany imported 28,500 tons of oleomargarine in 1906 and about 23,000 tons in 1909, and exported 297 tons of artificial butter in 1906 and 525 in
quality

In North Germany, margarine of first is used, but in the South margarine without butter and without milk. In 1907 there were 31 margarine factories
1909.

in

in the

Norway. Thirty-seven factories existed United States in 1886, and the output, which was less than 6000 tons in 1902, rose to 45,000 tons in 1908 and 70,000 in 1910
(almost all not coloured), the exports being 1550 tons in 1910 (almost all coloured). In 1910-191 1 the output in the United States fell to about 65,000 tons. In Denmark 22 factories

produced 30,000 tons in 1909 and 34,300 tons

in 1910, when the exports amounted to 1100 tons. England imported 1650 tons of oleo-

margarine in 1909 and 405(1 tons in 1910 and exported 3295 tons in 1909 and 8138 tons (206,360) in 1910. The principal exportation from the United States consists of the prime material, oleo oil, which is largely used in other

FIG. 264.

countries for preparing the different margarines or artificial butters ; in 1910, 50,000 tons of this oil (of the value of 2,360,000) and 1700 tons of oleomargarine (80,000) were exported, and in 1911, 77,000 tons of oleo oil (of the value 3,120,000), and 18,000 tons of oleoIn 1907, Sweden produced 15,000,000 kilos, and in Holland there

margarine (84,000).
(of the value

Tuscany

The total output of Holland and Belgium in 1910 was 65,000 tons In Paris, more than 30 tons 3,600,000), about 48,000 tons being exported. of margarine were manufactured per day as early as 1875. In Italy, the first factory, that of Regondi and Chierichetti, was erected in 1874 at Milan, with branches in Rome and almost 400 tons of margarine, and at the even in 1888 this firm
are over 100 factories.
;

produced

it still occupies the premier present time, as a company (Chierichetti and Torriani), from the industry in Italy removed was of amount A considerable suspicion position. as the result of a valuable report prepared for the Royal Italian Society of Hygiene by Korner and Gabba in 1888, and in 1911 the consumption (largely for adding to butter) reached about $000 tons the importation of artificial butter was 121 tons in 1908, 64 tons in 1910, 49 tons in 1914, 119 tons in 1916, and about 500 tons in 1919 and 1920, while the amount exported (tons) was 216 in 1908, 286 in 1911, 808 in 1914, 47 in 1915, and 5 in 1919. In the Customs returns for Italy oleomargarine is included with other fats, so that the quantity imported is not known.
;

and (M c.c. of 1 per cent, solution of furfural in alcohol (absolute) for half a minute. If, after red coloration, the margarine contained the required standing, the layer of acid shows an intense been criticised as being in some cases quantity of sesame oil. This reaction has, however,
indecisive.

VOL. n.

31

474

ORGANIC CHEMISTRY

Owing to the high price of tallow in recent years, attempts have been made to prepare margarine by the addition of coconut oil in the kneader, after complete expulsion of the water (so as to prevent rancidity). There is now on the market margarine which bears the name of cunerol (or kunerol), and is made exclusively from coconut oil kneaded and treated
with a saline solution of yolk of egg (instead of milk). BUTTER is the fat obtained from milk, 1 in which
1

it

occurs emulsified in small drops

cows in 1917. In Denmark the dairy industry has attained a high degree of perfection, 1150 co-operative dairies treating 77 per cent, of the total milk produced in 1909. Marked improvements have been effected in*the selection of milk cows and in their feeding, the mean yield of milk per cow the number of cows was 900,000 increasing from 1400 kilos in 1884 to more than 2600 in 1912 in 1881 and about 1,030,000 in 1912. The mean percentage composition of the milk obtained by compkte milking is found from some thousands of different analyses to be as follows: water, 87-22; fat, 3-62; nitrogenous substances (casein and a little albumin), 3-66 milk sugar, 4-82 and mineral matter, 0-68. The casein forms a kind of colloidal solution, which holds, in an emulsified and suspended condition, fat-drops of varying magnitude (diameter, 0-01 to 0-0016 mm.). Casein in milk occurs, indeed, in the form of a non-reversible hydrosol (see Vol. I., p. 106) and its coagulation by acids or heat can be retarded or prevented by the presence of a reversible colloid (protecting In cows' milk the relation between casein (non-reversible) and colloid, like gelatine or gum). albumin (reversible) is 3-02 0-53, whilst in human milk this relation is 0-75 1-00; in human is there abundance of albumin (reversible) and the coagulability is eight times less milk, then, than with cows' milk. These relations explain the different nutritive effects of the two milks on infants. Boiled milk may be distinguished from raw milk as it no longer contains reductase or catalase also oxidation of the whey with a little (see p. 135) hydrogen peroxide and treatment with pyramidone at 60 yields, with raw milk, a violet coloration, while that of boiled milk gives no The sugar and, partly, the salts are found in the aqueous solution composing the coloration. whey. Milk has an acid and an alkaline reaction (amphoteric reaction) at the same time, owing to the presence of primary (acid) and secondary (alkaline) phosphates. The natural acidity of
:

a liquid secreted by female mammals after parturition, and serves as the first nutriment of the offspring, but that of certain animals (cows, goats, etc.) has been largely used, from the earliest times, for feeding infants and adults, and for the preparation of cheese, casein, milk-sugar, etc. The mean daily consumption of cows' milk per head is about 200 grms. in England, 450 in Canada, 600 in Holland, 260 in Paris, 600 in Munich, and 150 in London. The supply of milk to large towns constitutes a serious problem, since, for example, Genoa consumes 500 hectols. per day, Turin 700, Milan 1300, Berlin 8000, Paris 9000, and New York 16,000. In 1903 the United States exported 3,200,000 worth of condensed milk to China, Japan, the The number of cows in France in 1909 was Philippines, Corea, Russia, Africa, and Mexico. 7,336,000, and the yield of milk 132,000,000 hectols. Hungary in 1909 produced 26,000,000 In 1913 the large Swiss companies exported condensed milk to the value of hectols. of milk. In 1903 Australia obtained from 2,000,000. 1,300,000 cows about 16,000,000 hectols. of milk, 50,000 tons of butter (one-third being exported), and 6000 tons of cheese (barely one-fifth In the United exported). Kingdom 4,000,000 cows produced in 1909 about 72,000,000 hectols. In 1910 Norway produced 10,000,000 hectols. of milk. Germany possessed 10,000,000 of milk.
is

MILK

milk is due, not to lactic acid, but to phosphates, carbon dioxide, citric acid, etc. Milk is alkaline to methyl orange and acid to phenolphthalein ; lactic acid acts on methyl orange only when it has precipitated the casein and transformed the dicalcium phosphate into monocalcium phosphate (Bordas and Touplain, 1911). Urea, dicyandiamide, ammo-acids, polypeptides, urethane, albumoses, xanthine bases, albuminoids, etc., are also amphoteric in reaction. Milk changes very readily and, especially in hot weather, becomes acid and coagulates in a few hours. It keeps sound longer if cooled, boiled, sterilised or pasteurised, and then kept in hermetically sealed vessels ; to prevent separation of the fat from the milk, the latter is first passed under great pressure through capillary orifices so as to rupture the fat globules. The sterilisation of milk by means of ozone has been suggested, but this is impracticable, since ozone acts quantitatively on the fat, forming ozonides which readily decompose, giving free fatty Sterilisation by ultra-violet rays is incomplete and alters the acids. composition and taste of the milk to some extent. defatted From milk by centrifugation (skim-milk, containing less than 0-3 per cent, of fat), casein for making cheese and for industrial purposes is separated by addition of rennet (from of mucous membrane the fourth stomach of young calves), which induces clotting owing the to the enzyme it contains. Coagulation, with formation of lactic acid (increase from 3 to 15 of acidity), is also caused spontaneously in 24 to 48 hours by adding a dilute acid and keeping the casein probably exists as calcium salt (1-55 at 55 to 6J per csnt. CaO), which is decomposed in the the increase amount of soluble calcium salts favouring the separation of the casein. by acids, This casein, separated in the hot and pressed, gradually undergoes fermentation and conversion The latter may be either whole-milk cheese or filled cheese, prepared from milk the into Cheese. fat of which has been partially or completely removed and replaced by margarine. Copper vessels turn the cheese green on exposure to the air, and to avoid this, all the operations are carried out in vessels of wood, zinc, tinplate, or tinned copper (Besana), although, according to Fascetti, traces of dissolved copper are advantageous in cheese since 'they retard lactic fermentation ; the latter author suggests, however, the addition of hydrogen peroxide, which haj the advantages of the copper without its disadvantages. To avoid secondary fermentations
;

MILK
which separate at the surface on standing,

475
on centrifugation

in a separator of or, better, the de Laval type (Fig. 265). After filtration through cotton- wool or, better, after a brief centrifugation to remove

during maturation and prevent the swelling and spoiling of the cheese which otherwise frequently occur certain selected ferments are initially added under favourable conditions (Gorini, 1905), or attention is paid (Soncini, 1910) to the chemical surroundings in which maturation takes
place (see p. 151). After the cheese has been separated from the skim-milk, further boiling and coagulation of the latter yield the dissolved albumin (ricotta), the whey finally remaining being used either as food for calves or pigs or for the manufacture of milk-sugar (see later, Lactose). Skim-milk is used in some countries for the preparation of cheap and highly nutritious bread or of Tcephir (see p. 191), while in recent years it has been utilised for making milk-powder by evaporating it rapidly on a large rotating cylinder of metal heated by steam at 147 and in some cases enclosed knife is arranged to detach the dry powder, which falls into a box. in an evacuated chamber. The milk may also be concentrated to some extent in vaciio and then either pulverised with hot air at 150 or passed in a thin film on to two revolving drums heated internally by hot water at 48, the dried crust being scraped off, dried in a vacuum and powdered. In some cases the water is removed from the milk by freezing and continual stirring, the residue being subsequently dried. Being deprived of fat, this powder does not become rancid, and if a little calcium sacqharate is added, it dissolves and gives skim-milk on dilution with water. Milk-powder is also used by pastrycooks. When casein is to be separated for industrial purposes, to 60 with a current of it is obtained pure by treating the skim-milk at 50 sulphur dioxide (Soncini and Todtenhaupt, Ger. Pat. 184,300) ; it is dried in a stream of hot air or, to obtain it in a more soluble state, in a vacuum, while, if a highly pure is product required, it is dissolved in alkali and reprecipitated with nitric acid (it then has the percentage composition C, 52-96 ; H,7-30; N, 15-60; 0,22-54; S,0-76; P, 0-84). Besides being soluble in alkalis and borax, casein dissolves in solutions of potassium iodide, sodium thiocyanate, sodium

phosphate,

etc.

When

dry and powdered,

it

may

be used

for certain concentrated food products (plasmon, nutrosc, tropon, sanaiogen, somatose, etc.), either in conjunction These with, or in place of, meat extracts and peptones.

concentrated foods are obtained by heating the powdered casein on a water- bath with alkali solution or hydrochloric acid, the latter being afterwards neutralised with sodium carbonate and the liquid filtered and concentrated in a vacuum. Casein serves also for dressing textiles and for making greased paper (rendering it soluble with 'sodium carbonate or borate) and material

by compressing it when with formaldehyde ; gallalith and lactite are made in this way. Fro. 266. ANALYSIS OF MILK. Milk being a valuable nutrient for man, and being also easy to adulterate, it is usually analysed chemically to test its genuineness. Milk from cows of different breeds and districts varies within relatively narrow limits, but, in doubtful cases of adulteration, a mixture of the total milk of all the cows of the herd from which the suspected sample is furnished is also analysed. The specific gravity is measured with a hydrometer or a Westphal balance at 15 (see Vol. I., p. 76) for natural milk it varies between 1-0295 and 1-0335, and for separated milk between 1-033 and 1-036, while if much water has been added it is below 1-0295. The value of the specific gravity is not sufficient to prove watering, as this value is sometimes maintained unchanged by simultaneous removal of cream and addition of water. In such a case, use may be made of the specific gravity of the whey, which is never less than 1-027 with pure milk. Watering, even to the extent of only 5 per cent., is also readily detectable by the cryoscopic method examined in 1898 by G. Cornalba (for fresh, non-acid milks free from antiseptics, the cryoscopic point varies from 0-54 to 0-56) or by observing the whey in the Zeiss butyro-refractometer (see p. 463).
similar to bone or celluloid,
it

hot and hardening

The latter method was proposed recently by Ackermann, who prepares the whey rapidly by clotting 30 c.c. of milk with 0-25 c.c. of a calcium chloride solution of sp. gr. 1-1375, heating for 15 minutes on the water-bath, cooling to 17-5 and separating the serum by decantation; the reading on the Zeiss scale is 38-8 to 40 for pure milk, 37-7 for milk -}- 5 per cent, of water, 36-7 with 10 per cent., 34-8 with 20 per cent., 33-3 with 30 per cent. 32 with 40 per cent., etc. G. Cornalba (1908) holds that genuine milk contains at least 6 per cent, of soluble substances (i.e. dry residue less fat and casein), every 0-2 per cent, less than this amount indicating 5 per cent, of added water. Since natural milk does not contain nitrates, which are, however, present in nearly all waters, watering may also be detected by testing the milk for nitrates in the same way as wine is tested. Watered milk appears slightly blue when compared with genuine milk. Comanducci and Frontera (1912) detect watering by means of the rotatory power of the whey in a 10 cm. tube at 15; for pure milk this is 2-38 to 2-48, whilst milk with 10 per cent., 30 per cent, and 60 per cent, of added water shows respectively 2-31, 1-50 and
0-58.

The total residue and ash are determined by evaporating 5 grms. of milk with a drop of acetic the dry residue thus obtained acid in a platinum dish; drying in an oven at 105, and weighing is then heated to redness until completely incinerated, and weighed ; the ash is used for the detection of borax or sodium bicarbonate.
;

476

ORGANIC CHEMISTRY

suspended impurities, the milk passes, while still tepid, to the chamber of the centrifuge, A, mounted on the axle, S, actuated by a pulley which is not shown in the figure (265) arid which rotates several thousands (6 to 7) of times per minute. In this manner the skimmilk is expelled to the periphery and carried off by the tube, 6, into the collecting plate, Be, whilst the lighter cream rises and is discharged by the channel, into the collector, Cf. These separators easily treat 10 hectols. of milk per hour. The cream that separates
,

is

agglomerated into small lumps of butter by churning

ing,

(see, for instance, Fig. 262), kneadjust as with margarine. To obtain a butter that will keep, however, the cream is subjected to

and so on,

pasteurisation and acidification (see Note on p. 472), the butter being worked with water that has been sterilised, for instance, by ozone or ultra-violet rays. The flavour of
butter, which was formerly regarded as due to the estcrification of the fatty acids, seems to result from the fer-

mentation of lactose and the formation of aldehydes.

The percentages of the various fatty acids entering into the composition of the glycerides of butter are as follow stearic, 7 to 11 palmitic, 14 to 18 myristic, 11 or more lauric, 14 to 16 ; oleic, 25 to 30 higher unsaturated
;

acids,

4 to 5*7

also the volatile acids, butyric, caproic,

;

FIG. 265.
thin,

caprylic,

arachic,

and capric further, small proportions of acetic, and hydroxy-acids, cholesterol, phytosterol, leci-

and a yellow colouring-matter ; winter butter is less yellow than that of summer (green feeding of the cows). Unlike other fats, butter contains a mixed palmito-oleo-

butyric glyceride,

C
?

6 (C

Also, in comparison with all other fats, butter contains a large quantity of volatile acids soluble in water. The mean percentage composition of natural butter is water, 15 ;
:

1?

H 81

2 )(G I8

H 33 O 3 )(C 4 H O
7

8 ).

and mineral salts, 0-5. fatty substances, 83 ; lactose, 0-5 proteins, 0-7 Commercial butter should contain not less than 82 per cent, of fat, the remainder consisting of water, about 16 per cent., and salt, 2 per cent.
; ;

In judging the purity of butter, an examination is made of the butter fat obtained by heating the butter to about 50 and then leaving it to clarify and to deposit the water salts, etc. The constants for this fat are compared with those given in the Table on p. 466, attention being paid to the remarks on pp. 460 and 463 referring to the soluble volatile acids

and

ferent temperatures 48-1 at 33, 49-2 at

to the butyro-refractometric reading, which should have the following values at dif41 -5 at 45, 43-6 at 43, 43-7 at 41, 44-7 at 39, 45-9 at 37, 47 at 35, 31, 50-3 at 29, 51 -4 at 27, and 52-5 at 25.
:

not

Genuine milk has not leas than 12 per cent, of dry residue, or, subtracting the amount of fat, less than per cent. The dry residue (r) may also be calculated from the specific gravity (a)
fat (g)

and the percentagcof

by Fleischmann's formula
is

l-2g -f 2-665

~^

10
.

usually made with the Gerber butyrometer (Fig. 266). Into special wide-mouthed flask with a long, narrow, graduated neck are pipetted 10 c.c. of concentrated sulphuric acid (sp. gr. 1-825), 1 c.c. of amyl alcohol, and 11 c.c. of milk, which are allowed to flow gently down the side. The flask is then tightly closed with a rubber stopper, wrapped in a cloth and shaken rapidly and vigorously ; the flask with the pink or red liquid is immersed for six or seven minutes in a water-bath at 65 to 70 and then centrifuged on a flat plate, being arranged radially in After clips with the mouth towards the circumference. a few minutes centrifugation, the fat is separated from the acid casein solution and the percentage of fat by weight is read off on the graduated neck of the flask after the latter has been left for a few minutes on the water-bath.

Determination of Fat.

This

is

The official method which is used rarely and only in cases of dispute of estimating fat that of Soxhlet, and is based on the density of the ethereal solution of the fat extracted from the milk after rendering alkaline. In nearly all countries in has been established that a natural milk, obtained by milking completely a number of cows, contains as a rule not less than 3 per cent. of fat, in very rare cases 2-9 per cent., and more frequently 3-5 per cent. If the specific gravity (s) and the dry residue (r) of a milk are known, the fat (g) that it 22 ( 10Q * ~" 1Q0 should contain is deduced from Fleischmann's formula g 0-833r To ^
:

calculate the dry residue

formula

l-2g

-\

-- - (r)
5

of a

whole milk use

\

may

be

made

of Fleischmann's corrected
:

i_Z

w ^\e

t h at

Of a gkijn.niiik i s given by

r'

= Q-2g -f

2-665 (100-9

100)

BUTTER
The most
certain

1,77

of detecting adulteration of butter with coconut oil is by deter1 mining the volatile fatty acids insoluble in water (Polenske number), and for other adulterations various tests are made.

method

degree of rancidity is determined as described on pp. 463 and 464. In order to avoid rancidity, butter must be kept or despatched in ice or in cold chambers. Butter may be coloured yellow by saffron, turmeric or, more commonly, annatto which is an extract of the fruit of Bi$a orellana made into a paste with an oil the use of coal-tar
.
9 ;

The

dyes is prohibited. Renovated butter

solution of

is prepared in America from rancid butter, which |s kneaded with a sodium bicarbonate (e.g. in the Werner and Pfleiderer kneading machine, Fig. 264, p. 473), and is then washed with just tepid water in the rotating-plate kneader (Fig. 263, p. 472) until it no longer gives an alkaline reaction. It is then kneaded again in the former machine with milk, cooled with a jet of very cold water and treated like ordinary butter a second time in the latter kneader. Natural butter can be distinguished from renovated butter since when melted at a moderate temperature, the former gives a limpid and the latter a turbid mass. BONE FAT is obtained mainly from glue factories, and is extracted from the crushed bones either by boiling with water (see Vol. I., p. 647) and skimming the fat which collects at the surface, or by treatment with benzine or carbon disulphide in an extraction apparatus The first method yields 3 to 4 per cent, of fat, and the second 7 to 9 per cent. (see later). The latter has, however, an unpleasant smell and is dark and of inferior quality it may be refined by means of dilute sulphuric acid or sulphuric acid and dichromate or barium peroxide (see Tallow). Its constants are given in the Table on p. 466. It is used in making soap, especially resin-soap, and also candles and cart-grease.
;

1 Polenske (1904) showed that coconut oil contains a high and constant proportion of volatile If the Polenske number fatty acid insoluble in water, whilst butter contains very little of these. (or new butter-value] is expressed in c.c. of deeinormal necessary to neutralise the insoluble is 5 to 17-8 16-8 for coconut oil and 1-5 to 3 volatile acids contained in grms. of the fat, its value The Reichert-Meissl-Wollny number and the Polenske number may be for pure butter. determined by a single operation, the butter being saponified in the following manner (Leffmann 5 grms. of the filtered butter, together with 20 grms. of glycerine and 2 c.c. of and Beam) are placed in a flask of about 300 c.c. capacity, to 100 caustic soda solution (100 2 O), After 5 to 8 minutes' boiling, the water evaporates, this being heated with a naked flame. frothing ceases, and the mixture becomes clear, the heating being then continued for a few minutes longer. When the liquid has cooled to 80 to 90, 90 c.c. of water at 80 are added, To this solution, a clear and almost colourless solution of the soap formed being thus obtained. heated nearly to boiling, are added 50 c.c. of dilute, sulphuric acid (25 c.c. of the concentrated acid in a litre) and J grm. of powdered pumice, the volatile acids being then distilled so that 110 o.c. is collected in 19 to 21 minutes in an apparatus corresponding exactly with that shown in Fig. 254 on p. 461. The 110 c.c. flask is cooled in water at 15 and inverted several times to cause the drops The liquid is filtered, titration of 100 c.c. of the filtrate with of insoluble fatty acids to collect. deeinormal giving the Reichert-Meissl-Wollny number. The tube of the condenser and the 110 c.c. flask are then washed with three separate amounts of 15 c.c. of water, which is passed through the filter, the flask being subsequently washed with three quantities, each of 15 c.cc. Titration of the whole of the alcoholic filtrate with deeinormal of neutralised 90 per cent, alcohol. gives the Polenske number, which allows of the detection of 10 per cent, of coconut oil in butter. The result has beon stated to be inconclusive if the cows have been fed with coconut

KOH

NaOH

KOH

KOH

cake.

Adulteration with margarine is readily detected by the content of aggregated crystals which are observed under the microscope in polarised light or, better, in light which has previously passed through a selenite plate. Fresh, non-melted butter does not, indeed, yield crystals, but old and rancid or melted butter does give them, so that, in this case, the test is invalid.

The determination of water, fat, solids not fat (casein, lactose, and mineral salts) can be simply carried out, according to Fahrion (1906), as follows in a platinum crucible, tared together with a glass rod, are weighed 2'5 to 3 grms. of butter, which is then heated over a small flame and stirred until it is melted and clear reweighing gives the proportion of water. The residue is then dissolved in light petroleum and the solution filtered through a tared filter, which is well washed with solvent. The filtrate is distilled in a tared flask and the remaining fat dried for an hour in an oven at 100 to 102 and weighed. After drying at 100 the weight of the filter less the tare gives the non-fat. By burning the filter in the crucibb, incinerating and weighing, the salts (NaCl) or mineral substances are obtained. No addition of antiseptic, for the keeping of butter, is allowed boric and salicylic acids can be detected as in beer. The presence of formaldehyde may be ascertained by distilling 25 c.c. of water in a current of steam from a flask containing 50 grms. of butter and 50 c.c. of boiling water; the distillate is tested by means of Rimini's reaction (see p. 131). Addition of artificial yellow colouring-matter is shown by the intense coloration assumed by absolute alcohol when shaken with the fused butter.
:

478

ORGANIC CHEMISTRY
by the lower classes as a employed in making soap and

purposes, and in Italy almost the whole of this product is used substitute for butter and oil. Considerable amounts are
candles.

HOG'S FAT (Lard) is obtained by melting the fatty parts of the pig, as in the case of tallow (Kefining, see p. 470). In Germany large quantities of it are consumed for culinary

was prepared with

In 1891 Germany imported 75,000 tons from the United States, but since this all the refuse of oxen and pigs, and also with the residues of diseased

animals, while addition of appreciable quantities of cottonseed oil and bleaching by the addition of lard stearine were also resorted to, the food- value was greatly lowered. The Table on p. 466 give its constants. The presence of cottonseed oil is detected by Halphen's
test (see p. 470).

In the United States the production of lard is continually increasing, 21 millions of pigs being killed in 1902 and 251 millions in 1905, the exports amounted to 250,000 tons (10,800,000) in 1911. FISH OILS OIL and COD-LIVER OIL. The fat of the whale, seal, and dolphin is extracted from a species of lard contained in the membranes of the brain and back ; it is, however, worked jn a primitive manner, being left to melt and putrefy in barrels exposed to the sun. The oil being thus separated, the residue is boiled with water to extract the tallow. When heated with water, the oil loses its unpleasant odour to some
:

WHALE

extent.

The head and other parts of the body of certain whales, especially Physeter macrocephalus (Cachelot whale), contain an oil already separated and different from that of the it solidifies at the lard ordinary temperature, giving the so-called SPERMACETI (or Sperm Oil), which, after filtration, pressure (to separate the stearin or solid wax), boiling with water and a little caustic soda and repeated washing with water, forms a fat or oil
;

of great value in the

manufacture of pharmaceutical products, perfumes, and high-class

candles.

and elsewhere)

Cod-liver Oil (from the fresh liver of Gadus morrhua, caught in large numbers in Norway is used in considerable quantities as a recuperative medicine in virtue of the small proportion of chemically combined iodine and of the large amounts of readily emulsifiable fatty acids it contains. It is now obtained with a less unpleasant taste and
smell, as it is being prepared in a more rational way by melting it in closed vessels with hot water or direct steam, the best results being obtained in absence of air in an atmosphere

hydrogen or carbon dioxide or in a vacuum (Eng. Pat, 25,683, 1906). Natural cod-liver oil, prepared by the old process, has a considerably higher acidity (acid number, 8 to 25) than that separated by the more modern methods (acid number,
of

0*7 to 1-4).

The production of cod-liver oil in Norway shows a continual increase, although it varies in different years, according to the abundance or scarcity of the fish, from 20,000 to 100,000 tons per annum, about one-half of this amount being obtained by the newer
methods
in the

of extraction.
oil is

Adulteration of the

detected by analysis, taking account of the constants given

Table on

p. 466.

Fish-oil Waste consists of inferior oils of unpleasant odour and taste, the odour being due especially to an unsaturated compound, clupanodonic acid, C 1S H 28 O 2 which combines with 8H to form stearic acid. These oils are used in dressing leather, in the manufacture of DEGRAS, 1 also employed for treating skins, and in the preparation of fatty acids for soap,

of lime, soda, and sulphates) and residues of skin, membranes, hair, etc. (about 5 per cent.). It has an acidity number of 25 to 35, an iodine number of 34 to 36, a saponification number of 144 to 155, an acetyl number of 32 to 44, and 1 to 3 per cent, of non-saponifiable substances. It is yellowish brown, has an odour of fish oil and readily forms a very persistent emulsion with water. Dfyragene is the characteristic constituent and, unlike other resins, is insoluble in light

1 DIiGRAS is obtained in the chamoising process (separation of the fat from the skins after has served to oil them during tanning) and is used for tanning other skins. It consists essentially of water (30 to 40 per cent.), rancid fish oil, resinous substances (ddgragene or degras -former, 14 to 20 per cent.) from the oxidation of the oil, mineral substances (about 2 per cent, consisting

it

petroleum. Its value in dressing skins lies in its property of penetrating readily, and in large quantities the semi-moist skins, in the pores of which it becomes uniformly distributed, imparting very desirable softness and fullness, as well as keeping qualities. This use of degras has been known for many years and has increased so rapidly that the supplv is no longer sufficient, factories for making artificial degras having been established. This is prepared by kneading refuse and clippings of skins with fish oil, exposing the mass to the air to oxidise and pressing out the artificial degras or moellon ; the residue is then treated with a

WOOL FAT
Norway

479

making ; these fatty acids are deodorised by heating with 15 to 20 per cent, of concentrated sulphuric acid at 30 to 40, washing and distilling with superheated steam. Successful attempts have been made to harden these oils by hydrogenation (see, p. 480). In in 1913 a single factory treated daily 150 tons of these oils with 4500 cu. metres

of electrolytic hydrogen.

Pliny mentions the use of this fat in medicine, and its employment for extended to the seventeenth century. In 1856 Chevreul classified it with the waxes owing to its richness in cholesterol, and in 1867 Vohl proposed its preparation from the wash- waters of wool. When washed with tepid water, soap, and a little potassium or ammonium carbonate, certain greasy wools (from Australia) lose as much as 40 to 50 per cent, of their weight as soil, fatty acids, potash soapy substances and fat, secreted by the superficial cells of the skin. The wool from certain races of sheep may contain from 7 to 35 per cent, of true fat (if the sheep are not washed before shearing). In some factories the wool fat is extracted from the dried wool by means of carbon disulphide or, better, of benzine (at Verviers, in Belgium, the wool from all the establishments in the city has for several years been washed with benidrte in a large works), subsequent washing with water and a little soap being then more easy and economical. The crude fat obtained in this way after distillation of the solvent is slightly coloured and almost free from water, and is ready for the market, Usually, however, the dirty wool is washed in the Leviathan machine, the soapy, greasy wash-waters being first allowed to stand to deposit jearthy matters and then treated with dilute milk of lime or, better, with calcium The soaps and fatty acids .chloride solution slightly acidified with hydrochloric acid. (palmitic, cerotic, a little caproic and oleic and traces of stearic, isovaleric, butyric, myristic, carnaubic, and lanoceric) are precipitated as calcium salts and carry down t^e wool fat. which is only slightly saponifiable owing to its large content (55 to 60 per cent.) of
this purpose

WOOL

FAT,

(C 24
is

cholesterol, isocholesterol, ceryl alcohol, lanolyl alcohol (C 12 24 0) and carnaubyl alcohol After this treatment the wash- waters are 60 0), which do not contain glycerides,

mass in some cases the water removed from the calcium soap and fat by centrifuging in a separator similar to that used for milk (Fig. 265, p. 476). The paste thus obtained is dried in the sun or in an oven and then made into cakes with sawdust, etc., the rather dark crude wool fat being extracted from these by means of carbon disulphide or, better, benzine. The residue from the cakes, when treated with dilute sulphuric acid, yields fatty acids, and the resultant aqueous emulsion, coarsely filtered to remove solid substances, deposits the fatty acids when heated. Thus obtained, wool fat is dirty yellow, transparent, and very viscous (it can be obtained it melts at 35 to 40, and has the pale yellow by special refining processes) saponification number 85 to 105, the iodine number 13 to 17, the acid number 0-5 to 1-3, the Hehner number 85 to 95, the Reichert-Meissl number 6 to 7, and 0-5 to 1 per cent, of water, while its rotatory power in saccharimetric degrees is -f- 10-2 to -f 11-2. Commercial lanoline does not contain more than 30 per cent, of water. Wool fat is better suited than any other fat or even vaseline as a basis for salves and ointments, and has also considerable power to penetrate the skin. It mixes readily with large proportions (up to 105 per cent.) of water (which separates in the hot) and, if mixed
;

either left to stand or coarsely filtered to separate the pasty

with 20 per cent, of olive oil, it can absorb 320 per cent, of water. In some cases the crude wool fat is distilled with superheated steam, this procedure giving a wool oil or wool oleine containing 40 to 50 per cent, of fatty acids, 35 to 45 per
fresh quantity of fish
oil, this operation bein^ repeated until practically no residue remains. Attempts have also been made to obtain moeilon by pulverising fish oil in the air at 120 and emulsifying with water. At the present time, the term d&jras is applied to a complex substance for dressing skins and consisting of a mixture of moeilon with wool fat, tallow, and other solid Artificial dgras fats, whilst by moollon is indicated the aqueoua emulsion of oxidised fish oil. is now preferred to the natural product, since different types can be prepared for different purposes, such types being of more constant composition, and hence more certain in their effects. A good artificial de^gras usually contains 15 per cent, or more of degragene and less than 20 per cent, of water. When such d6gras contains more than 1 to 2 per cent, of non-saponi iable substances, these are derived, not from the fish oil, but rather from the wool fat, resin oil, mineral oil, etc. French d6gras sometimes contains 1 to 2 per cent, of soap and as much as 5 to 6 per cent, of in general, it should contain less than 0-05 per cent, of iron and, when spread in a skin fibres thin layer on glass and kept for 10 hours in an oven at 100, it should not form a "varnish, but When smeared on moist and well-pressed paper, should assume only a horny consistency. it should be absorbed within an hour, leaving only a minimum residue. Natural degras costs about 28$. per cwt., the artificial product of the first quality about 20s., and the French (moeilon^ about 34<?.
:

480

ORGANIC CHEMISTRY

and 5 to 10 per cent, of alcohols, while the distillate deposits a wool stearine, which melts at 42 to 55, has the iodine number 37, and the saponification number 170, and contains cholesterol and, altogether, 73 to 88 per cent, of free, solid
cent, of hydrocarbons,

fatty acids.

In 1905 Germany exported 134 tons (130

in 1903) of lanoline, of the value

10,000.

CHRYSALIS OIL. The dead silkworm chrysalides remaining after removal of the silk from
the cocoon contain 25 to 27 per cent, of oil recoverable by pressure or extraction by solvents. The oil is reddish-brown and of somewhat unpleasant odour, deposits stearine at the ordinary temperature and sets to a buttery mass at 0. Its iodine number is 112 to 118, and its saponification number 190 to 195, and its fatty acids melt at 32 to 36 and solidify at 28 to 30. The oil contains up to 30 per cent, of free fatty acids and may be decolorised with fuller's earth. The chrysalides were formerly used directly as a nitrogenous fertiliser (7 to 8 per cent. N), but, nowadays, the oil is first extracted, the residue, containing 10 to 12 per cent, of organic nitrogen, being used as a fertiliser. The crude oil was utilised partly for making inferior, odorous soaps, and also for the separation of the fatty acids. After distillation in a vacuum fhe oil gives hard, odourless, fatty acids (Molinari and Fachini,
1907).

Tsujimoto (1914) deodorises and decolorises chrysalis oil by shaking it for an hour with 6 to 8 per cent, of 50 per cent, sulphuric acid at 100, then washing it well with water and treating it at 130 with 15 to 20 per cent, of Kambara earth (a Japanese earth superior to
see Vol. L, p. 738). Thus prepared, the oil yields consistent fats oi} hydroFlorida earth genation (vide infra). Italy produces about 50,000 tons of fresh cocoons, giving about 15,000 tons of air-dried chrysalides, from which at least 3000 to 3500 tons of crude oil is obtainable.
;

INDUSTRIAL HARDENING OF OILS BY MEANS OF HYDROGEN

Glycerides of unsaturated fatty acids (oleic, linolic, linoleic, etc.) preponderate in ordinary liquid oils and fats, and those of saturated fatty acids in ordinary solid fats, which are largely used as fatty foods and for making soap and candles. Large quantities of certain oils are, therefore, converted into solid fats which are of higher value and more readily utilisable (see note 1, p. 359). Although various hydrogenation processes had been known in the laboratory, industrial application of these to the hardening of oils was not attempted until after the work of Sabatier and Senderens on the hydrogenation of organic compounds in general (see pp. 35, On the basis of these investigations, Normann (Ger. Pat. 141,029, 1902) first 67, 124). applied hydrogenation to unsaturated fatty acids and glycerides (oils). The process was not, however, at once applied on an industrial scale in Germany, but was used first in England by Crosfield and Sons, of Warrington, and also in Holland only in 1911 was it utilised
;

in

Germany,

finely divided nickel being employed as catalyst. Better results are obtainable with finely divided palladium,

which works at 80 to 90

(in 1908, Paal used colloidal palladium at almost the ordinary temperature), but, although a large part of the palladium (which serves for a long time and is not so sensitive as nickel
is to poisons such as sulphur, 2 S. CS^, Cl, organic thio-compounds, hydrocarbons, etc.) recoverable, it is, nevertheless, very expensive. Palladium chloride, which Skita proposed to use at a pressure of 2 to 3 atmos., is cheaper, and at 100 one part of palladium suffices

for 100,000 parts of oil. The nickel catalyst is prepared by reducing the oxide obtained either by calcining the nitrate or by precipitating the sulphate by means of an alkali, the oxide being deposited on

an

hydrogenates
Vol.
I.,

inactive, porous support such as pumice, coke, asbestos, etc., and then reduced by hydrogen at about 300. The active, finely subdivided nickel thus obtained completely oil at temperatures below 150. Decomposition of nickel tetracarbonyl (see
p. 846) also yields

an active product.

When prepared in this way, the catalyst is emulsified with the may be mixed with some of the oil and then reduced by hydrogen in
at 230 to 240 for two hours
;

the emulsified catalyst thus formed is be hardened, a temperature of 120 to 160 being sufficient for this operation. Bedford and Erdmann (Ger. Pat. 292,649, granted in 1916 in spite of opposition from Normann) applied to unsaturated fatty acids the methods developed in 1907 to 1909 by of organic Ipatiev and in 1910 by Wilbuschewitsch (who effected catalytic hydrogenation

The oxide itself oil. a jacketed autoclave mixed with the oil to

HARDENING OF OILS

481

substances in the hot at pressures of 8 to 10 atmos. by means of nickel). Erdmann used apparatus of copper or aluminium, which may, however, influence the taste and odour of the product. Wimmer and Higgins use as catalyst nickel lactate, acetate or formate, the action of which is improved by addition of carbon ; nickel borate has also been used. Nickel oxide has a slow action and hardens oils at temperatures above 200 to 240, the oil

being darkened. Erdmann considers the catalytic action of the oxide as due to the alternate formation of the oxide and suboxide, but others suppose that the oxides are reduced by the hydrogen to nickel, to which the true catalytic effect is du. A diagram of the plant proposed by Wilbuschewitsch (Eng. Pat. 30,014, December 10th, 1910) for use in the preparation of the catalyst, and in the hardening of the oils, is shown
in Fig. 267.

The highly active nickel catalyst is obtained by soaking burnt clay in sulphuric acid, then in nickel sulphate solution, and afterwards in sodium carbonate solution, the nickel carbonate thus formed being converted by heating into the oxide and this into nickel by the hydrogen. The finely powdered mass is readily oxidisable and is emulsified
directly with oil

and kept. In R is placed the oil to be treated and in the catalyst, the drawn by the pumps, A and A 19 in the proper proportions to be emulsified in B and passed through the pipe, G, and distributed by the valve, H, and the pulveriser, C, to the jacketed autoclaves, J 19 J 2 e ^ c The hydrogen is injected by a compresser, K at a

two

liquids being

FTG. 267.

pressure of 9 atmos. through the tube, Jf to the bottom of the autoclave, where it is finely subdivided by the distributors, Z^, D.2 D%. The autoclave is heated first to 100 to 160, according to the kind of oil, the partly reduced oil collecting in the conical base of J l being drawn off by the pump, E and injected into J 2 while the hydrogen escaping from J\ passes
,

the oil then goes through the pump 2 to J 3 In the passage into J.2 through the pipe, Y of the oil through each autoclave, the melting-point is raised by about 15, and when the
;
.

is discharged through the cock, U into the while the oil containing the the solidified oil being separated in catalyst passes through the pipe, Z, and the cocks, $ and T to be circulated again in the autoclaves. As the catalyst becomes exhausted the amount used is increased (1 per cent, of the fresh material suffices), being discharged into P when almost completely exhausted. On

desired melting-point has been reached, the oil

centrifugal separator,

N
9

the other hand, the hydrogen not absorbed in the last autoclave, J 3 issues from the valve, W> and through the tube, Q, to the cooling coil, L, and thence to the washer, (containing sodium carbonate), from which it returns to the cycle through the compressor, K. The
,

reduction generates heat and the temperature in the autoclaves is sometimes regulated by passing cold water through the jackets. The amount of hydrogen required varies with the nature of the oil and the degree of hydrogenation required, and is usually 8 to 12 cu. metres per 100 kilos of the oil. The hydrogen from water gas should, after purification, contain less than 2 per cent, of CO and

482
less

ORGANIC CHEMISTRY
H
2

than 0*1 per cent, of

(see Vol.

L, p. 141). The rapidity of the reaction and the life of the catalyst increase with the purity of the gas. The iodine number of all hardened oils is very low

The cholesterols and phytosterols undergo no change and serve to indicate if the original oil was a mixture of vegetable and animal oils. Hydrogenation is
(5 to 25).

applied to inferior oils (olive, cottonseed, fish, etc.) to obtain consistent fats for making margarine and candles. In general, oils thus treated lose their original odour and assume that of tallow.

In Germany about 200 tons of hardened oils were produced per day in 1913, and during the European War the manufacture assumed enormous importance. In France two factories have an output of 20,000 tons per annum. Before the War the total cost of hydrogenation

was calculated at 6 to 8 per ton of oil. Hardened oils, sold under different names (talgol, talghin, candelite, cruteolin, etc.), have m,-pt. 38 to 50, acid value 3-5 to 4, iodine number 20 to 60, saponification number 189
to 192, non-saponifiable substances 0-3 to 0-5. They give increased yields of soaps, but these form less lather and

FIG/ 268.

wash more slowly. The refractive index is lowered somewhat and the colour reactions are attenuated or annulled. Almost all of them retain minimum traces of catalyst, and nickel may be detected in the ash by means of dimethylglyoxime
(see p. 398).

VEGETABLE
In plants
oils

OILS

accumulate e&p3cially in the seeds and the fleshy parts of the The composition of these oily parts varies somewhat fruit, rarely in the roots. with the locality and with the character of the season. 1
1

The Mean Compositions

15 per cent, above and below the

of Oily Seeds and Fruits (the mean values) are as follows

:

maxima and minima

are 10 to

VEGETABLE OILS
The
oil is
:

483

extracted by two processes by pressure and by means of solvents. are always obtained by the former method, as also are most of the others, solvents being used to extract the remaining oil from the pressed residues (oil-cake), when these are not to be used for cattle-food. According to the power and degree of perfection of the pressing appliances, from one-fourth to one-seventh of the total oil is left in the cake. Extraction of the powdered cake with solvents removes all but the fifteenth part of the total amount oftoil (1 to 2 per cent, instead of 10 to 12 per cent.). The seeds are not worked up immediately after gathering, but are first matured, dried, and turned in bins or silos. They are then cleaned with sieves

Edible

oils

FIG. 269.

FIG. 270.

and fans, crushed in a kind uf roller press (Figs. 268, 269) and powdered (sometimes this is done directly) in vertical cast-iron or stone mills like that illustrated in Fig. 185 on p. 269. A mill with a diameter of 1 -7 metre converts about 35 litres of linseed into flour in twenty-five minutes. To obtain the edible and so-called virgin oil, the flour is pressed cold, although more commonly the pressing is carried out in the hot, this increasing the yield but injuring the quality and colour. The flour is heated in the apparatus shown in Fig. 270, this being furnished with discharge orifices, a, which allow the quantity corresponding with each cake to be delivered. Steam heating is applied in the upper chamber, c, while the lower one, &, is well insulated so as to maintain the temperature of the mass.
forms,

Nowadays the pressing is effected almost everywhere with hydraulic presses of various 1 and only in small works are wooden or metal screw-presses still employed.

1 The HYDRAULIC PRESS is based on Pascal's principle, according to which a pressure exerted on any point of a liquid mass is transmitted with the same intensity in all directions. So that, if a pressure of 1 kilo is exerted, by means of a piston 1 sq. cm. in area, on a liquid in one arm of a U-tube, the other branch of which is closed by a piston 16-sq. cm. in area, this would require a pressure of 16 kilos to balance the first piston (Fig. 271), the pressure transmitted by the pressing surface being proportional to the area receiving the pressure. The hydraulic press consists of a suction pump, (Fig. 272), which draws water from the reservoir, A, and forces it through the strong copper tube, t, into the thick -walled chamber, .0, hermetically sealed at the upper part by a large piston, 6, carrying a wide plate, c, on which The compressing surface is that of the base of the is placed the material to be compressed. small pump-piston and the surface receiving the pressure is given by the base of the piston. Z>, the pressure received being dependent on the ratio of the sections of the pistons and on the

484

ORGANIC CHEMISTRY
OP

A hydraulic press which is widely used is the ring-press of Briick and Hubner, of Mannheim, shown in Fig. 275. The powdered seeds are placed on the rings, a, the base of which
ratio between the arms, and PR, of the pump-lever. If is ten times as long as and the force exerted at is 30 kilos, the piston of the pump receives a pressure of 300 kilos (30 x 10) ; if, on the other hand, the section of the large piston, 6, is fifteen times as great as that of the small piston, the pressure exerted on the former will be 4500 kilos (300 x 15).

PR

PO

ttt-

Via. 271.

FIG. 272.

the piston, &, rises, the plate presses the substance against a strong cover, d, fixed by three or four columns, c,. When the pressure is to be released, the water is discharged from the chamber, B, and the piston descends. The pump is provided with a safety-valve which The large piston is made tight by encircling it at 6 regulates the maximum pressure desired. with a leather ring (devised by the Englishman Bramah) with an inverted U -section the water, in its attempts to escape along the sides of the piston, enters the ring and forces its edges against the piston with a pressure increasing with the pressure of the water, and thus forms a true hermetic seal. Nowadays horizontal hydraulic presses, which discharge the oil and cake more easily, are also used, but these occupy more space, while at the same time the piston does not recede of itself at the end of the operation. In practice, when a substance is to be compressed with a hydraulic press, two or more pumps are used. The first, which has a long stroke, raises the piston and plate rapidly, since at first the resistance is small ; when the pressure increases, the compression is continued more slowly by means of a small pump. To avoid attention to a number of pumps and
;

When

works employing many hydraulic use of the so-called hydraulic accumulators (Armstrong, 1843), which provide a store of water under high pressure for the feeding of several presses at once (Figs. 273 and 274). A piston, L, moving in a cylinder, B, just as in an ordinary hydraulic press, receives pressure from below by
loss of energy,

presses

make

of compressed water from a pump, passing the upper part of the piston is through p and v t fixed to the centre of a plate, C 9 which, by means of three columns, S, supports the plate, E, carrying the heavy iroir discs, D. When the piston is raised water entering A, the whole by the compressed T accumulator, E 6 , ancl the discs, D, are raised. When v 1 is closed A contains a store of water under great pressure which transmits pressure to a number of hydraulic presses simultaneously when FIG. 274. FIG. 273. the cock, v z communicating with these presses is opened. In order to prevent the piston, L, from being raised too much and so forced out of the the piston is provided with a small vertical channel with a lateral cylinder, .#, the lower part of exit ; when the latter is forced from the top of the cylinder, B, the water escapes, the pressure is lowered and the piston falls. Large works are supplied with two or more accumulators, so that when one is raised and the other at its low position excess of compressed water supplied by the pumps at any moment is directed to the latter accumulator, which is hence raised. In this way, also, the final pressure of the hydraulic press can be utilised before discharging it, energy that would otherwise be lost being thus saved. By these means, a uniform and persistent pressure may be exerted on several presses, but it is exerted, not gradually, but instantaneously, which may be disadvantageous in certain Accumulators cases, unless indeed various accumulators at different pressures are employed. with small pistons may be used for pressures up to 400 atmos. The circular iron rings composing the accumulator may be replaced by a single large cylinder filled with scrap iron or stones. The pressure of a hydraulic accumulator may be exerted in some degree gradually by connecting it with a compressed-air chamber (automatic accumulator). As liquid for use in the accumulators, water, glycerine, or oil may be employed.
; t ,

means

HYDRAULIC PRESS
woollen or Horsehair
plates,
e,

485

consists of a movable, perforated steel plate covered with a disc of woollen or horsehair material. The flour is well pressed by hand or by a suitable machine, covered with a second
disc, and passed along the guides, 6, being thus brought between two which are smooth underneath and grooved on the top and fit exactly into the

PIG. 275.

FIG. 276.

two rings containing the flour, one above and the other below. The grooved side of the plate has also a circular, peripheral channel which collects the oil issuing from the perforated
base of each of the rings when the press is working. The automatic changing of the rings requires one to two minutes, about the same length of time being occupied in discharging them, while, under a pressure of 200 to 300 atmos., the pressing is complete in eight to ten minutes. Especially with palm oil and coconut oil, the pressing may be carried out in the hot, the plates being arranged so that they can be heated ; this procedure shortens the time of and increases the of oil. In
pressing
yield

some cases the pressing is carried out first at a low pressure, which gives an oil of improved quality, the cake thus obtained being ground (e.g. by an Excelsior mill, p. 200) and squeezed
under a high pressure for the extraction of a further quantity
of oil of lower grade.

The
Fig.

presses
(in

276

plan at

number

most commonly used are of the type shown in /), d being a cylindrical cage made of a

of vertical steel bars fixed to stout horizontal rings

surrounding them (Fig. 277), so as to leave vertical slits through which the oil flows. The cakes consisting of 2 to 3 kilos of the hot flour and well wrapped in strong horsehair material,
fluted steel discs.

300 atmos. When batteries of several cages are used FIG. 277. (Fig. 278) hydraulic accumulators (Figs. 273, 274) are often employed. Double hydraulic presses are sometimes used (Fig. 279), the two cages being rotatable round the column s. One cage is discharged and recharged while the pressure is acting on the other cage.

are placed in d, the superposed cakes being separated by The pressure is raised gradually to 200 to

With the presses about 70 per cent, of the oil of seeds of suitable solvents 98 to 99 per cent, may be obtained.

and

fruits is extracted

by means

486

ORGANIC CHEMISTRY

Extraction of the oil by means of solvents (first attempted in England in 1856), from the crushed seeds or broken cake, is effected with carbon disulphide (see Vol. I., p. 493) which has considerable solvent action on fats, even in the cold, but also removes a certain amount of chlorophyll or with light petroleum (benzine), which exerts its maximum solvent effect in the hot. The use of carbon tetrachloride has also been suggested (see Vol. L, p. 470), since it is not inflammable like the other two solvents and, further, allows of the extraction of the oil from moist substances. The extraction may be carried out by direct exhaustion or by systematic exhaustion. In the former case, the substance is treated with pure solvent, so that large quantities of dilute solutions which must be concentrated are obtained ; in the other process, a number of apparatus are arranged in a series so that the solvent passes from one to the other and
leaves the last completely saturated, while the first apparatus, as it becomes exhausted, is in the charged with fresh material and placed last in the series (see exhaustion of beet solvent diffusers, under the heading Sugar, later). From the saturated solution of the oil, the

FIG. 278.

while s distilled by means of direct or indirect steam and is thus completely recovered, the crude fat remaining is refined. There are various formst>f apparatus corresponding with the first method of extraction, such as the Merz universal extractor, that of Pallenberg, and the Wegelin and Httbner used. In the last of these the fatty material is (Fig. 280) form, which is fairly widely r q. is introduced from D by means of the tube, solvent which into in the A, vessel, placed indirect of means the into where, is (7, still, fat with by The solvent saturated discharged steam passing through the coil, y, the solvent is distilled, its vapour ascending the tube, and condensing in B, and the liquid collecting in D. The fat remaining in C can then be drawn but if it retains solvent tenaciously, it is first heated by a current of the
,

off through tap, x, ; owing to direct steam, solvent and water then condensing together in the condenser, Florensuitable a of means be can separated by their mutual insolubility, these two liquids x and D, the water being thrown out. If the solvent tine receiver situated at w between

joined at the bottom The Florentine Receiver consists (Fig. 281) of an iron cylinder, the tube W* to the tube, C, and provided with a lateral tube, D, slichtly higher than the top of 2 to 4 cm., according to the difference in density between the two liquids to be separated, (h The tube, B, carries the condensed mixture of water and solvent to e.g. water and benzine). the bottom of the separator, the benzine rising to the top and being gradually discharged through
i

D\

EXTRACTION OF-OILS

487

saturated with fat, instead o being drawn off by the tube, u, is caused to rise to the top to the tube, I, whence it falls into the tube, v, the extraction is effected with continuous circulation of the solvent until the substance is exhausted. To expel and recover the solvent

retained

by the substance remaining in A, a current of direct steam is passed into the latter ;
the vaporised solvent along the
k,

this carries off

tube,

through the
f

valve, w, to the cooling coil, B the con-

densed water and

oil

being passed through the separator, w, be# fore the latter liquid
is

collected in D.

FIG. 279.

Merz extractor,
slightly modified by Fisher (Eng. Pat. 123,645), extraction may be effected in either an upward or a downward direction

By means

of

the

and also in the hot the extractor and still, shown- in front and side views in Figs. 282 and 283, form a single apparatus, the vapour of the solvent heating the mass to be extracted before it reaches the condenser. The material is introduced at A into the cylinder, B, having a closed base, (7, on which are a series of closed coils, D, for indirect heating, and the perforated coil, E, for the introduction of direct steam, which
;

to the tank (7), Fig. 280), while the water is discharged At the commencement of the operation water is through v introduced through the tap, t> into U until it flows out at 1 ; during the distillation a trickle of water enters at t. If at any causes a sudden excess or deficit instant irregular distillation

mixing the benzine and water layers. When a solvent heavier than water, such as carbon disulphide, chloroform, etc,, is used, the tube, v is connected with the solvent tank, the water discharging from the tube, D. When the extraction is complete and all the solvent has been expelled from the fat and from the residual cake, only water vapour condenses, as may be seen by collecting a sample of the liquid from the tap, W#

of pressure in the separator, either the excess of gas may escape momentarily from s, forcing a column of water into u, or suction at 8 is absorbed by a small quantity of water falling into the funnel, e, which leads it to the bottom of the separator without

FIG. 281.

488
which
is

ORGANIC CHEMISTRY
;

Steam enters the coil, F, above a double perforated plate supporting the mass to be extracted at the level of this plate is a rectangular door, 0, for the discharge of the exhausted material. The solvent arriving from the tank through the pipe, H, may be directed to the top or bottom of the mass by the 3-way cock, 2. At the top it enters at 9 escapes through the holes of the annular tube, J, is heated by falling over the double steam coil, /, and is distributed over the mass to be discharged through I into the still, below CEF. In order to extract from the bottom upwards, the solvent is passed in at and overflows the upper perforated plate, N, to collect in the channel, 0, and thus pass through P and the inspeotion glass, Q, into the still beneath. The still is furnished with a heating coil which can be dismounted and withdrawn, for cleaning or repair, through the manhole, R. Direct steam may be introduced, by the coil, 8, to eliminate the last traces of solvent from the oil. The hot solvent vapour surrounds the extractor, keeping the mass to be extracted hot, and escapes at the top of the apparatus through the cast-iron pipe, T, to the

serves for expelling the solvent from the extracted mass.

cooling
oil is

and condensing coils. The residual discharged from the still through

the

valve,

3,

at
is

the

bottom.

separated from the solvent tank by a plate, 7, and consists of three coils round which the cooling water flows.

The condenser

The condensed

solvent- psfsses,

together with the steam, into the

automatic separator, V (see Pig. 282). The steam for the extraction should be at 4 to 5 atmos. pressure and should be dry, and
if

possible, slightly superheated.

Large works, however, always use batteries of extraction apIn paratus arranged in series. a good extracting plant, the loss of solvent does not usually exceed
Fia. 282.

0-5 per cent, of the weight of oil extracted and is always less than
1
1 per cent.

REFINING of oils, to separate as far as possible the tannins, proteins, and colouringmatters extracted from the oily seeds and fruits, is generally effected by means of dehydrating or oxidising agents (the latter attack the colouring- matters more especially). In order that sulphuric acid may not act on the glyceiides (forming ethers) and heat and partially carbonise the oil, it must be used at a concentration of about 60 Be. and in small quantity (1 to 2 per cent.) with oil heated to 50 to 60, or with the cold oil ; under
1 The solvents most commonly used for extracting oils f&r industrial not food purposes are benzine, carbon disulphide, benzene, ether, etc., which are insoluble in water, but are highly inflammable and give explosive mixtures with air. The use of such solvents caused 206' accidents, 60 persons being killed and 187 injured, in Germany in 1911. For this reason increasing use such as carbon tetrachloride and other chlorois being made of non-inflammable solvents derivatives of hydrocarbons (see p. 122).

REFINING OF OILS
these conditions the few impurities are first carbonised and the after filtration it is obtained paler, purer, and clear.
oil

489
becomes coloured, but

Zinc chloride often gives almost the same results as sulphuric acid, and is added in concentrated solution (sp. gr. 1-85) and in amounts up to 1-5 per cent, of the oil ; the black flocculent matter formed separates on standing or filtration. In some cases it is sufficient to leave the oil in large closed tanks of tinned iron with conical bases fitted with taps so that the impurities which gradually settle may be removed. Fragments of coal, peat, willow, etc., may be added, these carrying down the impurities as they settle. In order to avoid prolonged contact of the oil with the air, pressure filters (described in the section on Sugar) are preferred ; either the oil is placed at a higher altitude than the filter, or the pressure is
applied
in this

by means
to

of

way

filter

pumps, it being possible 1000 to 2000 kilos of oil

in 24 hours.
(see
later,

To purify with sulphuric acid Twitchell process), the latter is

in a lead-lined vat

poured in a thin stream into the oil contained and kept well stirred. After seven to eight hours, by which time
small black
clots

of carbonised impurities

have deposited, the oil is decanted into a se.cond vat, washed two or three times with water at 40 to 60 (in some cases a small quantity of sodiuni carbonate is added to the second water), being stirred meanwhile or emulsified by air from a Korting injector
;

^ f7

~r

J-J12

after being left to stand,

it is

either decanted

or filtered.

The water is sometimes intimately mixed with the oil to be washed by means of the
so-called emulsor -centrifuge (Fig.
sisting of

284),

con-

two superposed metal plates with the concave parts inside and mounted on a
hollow axle rotatable at 8000 to 10,000 revs, per minute, while through a central aperture

commanded by two

taps exactly adjuc,' ,ble . water are introduced in the the oil desired proportions. The distance between the two plates can be altered so as to give a
slit between their edges from 0-02 to 2 mm. in width, the more or less completely emulsified mass being forced out through the slit by the plates themselves. If the oil does not separate

from the water on standing, the emulsion may be destroyed by adding powdered and calcined sodium sulphate or carbonate (which act as
dehydrating agents) or by agitating the emulsion with animal black or magnesium silicate
FIG. 283. (which separates the components), but the best results are obtained with centrifugal forced to the separators, like that used for milk (see p. 476), the water and impurities being The acid also tube. central the is while the oil whore adhere, discharged by they periphery, may be mixed in the same way, and continuous working may be attained by means of a well to purify battery of emulsors and another of centrifugal separators ; the latter serve the dregs of the oil and, in general, colloidal and soapy products of oils. When the emulsified or colloidal condition is due to the presence of gum or wax, it is preferable to initiate be filtered. When freezing of the glycerides, this breaking down the emulsion so that it can
stable

emulsions of oil and water are required, as is sometimes the case, they can be obtained and by pouring the oil, mixed with salified stearo-amilide, iut/o a. boiling mixture of water 32 VOL. ii.

490
aminosteario acid
1907).
;

ORGANIC CHEMISTRY
when mixed, the dense emulsion
is

stable,

even in the cold (Kosters,

,

elm-bark, ine they are passed through bone-black or, sometimes, results. In better 200 about to oil heated the gives passage of superheated steam through them some cases, and more especially when very rancid, oils are purified by deacidifying Be. for olive to 38 36 and oil cottonseed for Be. 10 to with a concentrated solution (8 that calculated from the acid number oil) of caustic soda in amount slightly exceeding of persistent emulsions and to loss formation the to leads this treatment, however, readily are due to the presence of of glycerides and also of fatty acids. These emulsions, which heated to 50 to 60. first being manner in the .described, already soaps, are broken down or ammonia to neutralise the Emulsification is sometimes avoided by adding sufficient lime If the acidity of steam. free acidity and then completing the refining by the passage such is not advisable exceeds 30 per cent., the losses would be so high that deacidification used as lubricants be cannot with acid) oil after olive sulphuric refining oils (e.g., highly acid the fatty acids are transor for softening wool, but are used solely for soap, unless indeed on described as p. 461. with treatment glycerine formed into glycerides by or permanganate is carried out as with Bleaching with hydrogen peroxide, dichromate

_,

To

deodorise

oils,

tallow (see p. 470), but if the oil is first deacidified, 1 kilo (instead of 15 kilos) of dichromate per ton is sufficient. If it is required to eliminate

oil is heated with a every trace of soap, the acid. boiling solution of 5 per cent, sulphuric nowa* decolorised are oils frequently Vegetable 1 Vol. I, p. 738), and -days with fuller's earth (see results are obtained also by heating with

good

alkaline solutions of

sodium hydrosulphite.

obtained by pressing the fresh olives of Olea europcea in the period from October to December (in Morocco, in August and SeptemThe olive grows in abundance in Central

OLIVE OIL

is

ber).

and Southern
Spain,

Lake Garda, Italy, on the shores of on the Genoese Riviera, and in Southern Franco,

Greece, Istria, Dalmatia, Portugal, Morocco, California, and Southern India. The composition of the fruit is given in the

Table

p. 482.

to extract the oil from stored or fermented oiives, ^ V n10 the

Dsae

c^^

so-called huile tournante, which is rich in fatty acids and yields a persistent emulsion wheii
Fio. 284.

shaken with soda solution, and a Turkey -red

oil

similar to the sulphoricinate (see p. 390) treated with concentrated sulphuric acid. If the olives cannot be worked at once, fermentation" is prevented by storing them in a cold, dry, and well-ventilated The fermentation (according to Tolomei) is due place. to an enzyme (olease) occurring with the oil, which, in the presence of air and light, it decolorises ; if the olease is removed by washing the oil with water, the oil is not decolorised under the influence of light.

when

The extraction of olive oil is not always effected by rational processes and plant but usually the olives are first crushed by means of the ordinary
edge-runners
p. 269).

(see Fig. 185,

earth has been long used in Northern Africa for clarifying olive oil; in Chicago d a8 ear y aS 18 8 ' but its U8e was pl ? considerably extended subsequently Tt consists of f i l to TftSo 1890. It aluminium and magnesium hydrosilicates, and is found in granular or Flonda and als afc Fraustadt, in Silesia. The 7 5 ? decolorising action of this earthd e d 2 the T a tin is carried to *ar so that alTthe water *o 0) ' While ? ? hydSttoa fl decl ? sln Power !s entirely Je^royed. The oil is shaken with 1 to 3 per cent. ?? nf the tvS'i^fv, 5 'Of and the mass earth, heated for a short time at a temperature (60 to 100) varying with 6 *P *e filter-press, the first turbid portions of tte filtrate

u /

F "ller

'

!I

T m
-

L^

^Sf e?

^St

*'P*d

OLIVEOIL
The pulp
is

491
fibre or

next placed in suitable bags of tenacious vegetable

wool surrounded

by horsehair and then pressed, the type of press employed varying widely with the locality. The ring hydraulic press (see Fig. 275, p. 485) and other forms, still further improved, give excellent results. In some cases a moderate pressure is first employed, the result being oil of superfine quality (virgin oil). The residues are steeped in hot water and subjected to
increased pressure.

an

Repetition of this procedure, employing a still higher pressure, gives pressing may, however, be agitated in a vat through which water flows ; part of the remaining oil is thus removed, this being collected in a second, vat, where it undergoes protracted washing with water, yielding so-called
industrial
oil.

The cake from the second

washed

oil.

The Kuess-Funaro
The
cent, of

extraction*, consists in emulsifying

process (1902), which results in an improved yield and a readier each time with feebly alkaline aqueous solutions. 1 residual cakes (known in Italy as sanse), after being dried, still contain 7 to 11 per

oil, which is nowadays extracted in large works by means of carbon disulphide, which gives the very green, so-called sulphocarbon oil, almost all of this being used in the manufacture of green soap for the textile industries. 2 This soap is sometimes called Marseilles soap, and is used especially for the treatment of raw silk in France, however, and to some extent in Italy, this name is given to high-grade white soap, mostly prepared from copra and arachis oils. Pure olive oil is yellowish or, in some cases, almost colourless or slightly green. The finer qualities taste but little freshly pressed Puglia oil has a rather bitter and unpleasant taste (due to camphene, eugenol, and other substances investigated by Canzoneri), which
;
;

it

* gradually loses. The composition of olive oil varies with the district of origin and with the conditions of extraction, the solid glycerides fluctuating from 10 to 28 per cent, (more especially

The liquid glycerides, which occur to the extent of 70 to 90 per cent., were formerly thought to consist of triolein alone, but the presence of linoleic acid (as much as 6 per cent., this explaining the high iodine number of the oil) has now been proved, and there appears also to be about 1-5 per cent, of a mixed glyceride and 0-2 to 1-5 per cent.
palmitin).
1 A new process of extracting olive oil proposed by Acapulco (1910-1911), and tested with favourable results in the experimental oil plant of the Portici Higher Agricultural School, is based on the different surface tensions of the two liquids (oil and water) which are present in the pulp of the olive and have to be separated, and hence on their different capillary behaviour towards the vegetable tissues constituting the pulp. The surface tension of the oil is about one-half that of the water, so that separation of the two liquids is easily attained by even slight diminution of the pressure below that of the atmosphere. The separation is also facilitated by rise of temperature and by the fact that the water present has a cajJfllary constant higher than that of the oil, so that it remains more strongly adherent to the vegetable tissues. The after the stones have been separated from the essential part of the machinery of this process pulp consists of the so-called filtering extractors, formed of superposed metallic cylinders, inside which is a metal filtering cloth, an annular space communicating with the vacuum pump being left between the walls and the cloth. A stirrer fitted with vanes continually moves the mass of pulp contained in the extractor and spreads it in thin layers on the filtering cloth so that the liquid portion is separated from the pulp. By steam-heating the extraction can be carried out at that any temperature, but even in the cold the exhaustion of the pulp is more complete than " " obtained by the older systems, while in the hot it surpasses that reached by pressing the sanse is in the most powerful hydraulic presses. the said more economical is that It Aeapuleo process than those previously used and that it lends itself to the production on a large scale of pure, slightly coloured oils of constant type, but, as yet, this process has not been subjected to decisive

commercial
2

tests.

distinguish sulphocarbon oil, which has a lower iodine number (77 to 80), from that obtained by pressure, Halphen's test may be employed. To 50 c.c. of the oil heated to 100 is added 12 c.c. of alcoholic caustic potash diluted with an equal volume of water, the mixture being heated for 10 minutes at 110 and cooled to 100 ; 200 c.c. of hot water is then added and the liquid, after cooling, shaken with 200 c.e. of saturated sodium sulphate solution ; 20 c.c.

To

30 per cent, copper sulphate is then added, and the liquid filtered. If the filtrate is not green more of the copper sulphate solution is added and the liquid filtered again if necessary. 5 c.c. of silver nitrate solution (containing 1 vol. of 1 per cent, aqueous silver nitrate solution and 5 vols. of glacial acetic acid) is then added to the liquid, which is boiled, allowed to cool, supersaturated with ammonia and filtered, the filter being washed with dilute ammonia. If black silver sulphide remains on the filter, the presence of sulphocarbon oil (or impure cruciferous oils which cannot be detected otherwise) is certain. Cusson (1909) colza, mustard, etc. has devised a simple test 200 grms. of the oil is vigorously shaken with 50 grm| of 90 per cent, alcohol and then distilled on a water-bath, the distillate being collected in a well-cooled flask containing a little alcoholic potash. Even traces of carbon disulphide thus yield potassium xanthate, which gives a yellow coloration or precipitate on addition of alcoholic cupric acetate
of

little

solution.

322

492

ORGANIC CHEMISTRY
oil

16 per cent, of non-saponifiable substances (phytosterol not yet defined). It contains a variable quantity of free fatty acids, and when impure readily becomes rancid. If the acid number exceeds 16 as oleic acid), it cannot be used as machine oil, as it (i.e., 8-1 per cent, of acids calculated
of volatile acids, besides 0-7 to

and, according to Sani, an

attacks metals.

Pure

olive oil is

used as a comestible and the very pure and more liquid qualities for

in the manufacture oiling clocks, while the other qualities are employed in large quantities of soap, lubricants, burning oil, and Turkey-red oil. The purity of the oil is controlled by various tests referring to the constants given in

the Table on p. 466, and by certain special tests. Olive oils of certain origins give abnormal constants, e.g., Algerian and Moroccan oils have an iodine number of 96 and are reddened by nitric acid ; pure Tunisian olive oil gives the reaction for sesame" oil (Villavecchia and Fabris' test) but not the Belliez reaction (test for sesame oil with a saturated solution of

the extraneous substances of Tunisian oil which resorcinol in benzene and nitric acid) give the Villavecchia and Fabris test can be removed by shaking the oil with hot water. Detection of added sesame oil is effected by Tortelli and Ruggerf s modification of Baudouin's test on the fatty acids (see p. 472), or more rapidly on the oil itself by means of Villavecchia and Fabris' test, taking care to dilute 5 c.c. of the resulting red acid liquid with four times its volume of distilled water and to shake the mixture in a cylinder, and observing the lapse of time required for the disappearance of the red coloration. With any
;

five minutes or, in exceptional pure olive oil, if there is a coloration, this disappears within cases, in eight minutes, whilst if sesame oil (even only 3 per cent.) is present the colour will The presence of cottonseed oil is indipersist for 30 minutes (Zega ajid Todorovic, 1909). the Halphen reaction (see p. 470) or by Tortelli and Ruggeri's modification of cated

by

Becchi's reaction, which is carried out on the liquid fatty acids in the following manner 20 c.c. of the suspected oil is hydrolysed with alcoholic potash in the ordinary way (see of the soap being neutralised with acetic acid and precipitated p. 468), the aqueous solution the lead salt, separated by filtration, is shaken with ether and the with lead acetate
:

decomposed in a separating funnel by dilute hydrochloric acid. ethereal layer is filtered and the ether evaporated, and to 5 c.c. of the residue (liquid L and 1 c.c. of 5 per cent, aqueous fatty acids) are added 10 c.c. of 90 per cent, alcohol
filtered ethereal solution

The

if a black precipitate is then formed on heating for some time on a water-bath at 60 to 70, the presence of cottonseed oil is proved. In certain special cases the Becchi reaction alone is insufficient to indicate with certainty the presence of cottonseed oil. Traces of mineral oils in vegetable oils are detected by the formation of a of a benzene solution of commercial picric acid (F. Schulz, yellowish red solutiorwm addition To detect fish oli in vegetable oil, 100 drops of the latter are see Note, p. 468). 1908 treated with a mixture of 3 c.c. of chloroform and 3 c.c. of acetic acid, sufficient bromine after 10 minutes' rest the being then added to produce a persistent brown coloration vessel is introduced into boiling water, when the liquid will remain liquid if the vegetable

silver nitrate solution

With will separate if fish oil is present. pure, whilst insoluble bromo-compounds Where the oil has been coloured yellow with oil, the metals are first eliminated. auramine, this is detected by boiling 1 c.c. of the oil with 20 c.c. of 8 per cent, alcoholic 20 c.c. of pure benzene and 50 c.c. of water potash and a little zinc dust in a reflux apparatus, and the residue taken up in being added after cooling ; the benzene solution is evaporated on darker blue a acetic coloration, being formed if auramine heating, becoming acid, glacial Sanse oil or sulphocarbon oil, extracted from the cake or marc by means of is present. carbon disulphide, has a dark green colour, and the corresponding fatty acids have a rather low iodine number (as low as 75) and a somewhat higher melting-point than usual. The presence of arachis oil in olive oil is shown by the Tortelli and Ruggeri test, which 20 grms. of the oil is saponified Fachini and Dorta (1910) as follows has been modified
oil is

boiled

by

with alcoholic potash, the alcohol being then expelled, the soap dissolved in water, the fatty acids liberated by hot dilute sulphuric acid, and the clear fused acids collected on a moist in 150 c.c. of pure, tepid acetone, filter they are then washed with hot water and dissolved water being subsequently added, drop by drop, until a turbidity is formed ; the liquid is
;

to a quantitatively, liquid fatty acids can be separated, solid ones by dissolving the mixtures in light petroleum or, better, in acetone and 20 (Fachini and Dorta, 1910). solid fatty acids by cooling to crystallising out almost all the acids are separated from the According to Twitchell (U.S. Pat. 918,612, 1909) the liquid fatty fusion with 1 per cent, of aliphatic sulpho-acids, which render the liquid acids solid ones
1

The

considerable extent

if

not

from the

by

soluble even in water.

CASTOR OIL
finally

493

rendered clear by the addition of a few drops of acetone at 40 to 45 and then left In presence of arachis oil, characteristic shining crystals separate at 15 after an hour these are collected on a filter, washed with 10 c.c. of dilute acetone (32 vols. acids by the Tortelli 68 vols. acetone) and examined for arachic water
to crystallise.
;

and Ruggeri test one-half is dissolved in 100 c.c. of 70 per cent, alcohol, warmed slightly and allowed to cool, separation of crystals indicating arachidic acid (m.-pt. 75 to' 76) with
:

and^lignoceric

certainty.

STATISTICS.
put

The

cultivation of the olive

:

is

widespread in Italy and Spain, the out1910

1914
160,560

of oil (tons) being as follows

Italy

Spain

.... ....

1907
260,540 306,415

1916
206,200 207,115
olive trees

124,610
108,510

207,765

to the high price of coal during the as fuel. Porburnt largely

Owing

European War, the old

were

tugal

produces annually about 25,000 tons of olive oil, Algeria about 32,000 and Tunis about tons,
36,000 tons.

and

The output vary with the season and with the demand. In some years the producers sell at 4 and in others at about 2 10s. per but during the hectol.,
price

European War far higher prices were obtained. CASTOR OIL is extracted from the seeds of Eicinus communis (Fig. 285), a
plant cultivated in India, Indo-China, Java, Italy,

Mexico, California, Egypt, Algeria, Tunis, Paraguay,

Argentine, United States, The Spain, and Greece. oval seeds are 10 to 15 mm. long, about 6 mm. broad, and rather flat, and are

FIG. 285.

covered with a brownish or

Ricinus communis : Shoots with flowers, male below and female above.
;

marbled,
skin
;

shining,

brittle

1,

stamens
;

4, fruit, peeled they sections thereof. contain 45 to 55 per cent, of oil. The seeds contain about 19 per cent, of nitrogenous substances and an enzyme capable of hydrolysing the fats subinto free fatty acids and glycerol (see Soap). The husks of the seeds contain poisonous stances (ricin, ricinin); which do not pass into the oil, but the pressed cake cannot be used as cattle food, and is employed as fertiliser, as it contains about 4 per cent, of assimilable of P 3 5 and 1-12 per cent*, of 2 0. organic nitrogen, 2 per cent, The oil was at one* time extracted by pressing the ground seeds twice in the dry state and then pressing the residue after steeping in hot water. Nowadays, however, three conmodern secutive pressings of the hot crushed seeds with increasing pressures are employed, first a fairly pure pale oil, then one This used. yields procedure hydraulic presses being industrial purposes. One less pure, and finally a more highly coloured oil for secondary hundred kilos of the seeds yield 9 kilos of husks, 43 of residual cake (with 8 per cent, of 20 to 25 of oil of the first, 6 to 8 of the second, and 4 to 6 of the third pressing. The oil

when

mata

2, anthers, magnified ; 3, ovary with three stighalf size ; 5-8, sections of fruit ; 9-12, seeds and

oil),

which precipitates many by heating with an equal volume of boiling water, or by the ordinary of bone-black means decolorised is it substances by protein and gummy medicinal oil is obtained by a first cold pressing, and is then processes given for tallow. The filtered in a vacuum to prevent rancidity.
is

purified

494
The
refined oil
is

ORGANIC CHEMISTRY

almost colourless or faintly yellow, and has a high specific gravity, considerable viscosity, and a peculiar, unpleasant taste and smell. It forms an excellent purgative, the less pure qualities being used in the manufacture of sulphoricinate (see

and of transparent soajps capable of retaining considerable quantities of water. It used for softening leather and for making pegamoid. Its soap differs from others in not rendering water opalescent. Its specific gravity mostly lies between 0-961 and 0-964, and it freezes between - 12 and 18, and owing to its high viscosity even at high temperatures, its slight solubility in
p. 300)
is

benzine, and the small amount of solid residue left on combustion, it serves as an excellent lubricant for high-speed engines (for aeroplanes, etc.). Castor oil contains various glycerides but is free from tripalmitin. Triricinolein is solid, and there appear to be glycerides of a ricinoleic acid and of a ricinisoleic acid, also of a

liydroxystearic acid (melting at 141 to 143) and a dihydroxystearic acid (which explains the characteristic high acetyl number of castor oil). The oil yields, besides ricinoleic acid, more or less highly polymerised compounds with
less

and

less

marked acid characters

(e.g.

ricinisoleic acid), these increasing in

amount

with the age of the oil. Castor oil is strongly dextro-rotatory (24 to 25 saccharimetric degrees in a 20 mm. tube-). Unlike other oils, it is soluble in all proportions in absolute alcohol, glacial acetic acid, or ether at 15 it dissolves in 2 parts of 90 per cent, alcohol or 4 parts of 84 per cent, alcohol, but is insoluble in light petroleum or vaseline oil (which dissolve all other oils and fats). Hence, if a castor oil is insoluble in light petroleum and gives a clear solution with 5 vols. of 90 per cent, alcohol, it may be regarded as pure. The solubility relations are completely inverted if the oil is heated to 300 and 10 to 12 per cent, of it distilled ; there then remains a product termed floricin, which solidifies at 20, is insoluble in alcohol, dissolves in all proportions in mineral oil, and forms a stable emulsion with 5 parts of water. A similar product is also obtained by heating castor oil to 200 in presence of 1 per cent, of formaldehyde ; if heated with zinc chloride solution, it thickens. The potassium salt of the thickened product, with water and formaldehyde, gives a disinfectant solution producing the same effects as lysoform or ozoform. The constants of castor oil are given in the Table on p. 466. LINSEED OIL is a drying oil, as it contains much linoleic and linolenic acids (see pp. 563 and 364), and when spread out in a thin layer on a sheet of glass slowly forms a solid skin (varnish), this forming more rapidly with the boiled oil. Linseed oil is extracted from the seeds (containing 35 per cent, of oil) of Linum usitatissimum, which are converted into flour by the ordinary edge-runner mills and pressed hot
;

in hydraulic presses. Linseed is cultivated especially in the Baltic provinces of Russia, and also in Southern Russia, Eastern India, the United States, and the Argentine, and to a less extent in Egypt, Belgium and Italy. Linseed oil extracted by means of solvents contains more unsaturated fatty acids and less volatile acids than the expressed oil.

According to Fahrion (1903 and 1910), the fatty acids separated from linseed oil contain 17-5 per cent, of oleic acid, 30 per cent, of linolic acid, 38 per cent, of linolenic and isolinolenic acids, 8 per cent, of palmitic and stearic acids, all combined with 4-2 per cent. of glycerine and 0-6 per cent, of non-saponifiable substances.

The purity of the oil is indicated by means of the constants given in the Table on p. 466, especially by the iodine number and the refractive index, which, in the different qualities, varies from 1-484 to 1-488 at 15 (or from 81 to 85 Zeiss at 25 or 87 to 91 Zeiss at 15),
whilst cottonseed oil gives no more than 1-477 and maize oil no more than 1-4765 at 15. good proportion of the oil is used in the form of boiled linseed oil (see Note on next page), since on boiling it acquires drying properties especially necessary to the varnishes

prepared with the oil. The drying power may be determined by Livache's method. On a watch-glass is spread 1 grm. of lead-powder (obtained by immersing a strip of zinc in the solution of a lead salt and washing the precipitate with water, alcohol and ether, and drying), on which 0-6 to 0-7 grm. of oil is allowed to fall slowly in drops, the whole being then weighed exactly and left at a moderate temperature in a well-lighted situation. After 18 hours the weight begins to increase, the maximum increase (12 to 15 per cent.) being obtained within two or at most three days (it then diminishes slightly). Other drying oils give the following increases : walnut oil, 1 -9 per cent. ; poppyseed oil, 6 -8 per cent. ; cottonseed oil, 5 *9 per cent.

VARNISHES
cod-liver oil, 7-4 per cent.
fifth
;

the remaining

oils increase

in weight only after the fourth or

day to a maximum of 2 '9 per cent, after seven days. The drying properties are determined Best and most rapidly by spreading a given weight of the boiled linseed oil on a definite area of glass (J, mgrm. per sq. cm.) and leaving latter in a horizontal position the^ until the oil is no longer adhesive when pressed lightly with the finger (the temperature should always be noted). The drying power of an oil may be determined also from the ozone number (Molinari and Scansetti, 1910).
In a 20mm. tube, pure linseed oil gives a rotation of 0-3 in the Laurent saccharimeter at 15, whilst other resin oils and sesame* oil are dextro-rotatory. Linseed oil is used mostly in the manufacture of lacs and varnishes, 1 mastics and lino1 Oil Varnishes and Lacs are liquids which, when spread out in a thin layer on an object, leave on drying a solid, shining skin insoluble in ether and water and almost impermeable. Varnishes and lacs have linseed oil as a basis, and are of ten "mixed with mineral or organic Oil varnishes are formed from linseed oil rendered drying by dissolving colouring-matters. small quantities of certain minerals in the hot. Oil lacs are obtained by adding to the almost boiling oil varnish (free from gummy matter) fused copal or other resin, and diluting with oil of turpentine at the moment of using all these new components contribute to increase the fixation of oxygen. The harder Copal is a resin derived from various species of "more or less fossilised plants. copals melt at temperatures up to 300 and the softer ones at 100. They have specific gravities lying between 1-035 and 1-07, and they dissolve partially in ether, alcohol, benzene, acetone or chloroform, and almost completely, but slowly, in a mixture of alcohol and ether ; they are insoluble in petroleum ether, fatty oils and oil of turpentine, but soluble in rubberseed oil or copal oil (from the distillation of copal). To render them soluble in linseed and other oils and in oil of turpentine, they are heated for 6 to 10 hours at 300 to 320, best in presence of either stearic acid or the fatty acids of linseed or castor oil. Copal consists of resin acids (trachylolic and isotrachylolic acids], resens (copal resens), a bitter substance and an essential oil. The acid number varies from 80 to 150, the iodine number from 58 to 70, and the saponification number from 100 to 165. Before the European War copal was sold at 32$. to 100$. per cwt. Crude linseed oil requires four to five days to dry in a thin layer, but the fixing of oxygen, that is, the drying, may be markedly accelerated by the presence of small quantities of dissolved metals which act as catalysts. At one time oil varnish (boiled linseed oil) was prepared by heating the oil to 220 to 300 for two to three hours in presence of minium, litharge, or manganese dioxide (dryers). This procedure yielded dark varnishes (boiled varnishes), and was accompanied by danger from fire, the heating being carried out in open iron vessels furnished with stirrers and heated directly over the fire. Nowadays the dryer (0*1 to 0-25 per cent. Mn or 0-5 per cent. Pb 0-1 per cent. Mn is sufficient) is dissolved by heating at a far lower temperature (100 to 120 ana best in a vacuum) for four or five hours (by indirect steam at 135 to 150), it being added (when the oil ceases frothing) as manganese borate or, better, manganese linoleate or resinate, and the mass stirred with compressed air ; in this way, the so-called cold varnishes are obtained. These are paler varnishes which dry in 6 to 8 hours, whilst the others require as long as 24 hours. It has been proposed to decolorise boiled linseed oil with ultra-violet rays. The drying ie far more rapid in the hot than in the cold. Prolonged boiling of Unseed oil without dryers increases not so much the drying properties as the consistency, certain components of the oil being polymerised and linoxyn formed, and the iodine number consequently diminished (e.g., from 154 to 27) these oils, thickened at 295 to 340, bear the names Dickol, Standol, and lithographers' varnish. The action of oxygen during the drying of varnishes seems to lead to the decomposition of the glycerides of the saturated acids and of oleic acid with subsequent complete oxidation of the glycerine and acids, the glyceride of hydroxylinolic acid (hydroxylinoUin), insoluble in If 2 to 3 per cent, ether, being also formed as well as anhydrides and polymerised substances. of pyridine, quinoline or other organic base is added to a Unseed oil varnish, cracking will not occur, even after years (Ger. Pat. 239,289, 1908). In the manufacture of lacs, a difficult and important operation is the fusion of the copal previously prepared in lumps in cylindrical or slightly conical, enamelled iron or aluminium vessels ; these are protected at the bottom by an iron or copper casing when heated by direct fire heat and are provided with a cover and chimney to carry off the noxious vapours, which are The temperature is closely watched by means of a thermometer carefully condensed or burnt. immersed in the fused copal (300 to 3602). It is nowadays regarded as preferable to heat with hot water under pressure (up to 300) circulating in coils situate in the lower part of the boiler. Complete, uniform fusion occupies 3 to 4 hours (with a loss in weight of 15 to 30 per cent.), the linseed oil containing the dryer and heated to about 100 being then mixed in ; if any turbidity appears, the mass is heated to 300. It is then allowed to cool to 150 to 200, the addition of the oil of turpentine which dissolves the lac and, if necessary, of the dryer, being then begun. The diluted lac is filtered under pressure and discharged into smaller vessels, in which it is allowed to cool completely. The addition of calcium salts of colophony renders the lac harder but more
:

brittle.

The copal is sometimes replaced by colophony* and other resins, which are, however, readily lime giyes a good lac. Lacs Baponifiable ; a mixture of Japanese wood oil with resin and a Uttle are improved by prolonged storage (at least a year). Linseed oil for making lacs should be free

496
hum.
is

ORGANIC CHEMISTRY

The last, first prepared by Walton in 1860 and improved by Parnacott and Taylor, obtained by oxidising (blowing) hot linseed oil, after addition of the dryer (see Note), for 18 to 20 hours with hot air until it thickens to linoxyn ; about 30 per cent, of colophony is then added, the whole being converted into a paste with cork-dust at a temperature exceedtextile previously ing 100. The mass swells and is compressed hot (140) on a strong varnished to protect it from moisture, the whole being repeatedly pressed between hot It is finally dried for some weeks in suitable chambers at 30 to 35, where it loses rollers. It is coloured in the pasty condition with its smell and acquires elasticity and weight. mineral colouring-matters. According to Bitter (1911) linoleum exerts a marked germicidal action.

ah being passed through linseed oil at 100 for some days until a dense mass is formed. This is mixed with white chalk and other on to strips of paper by means pigments and cement, the mixture being spread and pressed of hot rolls which impress designs on to the surface.
Linerusta also
is

made from

linoxyn, a stream of

Linseed
for

oil is

used also
trans-

making

soft,

parent soaps

(see later).

The mean annual

pro-

ductionof linseed
throughout the world in 1907-1916 amounted to about 2,750,000 tons. WALNUT OIL. This is a drying oil like linseed oil. The fresh nuts are
freed from the outer green husk and left to dry for

some weeks,

after

which
;

they are stored in heaps months for 4 3 to this treatment increases the yield of oil arid leads of to the disappearan^j, the milky juice ^rthe nuts, which would be
difficult to

PIG.
,
,

the dried nuts 2 1, male flowers 4, 3, male flowers, magnified Of ork f lve 25 to 30 P er cent S f S stamens; 5, fruit with three stigmata; 6, nut with three to 35 30 fruit per yielding 7, section of the nut with the seed apertures at the top
n
i

286.-OU palm (Slab guincensis).

;

010 and

**
-^
i

oil

'

f
.

tne

shell,
,

/^ ^f^f
.

separate from
1

'

inside

8,

transverse section of the seed.

cent, of pale yellow, virgin oil in a first pressing in

bags in the cold, and a further 15 to 20 per cent, of greenish oil when the residual cake is The fresh virgin oil is sometimes used broken, treated with hot water and pressed hot. as a comestible, but it quickly turns rancid and has a pronounced flavour it is used more commonly for lighting and as a drying oil for varnishes and for artists' use. It contains glycerides of oleic, linoleic, linolenic, lauric and myristic acids and has the
;

number 142 to 152, saponification number 186 to 197, Tortelli thermo-oleometer reading 104, Zeiss butyro-refractometer reading 64 to 68 at 40, meltingpoint of the fatty acids 16 to 20. PALM OIL is extracted from the fruit of certain varieties of palm (Elais guineensis
specific gravity 0-925, iodine

and Elais melanococca, which grow

in

Western and Central Africa and

in America,

and

Astrocaryum acuale and Astrocaryum vulgar e, growing in Guiana). The orange- brown fruit, of the size of walnuts, hangs in bunches ; each bunch weighs 10 to 20 kilos and contains 1000 to 2000 fruits, and each plant yields, on the average, four bunches per annum.
from gummy matters, which may be removed by -filtration through Florida earth (see p. 490 and Vol. I., p. 738). The softer lacs contain more than 50 per cent, and the harder ones less than 50 per cent, of linseed oil.

PALM OIL
:

497

The pulp constitutes, according to the variety, 25 to 75 per cent, of the fruit, which contains a nut, and this a white seed also yielding an oil (palm-nut or palm-kernel oil see Fig. 286). The extraction of the oil in the districts where the palm is grown is carried out in an irrational manner, the fruit being sometimes heaped up until it putrefies and the oil then pressed out. In other cases the fruit is stored and compressed in excavations in clay soil,
being left to putrefy until the oil separates at the surface. In other places the fruit is fermented for a month and then heated with water, so that the pulp becomes detached from tlte stone and can then be heated and pressed again with water until the fused oil comes to the top and can be decanted off. In these ways more than one-half of the oil is lost, and machinery is now being introduced for detaching and disintegrating the pulp

and

for the rational pressing of the latter.

oil

has a buttery consistency, an intense orange-yellow the colour and odour persist in the soap prepared from it. It can be decolorised by heating it when exposed to the air and light, but this is effected best and most rapidly by fusing and heating it until it loses the water remaining from
freshly expressed, the colour and a faint smell of violets
;

When

any preliminary heating with water for the removal of impurities this separates from the fused mass in 24 hours. After this it is introduced into a metal vat or cylinder (Fig. 287 provided with a cover and tube for carrying the gases to the chimney the fat is heated to 120 to 130 by means of an indirect steam coil, FP, and a vigorous and finely divided stream of air passed through the oil from a perforated tube, R. In 3 to 4 hours' at the same time the pleasant decolorisation is complete
;

although it is destroyed if the fat is decolorised by simple heating to 220. Chemical decolorisation is often employed, the oil (1000 kilos), already purified by treatment with water and by fusion, being heated in a boiler to 50, at which temperature 30 to 50 kilos of commercial hydrochloric acid and 8 tp 10 kilos of potassium dichr ornate dissolved in 18 to 20 litres of boiling water are stirred in. After 15 to 20 minutes, 1 to 2 kilos of sulphuric acid are sometimes added, the stirring being continued until the oil becomes limpid ; stirring is then stopped and 70 to 80. kilos of boiling water sprayed on the oil to wash After standing overnight, the water is decanted off, the it, and the oil washed once or twice by acid^ejarated from below, boiling with water.
of the fat remains,

odour

Even when
and as
it

fresh

it

contains 12 per cent, of free fatty acids,

it

becomes older

decomposes spontaneously with

FIG. 287.

increasing ease, separation of fatty acids (up to 55 per cent.)

and glycerine

which can be extracted with water taking place. Besides free palmitic acid, the principal components are the glycerides of oleic and palmitic acids, up to 1 per cent, of stearic acid, a little linolic acid, and about 1 per cent, of heptadecylic acid, C 17 34 2 .

H
:

colouring -matter of palm oil admits of various characteristic colour reactions with whilst mercurous nitrate colours it first sulphuric acid, a bluish green coloration is obtained,

The

canary-yellow, then pale green, and finally straw-yellow. Palm oil is used in large quantities in the manufacture of soap and candles, its value that the palm* oil being related to the melting-point of its fatty acids. It is calculated where produced), consumed amounts of the exclusive market the on is, large (that placed amounts to 70,000 to 80,000 tons per annum. Before the European War, the price varied

with the year from 20s. to 26s. per cwt. The best qualities of palm oil are from Lagos then come those of Old Calabar, Benin, and Acora while among the more impure varieties are those from Gabun, Liberia, and the Cameroons. PALM-NUT OIL (or Palm-kernel Oil) is obtained by crushing and then either pressing in hydraulic presses or extracting with solvents the stones contained in the fruit of the West African palm (Elais guineensis) ; freed from shell, the seed forms 9 to 25 per cent, of the weight of the fruit and contains 43 to 55 per cent, of fat, which is white or strawcoloured and free from fatty acids when fresh, although it turns rancid fairly easily in the air; it melts at 26 to 30. It consists of about 15 to 25 per cent, of triolein, 33 per cent, of triglycerides of stearic, 45 to 55 per cent, of triglycerides of lauric (in palmitic, and myristic acids, and about
;
;

preponderance), capric, caprylic, and caproic acids.

498
It bears

ORGANIC CHEMISTRY

a great resemblance to coconut oil, even in the property of its soaps of taking up large proportions of water as much as 600 per cent, (coconut soap up to 1200 per

and of being somewhat soluble in solutions of salt. The total quantity of palm cent.) nuts placed on the market is^about 1,125,000 tons. COCONUT OIL (or Coconut Butter) is obtained from the coconuts yielded twice a year by the palms Cocos nucifera and Cocos butyracea, which grow abundantly in Africa, Ceylon, Cochin China, and the Indies. The coconut is oval (Fig. 288) and about 20 to 25 cm. long and 12 to 16 cm. l$road ; it is covered with a fibrous mass, used for making matting, cord, and baskets, and with a hard, woody shell, 8 to 12 mm. thick, which some time before maturation contains a
sweetish, watery liquid (coconut milk), this subsequently disappearing and giving place to a soft edible pulp. The latter hardens in the air and is sold under the name of copra

FIG. 288.
1,

Cocos nucifera.
;

round female flower and two male flowers 3, male flower ; 4, male flower, 5, female flower, separated from leaves and separated from leaves and calyx, magnified 7, same in longitudinal section, the bony seed being surrounded 6, fruit calyx, magnified by a fibrous layer 8, the seed with one-half of the fibrous layer removed ; 9, the bony seed with three orifices 10, section of the inner seed with chamber filled with latex ; 11, lower portion of the husk with the embryo ; 12, embryo.
flowers
;

2,

(60 to 70 per cent, of oil) for the extraction of oil. At the place of production this is carried out in a very primitive manner, but in European factories the dry pulp is ground, steeped in boiling water and pressed, first cold and then hot. The oil is nowadays decolorised with bone-black or absorbent earths (magnesium hydrosilicates), and in the white form thus obtained is used as a comestible (coconut "butter ; see Margarine), after the free acids have been removed with highly concentrated solutions of caustic soda and after the odorous constituents have been expelled by means of superheated steam. The best form for use as food is the softer, almost liquid butter obtained by the first pressing in the cold. Jts digestibility is equal to that of margarine and butter. If it contains more than 2 per cent, of free fatty acids (expressed as oleic acid), it cannot be used for food and then goes to the soap factory as industrial coconut oil. Its composition is variable, and of the unsaturated acids it contains only oleic acid (about 10 per cent.), while glycerides of myristic and lauric acids are present in large quantities and those of caproic, caprylic, and capric acids to the extent of 2 to 3 per cent.

COTTONSEED OIL
The pure
fat contains

499

tioned that
it is

traces. It has already been mengives a soap separable from solution only by very large quantities of salt ; is, however, capable of absorbing as much as 10 to 12 times its own weight of water, and hence highly valued by soap manufacturers. It is used alone for culinary purposes and
it

no

free fatty acids, or at

most

mixing with margarine and adulterating cacao butter. In its analysis, attention is paid to the physical and chemical constants given in the Table on p. 466.
for

large area of the earth's surface (about 1,400,000 hectares) is^under coconut palms,
oil.

which in a good year would yield 4)60,000 tons of coconut

obtained by pressing the fruit (separated more or less from the seeds) of Stillingia sebifera (tallow-tree), which grows in China, IndoChina, etq. Pressing of the seeds (3 per fruit) yields stillingia oil, which is to some extent drying (iodine number more than 138). The tallow, however, serves well for making soap and has an iodine number of about 30, but this varies somewhat owing to variation of the amount of stillingia oil present. The tallow melts at 35 to 44, and is sold in 40- to 50-kilo cakes wrapped in straw.
(Chinese Tallow)
is

VEGETABLE TALLOW

COTTONSEED OIL is obtained by pressing the shelled, washed seeds of the cotton plant (Qossypium herbaceum and barbadense cultivated in North America, and G. religiosum, hirsutum, and arboreum, cultivated in Egypt, India, China, Siam, etc.). The whole cottonseed, with the husk, contains 7 to 10 per cent, of water, 15 to 20 per cent, of nitrogenous substances, 18 to 22 per cent, of oil, 15 to 23 per cent, of cellulose, 24 to 30 per cent, of nonnitrogenous extractive matter, and 3-5 to 4-5 per cent, of ash ; the decorticated seed contains 28 to 38 per ent. of oil. About 1 per cent, of down remains adherent to the husk (45 per cent, of the weight of the seed), and this is separated to make cotton wool, paper,
and nitrocellulose. The whole, or decorticated, seeds are ground and the flour pressed at 100 in hydraulic presses in two or three stages. The pressed cake is used as fodder or as fertiliser, and contains 3 to 9 per cent, of oil and 15 to 30 per cent, of nitrogenous matter if from the whole seeds, or 8 to 20 per cent, of oil and 35 to 50 per cent, of nitrogenous matter if from decorticated seeds.

The crude oil is reddish-brown (sulphuric acid produces a red coloration) and is decoby stirring with 6 to 10 per cent, of caustic soda solution of 10 to 15 Be. and passing through it a vigorous current of air, first in the cold (40 to 50 minutes) and then when heated to 50 to 55 by indirect steam. It is then allowed to settle, and is afterwards washed with 10 per cent, of salt water (at 10 Be.) to remove the last traces of soap, decanted off, and passed through filter-presses to obtain it clear and of a fine straw -yellow colour. It may be bleached also by heating it to 70 with 10 per cent, of fuller's earth and 1 per cent, of salt. The fatty acids separated from the glycerides of cottonseed oil contain about 26 per cent, of oleic acid, 47 per cent, of linolic acid (the oil is hence partly drying), and about 24 per cent, of saturated fatty acids (palmitic and up to 3 per cent, of a hydroxylorised
acid), besides

siiall

proportion of an aldehydic substance (to which Becchi's reaction

is

duof

It contains also 1 -5 per cent, of a non-saponifiable sulphur

compound and apparently

a chloro-compound.
(p. 492),

Tests for the detection of cottonseed oil in other oils have already been described and the analysis of the oil is carried out with reference to the constants given

on

p. 466.

food

of all the cottonseed oil is used directly or indirectly (as adulterant) as the remainder (second and third qualities) serves, with palm oil and coconut oil, for making white soaps, although in some cases it gives rise, after some time, to yellowish spots. The total output of cottonseed should be about double that of the cotton produced. The United States produced 6,997,000 tons of the seed in 1911 and 6,104,000 tons in 1912, the output of the oil being 800,000 and 750,000 tons respectively in the two years. KAPOK OIL. This oil, obtained in 25 per cent, yield by pressing kapok seeds (from Eriodendrum anfractuosum, growing in Java, East Africa, the Antilles, and Central America), exhibits slight drying properties and has the specific gravity 0-920, iodine number 95 to 115, and saponification number 180 to 195. The crude oil has an acrid odour and a repulsive taste, but the refined product is insipid and odourless and is used mostly for making With Becchi's reagent it gives an intense reddish-brown coloration, and with soap. Halphen's reagent a pale red colour.
;

About two-thirds

MAIZE OIL

(in

America, Corn

Oil) is

now

prepared in large quantities in America and

500

ORGANIC CHEMISTRY

Italy from maize germs, which are separated during grinding. These germs contain 40 to 50 per cent, of oil, and after being pressed hot leave an excellent cake for cattle- food (5s. to

per cwt.). The dense oil has a fine golden yellow colour and a faint odour of maize, and serves well for soap-making and for adulterating edible oils and linseed oil. That obtained by extracting the dried grains from spirit manufacture (see p. 182) is reddish brown, and is
6$.

used for burning and as a lulfricant when mixed with olive and mineral oils, but is not used
alone, as it tends to resinify. As a drying oil it has no great value. The fatty acids of the glycerides of maize oil are stearic and palmitic (4 to 25 per oil cent.), oleic (about 40 per cent.), linolic and linolenic (about 45 per cent., so that the
:

partly a drying one), and small proportions of arachic, hypogaeic, caproic, caprylic, and capric acids ; the oil contains also about 1-2 per cent, of lecithin and 1-4 per cent, of nonthat saponifiable substances, mostly cholesterol, or, more precisely, sitosterol, identical with
is

obtained from wheat and rye.

If in North America (Illinois) alone the oil were extracted from the germs of all the maize produced (about 6,000,000 tons the world's total production being over 7,500,000 tons, 900,000 of this in Italy), more than 250,000 tons of the oil should be obtained, but only about 40,000 tons of maize oil are produced at the present time, about one-half of it being

exported.

SESAM& OIL

(Gingelly Oil, Teel Oil)

is

obtained from the seeds of Sesamum indicum flat seeds, 4 mm. ( brown, oval, long, 2 mm. broad, and 1 mm. thick Fig. 289) and of Sesamum orientate (violet- brown or
:

black),

the

latter

giving

as

much as 50 per cent, of oil when pressed once in the cold

and twice
hot.

The

first

oil

expressed serves as a food for. 250 millions of the inhabitants of India, where the area under

sesam6 exceeds
of

acres

(i.e.,

ten millions 4,000,000 hec-

FIG. 289.

Sesamum indicum, with white

exportation of India from amounts to about 120,000 tons

tares).

The

sesame
seeds.

seeds

ripe" fruit seen from the front and side ; C, longitudinal section of fruit ; D, transverse section of the fruit and four rows of seeds; E, seeds. All natural
size.

and B,

annually, nearly all of this being directed to the Marseilles market, whence other countries are supplied.

The Levant

pro-

duces about one-tenth as much as India, and a little is produced in Africa, China, and Japan. In France the sesame oil industry is declining owing to the obstinate empiricism of the older manufacturers and to the almost prohibitive Customs duties of various countries, but more than 1000 truckloads of the oil are still exported per annum. Sesame cake (dark or pale), so largely used as cattle-food, has the composition water, 10 to 12 per cent. ; protein substances, 37 to 39 per cent. ; fat, 9 to 10-5 per cent. ; and ash, 9 -5 per cent. Sesame oil has a golden-yellow colour, that from the Levant being the paler it consists
: ;

of glycerides of stearic, palmitic, oleic, and linolic acids, 78 per cent, of the fatty acids being liquid with an iodine number of 140. The physical and chemical constants are given

in the Table

other

oils

on

on p. 466, and the characteristic reactions for detecting it It is dextro-rotatory 0-8 to 24). p. 492.

when mixed with

(+

The characteristic reactions, especial^ the colorimetric ones, are due to special components, such as sesamin ; a Isevo -rotatory alcohol, sesamol, C 26 44 O, JH 2 O, which gives Baudouin's reaction (p. 472), and the methylene ether of hydroxyhydroquinone, C 7 6 3 Sesame oil is used in the manufacture of oleomargarine and soap and as burning oil ARACHiS OIL (Earthnut Oil, Peanut Oil) is obtained from the seeds of Araahis hypo-

a herbaceous annual^in Africa (largely in Senegambia and in less degree in other parts), India, United States, Java, Sumatra, the Philippines, Japan, Formosa, the Plate, Southern China, Indo-China, and to some extent in Spain, the south of France and Italy.
gcea, cultivated as

ARACHIS OIL

501

The fruit develops in the ground and attached to the roots, and consists of a yellow Senegal ibrous husk containing two seeds covered with a reddish-brown skin (Fig. 290). of nitrogenous seeds contain about 14 per cent, of water, 48 per cent, of oil, 25 per cent, substances, 3 per cent, of cellulose, and 2 per cent, of ash ; the African seeds contain up to 50 per cent, of oil, the Indian 44 per cent., and the American 42 per cent. The toasted seeds, which are consumed as a fruit, readily turn rancid and acquire a
and are usually eaten immediately after toasting. Large quantities of repulsive flavour, the nuts prepared in this way are consumed in America, while considerable amounts are butter. also ground, converted into a paste and slightly salted (4 per cent.) to make peanut
Before the War the nuts were sold in the husk at 10s. to 12s. per cwt. and the dehusked nuts
at 16s.

The ground, dehusked nuts

7 to yield about 30 per cent, of oil at the first cold pressing,

FIG. 290. Arachis hypogcea. B, fruit (three-fourths natural natural whole size) with fruit A, plant (one-third D, separate flower (double natural size). C , fruit open, with one seed cut
;
f

size)

the third pressing when hot. 8 per cent, at the second cold pressing, and about 7 per cent, at of beans, The oil obtained by the first cold pressing is almost colourless, has a slight flavour it readily turns olive for oil, although and a comestible as used adulterating and is largely oil for The second pressing in the cold gives burning oil, and the third, in the hot, rancid. causes abortion in cattle. The liquid components contain
triokin

and trilinolein the presence of hypogadc acid is uncertain the solid of arachic acid (5 per are composed of triglycerides of lignoceric acid, and to a less extent as modified by Tortelli Renard's test, detected is oil In olive oil arachis by cent, of the oil). and Ruggeri and by Fachini and Dorta (see p. 492). COLZA OIL. This is obtained by pressing the seeds of Brassica campestns which is most of the seeds come from India. The grown in France, Belgium and Germany, although of water, 4 to 6 per cent, of ash, 6 to cent, 7 to 5 contain and per seeds are reddish-yellow cent. cent, of nitrogenous substances, and 38 to 45 per cent, of cellulose, 19 to 22
; ;

soap-making.

Arachis cake

constituents

15 per

per

502
give mustard
oil

ORGANIC CHEMISTRY
by

of oil (the Indian seeds are the richest, but contain also

more sinigrin and my rosin, which with water, so that the cake is not utilisable as cattle food). The ravison( Brassica nagus) yields the brownish -yellow ravison oil, with an unpleasant taste and penetrating odour ; its colour and taste are improved by refining means of
concentrated sulphuric acid, zinc cliloride, etc. The oil consists of glycerides of oleic, erucic, stearic and arachic acids, with 1 per cent, of phytosterol. It is used for illuminating it serves also for making soft soap and, purposes, as it gives a bright, non-smoky flame when heated to a high temperature in a current of air, yields a viscous product (oxidised oil). Rubber substitutes are obtained by heating it with sulphur or sulphur chloride.
;

(Chinese Bean Oil) is extracted from the beans of Soja Uspida (or Soja japonica or Phaseolus hispidus), which are cultivated in China and Japan (Formosa). The crushed beans are heated in jute bags over jets of steam and then pressed. A large After purification by standing, the oil ha the sp. part' of the oil is used for soap-making. iodine number, 135 ; Hehner saponification number, 193-2 gr. 0-9255 at 15 ; acidity, number, 95-95; Keichert-Meissl number, 0-45; Maumene number, 86 to 87; index of 8 o 16 ; melting-point of the fatty refraction, 1 4750 at 20 ; solidification point, acids, 27 ; and solidification-point of the fatty acids, 22 (Oettinger and Buckta, 1911). The exportation of the oil from China amounts to 60,000 tons per annum. GRAPESEED OIL. The seeds of the grape contain 10 to 20 per cent, of oil (more in white and sweet grapes). They are separated from the skins by drying in the sun or in ovens and then beating, the sun-dried seeds containing 10 to 12 per cent, of water, 9 to 12 per cent, of carbohydrates, 10 to 11 per cent, of nitrogenous matters, and 2-5 to 4 per cent, The sieved seeds are dried completely, ground, steeped in 10 per cent, of water, of ash. heated, and pressed ; the cake is broken up, treated with 20 to 25 per cent, of water, and pressed again, this treatment being repeated so that all the oil may bo extracted. The oil can also be extracted by means of solvents (benzine or carbon disulphide). When darkcoloured (extracted from the seeds of distilled marc or in the hot with solvents), it can bo It has not a very pleasant odour readily decolorised with animal-black or fuller's earth. and is rather bitter (if expressed in the hot). Pressure of the seeds yields 9 to 13 per cent,
; ;

SOJA BEAN OIL

of

oil.

This

oil

consists of glycerides mainly of linolic acid, together with those of solid fatty

acids (10 per cent.), 0-9202 to 0-9350.

and a

little erucic, linolenic,

and

ricinoleic acids.

It has the sp. gr.

its

It has slight drying properties

and solidifies between

10

and

15

saponification

number

178 to 180; iodine number, 130 to 140; Wollny number, 0-46; Maumene number, 52 to 54 and butyro-refractometer reading, 60 at 40. The acetyl number of the it thus resembles fatty acids varies from 43 to 144, according to the extent of oxidation
is
;

castor

oil

to

some

extent, so that

it is

recommended

for the

manufacture of sulphoricinatc

(see p. 390).

The pure oil expressed in the cold is used as a food, and the other varieties for soapmaking, but if purified with sulphuric acidi t serves well as a lighting oil, not so much on account of its luminosity, which is rather low, but more especially because it gives a smokeless flame.

After the removal of the fat, the cake contains 10 to 15 per cent, of water, 14 to 18 par cent, of protein substances, 6 to 18 per cent, of fat, and 6-5 to 7 per cent, of ash, and is used as cattle-food and also as a fuel. In Italy the extraction of grapeseed oil is capable of considerable development. A

few oil-crushing mills of Southern and Northern Italy treat a certain amount of the Seeds obtained from distilled vinasse are of less value, as they yield an inferior, seed.

brown

oil.

TOMATOSEED

OIL.

Dried tomato seeds

contain 18 to 22 per cent, of

oil,

two-thirds

1 Tomatoes are the fruit of a herbaceous plant (Solatium ly coper sicum) of Peruvian origin, and from 1700 to. 1850 were cultivated in various countries as a garden plant for local domestic use. Since 1860 they have been grown extensively in North America, especially in California,

where in 1911 15,000 tons were marketed, large quantities being exported to other countries in the fresh condition. In Italy also they are cultivated on a large scale. Fresh tomatoes contain 92 to 95 per cent, of water, 1 to 3 per cent, of skin, 2 to 5 per cent, of seeds, 0-9 per cent, of nitrogenous compounds, 0-2 per cent, of fat, 2-5 per cent, of sugars, 0-8 per cent, of cellulose, 0-6 per cent, of ash, and 0-4 per cent, of free acids (mostly citric). Concentrated tomato preserve is prepared by rupturing the fresh fruit, centrifuging and hydraulically pressing the mass, and concentrating the whole of the liquid in vacuum pans

SAPONIFICATION OF FATS
extracted by subjecting the ground seeds to a pressure of 300 to 400 atmos. an excellent cattle food (superior to linseed cake), as it contains 36 to 38 per cent, of proteins, 10 to 12-8 per cent, of fat, about 30 per cent, of non-nitrogenous extractives, 8 to 10 per cent, of water, 6 per cent, of cellulose, and 5 per cent, of ash. * The oil expressed in the cold from sound seeds is straw-yellow, and with 20 per cent, of tallow gives a good washing soap. & f Analysis of the oil gives the following results (Fachini) density at 15^, 0-9215 ; refractive index, 1-4765; acid number, 0-46; saponification number, .191-6 ; iodine number
of

which

is

The

residual cake forms

iodine number of the fatty acids, 122-7 ; iodine number of the 114 liquid fatty acids' Hehner number, 93-8 acetyl number, 204. 142-2 OIL (from Japan and China) is derived from the seeds of Aleurites cordata. These contain as much as 53 per cent, of oil with an odour like that of castor oil and yield 42 per oent. when pressed cold the oil has the specific gravity 0-936 to 0-943, and the iodine number^ 155 to 166, and exhibits drying properties. At 250 it sets to a solid, transparent, elastic mass^ and it is used for making paint and for rendering wood and fabrics impermeable.
; ; ;

WOOD

TREATMENT OF FATS FOR THE MANUFACTURE OF SOAP AND CANDLES

made from solid fatty acids (stearic and palmitic) obtained by and oils into glycerine and fatty acids and pressing from the latter the which are either alone or used, liquid fatty acids, together with the solid acids, for soapmaking. Liquid oils and soft fats, which contain little stearic and palmitic are
Candles are mostly
fats

decomposing

'acids,

hence used not for candles but only for soap, but the and the same works for making candles and soap.

stiffer fats

are often treated in one

resolution of fats into acids and glycerine is carried out in very varied of lime, sulphuric acid, or superheated steam, or by biological or catalytic methods. (1) Saponification with Lime and Separation of

The means

ways

by

the Solid Fatty Acids.

Theoretically 100 kilos of

fat (see p. 467) require 9-5 kilos of lime for hydrolysis, but when this process was first used industri-

by Milly in 1834 as much as 15 per cent, of lime was used, so that a very large amount of sulphuric acid was consumed in liberating the fatty acids from the calcium soaps formed, while fatty acids were carried down by the enormous
ally

<

quantities of calcium sulphate formed

lost.

and hence

On this account the process was not used, but Milly showed later (1855) that, by Jieating in an autoclave under pressure instead of in open pans, the amount of lime could be reduced to 2 to 3 per
cent.

that

is,

less

than the theoretical quantity

practically complete saponification effected Indeed, after one hour 64 per cent, (see p. 457). after two hours, of the fat remained unsaponified 24 per cent. ; after four hours, 15 per cent. ;
;

and yet

FIG. 291.

FIG. 292.

after six hours, 9 per cent.

The
(5 to 6

saponification

is

after nine hours, 2 per cent. ; and after 12 hours, 0-7 per cent. ; now carried out in large vertical copper autoclaves (Fig. 291)

metres high, 1 to 1-2 metre in diameter, of sheet copper 15 to 20 mm. thick), into which are passed several cwts. (up to 2 tons) of the fused fat from the tank, A (Fig. 293),
or sauce containing about 60 per cent, of water is obtained. (see chapter on Sugar) until a red pulp This is mixed with 2 to 3 per cent, of salt and either bottled or sealed in cans after being sterilised
at

100.

The pressed residues, amounting to 7 to 9 per cent, of the weight of the original fruit, contain 6 to 8 per cent, of skin, 22 to 24 per cent, of seeds, and about 60 to 70 per cent, of water, and readily putrefy. Nowadays they are broken up immediately they come from the presses, and are then dried and beaten while hot to separate the skins from the seeds,

504

ORGANIC CHEMISTRY

and then about one-third as much milk of lime, containing 2 to 3 per cent, of lime (calculated on the fat), from the vessel B. The heating is continued for six to eight hours at a low pressure from pressure of 8 to 10 atmos., steam free from air being passed in, first at the boiler, D, and then at high pressure (10 to 12 atmos.) by the tube, e (Fig. 292), reachalone* ing to the bottom of the autoclave and terminating in a perforated coil. The steam

FIG. 293.

keeps the mass mixed without the special stirrers formerly used, if the precaution is taken of allowing a little steam to escape continually from a valve at the top. At the end of the operation the steam is shut off, and when the temperature has fallen to 125 to 130 (about 3-5 atmos. pressure) the internal pressure is utilised to discharge first of all the aqueous glycerine from below by opening the valve, c, connected with a tube reaching to the bottom of the autoclave. In a similar manner the fused and subdivided calcium soap mixed with .free fatty acids is forced into the tank, E, where a further quantity of aqueous glycerine separates, or the calcium soap is passed directly to the lead-lined vessels, F where it is 1 decomposed by a sufficient quantity of sulphuric acid to neutralise all the lime added. Alter shaking, the gypsum is deposited and can be separated, and the fatty acids, which float, are washed several times with hot water, and then, if the fatty acids are distilled as is done in certain factories where dark fats are treated they are forced by a pump, G, to the tank, H. The latter feeds a cast9

iron or copper (this

is considerably attacked) boiler, K, which is heated partly by almost direct-fire heat and partly by superheated steam (at 180 to 230)

"7

r7

passed into the interior from the superheater, J. The steam carries the fatty acids, which distil, into the tinned copper

condensing
collect

coil,

these acids finally

"7

V
FIG. 294.

a white condition, together with condensed water, in S, while the non-condensed gases are evolved from the tube, (see later Decomposition
in

with Sulphuric Acid).

Where the
they are

solidified

fatty acids are not distilled, by passing them into a

(Fig. 294) fed by, the tubes,

full,

number of superposed tin-plate pans D, from the fused fatty-acid tank, F. When all the pans are the tubes, D, are closed with wooden plugs, E, and in 24 hours many of the pans
:

1 During recent years several factories have replaced the lime by magnesia (calcined natural when it is used in the proportion of 1-5 carbonate), which possesses various advantages to 2 per cent., a pressure of 4 to 5 atmos. is sufficient to produce complete saponincation, since the magnesium soap formed gradually emulsifies and almost dissolves in the remaining Then, too, decomposition of the fat, which is thus easily resolved by the water and magnesia. magnesium soap with sulphuric acid, instead of giving an insoluble and useless salt (calcium, sulphate, which always retains a little fat), gives magnesium sulphate, which is soluble in water, For similar reasons, readily separable by simple decantatioji and in some cases utilisable. Bottaro (1908) has suggested the use zinc oxide is now used in some of the Italian factories. of sulphurous anhydride to decompose the calcium soap from the autoclave.

SAPONIFICATION OF FATS

505

contain solid cakes, consisting of a mixture of solid stearic and palmitic acids and liquid oleic acid. In order to separate the latter, the cakes are wrapped in woollen or camel hair or and pressed, first in the cold goat's hair cloths and are then placed between metal plates with a pressure gradually increasing to 200 to 260 atmos. A second pressing at 40, either in the same press or in a horizontal press, results in the almost complete separation of
the oleic acid, which, however, retains in solution a little palmitic and stearic acids. The latter acids are separated by cooling the oleic acid and, after some time, filtering or decanting off the oleine (p. 358), which is then put on the market or used for soap-making. The solid white cakes of stearic and palmitic acids, freed from the dark edges, bear the commercial name of stearine and melt at 56 to 56-5. These are often melted again, washed with warm water, poured into pans to solidify, and then pressed hot in hydraulic
presses so as to remove the final portions of oleic acid stearine, melts at 57 -5 to 58.
;

this product,

known

as

double

The solidification of the crude acids, after liberation by sulphuric acid, is now effected more rapidly and more perfectly by passing the fused acids at g (Figs. 295 and 296) into a casing into which clips a large, rotating, double-walled cylinder. Between the walls flows a non-congealing solution like that from an ice machine (see Vol. I., pp. 259, 621), and the of a scraper, h, and falls layer of fatty acid solidifying at the surface is detached by means
a cooled box, F connected with the pump, P, and functioning as a filter-press. This process of the firm of Petit Freres has now been improved by replacing the cylinder by a highly cooled toothed wheel. Tn some cases, also, channelled
into
9

cylinders are used, whilst in others the liquid fatty acids are withdrawn from the cold pasty
liquid oleine

mass containing the mixture of and the stearine in

small crystals, by immersing in the mass a rotating vertical

cylinder

formed 6f metallic gauze and covered with a w&l-

stretched cloth ; inside the cylinder the pressure is reduced

yIGL

295.

FIG. 290.

by means

a suction-pump, so that the liquid oleic acid is sucked

of

from in, while the stearic acid is gradually scraped the surface of the cylinder and pressed in a hydraulic press. Messrs. Lanza Bros, of Turin, instead of separating the liquid from the solid fatty acids acids with by means of hydraulic presses, suggest emulsifying and dissolving the liquid solutions of sulpho-oleic acid, so that they separate at the surface, while crystals of the solid fatty acids collect underneath (Ger. Pat. 191,238). The sulpho-oleic acid is prepared Be. in the cold and by shaking 100 parts of oleic acid with 50 parts of sulphuric acid of 66 then diluting with 4000 parts of water. The decomposition of fata by lime in an autoclave at not too high a pressure has the to render distillation advantage of giving the fatty acids in a sufficiently clear condition 1 also clear. are stearine and the ; unnecessary resulting glycerine
1 of the Krebitz process (Oer. During recent years, industrial application has been made of soda Pat. 155,108, 1902), which is a simplification of the lime process with direct production and plant, lo the liisecl tat soap, and is attended by considerable saving in fuel, caustic soda, with three is added the necessary quantity of lime (10 to 12 per cent. CaO) mixed to a paste to four times its weight of water, the mass being well mixed, boiled for five minutes, covered, and allowed to stand overnight. By this means saponification is completed and a calcium vat with this is washed soap is obtained which can be readily ground up in a mill. When a perforated bottom, the first portion of hot wash-water removes the major part of the glycerine as a solution of 10 to 20 per cent concentration, while a second washing gives a more dilute of a subsequent operation. glycerine solution which is used tor the first washing of the calcium soap When treated in the hot with sodium carbonate solutions, the calcium soap yields soda soap and case calcium carbonate, which require skilled manipulation for their proper separation. In this removal of impurities. also, fusion and treatment with hot water is employed for the complete

ma

This process VOL. II.

is

not applicable to the manufacture of soft soaps.

33

506
(2)

ORGANIC CHEMISTRY

Decomposition with Sulphuric Acid (proposed by Achard in 1777 and by Fre'my in This method is now used more especially for very dark fats, which should, however, be freed-' from impurities, dried by fusion at 120, and decanted after long stanjling. The fused fat is introduced into a double- walled, lead-lined, copper or iron boiler fitted with a hood for carrying off the sulphur dioxide which is always evolved. According to the nature of the fat, it is heated with 5 to 10 per cent, of concentrated sulphuric acid at 120 for 1 to Ij hours, steam being passed through the jacket and the mass kept mixed by a current of air passing through it. The operation is finished when a test portion, placed on a dark plate, crystallises on cooling ; 'the mass is then passed into large wooden vats and heated with water until the emulsion first formed is resolved into two layers, the glycerine below (this is separated and freed from sulphuric acid by means of lime) and the acids above. The latter is subsequently boiled several times with water until the excess of sulphuric acid is removed, the sulphuric ethers of oleic acid being decomposed with forma1836).

tion of solid hydroxystearic acid. The resulting fatty acids are dark, since they retain in solution ttte impurities of the fat partially carbonised by the sulphuric acid ; to purify and whiten them, they are distilled with superheated steam, as described above (see also Fig. 293^; the first and last portions which distil are the more highly coloured and these are
redistilled.

Hirzel (Ger. Pat. 172,224, 1906) has devised an arrangement for continuous that is required being a boiler of moderate size into which the crude fatty acids are run in a constant stream ; the pure acids distil over, while the tar remaining at the bottom of the boiler is discharged.
distillation, all

Redistillation of this tar gives a final residue of black stearine pitch, amounting to about 2 per cent, of the fatty acids distilled. In some works the fatty acids are distilled in a vacuum at a temperature not exceeding 240, higher temperatures than this giving a coloured product the acrolein and hydrocarbons given off are condensed.
,-

by distillation are separated into liquid and solid by pressure in hydraulic presses, liquid distilled oleine and white, solid distilled stearine being thus obtained. This oleine always contains a little acrolein and hydrocarbons, as the crude
fatty acids obtained
fatty acids which are distilled invariably include a small proportion of non-saponified neutral fat. On the other hand, distillation results in the formation of an increased amount of solid fatty acids (about 15 to 18 per cent.), since sulphuric acid converts oleic acid partly

The

into the corresponding sulphuric ether, which jdelds solid hydroxystearic acid, m.-pt. when boiled with water :

84,

H S0 4 =
2

C 17

^
2

H.

During the distillation with superheated steam, the hydroxystearic acid is transformed almost entirely into iso-oleic acid, m.-pt. 44 (see p. 359). It must, however, bo borne in mind that hydroxystearic acid is not very good for making candles, as it accumulates in a fused state in the cup formed by the burning candle round the wick ; further, when melted with stearic acid it tends to separate in layers instead of giving *a homogeneous mass. In order to obtain a greater proportion of solid fatty acids, some works combine these
of saponifying by means of lime and acid. The saponification is first carried out in autoclaves in the ordinary way, but not to completion, the acids and the remaining fat (4 to 5 per cent.) being then separated by means of sulphuric acid ; the fatty acids

two systems

and fat are dried and completely saponified with 2 to 2-5 per cent, of concentrated sulphuric acid at a temperature of 110 to 120 maintained for an hour. The resulting fatty acids are not distilled but are simply washed with boiling water, being thus rendered rich in solid hydroxystearic acid ; this process also yields a much purer glycerine. L. Fournier (Fr. Pat. 262,263) has suggested a method of increasing the amount of solid fatty acids by effecting the sulphonation with concentrated sulphuric acid in a carbon 1 disulphide solution of the fat, the reaction then proceeding immediately without heating.
Transformation of Oleic Acid into Solid Fatty Acids. For some years (about 1877-1885) okic acid was converted on an industrial scale in France and England (by the process of Olivier and Kadisson) into solid palmitic acid by utilising Varrentrapp's reaction, according to which this change is almost quantitative on fusion with solid caustic potash (see pp. 350 and 359) j C 18 84 O a 2KOH CH a -CO.K C. 6 81 O aK, but the greasiness and a unpleasant odour of the candles obtained compared with those made from stearine, the necessity
1

=H +

SAPONIFICATION BY ENZYMES

507

(3) Hydrolysis by Hot Water under Pressure (proposed by Tilghmann in 1854, and improved by Price in England) is but little used owing to the low yields obtained and the

very high pressures required. The fat, emulsified with water, is circulated in coils arranged in a furnace so as to attain a temperature of 290 to 315. Direct distillation of fats with superheated steam and collection of the glycerine and fatty acids in the distillate always gives low yields. (4) The Biological or Enzymic Process has been applied industrially since 1902, as a result of the work of W. Connstein, E. Hoyer, and H. Wartenburg, and is based on the observations of Pelouze (1855), of Green and of Sigmund (1890) according to which, when oily seeds are pounded with water, fatty acids are gradually liberated by the action of It is found that the most active enzymes are those of castor lipolytic enzymes (see p. 134). oil seeds (in which they occur to the extent of 70 parts per 1000 of fat),. especially after removal of the oil, but better results are now obtained by using aqueous emulsions rich in enzymes (extract of castor oil seeds), but much poorer in proteins (which are harmful) and containing 60 per cent, of water, 37 per cent, of castor oil, and 3^per cent, of proteins. Other active seeds are, according to Fokin, those of Chelidonium majus, Linaria purpurea, etc. When castor oil seeds are used, a milky emulsion is obtained by crushing the seeds in presence of the necessary amount of water (50 to 60 per cent.) arid is decanted off roughly from the skins and treated with 0-06 per cent, of acetic acid (calculated on the weight of fat to be decomposed subsequently). Of the seeds or the enriched extract, 50 to 80 kilos are used per 1000 kilos of fat (the maximum for fats with the higher saponification number, although tallow requires the maximum amount and a temperature of 40). To accelerate the decomposition, 0-15 to 0-20 per cent, (on the weight of fat) of manganese sulphate (activator) dissolved in a little hot water is added, and if the fat contains much protein or gummy matter*, it is well to clarify it by heating with 1 per cent, of sulphuric acid diluted with a little water the last traces of this acid are then removed by repeated and thorough washing with boiling water, as they would be deleterious to the reaction. With liquid fats, the decomposition is carried out at 23 and with solid ones at 1 to 2 above the melting-point, provided however that this does not exceed 42, since at 44 the enzymes no longer act in the desired direction if necessary, fats with high melting-points are mixed with liquid oils. 1 The practical working of the process is as follows (see Fig. 297) A leaden coil a, 6, for indirect steam and a tube, d, for the injection of air reach almost to the bottom of a leadlined iron boiler, A, with a conical base discharge cocks, /, are fitted to the boiler at the
;

of distilling the resultant dark acid, and the difficulty of eliminating all the acetic acid?, led to the abandonment of this process. Also de Wilde and Reychler's process for transforming oleine into stearine by heating in an autoclave at 260 to 280 with 1 per cent, of iodine or chlorine or bromine seems to have been given up in practice since 1890, the yield being less than 75 per cent, (the combined chlorine was eliminated by heating under 8 to 10 atmos. in presence of zinc dust or iron, and then decomposing the metallic soap). The industrial transformation of oleic acid into solid elaidic acid by treatment with a little nitrous acid (see p. 359) does not give satisfactory practical results, first because elaidic acid is not a very good material for candle-making, and also because the reaction is reversible and

succeeds well only with fairly pure and fresh oleic acid and not with the commercial acid (partly polymerised). Max v. Schmidt treats 10 parts of oleic acid with 1 of zinc chloride at 180, then decomposes the zinc soap by boiling first with dilute HC1 and afterwards with water, and finally distils the fatty acids, which can be separated into liquid and 'solid by means of hydraulic presses. By this process Benedikt (1890) obtained 75-8 per cent, of stearolactone, C 18 34 2 (the internal

anhydride of y-hydroxystearic acid t m.-pt. 48), 15-7 per cent, of iso-oleic acid, and 8*5 per cent, This method was applied in Austria, but was soon abandoned, as much of other saturated acids. of the oleine remains unaltered. K. Hartl, jun. (Ger. Pat. 148,062, 1903), in order to avoid the browning produced by the action of sulphuric acid on the impurities of the oleic acid, does not treat the oleine directly with concentrated sulphuric acid (as had long been the custom see Shukoff, Ger. Pat. 150,798, 1902), but first distils the oleic acid in steam and afterwards treats it with sulphuric acid of 58 to 60 B4. (e.g., at a temperature of 60 to 80 and using 1 mol. of sulphuric acid per 1 mol. the resulting fatty acids are then washed and decolorised by heating in open pans of oleic acid) with 1 to 10 per cent, of zinc dust at 100, the zinc soap being finally decomposed by hot dilute hydrochloric acid. W. H. Burton (U.S. Pat. 772,129, 1904) uses a process similar to that of Fournier (see above), benzine or naphtha being employed as solvent and the sulphonic ethers being decomposed in solution by the direct action of steam the final product melts at 85 to 90, but does not mix well with paraffin wax, even when fused. Nowadays, however, the industrial transformation of oleic into stearic acid is effected solely by catalytic hydrogenation (see p. 480). 1 Dunlap and Gilbert (1911) found that, when oleic acid is treated with glycerine in presence of defatted castor oil seeds and linseed, 26 per cent, of the oleic acid is transformed into glyceride
; ; ;

in 11 days.

332

508

ORGANIC CHEMISTRY
W
.

The fat, and about 35 per cent, of water heated to the heights. desired temperature in B (see 'above) are introduced and are kept stirred by means of a current of air from the compressor, L, and the reservoir, The castor oil seed extract,
mixed with 0-2 per
manganese sulphate and 0-06 per cent, of acetic acid (on the weight of fat ; the reaction, starts and proceeds well if the mass is faintly acid at first) is then added, the whole being mixed for about 15 minutes so as to give a homogeneous
cent, of

bottom and at various

The vessel is then tightly covered so that the temperature may be maintained, the mass being mixed from time to time to keep it emulsified. After 24 to 36 hours, when more than 90 per cent, of the fat is decomposed, the mass is mixed and heated to 80 to 85, 0-2 to 0-3 per cent, (of the weight of fat) of concentrated sulphuric acid (66 Be.) diluted with one-half its weight of water being then added. The whitish emulsion soon becomes dark owing to the separation of the fused fatty acids, and when this occurs the heating and stirring are suspended and the mass left overnight. The various taps are then set
emulsion.
in operation to separate the bottom layer of fairly concentrated glycerine, the intermediate emulsified layer (3 to. 4 per cent. of. the fatty acids, used for soap-making) and the clear fused fatty acids which are boiled with water to free them from sulphuric acid. Originally,

when
it

the seeds were used instead of the extract, the resulting glycerine was very dark, and decolorise it with bone-black (nowadays it is as good as that given by saponification with lime), while the intermediate emulsified layer formed as much as 22 per

was necessary to

FIG. 297.
cent, of the total fatty acids

of the

The aqueous glycerine (sweet water) cent.). concentrated to 10 Be. in open pans, the sulphuric acid being carbonate in the hot. The barium sulphate is removed by separated by means of barium filtered liquid further concentrated in a multiple-effect vacuum filter-pressing and the cent, of ash apparatus to 28 Be., a clear, brownish glycerine containing only 0-2 to 0-4 per being thus obtained. The biological process has spread rapidly during recent years, since the whole of the
(now only 2 to 4 per
enzymic process
is first
is readily recovered, while the fatty acids obtained are of far better quality than The fatty those prepared by decomposing the fat in autoclaves by means of lime, etc. acids from sulphocarbon olive oil retain, however, their characteristic green colour, and those from palm oil their orange colour. The fatty acids yielded by this process contain neither hydroxy-acids, as do those obtained under pressure, nor calcium soaps, and are hence more suitable for the manufacture of either candles or soap (see later, Soap). The decomposition is here analogous to that with (5) Twitchell's Catalytic Process. but with TwitchelVs reagent sulphuric acid (which also, strictly speaking, is catalytic), or acid ester) it takes place far hydroxystearonaphthalenesulphonic (benzenestearosulphonic more probably because this reagent dissolves in the fat more easily than does

glycerine

readily,

sulphuric acid.
vat,

The

(Fig. 298),

fats are first purified by heating to 90 to 100 in a lead-lined covered with 1-5 to 2 per cent, of sulphuric acid at 60 Be\, direct steam being

CARBOHYDRATES

523

content of fatty acids, and the degree of purity. The ordinary soaps used in laundries and in tjie textile industries, which are made from sulphocarbon olive oil and contain 60 to 65 per cent, of fatty acids, cost before the war 22 to 24 per ton, according to the conditions of the market and the prices of prime materials (fats and oils). Soaps loaded with water and other substances may cost much less ; fine, perfumed soaps cost up to 40 to 80 per
ton.

GG.

POLYHYDRIC ALDEHYDIC OR KETONIC ALCOHOLS

CARBOHYDRATES
(Sugars, Starch, Cellulose)

This group of substances might have been included in the preceding chapter, FF, where, in paragraphs D and E, certain \tery simple aldehydic-and ketonic alcohols have been considered. Partly owing to custom [since it has been the rule to include in the group of Carbohydrates only ketonic or'aldehydic polyhydric alcohols with six (monosaccharides) or a multiple of six carbon
of 2

atoms (polysaccharides) and containing hydrogen and oxygen in the proportion 1, as in water], and partly because this group embraces all the sugars, which exhibit special characters very different from those of glycollic
:

aldehyde (which should be the first member), the carbohydrates are, however, considered separately, although the brilliant researches of Emil Fischer, commenced in 1887, have extended this group to compounds with five, four, or three carbon atoms, on the one hand, and to monosaccharides with six, eight, or even nine carbon atoms on the other. These monosaccharides bear the name of Monoses (bioses, trioses, tetroses, pentoses, hexoses, heptoses, octoses, nonoses, etc., according "to the number of carbon atoms they contain), while the polysaccharides (formed by the condensation of two or more monose molecules) are called and, generally
,

polyoses

.the alcohol,

and treated with a measured volume, in excess, of normal sulphuric acid, the liquid being then heated in a beaker on a water-bath and on a sand-bath until the clear fatty acids (and the resin, if present) separate at the surface. After cooling, the solidified layer of acids is pierced with a rod and the liquid poured on to a tared filter in a stemless funnel, the fatty acids being then washed with hot water, and the whole brought on to the filter. The excess of free sulphuric acid in the whole of the wash-water is determined by titration with normal This then gives the amount of sulphuric acid lixed by the alkali of the caustic potash. soap and hence also the combined alkali expressed as Na 2 0. Evaporation of the liquid to dryness and extraction with absolute alcohol removes any glycerine present in the soap, this being weighed after evaporation of the alcohol. The fatty acids on the filter are treated with a couple of c.c. of alcohol to remove any moisture and then with sufficient light petroleum to dissolve all these acids; the filtrate is evaporated in a tared dish, dried at 105 to constant weight and the residual fatty acids weighed. To determine any resin which may be present in the fatty acids, part of the latter is weighed, dissolved in 20 c.c. of alcohol and, after addition of phenolphthalein, in the hot with a slight excess of alkali ; after cooling, the liquid is made up to 110 c.c. hydrolysed with ether, treated with powdered silver nitrate and allowed to deposit the precipitated silver One-half of the filtered solution (containing soluble silver stearate, palmitate, and oleate. resinate) is treated with 20 c.c. of dilute hydrochloric acid (1:2) and filtered, an aliquot part of ,the filtrate being evaporated in a tared capsule, dried at 100 and the residual resin weighed ; the weight of the resin is diminished by 0-00235 grm. for every 10 c.c. of ethereal solution of silver The true weight of the fatty resinate, this being the amount of oleic acid removed by the ether. acids, free from resin, can then be calculated. The residue from the Soxhlet apparatus, after (4) Soda, Salt, Sulphates, Silicate, etc. separation of the fat and soap, is treated two or three times with 50 to 60 c.c. of hot water and the solution filtered, made up to a definite volume and divided into four parts one of these is titrated with normal sulphuric acid, using phenolphthalein as indicator, to ascertain the sodium carbonate : in a second portion, the sodium chloride is determined by titration with silver nitrate ; the third is precipitated with barium chloride and the weight of the barium sulphate and hence that of the sodium sulphate in the soap, determined. The fourth portion is treated with hydrochloric acid and the silica, thus separated from the silicate, weighed. " The ash obtained by burning a definite weight of pure (5) Ash and Mineral Filling." is about 40 cent, greater than the total alkali (expressed as Na 2 0). If the proportion soap per is much, higher than is indicated by this relation, the excess represents mineral filling.
:

342

524

ORGANIC CHEMISTRY
formed by the

in particular, hexabioses, hexatrioses, etc., according as they are condensation of two, three, etc., hexose molecules.

A.

MONOSES

All the ijaonoses are aldehydic or ketonic polyhydric alcohols containing

the characteristic grouping,

i.e.,

a hydroxyl group united with a

OHO
carbon atom adjacent to a carbonyl (CO) group.

When

the carbonyl exists

as

an aldehydic, group,

C*H,

these monoses are called Aldoses, whilst

OH '6

H
|

when
that

it

exists as a ketonic group,

C
1

they are termed

ketoses, so

OHO
we have aldohexoses, ketohexoses, etc. 1 The monoses have the general properties

of the aldehydes or ketones and hence form, on oxidation, the corresponding monobasic acids, e.g. pcntonic, hexonic acids, etc. Since the aldoses contain a primary alcoholic group,

OH CH 2
-

[CH OH] n

C/ \H

they can also be oxidised to dibasic acids, containing the same number of carbon atoms, whilst when the ketoses are oxidised, the carbon atom chain is ruptured and acids with lower numbers of carbon atoms formed. On reduction, both the aldoses and the ketoses take up two atoms of the hexoses give hexilols and hydrogen, forming the corresponding alcohols
;

the pentoses pentitols. Like all aldehydes, they reduce ammoniacal silver solutions in the giving silver mirrors. When heated with alkali, they turn brown and then resinify. They reduce alkaline copper solution (Fehling's solution) in the hot
p. 255,

hot,-

(see

and

later).

When

heated with excess of phenylhydrazine dissolved in acetic acid, they

2 yield yellow, crystalline phenylosazones, insoluble in water.

1 The two classes of sugars, aldoses and ketoses, are distinguished by means of Romijn's reaction with a solution of iodine and borax, which oxidises all the aldoses (galaetose, glucose, mannoso, arabinose, xylose, rhamnose, maltose, lactose), while it either does not oxidise the ketoses or oxidises them but slightly (sorbose, fructose ; saccharose and raffinose are oxidised Betti (1913) finds that the aldoses, but not the ketoses, react with to a small extent).

jfl-naphtholbenzylamine, forming crystalline products. 2 They form first pfwnylhydrazones (see p. 240) :

C C
I

OH

II

OH

+H

N-NH-C 6H R

=H

C
I

N-NH-C C H 5

aniline,

these pheriylhydrazones then react with two other molecules of phenylhydrazine, giving ammonia, and pkenylosazone :
'
I

NH NHC H + H N-NHC H
2 6 5
:

= NH 3 + NH
6

2 -C 6 aniline

-f

H aO +

C=N-NHC 6H 6
|

N-NHC 6H 5

FORMATION OF MONOSES

525

In dealing with the hexoses later, we shall see how the constitutions of the monoses in general are determined. Of the various monoses, containing from 2 to 9 carbon atoms, only certain of the hexoses are fermentable, that is, give alcohol and carbon dioxide under the action of ferments or enzymes (see pp. 134 and 146). Of the hexoses, some ferment readily, others with difficulty, and others again not at til, in dependence on their stereochemical configurations and possibly on the asymmetric constitution of the enaymes. d-Glucose, d-mannose, and d-fructose ferment easily, and d-galactose with difficulty, whilst 1-glucose and 1-mannose do not
ferment.

GENERAL METHODS OF FORMATION OF THE MONOSES

(a)

the polyoses by hydrolysis with dilute acids, water being^added and several molecules of hexose obtained
:

From

Ci 2
(b)

H 22 O n (saccharose) + H O =
2

20 6 H 12 O 6
:

oxidation of the corresponding alcohols by nitric acid e.g., Arabitol, C^H n 59 gives Arabinose, C 5 H 10 O (pentose) ; xylilol (stereoisomeric with arabitol) gives xylose, and Mannitol, 6 14 O 6 mannose. CH 2 CO CH 2 OH, which (c) Oxidation of glycerol gives dihydroxyacetone, is a triose, its constitution being indicated by the fact that it forms a cyanohy-

By

OH

drin,

OH CH C(OH)(CN) CH OH, the latter yielding trihydroxyisobntyric acid, OH CH C(OH)(COOH) CH OH, and this, on reduction, isobutyric acid having a
2 2 2

known
(d)

constitution.

By

treating the bromo-derivatives of the aldehydes with baryta water.

Thus

monobrornaldehyde gives Glycollic Aldehyde,

CH 8 Br Of + Mi
which
(e)
is

H.,0 "

- HBr + OH CH

//
2

C<

\H
the reactions of the

the simplest member of the sugar group and does not gives

all

sugars.

With lime-water, formaldehyde undergoes

// H Of

aldol condensation (see p. 245), giving

Formosa,
6

- OH

\H
which
is

CH, CH(OH) CH(OH) CH(OH) CH(OH) Cf "

-

^ X
H

a syrupy mixture of compounds, C 6 12 O 6 influence of light and moisture, plants fix CO 2 and form starch (C 6 10 5 ) H , 6H 2 O C 6 H 12 O 6 -f- 6O 2 the hexose then giving up water which is a polyhexose, 6CO 2 and yielding starch. According to Baeyer (1870), the C0 2 gives first formaldehyde, then a
.

Under the

hexose (monose), and finally starch (polyose). 1

which is the characteristic group of the phony losazones. The latter crystallise readily and in a pure state from a dilute pyridine solution. Reduction of the phcnylosazones yields osamincs,
.

glucosamine, C 6 H n O 6 ']NH a From the analogy in the behaviour of haemoglobin and chlorophyll, Baeyer supposed the In such case the latter, like the former, to be capable of uniting with carbon monoxide. and 2 , the oxygen being chlorophyll would decompose CO 2 into O and CO, and water into evolved ; the CO, fixed by the chlorophyll, would split off and combine with the hydrogen to give formaldehyde, the chlorophyll being regenerated. Union of the formaldehyde with () would then yield methyleneglycol, CH 2 (OH) 2 , which would condense to glucose : 2 C 6 H 12 O 6 Baeyer' s hypothesis does not seem satisfactory, since 6H 2 O 6CH a (OH) 2 dissociation of two highly exothermic substances like C0 2 and H 2 O is difficult to conceive, while, in addition, plants are indifferent towards CO. and later by E. Fischer that glyceraldehyde Jt was shown by Butlerow that formaldehyde can, under certain conditions and in the presence of bases (baryta), give rise to sugar (a-acrose). no do other alkali hydroxides give an conditions In 1905 H. and A. Euler found that under appreciable amount of sugar, whilst with dilute solutions of sodium carbonate or, better, with calcium carbonate or lead hydroxide at 100, first glycollaldehyde and glyceraldehvde are formed and finally a keto-ardbinose, tta phenylosazone of which melts at 159 to 161. The conditions for the production of hexoses irom formaldehyde are not yet defined, but O. Loew stated that,
e.g.,
1

with milk of lime, he obtained formose, which is a mixture containing i-fructose (a-acrose). D. Berthelot and H. daudechon (1910) found that the action of ultra-violet rays on 10 per

526
tion

ORGANIC CHEMISTRY

Also 2 mols. of glyceraldehyde (derived, e.g., from acrolein) undergo the aldol condensaand yield a hexose (termed acrose) which is a constituent of formose. (/) It is possible to pass from one aldose to a higher one through the cyanohydrin, which is first hydrolysed to an acid with an extra carbon atom. 8uch an acid readily forms a lactone with the hydroxyl in the y-position, and treatment of the lactone with

sodium amalgam (addition of

2)

yields the higher aldehyde (aldose)

-

OH CH

CH(OH) CH(OK) CH(OH) CH(OH) C<f

-

OH CH 2 CH(OH) CH(OH) CH(OH)

-

12

OH

CH^- CH(OH) CH(OH)

-

OH CH(OH) CH(OH) CO + H 4 ~>

-

OH CH

CH(OH) CH(OH) OH(OH) CH(OH) CH(OH)

-

'

//*

->
7

\H
->

CH(OH) CH(OH) COOH

/3

Ifrptosc.

By the same ketonio (lactonic) synthesis, the hepto.se can be converted into octose and nonose.
TETROSES, C 4 H 8 O 4
,

and PENTOSES, C 6 H 10

Just as the hexoses can be converted into pentoses, the latter can give rise to TETROSES. For instance, d-, /-, and i-crythrose are obtained by oxidising
cent, solutions of various sugars at a temperature of of the following quantities of gas :

80

to 90

leads to the rapid formation

Levulose (ketose) Glucose (aldose) Maltose (gives 2 mols. glucose) Saccharose (gives glucose and levulose)

..... .....
.

CO
83 12 12

CH 4
8 12
11
*

CO,
15

9 76
77 47

22
21 16

.45

They found also that prolonged action of ultra-violet rays on a mixture of OO 2 and H 2 yields a small quantity of CO and of formaldehyde. These facts tend to confirm J. Stoklasa's observations (1906-1910) on the formation of hydrogen as final product of the degradation of carbohydrates by the action of ylycolytic. enzymes, which have an important function in the assimilation of carbon dioxide in the chlorophyll cells, and also to render valid Stoklasa's hypothesis (1907) that the formaldehyde necessary to the formation of carbohydrates by the simple polymerisation assumed by Baever may result from O 2 -f 2H-CHO. Stoklasa and Zdobnick^ (1910) have obtained the reaction, 2CO, -f 2H 2 inactive sugars and aldehyde by the action of ultra-violet rays on carbon dioxide and hydrogen in the nascent state in presence of caustic potash (with initial formation of potassium bicarbonate, which, in the nascent state and with nascent hydrogen, generates the sugar) and have disproved the view held by Fischer (1888-1889), Loew (1888-1889), Neuberg (1902), and Kuler (1906) the sugars they obtained that, in the synthesis of sugars from formaldehyde, pentoses arc formed are not asymmetric and are hence not fermented by ordinary alcoholic ferments. In 1912 Stoklasa, Sebor and Zdobriick^ showed that formic acid constitutes an intermediate product in the formation of CO 2 and H 2 O by the action of ultra-violet light on formaldehyde in presence of potassium hydroxide and air. Subjection of CO 2 and KOH, mixed with a ferrous salt, to the influence of ultra-violet rays gives hexoses (aldoscs and ketoses) which are optically inactive and non-fermentable. According to Stoklasa, the function of the chlorophyll in plants is to absorb the ultra-violet rays of sunlight. From the aqueous distillate of the leaves of various plants, F. Hartwig and T. Curtius (1910) have separated (by means of m-nitrobenzhydrazide,
;

<H

the hydrazone of which melts at 167.

According to Baur (1913) the formation of carbohydrates in green plants from CO 2 is probably accompanied by the transitory formation of various acids and alcohols. Similarly the genesis of sugars in the animal organism may result from the glycine which forms a product of the decomposition of the proteins and produces glycollic acid and formaldehyde in passing through the liver. Balv, Heilbron and Barker (1921) find that aqueous carbon dioxide solution yields formaldehyde when exposed to light of wave-length 200 p/x, the yield of the aldehyde being greatly increased in presence of paraldehyde, sodium phenoxide and certain 'salts which 'absorb light these substances protect the formaldehyde produced from the of wave-length 290 /u/u polymerisation to reducing sugars effected by this light (290 /up)! Chlorophyll appears to be an ideal photo-catalyst for both stages of the synthesis of carbohydrate from carbon dioxide and water, the absence of free formaldehyde in the growing leaf being thus explained.
;

PENTOSANS
:

527

d-arabonic acid, d-arabinosoxime, and natural i-erythritol respectively with hydrogen peroxide

OH -CH 2

[CH OH] 3

COOH +

=H 0+C0 + OH
2

CH 2 [CH OH] a -CHO

Tetrose

The tetroses are also obtained by oxidising (with 2 2 ) the calcium salts of pentonic acids in presence of ferric acetate, which acts a an oxidising catalyst. The pentoses (Arabinose, Xylose, etc.) occur abundantly as Pentapolyoses or Pentosans (Araban, Xylan) in many vegetable organisms '(straw, wood, maize husks, etc.), from which they are obtained by simple boiling with dilute acids. 1 So-called non-nitrogenous extractives present in abundance in plants and in foods consist especially of pentoses, hexoses, lignin and cuiin (Konig, 1913), which exhibit varying solubility in water and in acids at different temperatures and pressures. Pentoses do not ferment. Arabinose and xylose are aldoses, CH 2 [CH(OH)] 3 CHO. By bromine water these two pentoses are oxidised with formation respectively of arabonic and xylonic acids, CH 2 [CH OH] 3 C0 2H, which are stereoiso-

OH

OH

meant those polysaecharides which are related to the pentoses as are starch, inulin, etc., to the hexoses, and which give pentoses and also hexoses on hydrolysis. From starch they are distinguished by their leevo-rotation. From plants the pentosans are extracted by means of dilute alkali according to the method given by Tollens, Stone, and Schulze (1888-1901) : the finely divided vegetable matter is treated twice, for some hours at the ordinary temperature, with seven times its weight of 2 per cent, ammonia solution to eliminate in the soluble state part of the proteins, salts, etc., and to remove the more soluble part of the hernicellulose (this would give little pentose on subsequent hydrolysis). After the dark ammoniacal liquid has been separated by filtration through cloth and by squeezing in a press, the solid residue is extracted with ten times its weight of 5 per cent, caustic soda solution, with which it is first macerated in the cold for 10 to 12 hours, and then heated in a reflux apparatus on a water-bath for six hours. The mass is next filtered through cloth and the residue pressed and w ashed several times with water until the total volume of solution obtained is equal to that of the caustic soda solution used. This brown liquid is evaporated to some extent on a water-bath and is then treated in the cold with an equal volume of flO per cent, alcohol. The voluminous, nocculent precipitate of r/'um (pentosanfi) thus obtained is collected on cloth, washed and purified by repeatedly dissolving in dilute acid and reprecipitating with alcohol, this procedure being continued until the gum leaves a minimal ash on incineration. To pass from the pentosans to the pentoses, the moist gum is hydrolysed (Oonneler and Tollens, 1892 and 1903) by digestion for 12 hours with 25 parts of water and 2-5 parts of hydrochloric acid of sp. gr. 1-19, the mixture being finally heated on a water-bath until the furfural reaction (red coloration with aniline acetate paper) begins to make its appearance (about two After filtration of the cold liquid and neutralisation with lead carbonate (testing with hours). Congo-red paper), a few drops of barium hydroxide are added and the liquid filtered to remove The solution is concentrated on a water-bath precipitated lead chloride and barium carbonate. under reduced pressure, mixed with a little alcohol, filtered and concentrated to a syrup. This is taken up with methyl alcohol and the solution filtered to remove mineral and other impurities. The alcohol is then evaporated and the residue seeded with a few crystals of xylose or arabiriose and left in a desiccator until the whole mass crystallises (this sometimes requires several weeks). In order to separate the arabinose and xylose, which often occur together, Ruff and Ollendorff (1899) treat the mixed pentoses with eight times their weight of 75 per cent, alcohol and nearly After several their own weight of benzylpheriylhydrazine dissolved in a little absolute alcohol. hours' rest with frequent shaking, there separates arabinose benzylphenylhydrazone, which, in the pure state melts at 174 and, when treated with excess of formaldehyde, liberates the arabinose ; the latter is soluble in water, whilst formaldehyde benzylphenylhydrazone remains

By

the term Pentosans are

in the

same way

undissolved.

procedure yields crystals of cadmium bromoxylonate, C 5 H 9 O 6 BrCd. Before carrying out this or separation, however, it is necessary to make sure that the mixture contains no galactose These sugars can be detected by oxidising the mixture with nitric acid (sp. gr. 1-15) glucose. remains on the water-bath and evaporating the liquid to two-thirds of its volume. If the liquid turbid in the cold, the presence of mucic acid, derived from galactose, is indicated, and if, after neutralising with potassium carbonate, acidifying with acetic acid and concentrating, potassium hydrogen saccharate separates, the presence of glucose which gives saccharic acid on oxidation is demonstrated.

The aqueous arabinose solution, after separation and concentration to a syrupy consistency, The corresponding hydrazone of xylose is soluble in 75 per deposits pure arabino.w in crystals. cent, alcohol, and yields xylose when decomposed with formaldehyde in the manner described above. The xylose can also be separated, according to Bertrand and Tollens (1900), by treating the mixture of pentoses with 2 parts of water, 1 part of cadmium carbonate, and 0-5 part of bromine. The mixture is heated for a short time on the water-bath, then left for 12 hours, evaporated, taken up with water, filtered, again evaporated, and mixed with alcohol ; this

528
;

ORGANIC CHEMISTRY

acid of sp. gr. 1-06 (12 per cent.), they yield furfural, C^HgO CHO (aldehyde), which distils over and gives a characteristic and intense red coloration with aniline and hydrochloric acid, a phenylhydrazone with phenylhydrazine, and a 1 slightly soluble condensation product with phloroglucinol.

meric with more energetic oxidising agents, they give trihydroxyglutaric acid. On reduction they yield the corresponding alcohols, arabitol and xylitol (see pp. 225, 525), which are also stereoisomerides. By way of the corresponding cyanohydrins they can be converted into hexoses (via hexonic acids). All these reactions aid in establishing the constitution of these pentoses. As they contain asymmetric carbon atoms, these sugars are optically active, and they exhibit the phenomenon of mutarotation thus, for freshly prepared solutions of xylose, the value of the specific rotation is [a] D 75 to 80, while five minutes after the sugar is dissolved it has the .stable rotation 19. When pentoses are boiled with dilute sulphuric acid or with hydrochloric
;

any pentose or hexose with caustic soda in presence of air or other oxidisyields no trace of saccharic acid, but gives formic acid and monobasic hydroxy-acids (e.g., glycollic, dl-glyceric, trihydroxybutyric, and various pentonic and
of

Treatment

ing agent

(e.g.,

HgO)
if

hexonic acids)

air is excluded, aldotetroses,

formaldehyde, a

little

3 -dienols, bioses,

distillation of vegetable subderived not merely from true pentosans, but also from oxycellulose, glycuronic acid, etc. methylpentosans give inethylfurfural. Hence Cross and Bevan suggest the name furfttroids for substances other than true pentosans which give furfural. On the other hand, it has been proposed by Tollens that the term pentosan be applied to the whole of the substances (furfuroids and true pentosans) which give furfural when distilled with 12 per cent, hydrochloric acid. Hydroxymeihylfurfural (see below) does not distil in presence of acids but undergoes resinification, and hence escapes the Tollens method of estimating furfural. Until comparatively recent times it was assumed that the pentosans were derived from the hexoses and polyhexoses, since it was known that 4-hydroxymethylfiirfuraldehyde,

and glyceraldehyde are mainly formed. Recent work has shown that the furfural obtained on
stances with 12 per cent, hydrochloric acid
is
;

CHO C CH CH C CH 2 OH
: :

is

obtained on heating levulose, d-mannose, d-glucose, d-galactose, chitose, tube with 0-3 per cent, of oxalic acid, while 4t-broniomethylfarfural
9

etc., in

a sealed

1 Flint and Tollens (1902) distil Quantitative DiUrmination of Pcntoses and Pentosans. in a flask similar to that shown in Fig. 18 (p. 12), about 5 grms. of the substance with 100 c.c. of 12 per cent, hydrochloric acid, the heating being carried out in an oil-bath at 160. Thirty c.c. of liquid are distilled over every 12 to 15 minutes, in which time 30 c.c. of fresh acid are added by means of a tapped funnel, this procedure being continued as long as the distillate reddens a strip of filter-paper moistened with an acetic acid solution of aniline. To the distillate is added an excess (double the amount of furfural expected) of pure phloroglucinol dissolved in 12 per cent. hydrochloric acid. The volume of the liquid is made up to 400 c.c. with the same acid in a graduated flask, which is well shaken and left for 12 hours, at the end of which time the precipitate is Collected on a tared filter, washed with 1,50 c.c. of water, dried for four hours in an oven and weighed. The weight of furfural is obtained by dividing this weight by a variable factor, which has the following values for different amounts (in grms.) of the phloroglucinol compound 0-20 grm. (1-820); 0-22 (1-839); 0-24 (1-856); 0-26 (1-871); 0-28 (1-884); 0-30 (1-895);
:

0-32(1-904); 0-34(1-911); 0-36(1-916); 0-38(1-919); 0-40(1-920); 0-45(1-927); 0-50(1-930); 0-60 or more (1-931). The xylan is calculated by multiplying the quantity of furfural by 1-64, the araban by 2-02, while for mixed pentosans, the factor 1-84 is employed. If the phloroglucide is formed in alcoholic solution, it may be estimated colorimetrically or spectroscopically (Pinoff and Glide, 1913). Another method of procedure consists in precipitating the furfural with phenylhydrazine and estimating the nitrogen in the precipitate. Jolles (1906), however, neutralises almost completely (to methyl orange) the distillate containing the furfuraldehyde, then adds 10 c.c. (more, if necessary) of a decinormal sodium bisulphite solution, and after two hours titrates the excess of bisulphite with a decinormal iodine solution (1 c.c. of which corresponds with 0-0075 grm. pentose). Many plants contain methylpentosans as well as pentosans. The solubility of methylfurfuralalmost completely insoluble, serves phloroglucide in alcohol, in which furfuralphloroglucide is as a means of estimating the former (Ishida and Tollens, 1911).

HEXOSES
CHO C CH CH C CH 2Br,
:
:

529

obtained by heating levulose (or filter-paper, cotton, cellulose, straw, starch, dextrose, under pressure with chloroform saturated at with hydrogen bromide. Further, when the oxime of levulose is heated with concentrated caustic potash solution, the nitrile is first formed and then hydrocyanic acid and d-arabinose
is

lactose, glycogen, etc.)

OH CH 2

[OH OH] 4

CH NOH -> H O + OH CH CN -> HCN + OH CH 2 [CH OH] 3 CHO. [CH OH] 4

:
-

Oxidation of d-gluconic acid with peroxides also gives d-arabinose. Ketohexoses in general, when heated with dilute acids (e.g., with 0-3 per cent, of oxalio acid under a pressure of 3 atmos.), are largely transformed into hydroxymethylfurfural, whilst the aldohexoses undergo this change only to a very slight extent ; if mineral acids
are used, or oxalic acid in larger quantity, levulinic acid is obtained instead of hydroxymethylfurfural. U. Nefs work (1910) tends to show that, in plants, pentosans cannot be derived from the hexoses, but that they are formed rather from either aldotetroses and
or 2-carbon-atom sugars and glyceraldehycle. The hexoses, in their turn, would be formed, not from pentoses and formaldehyde, but rather from 2 mols. of glyceraldehyde or 3 mols. of a 2-carbon-atom sugar, or even from 1 mol. of a 2-carbon-atom and 1 of an aldo-

formaldehyde

sugar

tetrose.

XYLOSE is readily obtained by boiling with dilute sulphuric acid plants containing especially jute, bran, straw, or, better still, apricot stones or maize husks. It bears also the name of wood-sugar, and is yielded by the decomposition of gluconic acid. When pure, it crystallises and forms a phenylosazone melting at 160.
it,

rf-ARABINOSE is Isevo-rotatory, but is obtained from calcium d-gluconate and hydrogen peroxide and from d-glucose. In the pure state if forms prismatic crystals. i-ARABINOSE is the optically inactive racemic isomeride, and is found in the urine of
persons suffering from pentosuria. Z-ARABINOSE is obtained by boiling vegetable gum with dilute sulphuric acid. It is dextro-rotatory, but is designated a laevo-compound because it is related chemically to
1-glucose.

It

forms sweet-tasting crystals melting at 160, and

:

its

phenylosazone melts

at 157.

Two other pentoses are RIBOSE, which, with nascent hydrogen, gives adonitol (a pentahydric alcohol, OH CH 2 [CH OH] 3 CH 2 OH, and the only sugar-akohol yet discovered in plants, the leaves of which are able to transform it into starch the sap of Adonis vernalis contains as much as 4 per cent, of adonitol) ; and D-LYXOSE, which is obtained from galactonic acid and melts at 101.
;

Higher homologues are the Methylpentoses FUCOSE, contained in algae CHINOVOSE, ISORHAMNOSE, and RHAMNOSE (or Isodulcite), C 5 H 9 O 5 CH 3 which is_obtained by boiling quercetin and certain other glucosides with dilute sulphuric acid.
:

According to Rosenthalor (1909), Methylpentose in presence of pentoses may be recogby heating the solution for a few minutes on a boiling water-bath with HC1 of sp. gr. 1-19 and observing tho yellow liquid thus obtained in the spectroscope methylfurfural, from methylpentose (even as little as 0-0005 grm.) gives absorption bands between the blue and green. The reaction is still more sensitive if a little acetone is added before heating, the liquid then being coloured red (by the methylfurfural) and giving a sharp absorption band in the yellow (D line) pentoses do not give this reaction if the liquid is heated. Other sensitive reactions are obtained with phloroglucinol, orcinol, resorcinol, pyrogallol, aniline
nised
:

acetate, etc.

HEXOSES, C 6 H 12O

fl

These are of frequent natural occurrence and exist as various optically active stereoisomerides, since they contain four asymmetric carbon atoms, while they also form inactive racemic compounds. They are substances of sweet taste, and are extremely soluble in water, but in alcohol they dissolve but slightly and in ether not at all they crystallise with great difficulty and decompose
;

530

ORGANIC CHEMISTRY
-

when

distilled. Their phenylhydrazones are soluble, and their phenylosazones insoluble in water. When boiled with hydrochloric acid they all give CH 2 CH 2 C0 2H), the silver salt of which forms (1) Levulinic Acid (CH 3 CO

characteristic crystals, and (2) a brown amorphous mass of so-called humic substances. With methyl alcoholic ammonia, the hexoses form Osamines, e.g.,

Glucosamine, C 6 U 05 2 They reduce Fehling's solution or ammoniacal silver solution in the hot, and with oxidising agents they yield hexonic acids and then lower acids down
.

NH

to oxalic.

With lime they form additive compounds decomposable by carbonic acid with boiling milk of lime they turn brown and give Hexosaccharine (lactone of saccharic acid), C e 10 5 By the combined action of concentrated sulnitric and are converted into pentanitrales, while with alcohols acids, phuric they and gaseous hydrogen chloride they form ethers (glucosides). The aldohexoses give the fuchsine-sulphurous acid reaction (see p. 246), which is, however, not shown by the ketohexoses. The mode of formation of the phenylosazones is described on p. 524. With hydroxylamine they form oximes, e.g., rf-Glucosoxime, which can be converted into the corresponding nitrile and then, by elimination of HCN, into
;

the aldopentose (d-arabinose). The hexoses are formed in various organisms and can also be obtained by hydrolysing polyhexoses with dilute acids or enzymes. The optical activity of the hexoses indicated by the prefixes d-, 1-, and iindicates the sign of that of the substances with which they are connected genetically, but the fact that the actual direction of the rotation does not always correspond with this prefix is a source of some confusion. It must also be noted that the rotatory powers of the hexoses and pentoses are lowered when the sugars are dissolved in a centinormal alkali solution at 37. Synthetically the hexoses can be obtained from formaldehyde (see Note, p. 525), as well as from the hexahydric alcohols by gentle oxidation and from the hexonic acids by reduction. E. Fischer has synthesised d-glucose completely

from glycerine, by way of (1) glyceraldehyde, (2) inactive fructose, which, with hydrogen, yields (3) inactive mannitol, oxidation of this giving (4) mannose and (5) racemic mannonic acid, the latter being resolved into d-mannonic acid, in presence its (6) active components by means of strychnine of pyridine and water in the hot, produces (7) d-gluconic acid and this, on reduction, d-glucose. The relations between hexoses and pentoses were indicated in the Note on
;

p. 527.

d-fructose,

As was mentioned above, fermentation with yeast occurs only with d-glucose, d-galactose, d-mannose, and glycerose, no fermentation taking

place with sorbose, the pentoses, 1-glucose, 1-fructose, 1-mannose, or d-mannoheptose. Thus only the stereoisomerides of a certain group are fermentable.

The structures of the hexoses are deduced partly from their general reactions and partly from the following facts The chain of six carbon atoms in the hexoses is normal, since reduction with hydrogen yields a hexahydric alcohol, which is further reduced by heating with hydriodic acid to normal sec. hexyl iodide, CH 3 CH 2 CH 2 CH 2 CHI CH 3 the constitution of the latter is shown by the fact that the corresponding second:

ary alcohol
this,

is

on oxidation, giving

oxidised to n-propylacetone, CH 3 CH 2 CH 2 finally butyric and acetic acids of

CH 2 CO CH 3

known

constitu-

tion.

tives

The hexoses contain five hydroxyl groups, as they yield pentacetyl-derivawhen boiled with acetic anhydride and sodium acetate or zinc chloride.
:

Their constitutional formula hence cannot be other than

GLUCOSE
H H
C
II

531

H
C

H
since,

C/ x 11)11 OH OH OH OH OH
C C

if two hydroxyl groups were at any moment united with one carbon atom, a molecule of water would be eliminated immediately. Further, with hydrogen the hexoses form hexilols, which are nob aldehydic but only alcoholic in character under any conditions, so that two hydroxyl groups and do not give up 2 Neither can it be supposed are not combined with one carbon atom. that three hydroxyl groups are united with the terminal carbon, thus

OH
because
if

this

were so water would be readily separated and an

acid formed, in which case the aqueous solution should conduct the electric current and have a dissociation constant much greater than that of acetic but this is not found to be the case. acid Combination with bases does occur (with the hexabioses), but the compounds formed are additive compounds. Since then there are a number of different hexoses, all showing the same general behaviour, they must have the same constitution, the differences being due to differences in the spacial structure. Theoretically, 16 active stereoisomeric aldohexoses are possible and have been already prepared. The rotatory powers of the plienylowzones and phenylhydrazones may be of opposite signs to those of the corresponding hexoses.
;

d-GLUCOSE (Grape
abundance

Sugar, Dextrose, Starch Sugar), C 6 H 12

6,

is

an aldose found in

in grapes and many other sweet fruits in company with d -fructose ; it also occurs It has a sweet taste, which is less intense (about twoin the urine of -diabetic patients.

thirds)

It crystallises from water with 1H 2 O, which it loses at 120, anhydrous form, melting at 146. In aqueous solution it has the specific rotation -j- 53 at a temperature of 20, but it exhibits mutarotation, the rotatory power being about double the above value in freshly prepared solutions which have not been boiled. Owing to its rotatory power glucose may be estimated polarimetrically (see later. Sugar). Yeast resolves it completely into alcohol and carbon dioxide.

than that of sucrose.

in the

and from alcohol

When saccharose (a dextro-rotatory hexabiose) is heated with dilute acid, it is converted into a laevo-rotatory mixture of equal proportions of glucose ( -f- ) and fructose or Invert Sugar, 1 the change being known as inversion, levulose ( ), which bears the name since it is accompanied by alteration of the sign of the optical rotation.
On
oxidation, d-glucose gives d-Gluconic Acid,

OH CH 2

[CH

OHJ 4 COOH, and then

the dibasic Saccharic Acid,

which, like tartaric acid, gives a the latter serves to characterise d -glucose, it being slightly soluble acid potassium salt sufficient to oxidise with nitric acid and then precipitate the saccharic acid with saturated potassium acetate solution. When reduced, d -glucose yields d-sorltitol (hexahydric alcohol).
;

CO 2 H [CH -OH] 4 CO 2 H,

The sugar forms a phenylosazone, melting

melting respectively at 115
arid

at 204

to

205, and two phenylhydrazones,

144.
is

When heated above 140, glucose is converted into caramel. In dilute solution it reduces Fehling's solution in the hot, and on this reaction
the estimation of glucose. 2
1

based

and

preserves, etc. ; it is employed also to make artificial honey. 2 In the chemical way the estimation is effected by means of Estimation of Glucose. Folding's solution by the method described later in the section on Saccharose, about 10 grms. of solid glucose or 15 to 20 grms. of the syrupy product being dissolved in water, made up to 100 c.c. in a graduated flask and filtered through a dry, covered filter. Polarimetric estimation is not usually applicable, owing to the presence of dextrin, sometimes to the extent of 40 per cent., The dextrin is determined by dissolving 5 grms. of the glucose this increasing the rotation. in 400 c.c. of water, adding 40 c.c. of HC1 of sp. gr. 1-125, heating for two hours on a boiling and making up to 500 c.c. The total water-bath, cooling, neutralising exactly with
in

Invert Sugar, of the consistency of honey,

is

a commercial product used by brewers

making

NaOH

532

ORGANIC CHEMISTRY
:

Barfoed has proposed the following reaction for detecting the presence of minimum quantities of glucose (0-2 mgrm.) mixed with lactose, maltose, dextrin, and .saccharose to 5 c.c. of Barfoed's reagent (an acetic acid solution of normal cupric acetate) in a test-tube is added the dilute aqueous sugar solution (about 1 per cent.), the mixture being heated on a boiling water- bath for three and a half minutes, allowed to cool for 10 minutes, and filtered. If the filter retains red cuprous oxide, the presence of dextrose is demonstrated. MANUFACTURE OF GLUCOSE. One hundred kilos of starch are mixed with 300 litres of boiling water containing 3 kilos of concentrated sulphuric acid, or 1 kilo of concentrated hydrochloric acid, and the mass heated in a suitable autoclave or converter (conical or cylindrical, capable of withstanding 6 atmos.), coated internally with lead and externally with insulating material. A current of steam is then passed in and the temperature raised to about 120 for an hour if liquid glucose, consisting one-half of glucose and the other of dextrin, or to 140 for 2 to 3 hours if crystallisable glucose containing only 30 per cent, of dextrin is desired. By allowing the steam to escape subsequently, the empyreumatic oils (which are of disagreeable odour) are carried away the steam is condensed in cooled coils (the heat being used to heat water). The "temperature of the mass is then maintained at 80 until a test portion gives no blue colour with iodine and no precipitate with lead acetate (or potassium silicate), these being indications of the saccharification of the dextrin and gummy matters a further sign of this is the non-formation of a precipitate with alcohol. The mass, at about 17 Be. ( 30 per cent, of carbohydrates), is then decanted into the neutralisation vats, which are furnished with stirrers, and finely divided calcium carbonate, suspended in a large quantity of water, gradually added in order to neutralise and preci;

pitate the sulphuric acid. After thorough mixing of the mass, it is allowed to settle and the liquid then decanted into another vessel, where the calcium sulphate remaining in solution
is

precipitated by the addition of a little ammonium oxalate. If hydrochloric acid were used, this is neutralised with sodium carbonate. The liquid is next filter-pressed, evaporated in a vacuum to 30 to 32 Be. decolorised
,

by means of boneblack or dry blood mixed with powdered wood charcoal or by passing it through vertical filters filled with the charcoal similar to those used in sugar refineries. It is then concentrated in a vacuum (see Sugar Industry) either to 42 to 44 Be., to give solid compact glucose separating in the cooling vats (fitted with stirrers), or to about 65 The temperature is lowered to 18 Be*., when ready formed crystals of glucose are added. to 20, and after 3 or 4 days the separated crystals centrifuged and so freed from the syrupy portion, which retains the dissolved dextrin and other impurities. To obtain
in the hot

granulated glucose the solution is concentrated only to 32* Be. ; after 8* to 10 days in the cold, a granular hydrated glucose, C 6 12 6 2 0, separates. When a very dense liquid glucose (so dense that its specific gravity cannot be determined with the ordinary hydrometers) is required, a little dextrin is left in the sugar so as

to prevent crystallisation. The theoretical yield of pure glucose from 100 kilos of dry starch is 110 kilos. In some factories the starch is saccharified with a little nitric acid, which gives a less

highly coloured syrup and

by means
acid, this

of sulphurous acid,

more rapid in its action. The nitric acid is then eliminated which is oxidised at the expense of the nitric acid to sulphuric being readily precipitable with lime.
is

dextrose (including that formed by hydrolysis of the dextrin) in this solution is now determined by means of Fehling's solution. The difference between the amounts of glucose found before and after the action of acid, multiplied by 0-9, gives the quantity of dextrin. The acidity should not exceed 2 c.c. of normal caustic soda per 100 grms. of syrup. The proportion of ash varies from 0-2 to 0-7 per cent. Solid commercial glucose contains 65 to 75 per cent, of glucose and the liquid 35 to 45 per cent. In pure solution, glucose may be estimated by means of the specific gravity
:

FRUCTOSE

588

The advantages of transforming starch into glucose by means of hydrofluoric acid consist in rapid and complete hydrolysis, ready separation of the whole of the acid as barium fluoride, and the production of a glucose with a pure flavour. In 1901 Calmette found that, after heating crushed cereals with double the amount of 1 per cent, hydrochloric acid for one hour at 100, one hour at 110, and a third hour at 120, and then cooling, the mass may be converted completely into glucose by the action of
Mucedince.

USES.
mel,
1

Large quantities of glucose are consumed for making sweet syrups, carafermented liquors, sweets and wine, preserving fruit, adulterating honey, dressing
(Levulose, Fruit-Sugar ) occurs abundantly, together with glucose, in also found in large quantities in honey (which contains natural invert

textiles, etc.

d- FRUCTOSE

sweet

fruits,

and

is

sugar). alone.

OH
acid,

The hydrolysis of inulin (a polyhexose found in dahlia tubers) yields d-fructose The sugar is Icevo-rotatory and fermentable. It has the constitution of a ketose, CH 2 [CH OH] 3 CO CH 2 OH, hydrolysis of its cyanohydrin giving the heptonic

OH CH [CH OH] 3
-

C(OH)
I

CH 2

OH.

COOH
The phenylosazone
of d -fructose
is

identical with that of

d -glucose.

Methylphenylhydrazine forms osazones. only with ketoses and not with aldoses, withwhich, however, it forms colourless hydrazones, these being usually soluble and hence readily separable from the slightly soluble, intensely yellow osazones (see pp. 398 and 524). When phenylosazones are heated gently with hydrochloric acid, they lose 2 mols. of phenylhydrazine with formation of osones which contain two carbonyl groups. Thus
pheriylglucosazone yields Glucosone, OH CHg, [CH OH] 3 CO CHO, and this when treated with nascent hydrogen (from zinc and acetic acid) takes up 2H at the terminal carbon atom, fructose being thus obtained from glucose. On the other hand, reduction of a ketose gives the corresponding hexahydric alcohol, which, on oxidation, yields the monobasic hoxonic acid ; the latter loses water, giving rise to the lactone, and this gives the
aldose on reduction,

92 at a temperature of 20. d -Fructose is laevo-rotatory [a] D This sugar has been suggested for the use of diabetic and tuberculous patients and as a substitute for cane-sugar, since it is sweeter, and in syrups and honey it hinders the crystallisation of the other sugars. In view of these uses, attempts have been made to prepare fructose industrially. Konig in 1895 and Stciner in 1908 proposed its extraction from endive roots and dahlia tubers (these contain from 8 per cent, to 17 per cent, of insulin). The crushed tubers are treated in the hot (below 65) with a little milk of lime and with steam, and are then pressed. The a rotating cooler, the mass of juice, after defecation with clay, is allowed to crystallise in inulin crystals being centrifuged, redissolved in hot water, and converted into fructose by mgans of dilute acid (see Glucose) the fructose solution is concentrated in a vacuum. Stciner calculates that the sugar can be made by this process at a cost of Is. per kilo. A characteristic reaction for the detection of fructose in presence of other reducing to a solution of 12 grms. of glycocoll in sugars is obtained with the following solution hot water are slowly added 6 grms. of pure cupric hydrate, the liquid being heated on a water- bath for about 15 minutes until complete solution takes place and then cooled to 60 ; after 50 grins, of potassium carbonate have been added, the volume is made up to This reagent is reduced in the cold only by levulose (1 to 5 1 litre and the whole filtered. per cent, solution), the time required varying from 4 to 9 hours ; other sugars, including the pentoses, reduce it only at temperatures above 40.
; ; :

Caramel (or sugar colouring) is prepared by fusing and heating glucose or saccharose at a temperature of 160 to 180 (not beyond this) in an iron vessel fitted with a stirrer. To glucose 1 to 3 per cent, of soda (ammonia is also largely used) is added to accelerate the operation and to neutralise the acid formed (saccharose also yields acid, being first partly inverted by the heating), and after the change is complete, 50 per cent, of hot water is added and the mass well mixed and filtered through charcoal. A brown, syrupy mass is thus obtained which is soluble in water or alcohol, giving a brown or yellow solution according to the dilution. That obtained from saccharose, which does not contain dextrin and dissolves completely in 80 per cent, alcohol, is used for colouring spirits, whilst that from glucose, which contains dextrin and is entirely soluble in 75 per cent, alcohol, is used to darken beer and vinegar. The presence of more than 5 per cent, of ash indicates that a caramel has been prepared from molasses ;
1

good

qualities contain only 1 per cent, of ash.

534
is

ORGANIC CHEMISTRY
,

d-MANNOSE, C H 12 O 6 is an aldose stercoisomeric with glucose, and is fermentable ; it obtained from mannitol, the corresponding alcohol, by oxidation. It melts at 136, and differs from other monoses in forming a phenylhydrazorie m.-pt. 195 to 200, only slightly soluble in water. With oxidising agents it forms first monobasic d-mannonic acid and then dibasic d-mannosaccharic acid, COOH [CH OH] 4 COOH. A general method for converting one hexose into a stereoisomeric one, e.g., d-mannoso into d -glucose, is as follows the d -mannose is oxidised to d-mannonic acid and the latter dissolved in quinoline and the solution boiled ; in this way the acid undergoes partial transformation into the stereoisomeric d-gluconic acid, reduction of the lactone of which
*
:

yields

to

d -glucose. The reverse change of d-gluconic into d-mannonic acid is also produced some extent by boiling with quinoline, so that d -glucose can be converted intod-mannose.

These sugars (and acids) differ only in the space arrangement of the groups united with the asymmetric carbon atom in the a-position, CH 2 [CH OH] 3 CH(OH) CHO, since the phenylosazone of rf-mannosc is identical with that of d-glucose, a

OH
-

OH CH

[CH

OH] 3 C C
II

N NHC 6 H 5
5

N NHC 6 H
It
is

this a-carbon
is

atom, adjacent to the aldehyde group, which

is

influenced

when a hexonic

boiled with quinoline or pyridine. When glucose, fructose, or mannose is treated with a very dilute alkali solution, a mixture of all three sugars results. The fructose seems to be an intermediate product, since the

acid

dextro-rotation of mannose gradually changes to a laevo-rotation, owing to formation of fructose, the amount of the laevo-rotation subsequently diminishing as the fructose becomes converted into glucose.

/-MANNOSE and /-GLUCOSE, C 6 H 12 O 6 (Aldoses), are obtained together from /-arabinose by the cyanohydrin synthesis and reduction of the lactonos of the resulting acids. Application of this synthesis to an aldehyde yields, in general, two optically active stereoisomeridcs, since a new asymmetric carbon atom is created and the chances of formation of the two isomerides are equal. The final mixture will, however, be inactive only when the initial molecule is inactive, while, when this is optically active (as with arabinose), the mixture will bo active, as the components will not have equal arid opposite activities ; one of these will have a rotation greater than that of the original molecule by a certain amount and the other a rotation less by the same amount. d-GALACTOSE, C 6 H 12 6 (Aldose), is obtained by oxidising dulcitol, C G 8 (OH) 6 , or by

hydrolysing milk-sugar, in which case it is formed together with glucose. It melts at 168, It is an aldose, giving on oxidation first monois fermentable, and exhibits mutarotation. basic d-galactonic acid and then dibasic mucic acid, COOH [CH OH] 4 COOH, which is
inactive.

HEPTOSES, OCTOSES, and NONOSES have not been found

synthetically from

in nature, but are prepared

mannose by means

of the

cyanohydrin synthesis.

GLUCOSIDES
These are of frequent occurrence in the vegetable kingdom and, when heated with acid or alkali or subjected to the action of certain enzymes, decompose into a glucose and an alcohol (or phenol, aldehyde, or nitrogen compound) they are hence ethereal derivatives of the monoses (e.g., Amygdalin, Salicin,
;

Populin, Coniferin,
of

etc.).

have been prepared by E. Fischer by the interaction an alcohol and a monose in presence of hydrochloric acid (which withdraws water). The glucosides are analogous in structure to the acetals
Artificial glucosides

H
R (\
but only
1

+ 20H 3 OH = H 2 + R COCH 3 (acetal),

X)CH 3
:

X)

molecule of alcohol takes part in the reaction

OH CH 2

CH(OH) CH(OH) CH(OH) CH(OH) CHO

7/80
Glucoside

GLUCOSIDES
CH(OH) CH(OCH 3)

535

+ CH 3 OH=

OH CH 2 CH(OH) CH CH(OH)

+H

2 0.

The glucosides are readily resolved into their components, so that union of these directly through carbon atoms is excluded. The combination with the oxygen of the hydroxyl in the y-position is deduced from analogous reactions, such as formation of lactones. The constitution of bioses is explained similarly
(see later).

According to Auld (1908) the constitution of Amygdalin

is

as follows

II II OH H II OH H OH HC C C C C CH 2 0-C- O-C-C-C- CH,, OH H OH H OH H H

OH.

NO CH C 6H5
Ciamician and Ravenna (1908) showed that, when glucosides are introduced and beans), they are absorbed and transformed without whilst the decomposition products of the glucosides effect, producing any (bcnzaldehyde, salicylic alcohol, hydroquinone, etc.) act as poisons. Hence the formation of glucosides in plants seems to have the effect of paralysing the poisonous action of certain substances. The same authors (1909) found that, when maize is made to absorb saligenin, this is partly transformed into similar manner they obtained benzylglucosidc in a its glucosidc, salicin
into plants (maize
;

(1911).

B.

HEXABIOSES

Almost all the bioses at present known decompose into hexoses (either two different monoses or 2 mols. of one and the same monose). No biose gives a hexose and a pentose. This decomposition of bioses, which is known as hydrolysis,

C12 H 22
since

11

+H

= 2C H
6

12

6,

can be effected by boiling with dilute acid or by the action of enzymes, and it takes place with great readiness, it is assumed that the constituent monoses of the bioses are united, not between carbon atoms, but more probably between oxygen atoms. It would appear, however, that the hydrolysis is not a monomolecular reaction (ses Vol. I., p. 69). Synthetic bioses are obtained by treating, for instance, a hexose with acetyl chloride, the resulting acetochlorhexose, in presence of sodium alkoxide and a
elimination of the acetyl group hexose, giving the acetyl derivative of a biose the biose itself. then soda means of yields by Bioses may also be obtained by the action of certain enzymes on monoses thus, with maltase, glucose gives isomaltose (not, as was formerly thought, see p. 126). The lactase of kephir acts on a mixture of glucose and maltose with glucose alone it yields a different biose. galactose. giving isolactose Glutose and galactose may* also be condensed by the action of emulsin (see
; ; ;
:

p. 136).

Of the hexabioses, maltose, lactose, and saccharose melibiose, see later, under Kaffinose),

will

be considered

(for

536

ORGANIC CHEMISTRY
H

forms crystals of the formula C 12 22 U and is strongly dextro2 in considering the manufacture of alcohol and of beer, it is prepared industrially from starch by the action of diastase (see pp. 133, 134, 141). Hydrolysis of maltose by dilute acid yields only eJ-glucose. It gives reactions similar to those of the monoses. Thus, it reduces Fehling's solution, and with phenylhydrazine forms phenylmaltosazone, C 24 32 O 9 4 On oxidation it yields monobasic Maltobionic Acid, C 12 H 22 O 12 which gives d-Gluconic Acid, OH CH 2 [CH OH] 4 COOH, on hydrolysis. Hence maltose contains only one carbonyl group and not the two corresponding with the 2 constituent glucose molecules, the phenylosazone being formed with 2, and not 4, mols. of phenylhydrazine, while oxidation of the sugar yields a monobasic and not a dibasic acid. Hence the 2 mols. of glucose in the maltose molecule are joined in such a way that only one carbonyl group remains free to exert its characteristic reactions, the other serving to link up the 2 glucose molecules. It is usual to include between brackets the monose residue which has no free carbonyl owing to the oxygen atom of this group being joined to the other monose residue, and to place outside the brackets those monose residues which retain free carbonyl. Maltose would then be represented by the formula (CeHnOg O) CflHuOs- Maltose is not fermentable directly, the maltase of yeast first
rotatory.

MALTOSE

+H

As was seen

d-glucose

d-glucose

converting it into fermentable glucose (see p. 134). Isvrwltose is not fermentable and has [a] D
soluble phenylisomaltosazone.

+ 70

with phenylhydrazone

it

yields

LACTOSE
and is
less

(or Milk-Sugar),

C 12 H22 O n

+H

2 0, is

swoct than cane-sugar.

Its reactions are similar to those of

contained in milk (up to 5 per cent.) the monoses (reduces

Fehling's solution, etc.), and it yields d -glucose and d-galactose on hydrolysis. It does not ferment with beer-yeast, which contains no enzyme capable of hydrolysing it. The glucose residue has its carbonyl free, whilst the carbonyl of the galactose takes part in the union of the 2 monose molecules, so that it will be represented thus (CgHnOg O) C 6 H U 5
:

rf-galactoac

rf-glueose

In fact, oxidation of lactose by means of bromine water results in the formation of monobasic lactobionic acid, which, on hydrolysis, gives d -galactose and d-gluconic acid. Cold water dissolves 16-6 per cent, and boiling water 40 per cent, of the sugar. INDUSTRIAL PREPARATION. Unless a dairy has an average production of at least 60 to 80 hectols. of whey per day, it is not expedient to extract the milk-sugar. The preparation is now carried out as follows The whey, is treated immediately after the first coagulation of the cheese. 1 The concentration is carried out in single or double-effet vacuum pans, similar to those used in sugar factories. Whey is passed continuously into the concentrator until the liquid attains a density of 30 Be. in the hot (about 60 per cent, of the sugar). It is then collected in iron vessels holding about 700 litres, in which it is cooled by water In the course of 24 hours, during which the circulating through a surrounding jacket. mass is well stirred three or four times, the temperature is lowered to 20. A pasty mass of fine crystals then separates, with an oily layer at its surface. The crystals are separated by diluting the mass with a little cold water (-J) and centrifuging, the crystals being retained in the drum of the centrifuge by means of a cloth. When a sufficient quantity of crystals has been thus collected in the basket of the centrifuge, the mass is washed with a gentle spray of cold water, the crude, slightly yellow sugar thus
:

obtained representing 3-6 to 4-3 per cent, of the whey taken. This crude milk-sugar contains 88 per cent, of sugar and 12 per cent, of water and various impurities (proteins, etc.) The liquid from the centrifuge still contains about 30 per cent, of the total sugar (not crystallised but forming a syrup). This liquid, which usually has a density of about 15 Be., is heated to boiling by direct steam in a vessel with a flat, perforated false bottom, the albumin being thus coagulated. After half an hour's rest, the albumin collects as a compact layer at the surface, the liquid being then drawn off from below so as to leave the cake of albumin on the false bottom ; this is removed, pressed in bags, and given to pigs or mixed with white flour to make bread. The albuminfree liquid is concentrated in vacuum pans to 35 Be*, (measured in the hot) and allowed to cool for several days, with occasional stirring, in iron vessels. This procedure yields a dark pasty mass of the crystalline sugar, which is collected by diluting with a large quantity of cold water and centrifuging as before ; this sugar amounts to 0-3 to 0-7 per cent, of the
original quantity of whey.
1 Dairies not producing sufficient whey simply purify it by boiling with acid whey to coagulate the albumin, and filtering. It is then despatched to works which treat it further.

LACTOSE
The mean

537

yield of crude milk-sugar is 4-3 per cent, of the whey (the maximum of 4-8 per cent, being obtained in winter and the minimum of 3-9 per cent, in summer). The liquid from the second crystallisation arid centrifugation is not treated further, unless by osmosis ; it is preferably utilised as cattle-food, as it is rich in potassium salts, nitrogen, and phosphoric acid. The crude sugar is either dried and placed on the market or subjected to a refining
process.
If left in heaps, it deteriorates to

The

refining

is

carried out as follows

double bottom (heated by indirect-fire so as to obtain a solution of 13 to 15 Be. (24 to 27 per cent, of sugar). A little bone-black, or fuller's earth (see p, 490), and about 0-2 per cent, (on the weight of sugar) of acetic acid are then added, and the heating continued until the boiling-point is approached, when magnesium sulphate (about 0-2 per cent.) is added and the liquid subsequently The mass suddenly froths very considerably (if kept boiling for a few minutes. the boiler should not be too full initially) and necessary, the steam-cock is closed the temperature rises to 102 to 105 C The charcoal decolorises the liquid and absorbs unpleasant flavouring substances, while the albumin is coagulated in large flocculent masses (by the acetic acid) and the phosphoric acid is precipitated by the magnesium. The hot liquid is filter-pressed, and the solid residue, after being washed with water and treated with a suitable amount of sulphuric acid, constitutes an excellent nitrogenous superphosphate. The clear liquid from the filter-press is concentrated as usual in vacua to 35 Be. in the hot (65 per cent, of sugar), the formation of froth being prevented. It is then crystallised, and when the maximum quantity of crystals has separated, these are
;
.

some extent. The sugar is dissolved, in an open boiler with a heat), in water at 50, the liquid being well stirred
:

After subsequent concentrations of the separated by centrifuging, giving first product. These three products together mother-liquor, second and third products are 6btained. amount to about 3 to 3-5 per C3nt. of the original quantity of whey ; they may be kept separate or mixed and then recrystallised. To obtain the sugar in the very white powdery form in which it is now sold, the refined
is
(first, second, or third) is dissolved in hot water to give a solution of 15 Be., which boiled, and, after a little aluminium sulphate (0-1 per cent.) has been added, filter-pressed, the clear watery filtrate being concentrated to t 32 Be. It is then crystallised in copper vessels, centrifuged, and dried in revolving inclined drums round which hot water

product

passes. It is
is

dry when it no longer adheres when compressed between the hands. The cold sugar ground and sieved to an impalpable powder. The average yield over the whole year is 2-5 kilos of the powdered sugar per 100 litres of whey. This powder should be left in open vessels for some days, as, if packed immediately, it develops an unpleasant smell (which,
however, it loses if spread out in the air). To obtain the sugar in masses of aggregated crystals, solutions of the gravity 21
Be. arc crystallised in
crystallisation

to 24

wooden

sometimes which can be concentrated anew. The albumin separated when whey is boiled contains, after pressing, about 60 per cent, of water and 40 per cent, of dry matter composed of 17 per cent, of protein substances, 11 per cent, of milk-sugar, 2-3 per cent, of fat, 5 per cent, of ash (one-half of which is insoluble in water), and 1 -7 per cent, of lactic acid. The final mother-liquor, or lactose molasses, is brownish black, and contains about 73
per cent, of water, 6 per cent, of ash (two-thirds soluble in water), 0-10 per cent, of fat, 0'6 per cent, of nitrogen, 1-5 per cent, of acid (calculated as lactic acid), and 22-5 per cent, of substances which reduce Fehling's solution (calculated as milk-sugar). The pre-war price varied from 34 to 48 per ton. Tests for Milk-Sugar. Adulteration with mineral substances is recognised by the ash

vessels containing numbers of small wooden rods ; the occupies as much as a fortnight, and a liquid of 13 Be. remains

exceeding 1 per cent, in amount. When dextrin is present, this does not dissolve in alcohol, while the presence of glucose or saccharose (even as little as 2 per cent.) is indicated by evolution of carbon dioxide from a 10 per cent, solution of the sugar mixed with a little

and kept at 20 to 30 for two days ; the invertase present in the yeast inverts the saccharose, which then ferments, but it does not break down the lactose, which consequently does not ferment. It is also found that when the
(0-2 grm.) fresh pressed beer-yeast

Bulgarian ferment (Bacterium bulgaricum) acts on a mixture of saccharose and lactose, the
latter alone is destroyed.

VOL.

ii.

35

538

ORGANIC CHEMISTRY
SACCHAROSE
(Sucrose, Cane-sugar),

C 12H 22O n

Saccharose

may

two hexamonoses, glucose and fructose, which are generated by hydrolysis with dilute acid. The characteristic reactions of the monoses are lacking in
saccharose, which does not reduce Fehling's solution, form osazones, or turn brown when treated with caustic soda solutions. It must therefore be assumed that the saccharose molecule contains no free carbonyl group (aldehydic or

be regarded chemically as the condensation product of

two such groups in the two monoses being annulled in the conThis is seen clearly from the following equation, in which a constitutional formula with the lac tonic groupings so common to these substances (see p. 526) is attributed to saccharose
ketonic), the

densation.

OH CH 2 CH(OH) CH CH(OH)

CH(OH) CH

+ H OH
OH CH 2 CH CH(OH) CH(OH)
o
Saccharose

C CII 2
I

OH

OH- CH 2 [CH OH] t C< Glucose

The

+ OH CH
HU
6 .0-C 6
*

[CH OH] 3 CO
Fructose
:

CH 2 OH.

\JJ

rational formula (see Maltose) of saccharose will hence be

(C6

HU

5 ).

Saccharose and the bioses generally are not changed by the direct action of alcoholic ferments or of the majority of enzymes, so that they cannot be converted immediately into alcohol and carbon dioxide, as is the case with the hexoses. In order that alcoholic fermentation of cane-sugar may take place,
it is necessary that the sugar should be first inverted by the invertase almost always present in yeasts into fermentable glucose and fructose. Hence, yeasts which contain no invertase cannot ferment saccharose. Saccharomyces odofor leaves this instance, sporus, sugar unchanged, although it ferments maltose, owing to the presence of maltase, which hydrolyses the maltose to glucose. It has already been mentioned that saccharose is readily hydrolysed by heating it with a very small quantity of a dilute mineral acid, and that this hydrolysis is known as inversion (see pp. 531, 533) because the dextro-rotatory saccharose ( [a] 66-5) is changed into a laevo-rotatory mixture of equal

proportions of glucose and fructose (invert sugar). The velocity of inversion, ,9, is proportional to the amount of cane-sugar present in the solution at any is and hence s k (p moment, x), where p is the quantity of the expressed by original sugar and x that which has already undergone inversion. The inversion constant, k, varies with the nature of the acid employed and is proportional to the degree of electrolytic dissociation of the acid, the rate of inversion increasing with the number of free hydrogen ions. It is, indeed, possible to determine the ionic concentration of an acid solution by means of the velocity of inversion, or the amount of reducing sugar formed in unit time, in a saccharose solution of definite concentration. In the cold, sulphurous and carbonic acids have

any inverting power. Saccharose melts at 160 and, on solidification, forms an bpaque, amorphous, glassy mass, which then crystallises in inclined monoclinic or rhombic prisms with blunted angles ; at a higher temperature it caramelises to a brown
scarcely

HISTORY OF BEET-SUGAR
mass with evolution
100.

539

of gas (seey*. 533). It has the sp. gr. 1 -5813. When heated for a long time at 180 to 220, it yields acetone. One part of water dissolves 2-5 parts of saccharose at and 4-5 at

parts

It is almost insoluble in absolute alcohol or ether, but dissolves slightly in methyl alcohol. It readily forms supersaturated aqueous solutions, which then rapidly deposit anhydrous crystals ; this phenomenon is utilised in its industrial preparation.

Cane-sugar forms compounds (sucmtes) with inorganic bases thus, with lime it forms (1) Monocalcium Sucrate, C 12 22 11 CaO, 2H 2 0, soluble in water, (2) Dicalcium Sucrate, C 12 22 O n 2CaO, also moderately soluble in water, and, on heating a solution of either of these compounds, (3) Tricalcium Sucrate, C 12 22 O n 3CaO, 3H 2 0, insoluble in water. sensitive reaction for the detection of small quantities of sugar is indicated on p. 533.

Pozzi-Escot (1909) has devised a still more sensitive reaction for the sugars: into a test-tube are introduced 2 c.c. of the aqueous solution, 1 c.c. of 5 per cent, ammonium molybdate solution and, after mixing, 10 to 12 c.c. of concentrated sulphuric acid, which is poured carefully down the side of the tube. The formation of a blue ring within 20 minutes indicates the presence of more than 0-0005 per cent, of sugar, and if the blue ring

appears within 30 minutes when the upper part of the liquid solution contains at least 0-00002 per cent, of sugar.

is

heated to boiling, the

INDUSTRIAL PREPARATION OF SACCHAROSE

Saccharose
is

vegetable organisms.
1

contained in varying qtiantity (5, to 20 per cent.) in different For instance, the sugar-cane (Saccharum officinarum)

The first saccharine material worked and utilised by man History of Beet-sugar. was probably honey. The sugar-cane was known to the ancient Chinese, the Indians, and also the Persians and Arabs 200 years before Christ and only later was it introduced into the medicine-men of this epoch Employed cane- juice and honey Egypt, Greece, and Sicily as medicine. Tn the seventh century sugar in the solid form was an article of commerce, and in the eighth century the Persians extracted it from the sugar-cane qnd prepared it in cakes ; after the ninth century, the cultivation of the cane was extended by the Arabs to Egypt, Syria, In the fifteenth century, the Portuguese introduced the culture into Crete, Sicily, and Spain. Madeira and Brazil, while the Spaniards carried it to the East Indies and the Canary Islands, and the Dutch to Java and Guiana. At the present time the sugar-cane is largely cultivated in Cuba, Java, Manila, Martinique, Jamaica, Louisiana,, Brazil, Peru, China, Japan, India, Egypt, and part of Australasia. In Europe it is grown to a small extent only in Spain. In 1800, when France and the allied nations established the Continental blockade against England (lasting until 181-4) and the supply of Colonial sugar furnished by England to the whole of Kurope hence failed, attempts wore made to discover a substitute for cane-sugar. As early as 1705 the French agriculturist, Olivier de Serres, had observed that the beet contained a considerable proportion of sugar, and in 1747 the Berlin pharmacist, Sigismund Marggraf, attempted the extraction of the sugar, obtaining a yield of 6 per cent., but at that time it could not compete with the much cheaper Colonial sugar. Carl Achard, a pupil of Marggraf, after 20 years of experimental work on the selection of the best qualities of beet, etc., erected of for the manufacture at in Silesia a factory Kunern, beet-sugar (1801), but it was not found possible to extract more than 3 per cent, of crystalline sugar, which did not cover the expenses, so that the factory was closed. Achard, however, continued to perfect his process, and 'when the Continental blockade produced in 1811 a tenfold increase in the price of sugar, several beetsugar factories were started in Germany, but these were still so imperfect that they were obliged to suspend operations when the blockade ceased. At this same time Napoleon I. induced the most eminent scientific and technical men in France to apply themselves to this problem, and the extraction processes were rapidly improved, machines being devised for rasping and pressing the beets. With the introduction of the use. of steam for concentrating the juices and of granulated bone-black for decoloration, beet-sugar began to compete seriously with Colonial In 1828 there were indeed 58 large and flourishing sugar, even after the raising of the blockade. factories in France, producing annually 30,000 tons of sugar. Napoleon I. had distributed in prizes to encourage this industry the sum of 40,000 and had himself erected four factories and brought 32,000 hectares of land under beet cultivation. was started again in about 1836, especially in the neighbourIn Germany t^p sugar industry hood of Magdeburg, where a fortunate choice was made in the quality of beet employed, the time at that lot of the agriculturist depressed owing to goor grain crops being thus greatly ameliorated. The further development of this industry was favoured by protective duties imposed by the. Government, in France until a few years ago and in Germany and Austria,
as food
;

352

540

ORGANIC CHEMISTRY
; ;
;

gives 15 to 20 per cent. ; the beetroot ( Beta vulgaris), 7 to 17 per cent. ; Sorghum the pineapple, 11 per cent. strawberries, 5 to saccharatum, 7 to 12 per cent. maize stems, sugar maple, etc., also contain small proportions of 6 per cent. Most sweet vegetable juices, however, contain glucose (grapesaccharose. sugar) and levulose. The plants employed industrially for the extraction of sugar are the maple, sugar-cane, and beetroot. Unsuccessful attempts have been made with maize stems, which contain as much as 14 per cent, of sugar

when the
I.

unripe heads are cut, but the sugar extracted sometimes contains 12 per cent, of invert sugar and other impurities.

ACER SACCHARINUM NIGRUM

less extent, in

Canada, and, to a

proportion of sugar.

The sap

is

(Sugar Maple), which is largely cultivated in the United States, yields a sap containing a considerable withdrawn from the living tree by means of two or three
a |

holes bored in the stem a few feet

above the ground, a metal tube

fitted into

each hole commanding a

vessel.

tinned-iron

From

these

vessels the sap is collected twice a

season, which about three weeks in the A single tree yields from 12 year. to 24 gallons of sap each season, and from 4-5 to 6 gallons of the sap give 1 Ib. of maple sugar. In some cases the sap is treated with chemical agents which precipitate but certain of the impurities,

day during the sugar

lasts for

usually the sap

is

concentrated and

crystallised directly, since the commercial value of the sugar depends

the

principally "

on the flavour due to

"
or

non-sugars

impurities

In Canada the industry present. flourishes mainly in the province of Quebec, where the output of the
sugar amounted to 13,000 tons in 1919 and to 13,400 tons in 1920. II. THE SUGAR-CANE is the
principal source of Colonial sugar.
It is a plant (Saccharum qfficinarum, Fig. 310) which has been cultivated from the most remote times

in India, Persia,
it

and Arabia, whence

passed into Egypt and Greece. At the time of the Normans it was
cultivated in Sicily,
it
;

FIG. 310.

and from there

in

it to the East Portugal and Spain, and thence into the West Indies most Indies, where its development was very rapid. At the present time it is cultivated Indies (Bengal, widely in Cuba, Porto Rico, San Domingo, Havana, Brazil, and the East Java, and the Philippines). The plantations are made with shoots from the living plant (obtained from seed), these The cane begins being placed about 1 metre apart and weeded after four to five months.

was introduced the Dutch carried

1420

into

where the prosperity of the sugar factories is continually increasing, The industry then developed in Belgium and Russia, while in Italy it was initiated only towards the end of the last century. In England the cultivation of the sugar-beet has been attempted, apparently with success, *

on a small

In 1855 the world's production of beet-sugar already amounted to 1,500,000 tons, and in 1900 Central Europe alone produced 8,500,000 tons. During the same lapse of time the output of cane-sugar increased only from 1J to 2J millions of tons.

scale only during recent years.

CANE-SUGAR
of 9 kilos.

541

to sprout in 12 months and requires a further six months to mature, when it has a yellowish colour and is 3 to 6 metres high and 4 to 6 cm. in, diameter ; it sometimes reaches a weight

The

stem'

renewal.

and roots of each plant will The negro labourers remove

yield cane for twenty consecutive years without

the head (used for cattle-food) from the cane with a blow from a scythe, and

with another sever the cane at the base the leaves (used for thatching) are then removed, and the cane worked up each day, as it rapidly fer;

ments

if

left

in

heaps.

The omni-

vorous ant is the enemy most feared At one time the by the planter. bundles of cane were crushed in a
primitive mill formed of three vertical cylindrical tree-trunks, shod with iron

and worked by water-wheels or horses, but nowadays use is made of three

horizontal
cylinders,

the

distances

between which can be regulated so as to vary the pressure (Fig. 311). In large factories use is made of
to the next by

Fia. 311.

batteries of these three-cylinder groups (Fig. 312), the cane being passed from one group means of an endless band. Prior to this the cane is treated in a crusher

two toothed rolls. is termed raw juice, and the woody residue bagasse or megass. After each pressing the cane is moistened with water and finally contains 1 to 1-5 per cent, of sugar. In Mexicaiiagasse and-fchtrleaves o Henequen plants are now used for the manufacture of spiritr. The total juice, including that from the second pressing, forms about cent, of sugar. In the East 9lTper cent, of the weight of the cane and contains 15 to 19 per Indies, owing to irrational methods of working, more than one-half of the sugar is lost,
(Fig. 313), consisting of

The

liquid thus expressed

FIG. 312.

is

whilst in Brazil, where improved processes are in use, more than 60 per cent, of pure sugar obtained. 1 I A North America the diffusion process has been introduced, and the loss of
1 The following information has been furnished by Alberto Bianchi, who visited (in 1911) The most important centresJn South_America various cane-sugar factories in South America.

542
sugar reduced to
less

ORGANIC CHEMISTRY
than 20 per cent.
its
;

diffusion has also

1

been tried in

Brazil,

but was

Treatoent^j_th^fr^]xjince expense, especially as regards fuel. with a considerably amount^ of sulphur dioxide is often employed to prevent the jready fermentafjtoh wEcn otherwise ^ciTrT. Altemjpts have also been made to decolorise with sdcUurn hydrosulphite. 'Even recently" ^ane-sugar constituted about one-half of the total sugar produced,
but
it
is

abandoned owing to

nearly

all

consumed where
less refined con-

grown

in

a more or

a very large trade is done in beet-sugar in a highly refined form, and in some cases this sugar competes with cane-sugar in districts The where the latter is produced. output of cane-sugar in Cuba alone
dition, whilst

was

700,000

tons

in

1898

and

In order to en1,050,000 in 1904. courage the cultivation of the sugarcane, the United States Government have instituted a system of bounties
5.9. 6d. per cwt.), and in 13,800,000 in this way; in addition to this there is a pro-

(as

much

as

1910 paid

FIQ. 313.

tective

duty

of

24,s,

per quintal on

consumer.

sugar, this being paid by the In the East Indies the production increased to 2,166,000 tons in 1904. (The

the

European output

of beet-sugar is

about 8,000,000 tons per annum.)

:

for the production of the sugar-cane are in Brazil, the States of Pernambuco, Bahia, Kio de Janeiro, and San Paulo, and, in a less degree, Maccio and Maranhao ; in Argentine, much canesugar is produced in the northern provinces, especially in Tucuman. The varieties of cane most widely grown in Brazil have been imported from Java and Haiti and yield from 10 to 17 per cent, of crystallisable sugar. The works are erected in the plantations, and the more primitive ones, in which the juice is still concentrated under the ordinary pressure, are called Engcnhos, whilst those furnished with modern machinery and multiple-effet vacuum plant are

termed Usinaa. In the Engenhos, the broken cane

When

crushed between wooden rollers worked by oxen or horses. concentrated in large copper pans heated by direct fire, vessels, the molasses being subsequently decanted off in barrels with perforated bottoms, When defecation is employed, the juice is boiled with lime and skimmed several times, the defecated juice then in the last of these passing into a series of two or three pans, each lower than the preceding one the desired concentration is attained. The sugar thus obtained is always moist, owing to the residual molasses, and varies in colour from yellow to brownish black the yield is less than 6 per cent. In the Usinaa, where the yield may amount to 10 to 11 per cent, (by the wet process, or 7 to 9 per cent, by the dry process, or 6 per cent, when the cane is pressed in a single pair of rolls), the canes are pressed between three pairs of double rollers by hydraulic pressure, poorer juice (wet process) being gradually sprayed on to the partially pressed cane ; the pressed cane is used as fuel. The juice, with a density of 5 to 10 B., is pumped to the sulphitation tanks but this is not done in all factories) and thence (sulphur dioxide or calcium bisulphite is used passes to copper vessels with spheiical bottoms and holding 2000 to 4000 litres. In these it is defecated with milk of lime, being heated by steam coils and skimmed once or twice. After carbonation, the juice is transferred to other vessels of about the same size as the former ones and placed at a lower level in these it is again boiled and skimmed. It is next removed to the depositing tanks and, after some hours, is pumped to the triple-effet vacuum concentrators, from which it passes at 23 to 26 Be. to copper boilers of 2000 to 4000 litres capacity (elariiier^, where it is boiled by means of steam coils for about half an hour until it ceases to form scum (which is removed). The juice is next boiled in a vacuum apparatus, in which crystallisation commences ; the subsequent treatment and refining of the sugar are carried out as in beet-sugar
is

the juice

is

not defecated,

it in

and is then left to crystallise in wooden and the crystalline mass placed to drain

factories (see lattr). In many factories, the yield of white, first-jet sugar is increased by decolorising the juice, not by sulphitation, but by the addition of blankite (sodium hydrosulphite) in the proportion of 300 to 500 grms. per ton of sugar ; this is added partly to the clarifier and partly to the

concentration vessel. It is calculated that the cost price (pre-war) of cane-sugar in the factory, without reckoning interest on capital, was 7 12s. per ton in Java, 9 4s. in Cuba, and 12 8s. in Hawaii. 1 Since 1910 attempts have been made, especially in Cuba, to utilise the bagasse for the preparation of cellulose, the sugar being extracted ^y the diffusion process.

BEETROOT
Jfore

543

Cane-sugar molasses is of value owing to its agreeable flavour and smell, and it is there* converted, by fermentation and distillation, into rum, that of Jamaica being especially renowned.
III. The BEETROOT was formerly an annual, but became changed by selection into a biennial, giving flowers and fruit (or seeds) only in the second year. Different varieties of Beta vulgar is or Beta maritima (Linnaeus) are now grown. The original wild varieties con-

tained only 5 to 6 per 'cent, of sugar, but

and repeated selection during a period of 25 years, varieties have been obtained which, under the most favourable
after careful

conditions, contain as of sugar. 1

mucn

as 18 per cent,

Nearly

all

of

the best varieties

now

FIG. 314.

FIG. 315.

cultivated are derived from the Klein- Wanzleben. The shape of the root is of considerable importance. Thus, the rounder beets are generally rich in sugar but give a small crop roots of oblong and swollen form crop well but are poor in sugar ; whilst fusiform roots which are not too smooth and have little top and tail (waste products of the sugar factory) are the ones preferred by the agriculturists and manufacturers (see Fig. 314). Value attaches, besides to the shape, also to the specific gravity, and still more to the sugar>content. Fig. 315 shows the saccharine content of the various zones composing It will be seen that the richness in the beetroot. sugar diminishes from the centre to the periphery, and especially to the top and tail, which also give the more impure juices.
;

1 Achard himself recognised varieties of the beet best adapted for the manufacture of sugar, but it was Vilmorin, in France, who in 1856 rationally selected the first variety rich in sugar ( Vilmorin' s white) by repeated reproduction of the roots with the highest saccharine content ; this he arrived at by immersing the roots in saline solutions of different concentrations so as to determine their

from which he deduced the content of sugar. Later, however, Scheibler showed that there is not always proportionality between the specific gravity and saccharine value.
specific gravities,

In Germany, more rigorous methods of selection were introduced by Rabbethge and Gieseeke (1862), who analysed selected beets cut into portions and determined, not only the richness in sugar, but also the purity of the juice Kuhn then improved the selection still further by microscopic polarimetrically. examination of the seeds. Choice of seed is of great importance and seed should be obtained only from reliable firms ; a saving of a few shillings in buying seed sometimes involves
serious losses.

Special preparation of the seed (shelling, impregnation, etc.) does not appear to have any practical value, but, on the other hand, Briem (1910) states that repeated selection and adaptation to the new intensive culture methods is able to produce in 20 years an increase in the mean saccharine content from 14 to 19 per cent., besides an increase in the weight of the beets owing to the roots Fid. 316. becoming accustomed to more energetic fertilisers. * There are now numerous varieties of beetroot known by the names of their producers or of the places where they were first selected. Among such varieties the best are the KleinWanzleben, Dippe, Kuhn, Braune, Vilmorin, etc. ; these may be distinguished, although not always readily, by the shape of the roots and leaves and by the saccharine content.

544

ORGANIC CHEMISTRY
faulty or
to

Beetroots for fodder or for domestic purposes are yellow or red, but those selected for sugar are white, and any variegation or colouring with the original tint indicates

and degeneration or reversion to the primitive type. Roots with few leaves with long stems are poor in sugar, and denote that the soil is of a character not adapted
selection
their cultivation. 1

The proportions

of the principal

components

of the beetroot vary between the following limits (percentages) water, 75

:

to 86

sugar, 9 to 18 ; cellulose and lignin, 0-8 to 2-5 nitrogenous (protein and amino-) sub; ; ;

stances, 0-8 to 3 fat, 0-2 to 0-5 mineral matter (potassium

;

and other salts), 0-2 to 2. Other and less important components

of the beet are glucose, raffinose, organic acids (oxalic, malic,
:

tartaric, citric, rnalonic, succiriic,

glutaric,
lylic),

gluconic,

tricarbal-

amido- and ammo-com(leucine, asparagine, be-

pounds
taine,

tyrosine),

gums,

pectic

matters, coniform, etc. The value of the beets was

FIG. 317.

formerly arrived at by measuring the density of the juice with the Brix densimeter, but the results varied considerably with different varieties of beet and al ao from other causes. It is usual nowadays to determine the
;

quantity of the sugar in the juice by means of the polarirnetcr (e.g.., the Holeil-VentxkeScheibler or, better, the three-field instrument of Schmidt and Haensch see later).
Beet Cultivation. Sandy or very compact (clayey) soils are not suited to the growing The most suitable are medium soils which can be worked to a considerable depth of beet. In Italy, where the rain is not so well distributed as in Central (35 em.) in the summer months. Europe, it is necessary to sow early in order to avoid the excessively dry season. Fertilisation should be abundant, since from a hectare of soil beets remove annually as much Stable manure as 120 kilos of potash (K 2 O), 52 of phosphoric anhydride, and 69 of nitrogen. serves well as the fundamental fertiliser, but the sugar manufacturers require the farmers to apply it in the summer, during tilling, and not in the spring any large use of nitrogenous manures is inadvisable. According to Stoklasa (1910), the most suitable manuring for beet is obtained by a rational application of nitragine (see Vol. L, p. 349). As supplementary fertilisers, superphosphate (about 4 quintals per hectare) and sodium nitrate (1 to 1-5 quintal per hectare) are To ascertain if a soil requires also potash (kainit, carnallite, chloride, etc.), the largely used. presence or absence of potassium salts in the drainage water is determined by analysis. In general, however, 1-5 to 2 quintals of potash fertiliser are employed per hectare. In all cases these chemical fertilisers should be administered at intervals prior to May, as otherwise the sugar manufacturer may refuse the roots owing to the excessive amount of salts in the juice ; not only is the latter rendered more impure, but the salts, especially chlorides, prevent the crystallisation A large area of part of the sugar. Irrigation is inadvisable, and in some case's, is prohibited. of soil in the province of Magdeburg became infertile owing to the repeated cultivation of beet, but it recovered its original fertility after the discovery of the deposits of potassium salts at
;

Stassfurt.

In sowing (which is carried out between the beginning of March and the middle of April, with a drilling machine giving rows 35 to 40 cm. apart), excess of seed is always used, so that after the plants have begun to grow, 15 to 16 per sq. metre may remain. The roots then attain an average weight of 500 to 600 grms. (isolated beets sometimes weigh 4 to 5 kilos) and, under favourable conditions, a hectare yields 300 to 400 quintals of beet (in Ferrarese as much as 600 quintals are obtained, while in the other Italian provinces the average is about 300). If sowing is delayed too long, the roots do not mature well but remain acid and give very impure
juice.

high

Growth begins five or six days women and children proceed

maize. in the
If

Later on, the ground is weather. the season is a wet one, the roots are late in maturing (end of September

aftej- sowing, and when the seedlings are a few centimetres to thin them out with ordinary hoes, just as is done with hoed several times to remove weeds and to keep the soil sweeter

warm

or, in

Germany

EXTRACTION OF SUGAR FROM BEET

545

A sample of the beets arriving at the factory is obtained by allowing 50 to fall into basket while the waggon is being unloaded, placing the 50 in a row and taking the alternate ones, repeating this operation on the 25, and of the 12 thus obtained choosing tme small, one medium, and one large. From each of these three, a longitudinal portion is removed by means of the Pellet rasp, which gives directly a homogeneous paste, the juice being expressed from this by a hand-press (Fig. 317). Of the well-mixed juice, 26-048 grms. see later) are introduced into a 100 c.c. measuring (the normal weight of the polarimeter flask, which is filled to the extent of about two -thirds with water and 5 c.c. of basic lead after the flask has been well shaken, one or two drops of ether are added acetate solution to remove the froth, and the solution made up to volume with water, filtered through a dry filter, and read in the polarimeter in a 20 cm. tube (see later). At the same time the Brix densimeter is used to determine the density, so that the quantity of non -saccharine substance (non-sugar) and the purity may be estimated. The the true sugarquotient of purity is obtained by multiplying by 100 the ratio between
;

content and* that (greater) indicated by the densimeter. The sugar may also be determined by direct extraction for 2 hours in a Soxhlet c.c. of basic lead apparatus (see p. 462) of 26-048 grms. of the beet pulp, mixed with 3
cooled, tube.

pulp

The alcoholic sugar solution is acetate solution, with 75 c.c. of 90 per cent, alcohol. made up to 100 c.c. with water, filtered through a dry filter, and polarised in a 20-cm. from the very sensitive test for indicating if all the sugar has been extracted in the two hours consists in adding to a couple of drops of the last drainings from the

Soxhlet apparatus 2 c.c. of water and 5 drops of a fresh 20 per cent, alcoholic a-naphthol and then pouring 10 c.c. of concentrated sulphuric acid (free from nitric acid) down the side of the test-tube in presence of sugar, a violet ring (not green, carefully of the two liquids (see also p. 539). yellow, or reddish) forms at the surface of separation EXTRACTION OF THE SUGAR FROM THE BEET. After many and varied technical
solution,
;

and economic difficulties had been overcome, the beet-sugar industry became firmly established and has during the past 40 years assumed great importance, not only on account of its magnitude, but also owing to its technical perfection, which makes it a model of what a great modern chemical industry should be. 1
end of October) and are poor in sugar, and have soft tissues which readily give up their juice. In Italy, harvesting takes place normally in August, or, in some cases, earlier than this. When the beets are ripe the leaves dry somewhat and, if the roots arc not dug immediately, On this in warm climates new leaves may be formed to the detriment of the sugar-content. account the factories are arranged so that they can deal in a short time with the whole of the The harvesting is carried out in several portions, since the manufacturer requires roots crop. not more than 3 to 4 days old, alteration occurring on storing. Beets which have flowered prematurely (in a cold spring or a very dry season) are hard and difficult to exhaust, and the manufacturer demands that such plants should be pulled up or, Putrefaction of the roots, besides at least, that the flowering shoots should be suppressed. of the beet. a Among injuring the q uality and q uantity of the crop, sometimes damages large part the various insects injurious to the beet is one which destroys the feeble plants. ' In soil which is worked insufficiently and not deep enough, or is treated too late with stable manure, the beets tend to form bifurcated roots and so give an increased amount of waste, which is not paid for by the manufacturer. The manufacturer usually deducts 5 per cent, or, in exceptional cases, more, on account of admixed stones, soil, etc. As a rule, roots containing less than 9 per cent, of sugar are not
"

few years ago the proposal was made that the dried leaves of the beet should be utilised as fodder, of which Germany alone could produce 8,000,000 worth annually. 1 In his History of the Technical Development of the Beet-sugar Industry. earliest industrial trials, Achard (1786) extracted the sugar by boiling the beets in water, and allowing to crystallise in expressing the juice, concentrating this to a syrupy consistency, the cold. In France, to facilitate the separation of the juice, the beets were disintegrated by means of rasps which converted them into a fine paste, this being squeezed in screw presses and later in far more powerful hydraulic presses. The juice was then defecated with lime and, On cooking, crude after neutralisation with sulphuric acid, concentrated in copper pans. crystalline sugar was obtained. In Germany, however, the juice was first treated with sulphuric acid and, after a short rest, The saccharine solution was concentrated neutralised with chalk, heated with lime and filtered. The direct-fire heat and decolorised with animal charcoal, albumin, or even blood.

by

was carried out in wide, shallow pans. In some places use was made of the old Colonial process of concentrating the juice until, on cooling, it gave a dense mass of crystals which was introduced into inverted conical moulds. The point of the cone was closed by a plug, which was then removed to allow the liquid to flow away, the sugar-loaf being subsequently removed.
crystallisation

546

ORGANIC CHEMISTRY

whole of the working of a rational sugar factory as far as the refining of the crude sugar and the utilisation of the molasses. (1) Storing and Washing of the Beets. When the beets are topped and freed from soil

We shall now follow shortly the

FIG. 318.

and stones they are weighed

under long sheds
(Fig. 318)

(1 cu. metre weighs 500 to 600 kilos) and then discharged with pavements sloping to a longitudinal channel or flume, A,

neutralised

Weinrich, was the lime used for defecating the juice by sulphuric acid, inversion of the sugar being avoided and improved defecation obtained. At the outset, the carbon dioxide was prepared by the oostly method of treating calcium carbonate with hydrochloric acid, but later it was obtained from the combustion of coal, and finally by heating chalk in suitable retorts or furnaces, the

Only

later, after

a proposal

made by
of

by carbon dioxide instead

residual lime being also utilisable.

Further improvements were made also in the rasps, as the living cells of the beet, being coated inside with protoplasm impermeable to the cold saccharine liquid,.do not allow the sugar to exude it is hence necessary to rupture the cells as completely as possible. A considerable advance was made in 1836 by Pelleton, who introduced cold maceration of the rasped beet with a counter-current of water. This systematic exhaustion was improved by Schiitzenbach, who arranged the vessels of beet-pulp in steps, the water entering the top vessel and being collected after it leaves the lowest one and then pumped to the top, and so on *the pulp was exhausted with fresh water and the exhausted pulp replaced by a fresh supply. It was necessary to attend to the cleanliness of the plant in order to avoid the development of micro-organisms capable of inverting the sugar. In 1837 Schutzenbach suggested the preliminary drying of the pulp and its extraction with water at 90, which renders permeable those cells not broken by the rasp. Fesca and Schrottler, on. the other hand, centrifuged the fresh pulp directly just as is now done with the crystallised sugar (see later) and subsequently sparged the pulp with cold water in the centrifuge itself so as to obtain more perfect exhaustion, but ail these processes were too expensive and did not give complete extraction of the sugar,
; ;

of which was still lost. was only after 18(35, when the diffusion process was devised, that- complete extraction of the sugar became possible (see above and lattr). Defecation was also facilitated by separating the organic impurities precipitated by the lime, not with slow and cumbrous bag-filters, but by the filter-press invented by Needham in 1828, improved by Kite and employed in defecating by Danek in 1862. By this means, working was hastened and cheapened, and further improvement was made when the filter-press was so modified as to permit of the washing and exhaustion of the calcium carbonate with hot water It

much

in the press itself. The application of animal charcoal (bone-black) filters, which had been proposed for other industries by Figuier in 1811, proved of considerable advantage in the clarification and decolor isation. The bone-black readily fixes the colouring -matters and the chalk, but does not retain the sugar. As it becomes enriched in calcium carbonate, however, it loses its decolorising property and hence required frequent renewal at great expense. Subsequently the activity of the charcoal was restored by treatment with dilute hydrochloric acid to eliminate the carbonates and then fermenting at a suitable temperature and with a suitable proportion of moisture, in order to destroy much of the organic matter ; the charcoal was then washed thoroughly with water and dried in long iron tubes heated to low redness in a furnace (see later). factory with a capacity of 4000 quintals of beet per day should have at its disposal 6000 quintals of animal black throughout the whole season. The cost of this is considerable, and during recent years these filters are being dispensed with in the sugar factory, methods of defecation being and the filters used only in the refinery, improved The sugar solutions were, at one time, evaporated by direct-fire heat, a total of 40 kilos of coal being consumed per quintal of beets. In 1828, Moulfarine and Decquer in France introduced the use of steam-coils, and in 1840 the employment of the Hovard vacuum evaporator reduced the consumption of coal to 25 kilos. Since 1852, simple or multiple-effet vacuum evaporators (Rillieux) have come into use, and these, after many improvements, have still further diminished the amount of coal required, until nowadays it is only 7 to 8 kilos.

WASHING AND SLICING OF BEETS

is

547

which covered with movable boards or gratings and has water flowing through it (Fig. 319). The beets should not be kept long in these silos, as after a few days loss of sugar occurs. The sugar-works are, however, designed to deal with a large quantity of beets every day (4000 to 8000 'quintals), so that the whole of the year's crop may be worked up in 50 to 60 days. In order to transport the beets to the place where they are first required, the covering of the water-channel is gradually removed so that the roots fall into the water, which carries them half floating to the principal elevator, J5, this separating the mud and water and delivering the beets to
*

pIQ ^^

the washer, C.
consist of a large wheel fitted with a number of perforated plates inclined screw having a perforated sieve-plate at G (Fig. 321). Nowadays, however, the beets are conveniently raised by applying the principle of the Mammoth pump (see Vol. I., p. 303), which also admits of a more complete

The

elevator

may

(Fig. 320) or of

an

washing.

The washing

is

carried out in iron or concrete vessels, 4 to 6 metres long

and

1*5 to 2

FIG. 320.

metres wide, furnished with a longitudinal bladed spindle by which the roots are beaten in the water and transferred to the other end of the washer ; on the bottom are indentations or an in dined plane on which any stones collect, to be discharged from the orifices,

D and E (Fig.

321).

In 24 hours such a washer can treat as of water being consumed. From the washer the beets
fall

many

as 500 tons of beet, about 5000 hectolitres

into basins,

whence they

are raised
elevator

large vertical to a higher part of

by a

the factory and dropped into a double automatic weighing

to 100 kilos or

machine, which discharges 50 more at a time into the cutter or slicer ; in the latter they are reduced to thin
slices

suitable

for

extraction

by the
slicing

diffusion process.

The

machine is formed of a vertical chamber, A (Fig. 322), which receives the roots, and the base of which consists
of a circular cast-iron plate, C, rotated by means of a vertical shaft
(see

pIG

321.

and furnished with 10 to 15 rectangular apertures, a a In these apertures fit cast-iron frames carrying a series of plan and section, Fig. 323). undulating cutting blades which form knives of various shapes (Fip 324). The beets at
p

548
so sliced.
to

ORGANIC CHEMISTRY
The beet-chamber
is

the bottom, of the chamber are forced by those above against the rotating knives and The form of these slicers varies somewhat in different factories, and in some casei th.3 revolving plate has a diameter of 1-2 to 1 -5 metre and a velcc :ty of 100 140 turns per minute.

about 1-6 metre high. At one time use was made of knives with
several

superposed blades at various

distances

smooth slices or prisms (if cut longitudinally) which readily adhered one to the other and hence presented a diminished
apart, but these give

surface

Good

in the subsequent diffusion operations. results are, however, obtained with those

having a zig-zag section (Fig. 325) and giving slices having the form of triangular channels ; sometimes a blade is placed at the apex of each of wide slices. angle, so as to prevent the formation The side of the triangle in the blades is 6 to 7 mm.,

and the thickness

of the slices is regulated by the a ( Fig. 324). height of the knives above the plate, Centrifugal slicing machines are also used, these having knives fixed to the inner periphery of the vertical drum, which receives the roots and projects

These machines give a blades. the knives greater output and uniform working, knives The in action. when being replaceable occur in usually wear rapidly, especially if stones the interior or in indentations of the roots, and

them against the

otherwise they should be changed frequently, as this resulting in but cut do not tear, cleanly they The slow extraction of the sugar in the diffusors. knives are sharpened with triangular files or with
suitable milling -cutters.

EXTRACTION OF SUGAR BY THE DIFFUSION PROCESS. In the note on p. 545 mention has already been made of the various stsps
from
beets

FIG. 322.

made

in the extraction of sugar

and

advantages

osmosis (see 1., p. 80). enclosed in a porous membrane immersed in water, the sugar molecules pass slowly through outside to the inside the membrane to the outside (exosmosis), while water passes from the solutions inside of the the until sugar This process continues specific gravities (endosmosis). and outside are identical (equal numbers of memsugar molecules then pass through the
or, if it is brane outwards and inwards) from the required to remove all the sugar inside, the water outside is continually renewed. The same phenomenon is shown
;

of the diffusion process, which is now used and which presents marked over earlier methods. The diffusion process is based on the general laws of If a soluticri of sugar (or salt or, in genera), any crj sfcalloid) is Vol.

by the sugar-containing vegetable cells of The envelope of the cell functhe beet. tions as an osmotic membrane, although the sugar inside the cell and the walls of
the latter also are coated with protoplasm which, at the ordinary temperature, prevents or greatly retards the osmotic flow.
place

At a temperature of 70 osmosis takes more readily through the saccharine cells of the beet, the protoplasm then coagulating and the walls becoming permeUnder those conditions the complete extraction of the able to the osmotic currents, 0-3 more than to 0-4 per cent, is left). is sugar possible (not The first industry ^plication of this method was attempted in 1864 by Robert in the
FIG. 323.
1

DIFFUSION PROCESS
celebrated factory at Seelowitz (Moravia), and

549
by 1867

the results were so favourable that

about thirty factories had adopted it. It was soon found, however, that diffusion juices were difficult to filter after defecation with lime, but after Jelinek, in 1865, made use of the in London, it became possible to filter-presses first shown at the International Exhibition

FIG. 324.

Fia. 325.

defecate even with 2 to 3 per cent, of lirne in place of 1 per cent., which was the maximum formerly employable. It was then that the idea was evolved of cutting the beets into

the osmotic phenomena, the extraction being effected by systematic and continuous exhaustion in a series of cylindrical vessels containing the slices. Water at 70 enters the first cylinder, carries away part of the sugar, and then passes to the other cylinders in succession, until it reaches in the last the same density (about 10 to 12 per cent, of sugar)
slices to facilitate
it is

as the saccharine juice of the cells of the fresh beet. When the first cylinder is exhausted recharged with fresh slices and placed at the other end of the series. What was preafter viously the second cylinder now receives the pure water and is hence exhausted, which it is filled with fresh slices and made the last of the battery, and so on, In such

manner the process becomes systematic and continuous, being carried on day and night during the whole of the campaign. The circulating water is brought to a temperature of
while passing from each cylinder to the next. Diffusor Batteries. The diffusors are vertical iron cylinders with a capacity of 40 to 70 hectols. and a height double the diameter. They are furnished with an upper aperture

70

Fro.

32(i.

for charging with the slices

and one

at the

bottom or

side for the discharge of the exhausted

are arranged in batteries of 12 to 24 diffusors connected by pipes and valves, P tons of beet per 24 hours, tubes being placed between. For a factory treating heating

pulp.

They

diffusors

having capacities of

P hectols.

each are

now

used.

The diffusors are often arranged in two parallel rows (Figs. 326, 327, 328), and if they of a single are then discharged laterally the exhausted slices can be collected by means

550

ORGANIC CHEMISTRY
;

screw or travelling band, h, which carries them to the elevators, m where they are discharged through an aperture in the base (Fig. 329), two channels with screws are used. Sometimes the diffusors are placed in a ring, as is shown in section in Fig. 330 and in
plan in Fig, 331. The diffusors are charged by means either of suspended tubs coming from the slicing machine, or of an endless belt moving above

them on

rollers

fixed plate forming

and flanked with a an edge fitted with

doors corresponding with the various diffusors. By opening a door and

placing a plate diagonally on the belt, the slices are forced off the latter into

a sloping channel and so into the

diffusor; this operation is repeated until all the diffusors are full.

When
Era. 327.

the diffusors are arranged in

slicing

a circular battery, the

(D, Fig.
330)
is

machine
it

placed so that

commands the

diffusors,

which are

, charged by means of a shoot, E. perforated false bottom and an upper perforated disc in each diffusor prevent the penetration of the beet slices into the tubes that supply water or carry off the juice.

accidents when operations are started, the tubes are provided with safetyAir-cocks on the covers allow of the escape of the air displaced by the water Thermometers are inserted in the tubes to indicate the temperaentering the diffusors. ture of the water and of the circulating juice. There are tubes for cold water, transvalves.

To avoid

ference of the juice, washing water, discharge of the water, steam for the heaters, and discharge of the juice. The heaters used to regulate the temperature of the circulating juices consist of a series of steam-pipes (see 6, Fig. 327) round which the juice passes. A less rational method of
raising the temperature consists in blowing steam into the juice juice but may cause caramelisation.
;

this

not only dilutes the

Water

is

supplied to the diffusor battery through two pipes which join just before *the

diffusor is reached

one of these comes from a cold-water cistern 8 to 10 metres above the and the other from the boiler. Mixture of the hot and cold water in the proper proportions gives the temperature required for diffusion, this being at first about 36 and later 70 to 75, to which it is brought by the heaters. Fig. 332 represents diagrammatically the arrangement of a series of diffusors I to VII, with the heaters
;

level of the diffusors

DRYING THE PULP

between them
& 7 , c l to c 7 ,

551
top,

a l to a 7 are the air-cocks. ; and d t to d 7 denote valves.

,
,

The

juice-pipe

is

shown at the

and

&j to

The amount of juice extracted normally by every diffusor is about 48 to 55 litres per hectolitre capacity of the diffusor (i.e.*, 100 to 110 per cent, of the weight of the beets, since each hectolitre holds 50 to 60
kilos of slices). The diffusion (including

amount of water necessary for complete washing water) is 1-2 to 1-5 times the weight of the beet (hence the water-tank should have a capacity at least as great as three or four of the diffusors). In many factories the press waters from the exhausted slices are now recovered (Claassen process), and, together with that from the final diffusor, allowed to settle and afterwards roughly filtered, care being taken that they do not ferment. This procedure is advantageous where introduction of these
.

waters into public waterways is forbidden. Pressing and Drying the Pulp. The pulp (exhausted slices containing less than 0-5 per cent, of sugar) discharged from the diffusors is transported by a screw or endless band to an
elevator which discharges it into the pulp-press (J5, Fig. 333), where the water it contains (95 per cent.) is removed as completely as possible. Presses of various forms are used for this

FIG. 329.

purpose.

That

of the

Klusemann type
(Figs.

consists of

vertical, revolving

cone of perforated

333, 334), fitted with oblique vanes and enclosed in a stationary The vanes, which are arranged helically along the cone, comcylinder, also perforated. press the mass of pulp against the perforated cylinder and gradually move it downwards

sheet-metal,

FIG. 330.

where the space becomes narrower, so that a considerable part of the water is squeezed all the water is out through the cone and cylinder, which are enclosed in a jacket, E
;

carried off

by the tubes F,

annular

orifice, /.

An

discharged through the arrangement similar to this has also been combined with the pulp6,
is

and H, while the pressed pulp

552

ORGANIC CHEMISTRY
an inclined screw, the pulp being thus raised and pressed at the
press has been
less

elevator, which consists of same time.

improved by Bergreen and others in order to obtain water and from 14 to 18 per cent, of solid matter. Each 100 kilos of beet yields about 80 kilos of pressed pulp containing, on an average, 85 per cent.
pulp containing

The Klusemann

much

FIG. 331.

of water, 1-5 per cent, of ash, 1-2 per cent, of protein, 0-27 per cent, of fat, 3*5 per cent, of cellulose, and 8 per cent, of non-nitrogenous extractive matter (0-5 per cent, being sugar). The pressed pulp is loaded directly on the farmers' waggons to be used as fodder, about
8s. per ton being paid for it (pre-war) ; but part of it (30 per cent, of the amount of beets they supply to the factory) is given to them free of cost. If the pulp cannot be sold immediately, it is stored in silos until sold, but if this is done, it readily undergoes putrefactive fermentation, the gasogenic bacteria of which contaminate milk and cause inflation of

cheese, so that in

some countries an addition

of

pure

lactic acid

organisms

is

made, these

IV

VI

VII

CLJ
FIG. 332.
fuel is preventing other secondary fermentations and enhancing the digestibility. Where not expensive, it is preferred to dry the pulp at once. Tt is known, too, that fresh pulp in silos loses as much as 30 p6r cent, of its solid matter, which is rendered soluble and volatile by bacteria, the sugar being converted almost completely into lactic acid. Furnace gases are sometimes used to dry the pulp. Of the various types of apparatus for drying the pulp, that of Biittner and Meyer (see came into use in Germany, France, 335), which was devised in 1887-1888 and rapidly

Fig.

German factories were employing Belgium, and Austria, gives good results. In 1898 sixty is raised by means of an elevator, p, and dropped pulp- driers on this plan. The moist pulp at / into an upper chamber, B, composed of four semi-cylindrical channels containing mixers revolving in opposite senses which stir and- lift the pulp and at the same time transbelow ; thence it passes to a third chamber. port it to the mixers of the similar chamber A current of air at 400 from a furnace enters A at / and is moved in the same direction as

STEFFEN PROCESS

553

the puljf by the aspirator, C 9 which then forces it into the dust chamber, P, and thence to the shaft. The pulp should issue at a temperature of 110 so that moisture may not con dense on it, and the supply of pulp is regulated so that the final proportion of water present is 12 to 14 per cent. The composition of the dry pulp is as follows 12 per cent, of water, 6-5 per cent, of cent, of ash, 8 per cent, of protein, 1-2 per cent, of fat, 18 per cent, of cellulose, and 55 per
:

FIG. 335.

non-nitrogenous extractive substances (5 to 7 per cent, being sugar). Tests made by Gorini (1911) show that the dry pulp is not sterile, and may hence be harmful to milk. THE STEFFEN PROCESS. Some years ago Carl Steffen patented (Ger. Pat. 149,593) a process of extracting sugar from the beet without the use of diffusion, a process resembling that used by Achard 125 years ago (see Note on p. 545). The beet slices (containing 75 to 80 per cent, of water) are pressed, givinjj a juice of 20 to 25 Brix. The remaining pulp is then heated to 85 with more dilute juice (15 to 17 Brix), which is thus enriched with

sugar extracted from the pulp. The latter is compressed in a powerful press in the hot, the residual pulp being rich in sugar and hence of greater value for cattle-food. This
VOL, n.
36

554
process yields less

ORGANIC CHEMISTRY

molasses and more first-jet sugar, while it requires less expenditure of water, coal, and labour, an4 a less expensive plant, than when diff users arc used. For each 100 kilos of beet there are 45 litres of water less to evaporate. The Steffen apparatus is shown diagrammatically in Fig. 336. The beets pass into an ordinary slicer, H, and the slices fall into G and then into a horizontal cylinder, M, containing the juice heated to 95 to 98 (600 litres of this juice and 100 kilos of cold slices give a mixture at 85). A horizontal screw, Z, transports the slices to T, where they meet a doublejacketed (the inner casing perforated) worm-conveyor, F, which raises them and presses them to some extent, so that the juice runs back into At the top of this conveyor they are discharged into a press of the type described on p. 551 (Figs. 333, 334). The expressed juice returns Y and is conveyed to the through the tube, V 9 to , while the pulp falls into

tus.

drying apparaIn order to maintain the juice at a temperature of 85, part of it is continually forced by the pump, P, through the tube, J 2 to the sieve, K^ then to the heater, C v and through if necessary, steam is injected In ; 3 to the cylinder, by means of the injector, O

order to dilute the juice in so as to keep it always at 15 to 16 Brix, dilute sugar solution from the washing of the defecation mass in the filter-presses (see later) is introduced both directly into the cylinder, M, at J? 2 and into the inclined conveyor at R v The excess of juice flows continuously through the funnel, A, to the sbve, K^, which retains finely

divided

pulp,

and

then
to the

through the tube,

i9

defecation apparatus.

This process admits of the rapid treatment of large

masses of material, which is in 2 to heated to 85 3 minutes and yields 70 to 80 per cent, of juice purer than diffusion juice and about 30 per cent, of pulp (containing 70 per cent, of water and 10 per cent, of
sugar), which, aftor drying, contains 10 per cent, of

water, 7-6 per cent, of proteins, 0-4 per cent,

of fat,

FIG. 336.

10 per cent, of cellulose, 36 per cent, of non-nitrogenous extractive matters, 52 per cent, of sugar, and 4 per
is

cent, of

ah

the expense of drying in Germany

about 6-5d. per 100

kilos of the

dry

pulp.

The diminution
in various
;

of 2 to 2-5 per cent, in the yield of

commercial sugar

is

compensated

ways the dry pulp is worth about three times as much as diffusion pulp and before the War was sold in Germany at 5 10s. per quintal, in addition to which the diffusion
process leads to various small absolute losses.
It must be admitted that, after many trials and much discussion, during recent years, the most competent technical opinion varies with regard to the advantages claimed by the Steffen process. It can, however, be stated that only the most efficient diffusion plant can compete with the Steffen process, which up to the present has been found most advantageous in districts and in seasons in which prices for the dried saccharine pulp arc more favourable than those of raw sugar. In 1910 a dozen factories in Germany alone produced 130,000 tons of sugar by tho

Steffen process.

In a new process devised by Claassen, all the water from the diffusion of the molasses and that resulting from the pressing of the exhausted pulp are used directly for the extraction of the sliced beets in the diffusors. In this manner all tho soluble substances of tho beet are returned and utilised, so that an increased yield of sugar is obtained with a
diminished consumption of water.
This process requires, however,

much

supervision

and

care.

The new

process devised by H^roS

and Rak employs more perfect machinery than the

DEFECATION
little

555

Steffen process, yet is identical with the latter in many points ; the heating to 85 is, however, carried out in three stages and the final pulp is not dried. This process has been

used, but, according to Herzfeld, could be combined advantageously with the Steffen

process.

Other processes, such as those of Bosse, Naudet, Garez, etc., arc concerned mainly with the rapid heating of the slices below the slicing machine, pressure or diffusion then being employed. Measurers. These are automatic to measure the juice Juice special apparatus used extracted at intervals from the diffusors, each such quantity of juice being registered automatically on a strip of paper together with the time elapsing between one discharge and the next. This paper serves to control the working, while it also indicates any stoppages taking place. The underlying principle of such apparatus is the same as that on which alcohol meters (see p. 173) are based. The juice is then discharged through coarse filters to remove vegetable fibres, which its concentration is 13 to 15 Balling (11 to 13 are eventually rejected per cent, of sugar) and its colour dark brown, and it is subjected to further treatment to prevent its alteration. This dilute juice is turbid owing to the presence of pectic substances and other suspended impurities, and tends to undergo acid or alcoholic fermentation, as it contains spores which have withstood the temperature of the diffusors. The pectic matters ferment,
;

yielding two mucilaginous acids (Pectic acid, C 32 H 4i O 30 and Pectosinic acid, 32 H 46 O 3l ) which render the juice highly viscous and partially invert the sugar. The juice contains also potassium quadrantoxalate and minimum proportions of invert sugar, citric and malic
,

and

acids, cholesterol, resin, coniferin (which may then, by oxidation, vanillin ; the latter

undergo hydrolysis yielding coniferyl alcohol sometimes flavours the raw sugar slightly),

catochol, glutamine, betaine, allantoin, and lecithin. Decomposition of the inorganic ammonium salts always present and of the glutamine yields ammonia, which is evolved during the concentration of the juices.
is

DEFECATION WITH LIME. When the fresh juice is treated with lime, if the latter not iu excess, insoluble calcium pectates separate and part of the sugar may form soluble monocalcium sucrate (see p. 539), but if excess of lime is present, the juice is liable to lactic and butyric fermentations, with development of unpleasant odours. If the lime is added to the hot juice no fermentation occurs and part of the organic impurities is precipitated, part also being carried down by the calcium carbonate in the subsequent saturation with carbon dioxide. The latter also decomposes the monocalcium sucrate, liberating the The potassium oxalate is precipitated as calcium oxalate, soluble potash being sugar. the citric and malic acids and various colouring materials are also precipitated. liberated A small portion of the calcium oxalate rediasolves in the saccharine juice. The treatment of the juice with lime is carried out at 85 in suitable vessels provided with stirrers. The lime is added in the quantity previously determined in the laboratory (2-5 to 3-5 per cent.), and may be as lumps or powder, in which case it heats the juice, or in the form of milk of lime, the concentration of the latter being measured by means of automatic floating densimeters, which give the quantity of lime present. Kowalski and Kosakowski have shown that if, as was long ago recommended, the juice is well agitated during defecation and heating (for 15 to 20 minutes), the total quantity of lime required may be reduced to as little as 1-5 per cent. The lime in the juice is estimated by means of soap solution (Pellet's method) in a way similar to that used to determine the hardness of
;

water (Vol. L, p. 239). The defecation is followed immediately by carbonatation or saturation with carbon dioxide in some factories the defecation and carbonatation are carried out .simultaneously and continuously. The carbonatation is effected at 70 to 75, since at a lower temperature the monocalcium sucrate forms a voluminous double salt rendering filtration difficult. The operation of saturation with carbon dioxide must be controlled rigorously and
;

continuously in the laboratory, since

1

it is

the principal source of

loss. 1

The lime and carbon dioxide used in sugar-works are generally prepared in a vertical limo-furnace (see also Vol. 1., p. 615), the upper outlet of which communicates with one or two water-cisterns, into which the gas is drawn by an aspirator to be washed and cooled before being conveyed to the saturators. Chalk of good quality (free from iron and containing little sulphate or silica) is used and is mixed with 9 to 10 per cent, of coke (anthracite should be avoided, The gases contain in order to prevent the presence of odorous and tarry impurities in the gas). about 30 per cent, of CO 2 , and the size of the suction-pump is calculated on the basis that every The treatment of quintal of lime produced corresponds with at least 300 cu. metres of gas.

362

556
saturation

ORGANIC CHEMISTRY
;

In order to avoid the risk of redissolving the calcium carbonate (as bicarbonate), the is first carried on for 20 to 40 minutes at a temperature of nearly 90 until a the juice is then filtered, certain degree of alkalinity remains (0-11 to 0-13 per cent.) heated, saturated again for about 15 minutes until the alkalinity falls to 0-02 to 0-04 and finally filtered a second time. In Austria and Bohemia, however, a little lime (0-5 to 1 per cent., leaving an alkalinity of 0-05 to 0-07 is added
juice is then filtered

before the second saturation in the hot (95). The and the third saturation carried

out at 100 (10 minutes), the alkalinity being reduced to 0-01 to 0-03. After a fresh filtration, the juice is thoroughly heated for a long time in another boiler, again filtered and despatched to the concentrators. In some factories the third saturation is now made with sulphur dioxide, which has a greater purifying action than carbon dioxide and at the same time decolorises the solution. Liquid sulphur dioxide may be employed, but it is cheaper
to produce the gas in furnaces (see Vol. L, p. 278). In some works continuous saturation is practised,

but without great advantage.

The

iron saturation

vessels

(Figs.

337, 338)

FIG. 337.

formerly used were provided at the top with a of gas. That used for the first saturation is often large tube for the escape of the excess 7 metres high, but is filled with juice only to the height of 2 metres (30 toSOhcctols.), the that for the second remainder of the space gradually becoming filled with a dense froth saturation is 3 metres high, less foam being formed in this case (a large saturation chamber If too much froth forms, it can be is shown in Fig. 339). the addition of a little coconut oil. reduced
;

by

The

first saturation juice is heated for the

by means

of a steam-coil,

and the carbon dioxide

is

introduced at

the bottom by a perforated tube, 6. A glass is inserted to permit of the operation being viewed, and a closed and cleaning of the orifice, E, serves for the inspection
interior.

The completion
I

of saturation is

shown by phenolviolet.

ceases to turn phthalein paper, which

Trained

workmen

in Fig. 340.

is shown The air-pump, A, feeds the sulphur furnace, then B, and the mixture of air and sulphurous acid

also carry out titrations. dioxide plant for saturation with sulphur

into the saturator, D, the passes through the tube, 0, excess issuing by the tubes, E. Behm, Dammeyer, and Schalmeyer propose to purify at 75 with a current of 40 to 50 amperes at I the
I

juice

16 to 8 volts for 8 to 10 minutes, using zinc electo result in the deposition |trodes. This treatment seems but, although promising | of various organic impurities, well, the process has not been adopted.
Filtration
of

the

Defecated, Saturated

Juice.

The

FlG

338>
1

the juice through filter-presses,

is separated by passing precipitated calcium carbonate which allow the clear sugar-juice to pass through and

5000 quintals of beet per 24 hours requires about 300 quintals of chalk (occupying, in lumps, about 16 cu. metres), which give 170 quintals of quicklime with a consumption of about 85 quintals of coke (9-3 cu. metres in lumps). 1 a number of iron frames, alternately empty and ruled in Filter-presses are formed of and supported on two horizontal, parallel rods. An empty frame is shown at A (Figs. 341, 342) and a Med-in one at B (Figs. 341, 343). The latter is filled in with sheet-iron grooved on both channels communicating with a single sides, the grooves ending below in two horizontal of the two sides are covered with a perforated tap, r (Fig. 343), or / (Fig. 342) ; the grooves frames are stretched cotton or linen cloths, which form two filtering On the
.

plate.

empty

FILTRATION

557

retain the suspended impurities and the calcium carbonate in the form of cakes, which, after being washed, are readily extracted by unscrewing the press and removing the

FIG. 339.

frames

they

fall
first

fertilisers.

The

into conveyors or trucks underneath, and are often used as lime wash- water is added to the filtered juice, while the last is used to slake
'

the lime for defecation.

FIG. 340.

The filtering surface of the filter-presses necessary after the first saturation is calculated at 0-5 sq. metre per ton of beet worked in 24 hours ; after the second saturation 0'25 The pressed cakes of chalk form 12 to 14 per cent, of the weight of the sq. metre suffices.
The frames are squeezed together and against the surfaces of the same area as the frame. so that hermetic joints are formed at the edges of all strengthened block, P, by the screw, V, the frames. Each frame is provided with bored projections, a and 6, at the top and bottom. When the frames are joined up, the holes in the projections form two continuous channels. The turbid juice enters at a and thence passes through of into all the empty frames, the air When d is closed, the juice passes under d. being forced out from these through the valve, cloths on the two sides and the clear liquid flows down the grooves and pressure through the

558
beets
(i.e.,

ORGANIC CHEMISTRY

four times the weight of quicklime used). The washing of these cakes require water per kilo. After the second and third defecations, use is often made, not of filter-presses but of mechanical filters (Fig. 345) which also serve for removing suspended matter and residues of the slices from the diffusor- juice. During the whole of its course from the diffusors and saturators, the juice is under pressure and should rise in temperature from 70 to 100, but since heat is lost in all the pipes, in order that monocalcium sucrate may not be deposited or the liquor become turbid, the use of heaters is necessary for the first and second saturation juices, etc. These heaters consist of a species of tubular boiler divided into three parts by two each of the two end parts is divided into 10 chambers, communicating plates, p (Fig. 346)
1 litre of
;

'

FIG. 841,

Fra. 343,

FIG. 344.

in pairs at the two ends alternately. Opposite chambers are connected by groups of long tubes, 4 to 5 cm. in diameter, through which the juice circulates ; steam enters at C, follows a sinuous path round the partitions, V 9 and finally issues at D. The juice enters chamber 1 of compartment I at A, and passes through the tubes to chamber 1 of compartment II, then to chamber 2 of compartment II, through the tubes to chamber 2 of com-

partment

I,

and so on,

until it reaches

chamber 10

of

compartment

and hence leaves the

heater at B.
discharged at r into the tank, S. When the frames, A, are filled with calcium carbonate, the latter is washed with water to remove the sugar it retains. Since only the alternate grooved introduced under pressure at b will pass through plates communicate with the tube, 6, water the cakes of calcium carbonate in the direction of their thickness and into the grooved plates In this way, each cake is broughl (not communicating with b) to be discharged at the taps r. into thorough contact with the washing water, which can be measured in S. In other filter-presses there are no empty plates (Fig. 344), but each of these has a centra is screwed with a rin^ aperture over which the filter-cloth, with a hole exactly in the middle, from both sides. The juice is introduced into the chambers between adjacent plates, and th< wash -water passes under pressure into alternate (odd) plates from the tube, m, traversing thi but with k cakes, and collects in the other alternate (even) plates which communicate not with the air is initially discharged from the odd framei the wash-water being thus discharged o through i. Each press contains 20 to 50 plates, each 3 to 5 cm. thick, and with a length The juice to be filtered is pumped in under a pressure of 3 to 4 atmos. side 60 to 100 cm.
is

CONCENTRATION
After the third saturation the juice passes into a final heater or boiler, where thoroughly boiled but not under pressure. The is moved means of
juice

559
it is

separate one being used after each operation (for raw juice, saturation juice, etc.) ; double-action
piston

by

pumps, a

first

saturation juice, second

pumps

or Girard

an

efficiency of

pumps, with 80 to 85 per cent., are

is

employed.

When

the tax

based on the

volume and density

of the defecated

goes to the evaporators it passes into tanks under the supervision of the Inland Revenue authorities, who measure the density at 85 to 90 and then reduce it to the

juice, before the latter

normal temperature by means of tables.

CONCENTRATION
JUICE.

OF

THE

Tho

defecated,

saturated,

and

filtered juice is pale yellow and perfectly clear ; it contains 88 to 90 per cent, of water, 10 to 11 per cent,
1

of sugar, and 0-8 to The formation of

per cent, of

salts.

crystallised

sugar

requires first considerable evaporation or concentration and then boiling.

The concentration
juices
is

of

the dilute

one of the most important problems in sugar factories, the preFIG. 345. paration of 74 tons of massecuite containing 7 per cent, of water from 500 tons of beet with a sugar-content of 12 per cent, involving the evaporation of 426 tons of water. Enormous economies are effected by evaporating or concentrating at reduced
pressure, which also prevents excessive colouring of the juice, since the boiling-points of liquids are lowered as the pressure is reduced. 1
1

The

boiling-point of water for different degrees of vacuum,

;
;

is

as follows (Regnault-Claassen)
; ; ;

200 mm., 91-7 150 mm., 94 100 mm., 96-1 with a vacuum of 50 mm., 98-1 700 mm., 650 mm., 53-6 600 mm., 61-6 300 mm., 86-5 400 mm., 80-4 500 mm., 72-5 It must, however, be remembered 41-7 ; 720 mm., 34-2 ; 740 mm., 22-4 ; 750 mm., 11-8. that saccharine solutions boil at higher temperatures than water. Thus, under the ordinary 103-1 pressure, a solution containing 30 per cent, of sugar boils at 100-6 ; 60 per cent., 80 per cent., 110-3 ; 85 per cent., 115. The boiling-point of a liquid for a given degree of vacuum is obtained approximately by DAhring's law, according, to which the difference between the boiling-points of a liquid at two different pressures bears a constant relation to the corresponding difference for a second liquid. The values of this constant, </, when the second liquid is water are given, for a number of liquids, in the following table, which gives also the boiling-points under various pressures
;

560

ORGANIC CHEMISTRY

The commonest type of vacuum apparatus with a single vessel or effet is the spheroidal form shown in Hg 347, which is steam-heated and is simple and inexpensive, and is often used in small works dealing with alimentary and other products. In multiple-effet apparatus the evaporation bodies are simply large wrought or cast

FIG. 346.

iron (formerly copper) boilers surrounded by an insulating earth. These bodies are of various shapes and are placed sometimes vertically and sometimes horizontally. They arc usually divided (Fig. 348) into three compartments by means of two partitions, held rigid by a number of brass tubes, 2 to 2-5 cm, in diameter, connecting the first and third compartments. In boilers with horizontal tubes (Figs. 349, 350) the steam circulates in the
,

tubes in a similar manner to the

in the heater described

(I juice

above

aJ(Eig. 346), while

(Jail
ft*

the tubes.

the juice surrounds In vertical bodies

(Fig. 348) the steam, entering at

and issuing at B, circulates in the & chamber between the two partitions and heats the numerous connecting

Fro. 347.

348.

EVAPORATION APPARATUS
tubes.

561

The saccharine

and

circulates rapidly arrows in the figure.

solution is thus brought into a condition of vigorous ebullition between the lower and upper chambers, as indicated by the The level of the liquid, which can always be controlled by the

FIG. 349,

external glass tube, a, is kept just above the tubes ; in this way, less froth is formed, the free vapour space is increased, and danger of caramelisation is avoided. The boiling may be observed through the window, r. In order to separate the drops of liquid carried away in the steam, about two-thirds of the way up the boiler is placed a plate, P, with a large

FIG. 350.

central aperture, 0, above which

able

by the levers, e, w, and contains no sugar.

h.

arranged a kind of metal umbrella, p, at a height adjustThis height is chosen so that the liquid condensing above
is

of the Wellner-Jelinek Fign. 349 and 350 show a high-power horizontal evaporator therein. The heating tubes occupy only type, and Fig. 351 the arrangement of the pipes the lower part and are covered by a thin layer of the sugar solution, the steam passing through a long length of tubing. In a u/riple-effet plant (as in Fig. 352) the first effet or body on the left is charged with solution previously heated in A and is heated in by steam at 112 entering the bundle at <?. The steam from the liquid in the first efiet, which boils at 94-6 (vacuum of tubes and is condensed round the tubes of the second 112 mm.), passes through the wide pipe

ORGANIC CHEMISTRY
through

where the boiling-point is 77*4 (vacuum 442 mm.)- The steam from effet 2 passes to be condensed round the heating tubes of effet 3, which communicates directly by K with the barometric columns LNQ and by SR with the vacuum pump of effet 3 which gives a vacuum of 608 mm. in F, the liquid thus boiling at 60. The pipe, X, conveys the steam from effet 3 to the chamber, L, furnished with an iron barometer tube, M, at least 12 metres long, which
effet,

dips into a well or water-tank, T. The condensation water

collects in the tube,

M,

to a

height corresponding with the

vacuum formed in L, and hence

in the effet 3, but the majority of the steam condenses in the
||
1

into the top of chamber, which the tube, 0, introduces a fine cold-water spray which produces an abundant and rapid condensation of steam and a considerable lowering of pressure, so that a large quantity of hot water passes into the vessel, U, from the barometer tube, P. A little steam condenses in the chamber, Q, communicating by the tube, S, with the suction pump which maintains the vacuum, The vacuum pump may also be connected, by means of three narrow tubes, with the three evaporation bodies, in. which the vacuum may be regulated as desired. It is
9

evident that in the three

evaporation bodies, especially in P, the water must not be kept at too high a
temperature, so that it may not evaporate in its turn and may help the condensation of the steam. In small plants use is

made

of simple horizontal evaporators with bundles of heating tubes on to

falls

which the liquid

culation,

in a

thin film in continual cir-

while in Kest-

ner's evaporator the liquid circulates in a thin layer

in

system

of

vertical

tubes

(see Vol. I., p. 563).

In various industries
special

methods

>f

con-

centration of solutions are

applied,

and

of thise the

following tioned.

may

be men-

The
FIG. 352.

solvent

may

be

"frozen
solid

and removed
condition.

in the

Monti

(Ger. Pat. 194,235, 1907) suggested the industrial application of this process, which finds a use particularly in the wine industry but is not convenient in the manufacture of sugar,

The Hoiiigmann-Kayser system of evaporation is described in Vol. I. (p. 568). The auto-condenser evaporator of Prache and Bouillon is based on the principle
if

that,

steam emitted from a boiler at a certain temperature is compressed, its temperature is raised so that it may be used to heat the liquid in the boiler and thus cause co itinuous evaporation. This evaporator has been developed and has now reached a stat; of high
efficiency.

EVAPORATORS
A somewhat
heated by
is

563

similar method has been applied, in which use is made of a turbo-compressor of the Zoelly type giving an energy efficiency of 60 per cent, or more (Fig. 353). In this apparatus the liquid to be concentrated passes into the vertical boiler and is first

steam circulating round the system of tubes. When the liquid boils the steam the top to the turbo-compressor, which compresses it and forces it round tho heating tubes, as shown by the arrow. This compressed steam is condensed and thus evaporates the liquid to be concentrated. Thus the turbo-compressor functions as a thermal
live

drawn

off at

pump, transforming mechanical energy

started, very little live steam electrical energy is available.
is

into thermal energy.

After evaporation has

when very cheap not applicable under reduced pressures and cannot be used with liquids giving vapours which attack the metallic parts of the turbo -compressor. In factories where there is not an abundance of water (that required by vacuum plant is ten to twelves times the quantity of juice to be concentrated), it is convenient to utilise the hot condensed water from the steam-engines (an engine of 350 to 400 h.p. requires about 1 cu. metre of water per minute for condensation) and that from the vacuum concentration batteries. This water is cooled in suitable atmospheric coolers, T (Fig. 354), so that it can be used in the barometric tubes and also for the washing and hydraulic transport of
required.

This system

is

practicable only

It is

TO i

COW-

FIG. 353.

The tank, K, corresponds with that marked U in Fig. 352. A pump, A forces water to the top of the pile, T (see also Vol. L, p. 568), whence it flows down over tho faggots built up under a kind of hood, which produces a strong upward draught of air and so evaporates and cools the water (e.g., from 50 to 60 down to 25 to 30). The latter collects underneath in the tank, r, and is then transferred by the pump, M, to the chamber, F, where the dissolved air is separated and passes out through the pipe, g (higher than Q). The water rises in the tube, 6r, to the top of the barometric condenser, C, which is evacuated by the pump, B, and the tube, n ; the pipe, V or 8, corresponds with the tube, K, of the preceding figure and communicates with the third evaporation vessel. Other more efficient arrangements are also used for the cooling of the hot water. Fig. 355 shows a system consisting of numbers of vertical rods arranged in layers crossing one another in a manner similar to those of the apparatus depicted in Figs. 249, 250 (p. 343).
the beets.
this
9

The hot water, entering by the pipe, A, is distributed homogeneously by means of the the air drawn upwards tooth-edged channel, (7, and collects in the vessel, B, underneath between the rods carries with it a cloud of steam. Another arrangement is shown in Fig. 356 here a wooden cap or cover fits over walls composed of sticks arranged in the form of Venetian blinds, while at the bottom a Kdrting injector produces a powerful jet of pulverised water in the shape of an inverted cone. The upward air-current evaporates the water while the latter ascends or while it flows down in a thin film on the boards (in
;

this

manner only 4 per

cent, of the water

is lost).

Equally ingenious and simple

is

the

564

ORGANIC CHEMISTRY
;

with cooling effected by forcing the hot water under pressure into a circular pipe fitted a number of Kdrting pulverisers, catching the water in a large tank and, if necessary, but by this procedure more than 10 passing it again through the pulverisers (Fig. 357) of the is water lost. cent, per In those seasons of the year and on those days when the air is warm and dry, the temis cold perature of the water can generally be reduced to that of the air, but if the air and not very dry, the temperature of the water remains 6 to 7 above that of the atmosphere.

BOILING OF THE CONCENTRATED JUICE. The juice from the evaporators has a density of 28 to 30 Be 50 to 55 Brix) and an intense brown colour, and in order to induce crystallisation of the sugar it is necessary to concentrate it until not more than 15 per cent, of water remains (85 Brix). This concentration or boiling is carried out in simple vacuum boilers or vacuum pans, the juice being first filtered through mechanical filters, collected in tanks and drawn into the pans which are already evacuated.
(

FIQ. 354.

These pans resemble ordinary evaporators and are made of sheet-iron

they

may

be

either horizontal (like that shown in Figs. 349 and 350) or vertical. In the lower part of the pan is a dense coil of copper or brass pipes arranged either in a zigzag manner or in these passes the steam (Fig. 358) ; in some cases, however, concentric circles, and

through

the bottom of the pan is steam- jacketed (Fig. 359). The concentration or boiling is carried out at as low a temperature as possible and the pan is fitted with a froth-separator (see the removal of test-samples of the mass towards the end of the Figs. 348, 349), a tap for
* and a wide discharge pipe, K. The first thing to be done is to evacuate the pan by connecting it with the condenser and with the vacuum pump. Next the cock of the tube dipping into the concentrated juice tank is opened, the required quantity of juice being allowed to enter. Steam is then passed

operation,

of the juice is not allowed to fall through the heating tubes. During the boiling, the level otherwise since the of beneath the top sugar would dry on these tubes and heating tubes, so that fresh concentrated juice is introduced from time to time. At a be decomposed in certain stage of the concentration small crystals begin to form and gradually increase The operator extracts samples and spreads them out on glass in order to ascertain size. the size of the crystals and the density of the mass, and when he considers that sufficient of dark molasses of this massecuite consisting mainly of crystals with a certain amount
;

has been deposited on the tubes, the heating

is

stopped and the ordinary pressure estab-

BOILING

OF,

THE JUICE
Fig.

565

ished in the pan. The whole mass is then discharged from the outlet, K, into a large vessel furnished with stirrers, where it is gradually cooled and the crystallisation completed.

The boiling and discharging of the massecuite occupy altogether about 10 hours. shows a battery of Bock cylindrical crystallisers fitted with stirrers.

360

Larger crystals are obtained by adding to the crystallising vessels a little unboiled juice, which lowers the sugar-content somewhat and retards the crystallisation. When no further

FIG. 355.

FIG. 356.

crystallisation takes place, the mass is discharged, by means of a parachute at the bottom of the crystalliscr, into the centrifuges, which readily separate the liquid molasses from

the solid sugar. This process of boiling

thread,

termed boiling to grain to distinguish it from the boiling to In the latter case the boiling is not continued until crystals form, the proper density of the boiled juice being ascertained by squeezing a drop if a filament is between the finger and thumb and then sharply withdrawing the finger
is

now used

only in refining.

FIG. 357.

thus formed, the boiling

is

not finished, but the breaking of the thread with formation of

two projections

have drums of perforated stett with an inner coating of fine-meshed gauze. The of diameter of the drum is about 80 to 100 cm., the height 40 to 45 cm., and the speed and the centriis underneath, force motive The minute. 1000 applied 800 to rotation per either above (Fig. 361) or through a door fuged sugar remaining in the drum is discharged which can be opened in the base of the drum (Fig. 362). The massecuite is passed directly
cuite

indicates the end of the boiling. The syrup is then poured into moulds, which are kept lukewarm until the whole mass sets to an almost solid block composed of finer crystals than in the preceding case. CENTRIFUGATION OF THE FIRST MASSECUITE. The centrifuges for the masse-

566

ORGANIC CHEMISTRY

from the erystallisers to the centrifuges, and, in order to effect more complete separation of the molasses adhering to the surface of the crystals, especially in the layer adjacent to the gaufce, so-called covering or clearing is resorted to ; while the centrifuge is still in motion,

FIG. 358.

FIQ. 359.

is sprayed with finely divided cold or tepid water (Kig. 363), or even with a jot steam applied inside or, better, to the outside of the basket, the molasses being thereby rendered more liquid. This procedure naturally gives a whiter raw sugar (first product) but in diminished yield, a small part of the sugar being carried away with the molasses by

the sugar
of

Fro. 360.

This loss is diminished by using, in place of water or steam, sugar juices (syrups) gradually increasing in purity, so that the molasses and less pure syrups are removed and the sugar left covered with a solution of pure sugar. In this way minute, moderately white on the market without crystals of sugar are obtained, and these are sometimes placed and of adulterated but the them prefers quite white crystals being public suspects refining,

the water.

or cubes.

CENTRIFUGATION OF THE MASSECUITE

The molasses from the
eentrifugation of the
first-product sugar (first runnings), is further

567

first massecuite, after separation of the concentrated and boiled in syrup pans, which

tors

are similar to vertical evaporaand are worked under a

vacuum, but are usually of single enet. The boiling is continued until the syrup gives a long thread (see above), the impurities

present

preventing

boiling to grain.

This second massecuite is then placed in large tanks in the molasses room, where it is kept for 25 to 30 days at a temperature of 35 to 40. The
blocks of crystals which separate arc broken up with suitable bladed machines, and are

then delivered to the centrifuges by

means

of

screws or
resulting
is

piston pumps.
yellow.

The

second-product sugar

rather
FTO. 361.

The molasses which

is

then separates

further con-

since the various potassium

centrated and the third massecuite sent to the molasses room, but no more sugar separates, and other salts present prevent about five times their own weight of sugar from crystallising. This molasses is hence sold as it is for the preparation of cattle-foods or for the manufacture
of
spirit
(see

p.

166).

In some

countries, however, it is treated by special processes for the extraction of the sugar 1 still present. Every 100 kilos of beet

treated yield

to 3 kilos of molasses.

The

first-

and second-product sugars

from the centrifuges are sent to the stores, where they are sieved to break up the crusts, which retain molasses. The two
products are often mixed, put up in bags holding 100 kilos, and despatched to the
refinery.

SUGAR REFINING.
IG.

362.
(first

The raw sugar and second products, with a purity

Tn some works the second product is obtained rapidly by the Bock or the Oosse In the first of these, the molasses is not process. left for 25 to 30 days in the molasses room but is crystallised in 4 to 5 days by continually to shaking in large, jacketed drums heated to 90 95 and adding a considerable quantity (25 to 30 per cent.) of crystallised sugar. It is then allowed to cool slowly, but at certain times it is heated one or two degrees above the temperatures it shows at those times, so that the smaller crystals
1

much more

formed, and these only, are redissolved. When the mass has been cooled to 35, the crystalline blocks are crushed and centrifuged, the amount the molasses required (25 to 30 per cent. ) to induce f"*^ removed, m. I (see, above) to'crystallise being previously FIG. 363. In the Grosse process, the mass is kept in . motion by a vertical Archimedean screw rotating , With this procedure, crystallisation takes place in 48 hours and, after in the vacuum pan. and centrifuged. is mass disintegrated cooling to 40, the crystalline .,,,<.. j the molasses with fresh juice and Loblich, Zschene, Stenzel, and others have tried mixing
.

568

ORGANIC CHEMISTRY
on the market, but is purified in refineries, and less coloured qualities of high rendement l

of 88 to 96 per cent.) is not usually placed where it is dissolved in hot water, the purer

being kept separate from the more impure grades of low rendement. The solution, with a density of 37 to 39 B6., is treated with a little lime, with 3 to 4 per cent, of animal charcoal and often with 2 per cent, of ox- blood, after which it is boiled, the frothy crust forming at the surface being continually broken. The suspended*matter The residue (refinery is 'then removed by rapid mechanical niters or by filter-presses. black) is utilised as a manure, while the hot and still coloured solution is passed through a battery of four or six tower filters, 8 to 9 metres in height and 60 to 80 cm. in diameter, filled with animal charcoal (Fig. 364 A, tube for dense juice, J3, for dilute juice, G for for steam) and previously heated water, with steam (D) to prevent the sugar separating and to obtain the maximum decolorising action of the charcoal, this being exerted in the hot. The animal charcoal or bone-black has a considerable affinity for colouringmatter and for lime, but only a slight one for sugar, but in course of time the pores of the charcoal become obstructed
:

and
so

its

that

decolorising power diminished, after a few weeks it becomes

2 necessary to revivify the charcoal. The solution is passed through the filters in succession and, if necessary, this procedure is repeated. When the syrupy

liquid is decolorised, it is concentrated and boiled in ordinary single-effet vacuum pans (of copper) until it shows the grain

or short-thread test (see above). When the massecuite reaches

this

degree of concentration, it is poured into a jacketed copper vessel, in which it is kept at 85 to 90 to initiate the formaIt is then allowed tion of large crystals.
to flow into conical copper moulds with their apices, closed by plugs, underneath.

-E,

**

The mass, which has just begun to crystalUse, is well stirred, and when it has

defecating the mixture in the ordinary way, but this process does not seem to offer any great advantage. 1 The rendement expresses the percentage of refined sugar obtainable from the raw sugar and is determined indirectly on the assumption that every 1 part of ash diminishes the refined and 0-4 per cent, of ash sugar by 5 parts thus a raw sugar containing 96 per cent, of pure sugar 94 per cent. The rendement is regarded as low would give a rendement of 96 (04 X 5) if it is less than 94 per cent. 2 The charcoal is first treated with hydrochloric Revivification of Animal Charcoal. acid to remove the calcium carbonate, and if more than 1*5 per cent, of calcium sulphate then remains, this is eliminated by means of hot soda solution. After washing, the wet charcoal is allowed to ferment (first alcoholic fermentation sets in, then acid fermentation and finally with water, treated with steam, dried and putrefaction), and is afterwards washed thoroughly about 400 by the gases gently ignited in long cast-iron tubes, C (Fig. 365), which are heated to from the furnace, A, access of air to the retorts being excluded. The cooled, free portions are then gradually discharged from the lower parts of the retorts (E) into covered metal waggons, so that the charcoal, which is not yet quite cold, may not take fire in the air. The discharge of the putrid washing water from the fermented charcoal into rivers causes serious inconvenience, and nowadays this water is either passed on to the soil or subjected to biological purification (see Vol. L, p. 250). The plant for decolorising with animal charcoal and the revivifying furnaces are'very costly, a large amount of the charcoal being required. Soxhlet avoids the carbon decolorising plant by using filter-presses the chambers of which are filled with a cake composed of wood-meal mixed with various indifferent materials (ground coke or pumice, etc.). By this means sugar solutions can be decolorised moderately well even in the cold.
;

SUGAR REFINING

569

assumed a certain consistency it is left at rest at a temperature of 35, so that all the molasses collects at the bottom and can be discharged by removing the plug. In order the molasses completely, the sugar-loaves with their casings are introduced to^ remove into the moulds of a Fesca centrifuge (Fig. 366), which holds sixteen of them, arranged alter-

FIG. 305.

The point of the sugar-cone communicates with the aperture, 5', of the drum of the centrifuge, and when the latter is charged it is fitted in the middle with a cylinder, h h k, which rotates with the drum and is provided with channels, S, communicating with all the cones, so that the covering solutions (see above) may
nately in

two superposed

series of eight.
f

be run in from the tank, r. These solutions consist of three or four pale syrups and three or four concentrated solutions of pure sugar. In order to remove the last traces of yellow colour from the sugar and to blue it slightly,
as
is sometimes required, the final covering syrup is mixed with a minimum amount of ultramarine (5 grins, per 10 tons of sugar) or

methyl or ethyl violet or, better still, according to a recent suggestion, indanthrene. The

FIG. 366.

FIG. 367.

white loaves thus obtained are then dried in suitable chambers or in revolving apparatus,
at a temperature of

55.

obtain white sugar directly, the final massecuite is sometimes decolorised with 30 to 50 grms. of blankite per hectolitre (see Note, p. 542 ; blankite is pure, crystallised sodium works see Vol. I,, p. 586). hydrosulphite, the use of which is rapidly extending in sugarThe beet-sugar of commerce should always have a very faint alkaline reaction (towards

To

phenolphthalein), since otherwise usually a slight acid reaction.

VOL.
ir.

it

undergoes partial inversion.

Cane-sugar, however, has

37

570

ORGANIC CHEMISTRY
of loss.

Cube sugar was formerly obtained by sawing the large blocks, this entailing considerable loss, but at the present time suitable centrifuges (Adant type, Figs. 367 and 368) yield directly long rods of sugar of the requisite thickness, these being then sawn with a

minimum

platform, F, carries eight vertical prisms,

o,

furnished with screws by

which they are fixed to an upper annular disc. The latter is slotted (c) to allow of massecuite being introduced into the chambers (a a) remaining between each prism and the next, and divided into a number of tall narrow chambers by fixed plates in the grooves, b. The platform is introduced into the cylinder, H, which fits tightly the periphery of the moulds, these being closed inside by a second cylinder. All the chambers are filled with massecuite introduced through the slots, c, the whole being allowed to cool for 12 to 14 hours wi4h occasional shaking. After complete crystallisation, the whole platform is withdrawn by the crane, 0, and placed in the centrifuge, D, which makes about 700 revolutions'per minute. The covering is effected at a reduced velocity with sugar solutions entering by the tube, (7, from a reservoir at a height of 5 metres. After the sticks of sugar have been

FIG. 368.

are then ready to receive a removed, the platform and moulds are washed with water and fresh quantity of massecuite. Pile or crushed sugar is obtained in a more simple manner by covering the crystalline itself by means of water, steam, or pure sugar sugar (from massecuite) in the centrifuge which is solution. Slight prolongation of the centrifugation yields a hard, compact mass, a small into special broken by and sugar) (pi!6 blocks irregular pieces removed in
large

crusher having an indented drum (Fig. 369). Powdered sugar or farin is obtained by grinding lump sugar and any scraps between two smooth, horizontal rollers (d and d', Fig. 370) which are brought near to one another detach the powdered sugar ; the latter is by springs and are furnished with scrapers, /, to obtained by means of the Excelsior mill also be can subsequently sieved. Powdered sugar as much as 2000 kilos per hour of a sugar not too finely which
(see Fig, 164, p. 201),

yields

powdered.

The processes employed for the extraction of beetthe weight of beets) of molasses, 2-3 per cent, being obtained (of in the factories and 0-8 per cent, in the refineries. These are dense, dark-coloured syrups, does not crystallise owing to the presence in containing 40 to 50 per cent, of sugar. This five times their the molasses of 8 to 10 per cent, of mineral salts, which prevent about in general, it is difficult or almost impossible to from Hence, of crystallising. sugar weight

UTILISATION OF MOLASSES.

sugar yield about 3 per cent,

UTILISATION OF MOLASSES

571

extract sugar by direct crystallisation from syrups with a degree of purity less tha* 60 to 65 per cent. The percentage composition of molasses varies between the following limits
:

water, 19 to 28 (mean, 23) ; sugar, 45 to 54 (mean, 48) ; solids not sugar, 26 to 29 (mean, 04 (mean, 0*15) ; 28) ; ash, 6 to 8 (mean, 7 ; largely potassium salts) ; invert sugar, 0-1 to The degree of purity ranges from 62 to 67 per cent, nitrogen, 1 -25 to 1 -85 (mean, 1 -65). (mean, 64 per cent.). The molasses contains about 10 per cent, of the total sugar of the
beet.

The recovery

of the sugar

from molasses involves indirect processes which are not always convenient in practice, and when this is the case the molasses is employed for the manufacture of cattle-food or spirit (see p. 166). In spirit factories the molasses is diluted to 12
to 14

Be. (about 15 per cent, of sugar),

when

it

can be fermented (see p. molasses yield 23 to 25

.

Ten tons of 166). hectols. of alcohol

(calculated as anhydrous spirit) and 1800 kilos of C0 2 The potassium salts are extracted

from the residual vinasse by the process described in Vol.

I.,

p. 545.

100 kilos of molasses

give 35 kilos of concentrated vinasse (40 Be.), and by calcining this 10 kilos of vinasse charcoal

FIG.T369.

now

In some factories the vinasse is treated for tto recovery of the ammonia and fatty acids by the Effront process described
are obtained.
1

on~p. 183, without, however, losing the potassium salts. In Italy, before the modification of the fiscal regulations which taxed the defecated saccharine juices directly and left untaxed the sugar in th^ molasses, various factories applied certain of the chemical and physical methods used in other countries for the extraction of the sugar from molasses by means of osmosis, lime, strontia, baryta (formerly by means of alcohol), etc. When these methods (see later) are used, it is calculated that the final

molasses does not exceed 0-5 to 1 p*er cent, of the weight of the original beets. This was (1) Osmosis Process.
first

proposed by Dubrunfaut in and is based on the osmotic properties of crystalloids, which

1863,

pass through a

membrane immersed

in water (see Vol. I., p. 80). Different crystalloids traverse the

1

The

molasses

vinasse

(spent

wash) remaining after the distillation of the alcohol has a density of about 4 Be. and contains 6 to 7 per cent, of

When utilised, it is first concentrated to 40 Be. (100 kilos of molasses give 35 kilos of this concentrated vinasso), when it contains 75 per cent, of solids with about 4 per
solids.

isoleucme, besides varying quantities of amino-acids and nuclein bases ; the non-nitrogenous constituents consist of about 15 per cent, of fatty acids (formic, acetic, lactic, butyric, and homologous acids), and 15 to 20 per cent, Effront thinks it possible, from of other organic compounds not completely investigated. 10 tons of molasses, to obtain 75 kilos of ammonium sulphate and 95 to 120 kilos of fatty acids, into ammonia and fatty acids, separable by the action of yeasts which decompose the amino-acids transform amino-acids into alcohol by distillation. According to F. Ehrlich, however, yeasts and succinic acid, the formation of ammonia and fatty acids being due not to yeasts but to butyric and other bacteria which always occur with yeasts, and decompose the amino-acids into ammonia, Hence the effect of the Effront fatty acids, and various amines just as in ordinary putrefaction. to the aqueous vinasse a little putrefied' meat and process could also be obtained by adding masses of putrefied liquid would of large allowing putrefaction to proceed. The manipulation not, however, be very agreeable or jhygienic.

About one-half of cent, of nitrogen. the solid substances are nitrogenous compounds. The solids contain 10 to 12 per cent, of betaine, 5 to 7 per cent. , of clutamic acid, and 1 to 2 per cent, of leucine
.

uio. avu.

,.,.,., and

372

572

ORGANIC CHEMISTRY
at
first.

memljrane at varying speeds, the sugar, for instance, far more slowly than salts. Hence, if the molasses is placed in a dialyser and surrounded with water, after a time the water will contain more salts than sugar, while the molasses will be diluted with water but will contain
relatively

a series of wooden frames 4 cm. in thickness and of the size of those used in these are separated by filter-presses sheets of parchment paper, the whole being pressed tightly together. The compartments thus formed are filled alternately with water and molasses, The upper part of the whole of the osmogen constitutes an open reservoir formed by the upper vertical projections of the frames. The molasses for feeding the alternate chambers is placed in this reservoir and is kept circulating in various ways. The water chambers are fed from the lower part and are discharged through a common upper tube as they become enriched with salts. The osmotic effects occur best in the hot, so that the molasses is introduced at 80 and the water at J)0.
(Fig. 371) consists of
;

more sugar and less salts than The apparatus now used for osmosis

The taps through which the liquids enter and leave the osmogen are regulated by automatic floats which close or open the taps more or less so as to maintain a coiistaiit relation between the density of the oxosmosed aqueous solution and that of the osmosed molasses. This relation is determined beforehand in the laboratory, and corresponds with the conditions least favourable to the loss of sugar with the osmosis water and most favourable to the purity of the residual molasses.

FIG. 371.

together),

generally has a density of 3 Brix (3 per cent, of sugar and salt and the osmosed molasses 35 to 40 Brix (measured at 75 C.) the latter is concentrated and boiled in ordinary syrup pans until it shows the string test. Crystallisa;

The cxosmosed water

tion

is

carried out in the molasses

room

at 40

to 45

or in the Grosse apparatus.

The

crystallised sugar is separated by centrifugation and the new molasses obtained again subjected to osmosis. This operation is repeated once or twice more in fact, until the

quantity of sugar extracted would be insufficient to pay the cost. In some cases the osmosis waters are concentrated and reosmosed. The final molasses and the final osmosis waters rich in salts and also in sugar serve
for making spirit, shoe-polish, or potassium salts (see p. 183). They are also given to cattle, but must then bo diluted with solicl vegetable products as an excess of salts may exert harmful effects. (2) Lime Process. Steffen found that the addition of finely powdered, sieved quicklime in small portions to a solution of molasses of a suitable concentration (about 12 Brix, i.e., 7 per cent, of sugar, obtained from 1 ton of molasses + 70 hectols. of water), and kept at a temperature below 15, results in the separation of insoluble sucrate containing rather more lime than tricalcium sucrate, whilst the impurities remain (Jissolved in the

aqueous molasses.

The operation is carried out in a vessel (Figs. 372, 373) similar to the Grosse apparatus, the steam-pipes being used, however, for the circulation of cold water at about 12, so that after each addition of Erne, when the temperature rises 7 to 8, it can be brought rapidly down below 15. The addition of lime is continued until all the sugar is precipitated (about

SUGAR FROM MOLASSES

573

100 kilos of limo per 100 kilos of sugar), this being ascertained by reading the clear liquid in the saccharimeter. The resultant sludgy mass is filter- pressed at a pressure not exceeding 1J atmosphere, the filtrate still containing about 0-5 per cent, of sugar, which can be separated as tricaloium sucrate by heating the liquid to 90 and filtering. The cakes of sucrate are washed several times in the filter-press and the fairly pure residue used to defecate fresh diffusion juice before saturation with carbon dioxide ; or the sucrate may be treated with any cold saccharine solution so as to form the soluble monosucrate, the precipitated excess of lime being removed by filtration and the filtrate then saturated with carbon dioxide in the ordinary mariner. When an excess of crystallised strontium hydroxide is added to (3) Strontia Process. a dilute sugar solution at a temperature of about 100 and the liquid boiled, a granular,

FIG. 372.

Fro. 373.

sandy precipitate of strontium disucrate is obtained, which IH stable in the hot whilst in the cold it decomposes into sugar and strontium hydroxide. In a suitable boiler provided with steam-coils and Htirrers, a 10 per cent, solution of strontium hydroxide is boiled, further quantities of the hydroxide being added until a 20 to 25 per cent, solution is obtained. The molasses is now added in amount equal to about one-third of that of the strontium solution, which is stirred rapidly and heated meanwhile. Strontium hydroxide is subsequently introduced in such amount that the mass has 12 to 13 per cent, of excess alkalinity. The total strontium hydroxide is related to the sugar in the molasses in about the proportion 2-5 1. The precipitated disucrate is filtered rapidly in the hot through bag-filters and washed with boiling 10 per cent, strontium hydroxide, the latter being recovered from the filtrate. The disucrate is then dissolved in a cold strontium hydroxide solution and the solution introduced into metallic vessels situate in an apartment kept below 10. In the course of
:

three days one-half of the hydrate separates in a crystalline form, the .saccharine solution solution is then saturated with being then decanted and the residue centrifuged. The sugar carbon dioxide until it shows an alkalinity of 0-05, all the strontium being thus separated as carbonate. The very pure sugar solution obtained after filtration iB concentrated and

574
being refined.

ORGANIC CHEMISTRY

boiled as usual, the crystallised sugar obtained being placed directly on the market without

A somewhat different mode of procedure is that based on the formation of strontium monosucrate, but this does not yield the whole of the sugar as the above process does. In Germany the desaccharification of molasses is effected almost exclusively with strontia in large works specialising in such work. When solutions of molasses and of barium hydroxide are mixed (4) Baryta Process. in the hot in the proportion of 1 mol. of sugar to 1 mol. of the hydroxide, a heavy, sandy or cold water precipitate of barium monosucrate is formed which is stable to either hot this is collected as usual on filters and freed from impurities by washing with cold water.
;

is then saturated with carbon dioxide in order to liberate the sugar and, after dilution with other sugar juices, is filtered, concentrated, and crystallised. 1 'YIELD AND COST OF PRODUCTION. Formerly a hectare of land yielded with diffimethods of culty 20 tons of beet, but as the result of long-continued improvement of the cultivation, manuring, selection of seed, etc., as much as 30 to 40 tons are now obtained, and in certain special regions (e.g., Ferrarese) as much as 60 to 65. For every 100 kilos of beet worked, the loss is calculated to be 1-6 kilo of sugar in Italy and only 1 kilo in Germany. The cost of cultivating 1 hectare of beet, including manure, transport, etc., amounted before the war to 12. Italian manufacturers calculate that in bad seasons the production of 100 kilos of refined

It

sugar required 1 ton of beet, the cost of working this being 75. to 8s. (including 3*. for coal). Refining cost about 5s. 6d. (100 kilos of raw sugar give about 1)0 of refined). In Germany 100 kilos of beet gave not more than 8-4 of sugar in 1870, about 12-5 in 1890, and 15-8 (including that from the molasses) in 1909-1910. The mean production per

Germany was 35 kilos in 1867, 24 kilos in 1877, 10 kilos in 1890, and 7 kilos (8 in Italy) in 1900. By the use of Kestner concentrators (,w above) a further saving in coal has since been effected. The cost of manufacturing 100 kilos of cane-sugar in Java varied, before the War, from 12*. to 16s., and transport to England or the United States amounted to 2s>. STATISTICS. 2 The history of the development of the sugar industry in Europe and
1 The barium carbonate filtered off is converted into the oxide and then into the hydroxide by heating in suitable high -temperature furnaces. This barium process was used for some time in Italy, after it had been shown that no danger to health was to be feared from the use of a barium compound, since this is eliminated almost completely by carbon dioxide and the final traees by calcium sulphate. The barium hydroxide four factories had required is imported principally from America and Germany, but by 1903,

hectare was 24 tons of beet in 1871 and 30 in 1910. The consumption of coal in working 100 kilos of beet in

from barium sulphate another, at Milan, heats (he barium carbonate while the remaining two, at Foligno and Pont St. Martin respectively, from the sugar-works treat barium carbonate in electric furnaces, making first barium carbide, which with water gives acetylene and barium hydroxide (GarcUTs process). Such treatment of molasses in Italy was found feasible as long as the sugar extracted in this way remained free from taxation, that is, while the tax was levied solely on the defecated diffusion Since 1904, however, the total quantity of sugar produced, including that extracted juice. from molasses, has been liable to duty, and the molasses is consequently utilised in the distillery and in the manufacture of cattle-food. Recently some sugar factories have resorted to treatment of the molasses with barium sulphide, which is much cheaper than the hydroxide and is obtained directly from the sulphate in the electric furnace. 2 The Commercial, Customs, and Fiscal Conditions of the sugar industry in Italy and In some countries this great industry has been extended artificially owing other countries. to the direct and indirect help afforded by the State, and to the speculations of financiers. With the excuse of protecting national industries, Governments have levied heavy Customs duties, with the result that the public has paid dearly for its sugar, while manufacturers have accumulated enormous profits and have been enabled to export sugar at less than cost price to other countries. At first the protective duty was from 24*. to 32,v. per quintal, while in France it was raised to The form taken by the protection was then changed by the institution of export bounties, (54*. which allowed tho sugar to be sold abroad at a low price, while large profits were made owing First Belgium and then France established a to the high prices at homo and to the bounties. to an bounty of 8s. to 10.?. for every quintal of sugar exported, France being thus subjected enormous burden amounting to over 2,000,000, without counting the rebate on the freight from the factory to the frontier. This enormous sum has been paid by the mass of the population, to the exclusive advantage of a few manufacturers (rule of the Meline Ministry). In Germany and Austria, where the export bounties were relatively low, the manufacturers the manufacturers formed sale syndicates (cartels), which operated in the following manner who granted a bounty of 24*. per pledged themselves to supply all the raw sugar to the refiners,
factories, at C'alolzio, starts
;
; :

been erected in Italy for supplying

all

the baryta necessary to the sugar factories.

One

of these

SUGAR STATISTICS
this industry has

575
of

the importance been discussed on p. 545. Reference has also been made to the production of cane-sugar compared with that of beet-sugar. While in 1854 beet-sugar formed only 14- per cent, of the world's total production (1,423,000 tons), in 1866 the proportion was 30 per cent, (on

assumed during the past quarter

a century have already

a total of 2,000,000 tons) in 1878, 44 per cent, (on 3,000,000 tons) ; in 1887, 47 per cent, in 1893, 55 per cent, (on about 6,000,000 tons) in 1899, (on more than 5,000,000 tons) 64 per cent, (on 7,500,000 tons) in 1901, 67 per cent, on almost 9,000,000 tons. In 19081909 cane-sugar again assumed first place, which it has since maintained. To give an idea of the progress made by the beet-sugar industry during tho last 80 years, the production of raw sugar in tho two countries where this industry has developed most is given in the following Table
; ;

quintal to tho manufacturer and sold the sugar to the home consumer at a very high price, there being no fear of competition, as they enjoyed a monopoly. The sufferers, as always, were the consumers. The home profits were so enormous that sugar could be sold abroad at loss than On the other hand, England, the greatest consumer cost price and competition thus vanquished. of sugar, found its markets deluged with cheap Continental sugar, which competed seriously with that from its Colonies, which had also become considerable exporters. Under these conditions a more rational solution was found for the problem of sugar with The initiation of such an undertaking could come only reference to international commerce. from England, who was able finally to impose her conditions on all countries sending sugar to her markets. Tho Brussels Convention, convoked on September 1, 1902, was subscribed to by England, Germany, Austria, France, Belgium, Holland, and Italy. The result was the abolition of export premiums and tho reduction of the boundary duty to 5s. per quintal above tho manufacturing tax, from September 1, 1903, onwards. Such duty was to be enjoyed only by those countries conforming to the Brussels Convention. tho boundary duty remained as before, namely, Italy did thus conform in a modified way 23s. for first quality and 10.v. Orf. for second quality, while a pledge was given not to export sugar to other countries and to impose an exceptionally heavy ( Customs duty on countries not adhering to the Brussels Convention (especially on Russia and the Argentine Republic ; but Russia entered the Convention in January, 1908, and pledged herself to export for six years not more than 200,000 tons per annum of bounty-fed sugar. After 1908 England held herself free to import premiumed sugar without imposing supertaxation). Spain and Sweden wcro treated like Italy by the Brussels Convention, to which then Luxemburg, Peru, and Switzerland conformed. In
:

Spain an overproduction crisis arose. In Italy the price of sugar fell, owing to overproduction and frenzied competition, to 92<<?. per quintal, so that in 1901-1903 almost all the sugar factories showed either minimum profits or considerable losses. Indeed, deducting the tax of 50s., there remained 30.5. as the price of the sugar. According to the manufacturers, 10 quintals of beet, giving 1 of sugar, cost 10*., while the cost of production of crude sugar was 8*. (including 4s. for coal), that of refining about (is. 4d. and that of transport Ift. 8r/. total, 32.v. Thus only 4s. remained to provide interest on capital as well as depreciation. Hence, in 1904, all the sugar-makers combined to form a syndicate and raise prices, and early in 1005 an increase of 10.v. (to 108s.) per quintal was enforced with a production of 1,000,000 quintals, this amounted to an annual burden on the consumer of 800,000. Adding to this the protective duty of 1,200,000, it will be seen that, for the luxury of a native sugar industry, the Italians paid an annual tax of 1,200,000 to 2,000,000, tho sole gainers being some 30 factories with a capital of about 3,200,000. The European War brought all these conventions to an end, and in some countries the fiscal regulations have been rendered more severe.
:

576

ORGANIC CHEMISTRY

Some of the large factories in France and Belgium have diffusion plants in the middle of the beet-growing districts, the sugar juices after treatment with lime being forced through pipes, often several kilometres long, to the factories, where they are further
worked up.
In

Germany the
In
1

and from 1880 to 1902 Germany was the

output).

Convention,

its greatest perfection and magnitude, largest exporter (as much as two-thirds of its 1909-1910, in spite of the diminution of exports resulting from the Brussels Germany exported 423,000 tons of refined sugar and 310,000 tons of the

beet-sugar industry has reached

raw product, the home consumption being 1,260,000 tons. The exports were 740,000 tons in 1890, 883,000 in 1904, and 1,145,000 in 1906. In 1908-1909, 358 factories and 39 reCertain German factories, employing 46 workmen, fineries were working in Germany. treat 400 to 500 tons of beet, but in Italy many more employees are required. In 1909-191
10,600,000 tons of beet, hut in 1910-1911 only 5,200,000 tons. In Austria large batteries of diffusors are used and a more complete exhaustion is in general, indeed, the modern plants are more obtained even at a lower temperature AustriaIn 1908 in those than Hungary exported 610,000 tons of refined Germany. perfect

Germany produced

and 195,000

I, manufacturing tax in pence per pence per kilo ; III, mean annual consumption in kilos per head in 1899, 1909, and 1913; IV, kilos of refined sugar obtained from 100 kilos of beet; V, kilos of refined sugar from 1 hectare : and VI, number of sugar factories.

The
;

of raw sugar. following Table shows, for different countries

kilo

II, retail price in

1 The Fiscal System in Germany from 1841 to 1866 was based on the quantity of beets, the object being to bring about improvements in the cultivation of the beet and hence increase the tax corresponded with about 18s. per quintal, and was refunded to in the sugar-content the manufacturer for all exported sugar. From 1870 to 1886 the tax was Is. Id. per quintal 1 kilo of sugar, but even of beet, it being assumed that 12-5 kilos of beet were required to give kilos. Since in 1870 1 kilo of sugar could be obtained from 11-9 kilos of beet, and in 1887 from 8-1 the exports increased enormously and the taxes refunded remained the same, the manufacturers the Exchequer receipts from enjoyed indirectly a considerable export bounty, which diminished was hence made in the system of 3,000,000 to less than 760,000 (1888). A modification a tax of 1 per quintal, while that taxation, sugar produced and consumed at home paying 2*. 6rf. (raw) or 3s. Qd. (refined) per 100 kilos exported was freed from tax and received a bounty of Further, the import duty was left at 2 per quintal, so that German producers (1896-1903). were allowed to sell their sugar at high prices at home (oven during the abundance of 190O-1901) and to employ part of their profits to lower the price of sugar sold abroad in competition with other countries. After the Brussels Convention, however, export bounties ceased and the import was reduced, to 5s. -f 165. (manufacturing tax in Germany). Under these new conditions,
;

duty

ESTIMATION OF SUGAR
DETERMINATION OF SUGAR-CONTENt. Sugar
is

577

estimated in various ways. With an aqueous sugar solution, the content of saccharose may be determined by means of the specific gravity at 17-5, compared with water at 17-5, this being measured by hydrometers, py knometers, etc, (see Vol. L, p. 75). In the factory, use is generally made of a hydrometer (saccharometer) which, at 17-5, gives directly the percentage of saccharose
present.

These saccharometers were first proposed by Balling and were subsequently corrected by Brix, degrees Brix expressing the percentage of sugar. In France and Belgium, and sometimes also in Germany, saccharometers gauged at 15 and referred to water at 15 are used, and the Berlin Royal Commission for the control of standards prescribed the use of saccharometers giving the density of solutions at 20 referred to that of water at 4. The following Table gives the densities and degrees Brix (grms. of sugar per 100 grms. of solution) for the temperature 17-5, and also, for each 10, the values from the other two Tables, so that the intermediate values in these two Tables can be calculated roughly, The saccharometer is read with the precautions and in the manner indicated on p. 77 of Vol. I. and on p. 174 of this volume. The Table gives densities above 66 Brix, which cannot be determined by hydrometers, but which serve to calculate the degree of purity
of

impure saccharine solutions (molasses,

etc.

see later).

MATEGCZEK AND NCHEIBLEK'S TABLE, GIVING THE SPECIFIC GRAVITIES AND DEGREES BRIX OF SACCHARINE SOLUTIONS.

If the degrees Brix are

corrections

must be made by means

read with solutions at temperatures other than the normal, of the following Tables
:

-he

exports diminished somewhat, but the home consumption increased owing to the lowered mces. The wholesale price in 1910 was 2 per quintal (that of sugar for export, without tax, Tho (iermau >eing 19*.) ; the retail price was 14rf. per kilo in 1875, Id. in 1902, and (id. in 1!)10. Jovernmcnt received 5,750,000 in sugar taxes in 1900-1901, almost 8,000,000 in 1909-1910, md over 9,000,000 in 1913. In 1912 the manufacturing tax was 23.v. GV/. per quintal. Diminuion of the tax by 33 per cent, increased the consumption by GO per cent.

578

ORGANIC CHEMISTRY

STAMMER'S TABLE FOB REDUCING TO 17 -5 DEGREES BRIX READ AT DIFFERENT TEMPERATURES.

Example.
ture of

If

a sugar solution shows 40 Brix

40-4 degrees Brix at 17.

(i.e.,

40 per cent, of sugar) at a tempera;

23, 0-4 must be added to reduce the reading to the true Brix degrees at 17

so

that 40

+ 0-4 =

SCHEIBLER'S TABLE SHOWING DEGREES BRIX AT 15

AND THE CORRESPONDING DEGREES AT OTHER TEMPERATURES (FROM 10 TO 25).

of 25, this would correExample. If a solution reads 19-36 Brix at a temperature For intermediate of 15. normal the at values, either of Brix 20 with temperature spond results are easily obtained by intertemperature or of concentration, the corresponding 18 Brix at temperature 15 would give, at other temperatures, values polation. Thus, 15 Brix by three-fifths of the difference between higher than those corresponding with. the values in the 15 Brix and 20 Brix columns. Ho that a solution showing 18 Brix at 14-90) the temperature 15 would show, at the temperature 17, 14-90 |- (19-89

17-89 Brix. 14-90'+ 2-99 In the quantitative determination of sugar, use is commonly made of its action on this being measured in the polarimeter. The rotatory power of a polarised light (see p. 28), concentration and almost independent of the temperasugar solution is proportional to the In these determinations it is necessary to use pure sugar solutions, decolorised by ture. means of a little basic lead acetate (or, better, mercuric acetate or phosphotungstic acid), which precipitates the albuminoids, colouring-matters, and other impurities the filtered solution is examined in the polarimeter. If the saccharose is accompanied by another allowance must be made for instance, glucose (dextro-rotatory) optically active sugar for the rotation of the latter. In such a case the diminution in rotation produced by inver; '

sion of the saccharose with dilute acid

would give the amount

of this sugar.

POLARIMETERS
The
463
;

579

use of the refractometer for the estimation of sugar has also been proposed (see " also Villaveccbia, Applied Analytical Chemistry," Vol. II., p. 93).

POLARIMETERS SACCHARIMETERS. 1

AND
One
of

the best-known polarimetera is the Laurent shadow instru-

ment (Fig.
in

place

374), which contains, of the compensator

and double-polarisation quartz

plate,

special
'

semicircular

Fio. 374.

same luminosity is indicated on a graduated circle, means of the lens, N, and illuminated by the mirror, M.

quartz plate, D, half a wavelength in thickness and occupying one-half of the field. The B, is rotated by polariser, means of the rod, X, and the rotation which restores the two halves of the field to the C, provided with a vernier, read by

1 It has been mentioned already (we p. 27) that crystals of Iceland spar and quartz have the property of decomposing a ray of light into two polarised rays, the ordinary and the extraIf a of Iceland with ordinary. prism spar length greater than the breadth, with its acute angle of 68, is cut diagonally and lengthwise so as to divide it into two rectangular triangular prisms (Fig. 375), and these arc cemented together again with Canada balsam, the result is a Nicol prism. When a ray of light, Iw, enters the nicol, of the two refracted rays (mo, nip), the ordinary one, mo, is totally reflected by the layer of Canada balsam and is thrown out of the crystal (or), whilst the extraordinary ray, mp, passes through the .prism (pqs) and emerges This ray is able subsequently to traverse polarised. a second nicol only when the principal section of this analysing nicol is parallel to that of the first If, on the other hand, the two polarising nicol. 375. principal sections arc perpendicular, the ray undergoes total reflection and will not pass through the second nicol ; in intermediate positions, varying quantities of light are allowed to Jf a layer of water is placed between the perpendicular nicols, still no light will pass pass. through the analyser, but if a sugar solution is interposed, the light passes with a greater or less intensity through the analyser, which niust be rotated through a certain angle (proportional to the quantity of sugar) to produce total disappearance of the light. In order to determine exactly

ra

Fio. 376.

(even in this case a kind of half-shadow is always observed), attempted to divide the luminous field into two halves with complementary colours. Indeed, if a ray of polarised light is passed through a quartz plate placed between the two nicols, one half of this plate being dextro- and the other la? vo -rotatory, and the junction of the two lying exactly on the axis of the light, the two halves of the field will appear illuminated with complementary colours. If the plate is 3-75 mm. in thickness and the analyser is rotated through
Soleil

when the luminous ray is extinguished

580
The source
of

ORGANIC CHEMISTRY

monochromatic light is a double bunsen flame coloured with sodium chloride, the light being collected by the lens, B, and the observation made through the eye-piece, 0. The scale of the apparatus is regulated by the screw, Z, so that it reads zero

when the two halves of the field are equally illuminated. If a tube containing a liquid, interposed between the two nicols, causes the right-hand half of the field to darken, the liquid is dextro-rotatory, while darkening of the left-hand half indicates a laevo-rotatory compound. From the rotation read on the scale, the specific rotation may be calculated by the formulae given on p. 28. The practical examination of sugars is made with polarimeters furnished with special
scales

and known as saccharimeters

the Laurent polarimeter has a saccharimetric gradua-

tion as well as that showing circular degrees.

In the French saccharimetors (Soleil and Laurent) the 100 division corresponds with a normal aqueous solution of pure saccharose (obtained by precipitation of a very concentrated aqueous solution with alcohol and drying at 60 to 70) containing 16-3.50 grms. in 100 c.c. at 17-5, the reading being made in a tube 20 cm. long (the same reading is given by a quartz plate 1 mm. in thickness). In the German instruments ( Ventzke-Scheibler, Schmidt and Haensch) the 100 reading is obtained with a length of 20 cm. of a saccharose solution of ap. gr. 1-1, which contains 26*048 grms. per 100 c.c. at tne temperature 17 -5 1 Thus, a reading of one division corresponds with 0-26048 grm. of saccharose per 100 c.c., or 1 grm. of sugar per 100 c.c. gives a reading of 3-839 divisions.
.

The source
electric

of light for

modern saccharimcters
fitted

is

an incandescent gas-burner enclosed

in a blackened metal

with a ground-glass window, or an incandescent lamp of at least 32 candle-power with a ground-glass globe and also enclosed in a black case. In order that the apparatus may not become heated, the lamp should be placed at a distance of about 15 cm., and to render the luminous

chimney

more distinct the light is passed first through a glass cell with parallel walls filled with 6 per cent, bichromate solution in a layer 15 mm. thick ; in this way the more refractive rays are absorbed and The normal a uniform yellow light obtained. Fi. 377. tube of the saccharimeter contains a column of liquid exactly 20 cm. long, but for very dilute and slightly rotating solutions tubes of 30, 40, and 50 cm. are used, whilst for solutions which are not quite colourless tubes of 10 or 5 cm. may be employed in all cases the readings are referred to the normal length of 20 cm. Some tubes are provided with an aperaturo for tho introduction of a thermometer, so that the temperature of the solution may be read in the instrument. to 100 divisions on the positive side and to The saccharimeter scale extends from 30 on the negative side. The integral divisions are given by the zero of the vernier, (Fig. 377), and the decimal parts by that division of the vernier scale which coincides exactly 2-6 divisions. 2 with a division on the scale in Fig. 377 the reading is
fields
;

24-5, the two halves of the field are almost completely extinguished and assume a pale red If, however, a sugar solution is interposed, the two halves coloration, similar in the two halves. assume different colours, extinction being restored by rotation of the analysing nicol. Later Soleil suggested compensating tho rotation of the sugar solution by introducing, to a greater or less extent, between the nicols, a conical quartz plate or compensator, moved by a rack indicating on a scale the thickness of the plate and hence tho equivalent rotation. The more modern saccharimeters of the Soleil- Yentzke type have two compensators, each formed of two quartz wedges (MN and HK, Fig. 370) of opposite rotations, and are fitted also with the Lippieh 'polariwr formed of three nicols (P), which give a field divided into three zones ; when these zones are not equally illuminated, the two lateral ones show a colour different from that of the middle one. The analyser is enclosed in a metal box to protect it from dust. The two compensators with When the two scales indicate zero, the three their scales are regulated by two screws, V and V. zones should be equally illuminated. 1 That is, in 100 Mohr c.c., 1 Mohr c.c. being tho volume of 1 grm. of water at 17-5 weighed The true c.c. is the volume of 1 grm. of water at 4 weighed in vacuo : in air with brass weights. calculation on the basis of the coefficient of expansion of water shows that 100 Mohr c.c. are equal to 100-234 true c.c., so that 100 true c.c. of tho normal saccharose solution at 17-5 would contain 25-987 grms. of saccharose. The In ternational Commission for uniform methods of sugar of the 100 point of the saccharimeter by a length of 20 cm. analysis proposed in 1000 the fixing of a solution obtained by dissolving 26 grms. of pure saccharose in water to a volume of 100 true c.c. at 20 and polarising at 20 (100 true c.c. of water at 20 weigh 99-7174 grms. in air and 99-8294 grms. in vacuo). 2 With double compensation saccharimeters (furnished with two scales, a working scale

POLARIMETRY
=+
.

581

The specific rotatory power of saccharose varies little with the concentration (up to 30 per cent.) and with the temperature (between 15 and 25), but it is best to work near to 66-5 1 20, when a^

V and V, Fig. 376) the procedure is as follows When the tube with the sugar introduced between the nicols the control scale is placed at zero, the working scale being then moved by thp screw until the field is uniformly illuminated and its position read. The sugar solution is next removed and the control scale moved until the field is again uniform, the reading of this scale being nearly equal to the first reading of the working scale. The tube of solution is now again introduced and the position of the working scale, near to the zero-point, read after its adjustment to give uniform luminosity. Finally the tube is again removed anil the control scale moved until the field is uniform and its position read. The final result is obtained by subtracting the mean of the second pair of readings from the mean of the first pair. Thus, 0-05 if the readings were -f 78-6, 0-2, and 0-3, the result would be 78-5 784,
and a
control,
is
:

solution

-f 78-45.
1

CONSTANTS OF THE PRINCIPAL SUGARS.

invert sugar has a rotatory power varying markedly with the concentration and temperature. solution of saccharose containing the normal weight (2(5-048 grins.) contains, after inversion, 32-00 27-419 grms. of invert sugar, and if this is contained in 100 c.c. it gives a deviation of this reading The variation per degree of temperature is 0-5, so that at in a 20 cm. tube at 20. If no 42-66 -4- 0-5 /. 42-66 and, in general, at any temperature, /, it would be would bo account is taken of variations due to the concentration, 1 division Ventzke corresponds with 0-8395 grm. of invert sugar in 100 c.c. (Mohr), the solution being read in a 20 cm. tube at 20 The 1-191 division. or 1 grm. of invert sugar dissolved in 100 Mohr c.c. gives a reading of 1 to .35 per cent.) is specific rotatory power of invert sugar for different concentrations (from 2 0-0361 If, c indicating the weight of invert sugar given by the formula: [a] ;| ='19-657 20-2 may be taken for the specific For concentrations near 15 per cent, the value in 100 c.c. rotation of invert sugar, 1 circular degree then corresponding with 2-475 grm. of invert sugar in 100 true c.c. and 1 grm. of invert sugar in 100 true c.c. giving a rotation in circular degrees
; -

of

- 0-404.

Glucose has the specific rotation, [o]^ -= -f 52-8, which is constant after muta-rotation has ceased (see. p. 28), i.e., if the observation is made after the solution has been either left for 24 hours or boiled for 15 minutes. The concentration and the temperature have virtually no influence on the rotatory power. For fructose (levulose) the data are uncertain owing to the difficulty of obtaining pure crystals, and the rotatory power varies with the concentration (for solutions of about 10 per cent, strength, 93) and with the temperature (an increase of 1 of temperature diminishes the [aj ^
1

specific rotatory

Lactose.

rotation,

power by 0-67). For C 12 H 22 O n + H 2 0, after the disappearance of the muta-rotation, the 2 -f 52-53 which is but slightly influenced by the concentration, is [a] J

specific this ;

diminishes by 0-075 for every degree rise in temperature. Maltose has a specific rotation (after muta-rotation has been destroyed ; see (Jlucose) varying 140-375 with the temperature and concentration according to the equation [a]f, 0-095 t, where t indicates the temperature and r the percentage by weight of 0-01837 c -f 138-2. anhydrous maltose. For medium concentrations, [oJ5H O, has the C -f 104-5, which is almost rotation,
:

Maffinose,

18

H 32

16

specific

[aft

independent of the temperature and concentration.

582

ORGANIC CHEMISTRY

raffinose,

the exception of saccharose and the sugars (glucose, levulose, etc.) reduce Fehling's solution (an alkaline solution of copper sulphate containing salts of organic hydroxy-acids ; see pp. 255 and 400) in the 1 hot, with separation of a corresponding amount of cuprous oxide.

CHEMICAL DETERMINATION OF SUGARS. With

NON-SUGAR, APPARENT DENSITY, TRUE DENSITY, AND QUOTIENT OF PURITY.

Sugars and their solutions are distinguished, commercially and industrially, by their content of saccharose, water, and solids not sugar (e.g., salts and various organic substances). The Brix saccharometer is graduated with pure sugar solutions, and hence gives results which are increasingly inaccurate as the degree of impurity of the sugar solutions increases.
1 Fehling's solution is obtained by mixing, just before using, equal volumes of the two following solutions : (a) 69-278 grrns. of pure crystallised copper sulphate (CuSO 4 -f 6H 2 O), a^ir-dried until constant in weight, dissolved in water to 1 litre ; (b) 346 grins, of Rochelle salt (sodium potassium tartratc) and 100 grms. of pure solid sodium hydroxide dissolved in water to 1 litre. Since saccharose does not reduce Fehling's solution, it must be first inverted. For this purpose, 9-5 grms. of the sugar are dissolved in 700 c.c.. of N/3 -hydrochloric acid and the solution heated for 30 minutes in a water-bath at 75, neutralised with caustic soda, and made up to 1 litre. This solution, which contains 10 grins, of invert sugar, is then ready for testing. The Fehling^ test may be either volumetric or gravimetric,, the concentration of the sugar being reduced to about 1 per cent, (by a preliminary trial) and the details of the procedure being followed exactly. Volumetric method : 40 c.c. of water and 10 c.c. of Fehling's solution (5 c.c. of each of the component solutions) are brought to boiling in an Erlenmeyer flask, a measured quantity (4 to 5 c.c.) of the sugar solution run in from a burette, and the liquid again heated and kept boiling for a definite time (two minutes for glucose or invert sugar, four minutes for maltose, and six for lactose) ; the flame is then removed, a few drops of the liquid filtered, and the filtrate acidified with a little acetic acid and tested with a drop of potassium ferrocyanide solution. If a red coloration is produced, the test is repeated with a larger quantity of sugar This procedure solution, whilst if no red coloration appears, a less quantity of the sugar is tried. is continued until in the last two tests, representing excess and deficiency of the sugar solution, the difference between the two volumes is not more than 0-1 c.c. ; the mean of these two volumes 100 c.c. of undiluted Fehling's is employed in calculating the sugar-content of the solution. solution, under the above conditions, corresponds with 0-4945 grm. of glucose, 0-533 of levulose, 0-515 of invert sugar, 0-740 of maltose, and 0-676 of lactose (hydrated). The gravimetric estimation is carried out as follows (Allihn's method) : To 60 c.c. of Fehling's solution, diluted with 60 c.c. of boiled distilled water and heated to boiling, are added 25 c.c. of the sugar solution of about 1 per cent, concentration, the liquid being then again heated and kept boiling for a definite time (two minutes for glucose, levulose, and invert sugar, four for maltose, and six for lactose). The solution is then filtered at once, with the aid of a filter-pump, through a dried and weighed Soxhlct tube containing a layer of asbestos, the cuprous oxide being repeatedly washed with a total quantity of 300 to 400 c.c. of boiling water, then with two or three portions of alcohol, and finally with ether. The tube is then dried in an oven, and the cuprous oxide subsequently reduced to metallic copper by passing a current of dry hydrogen through the tube and gently heating the oxide with a small flame ; the hydrogen is kept passing until the tube is quite cold, when the weight is taken. From the weight of copper thus obtained, the corresponding weight of sugar is read off from the following Table, all the numbers representing

milligrams

ANALYSIS OF MIXED SUGARS

is

583

that shown by the Brix hydrometer, while the real density corresponds Apparent density with the true content of sugar determined by direct analysis (by the polarimeter or, after
inversion,

by Eehling's solution). The difference between the real and apparent densities, expressed in degrees Brix, indicates the non-sugar in Brix degrees, while the ratio between the real and apparent densities, in degrees Brix, is termed the quotient of purity and, when multiplied by 100, shows the percentage of sugar present independently of the water. In the analysis of a mixture of various sugars a number of optical and chemical tests must be made in order to deduce, directly or indirectly, the quantities of the separate
(see Villavecchia,
'

components
1

Applied Analytical Chemistry," Vol.

II.,

pp. 114

et seq. 1 ).

If only saccharose and another sugar are present, p grms. of the mixture are dissolved in water to 100 c.c. and the polarisation, P, read ; if a l is the rotation of 1 grm. of saccharose per 100 c.c. and a z that of 1 grm. of the other sugar, the quantities x and y of saccharose and the

other sugar .respectively are given by the formulae

(I)

=
</<!

*?',
rt

(II)

= a^
tf'i

~
'

'

since

an(i a i x -f a a2/ The values of a lt 04, and must bo given their (IV). ). proper algebraic signs (-}- or (A). In the special case of a mixture of saccharose and glucose, the components x and y may be determined in various ways (1) The glucose (y) may be estimated by means of Fehling's solution ; formula IV then

+y=

P (HI)

=^

^*2

gives x

--

--

(V).

Since saccharose reduces Fehling's solution to a very slight extent,

small proportions of glucose are best determined by means of Soldaini's reagent, which consists of 150 grrns. of potassium bicarbonate, 104-4 grins, of normal potassium carbonate, and 100 c.c. of the copper sulphate solution used for Fehling's solution, made up to a litre with water. (2) The solution of the mixture is polarised (P), the saccharose being inverted and the If a 3 is the rotation of 1 grm. of invert sugar polarisation again read (P A ). (^ 1-191), then, since 1 grm. of saccharose gives 1-053 grm. of invert sugar, we have 1*053 a^x -\- a 2 y P 1 (VI)

and hence x and

'

ftj

---!rJ.*UtJoCfjj

(Vll)

and y
.

-a
tf'g^Hj
1

-'

*?"*

P
(VIII), a, having the value 3-839

3-057,

it

follows that x

_ - p p

I'UOof/g)

^g^f-

(IX) and y

*i.ui/>

quantities of the
arid
-

two sugars

respectively.
-

p grms. of the mixture. The percentages For a mixture of saccharose and levitlosc, a z
in

^ J ^~
1-191

i.9p;j.P

(X),

which are the

be

will therefore

5-439, so that

3-839P ---

1-254.P ----

~97\m

^ or sacc ^ arofle
;

an d

invert sugar,

r/

and the denominator

a2

becomes (H)66 instead

of 27-701

for mixtures of saccharose

and
3-035.

maltose,

7-949

and

for Saccliaro8e

and

torto*? hydrate,

a2

in another portion of (3) The glucose is first determined by means of Fehling's solution the solution the saccharose is inverted and the reducing sugars again estimated with Fehling's solution the difference between these two estimations gives the invert sugar and this, multiplied by 0-95, the saccharose. (B). With a mixture of saccharose and raffinose, the polarisation is determined before (P) and after (PJ inversion j and a z being the known rotations of 1 grm. of each of the two .sugars of 1 grm. of the respective inverted products, it follows that and 3 and 4 those 1-036 a^y P^ (XIV) ; substitution in these of the r* f- a$ P! (XIII) and 1-053 a&
;
:

values a t

3-839,
'

7-11, 1-053
"^

+ =

1-254

and 1-036
^

3-643 gives x

and y

1-254P 4- 3-839 P ^' 22 :9~

f 3*2211
.

--

--

r ^^ e

determma ^ on

* ne

raffinoso

by means

of methyl-

phenylhydrazine, in presence of saccharose and invert sugar, see Rafh'nose, p. 585. (C). When two reducing sugars but neither saccharose nor raffinose is present, it is sufficient to 'measure the polarisation and apply formula) I to IV. But if a non-saccharine substance is also present, it is necessary to determine also the number (Jf) of c.c. of Folding's solution reduced by a weight, p, of the substance ; if & x and 6 2 are the volumes (c.c.) of Fehling's solution reduced by 1 grm. of each of the two sugars dissolved in 100 c.c., then a^x -\- a 2y (XV) and b hence x and and With a mixture y (XVI) -^. of a 2 i> 1 a^o^ a^pz' a z o 1 3-057, 0,1 5-439, b l 202-4, and b 2 glucose and levulose, a 1 186, so that x
:

=P

V + bM=*F

186P

- ^=^^ =
.

^_

+ 5-439^ -T

=
,

and y

3-057P -----

202-4P
-

-----

For mixtures of

glucose,

and

maltose, a a has the

value 7-940 and 6 2 135 ; these last two numbers hold also for mixtures of invert sugar and maltose, 1*191 and b l 194 ; for mixtures ofyluccse, and lactose, a l but then a t 3-057, a 2 3-035, 148, while for invert sugar and lactose, a 2 and 6 2 have the values just given, 202-4, and 6 2 fej

1-191 and & x = 194. With a mixture of saccharose (x), glucose (y), and kvulose (z), if a weight, p, is dissolved to 100 c.c., and a l9 a z a 3 a 4 represent the respective rotations of 1 grm. of each of these sugars and of invert sugar in 100 c.c., & 2 an(^ ^3 ^he number of c.c, of Fehling's solution reduced by 1 grm. of each of the reducing sugars, P and P 19 the polarisations before and after

but

(D).

584

ORGANIC CHEMISTRY

The total ash of a sugar is determined by weighing 3 grms. into a tared platinum dish, moistening it with a few drops of concentrated sulphuric acid, carbonising over a bunsen flame and incinerating in a muffle at a low red heat (about 700) so that the ash does not From the sulphated ash, one-tenth of its weight is deducted in order to correct for fuse the increase due to the formation of sulphates. By means of tables the quantity of soluble ash can also be deduced. The water is determined by heating 5 to 10 grms. of the sugar in a flat glass dish covered with a clock-glass at 105 to 110 first for 2 hours and subsequently to constant weight. Subtraction from 100 of the water and the sugar gives the percentage of total non-sugar, while further subtraction of the ash gives the organic non-sugar. The alkalinity of the sugar is determined by titrating an aqueous solution of 20 grms. of the product with decinormal sulphuric acid in presence of phenolphthalein ; the result is calculated as grams of OaO per 100 grms. of sugar.

PURIFICATION OF WASTE-WATERS FROM SUGAR-WORKS.

purification, in emptying

The waters

requiring

they are highly contaminated and readily ferment, are those used and washing the diffusors, those from the pulp-presses and, partly, those in which the beets have been washed. The first contain up to 0-5 per cent, of suspended matter and 0-6 to 0-8 per cent, of dissolved organic matter, with about 0-3 per cent, of sugar they have a bad smell, and it is usually prohibited to introduce them as they stand
since
;

into streams.

Chemical purification (with lime or iron oxide or sulphate) is costly and insufficient, while the mechanical method of filtration to remove the suspended matter does something but only partially solves the problem. Biological purification (see Vol. L, p. 249), preceded by filtration or by aeration (omitting the septic tank) gives better results than the older 40 to 70 per cent, of the organic processes, but is not entirely satisfactory (it eliminates

The principal bacteria which destroy saccharose are Leur.onostoc and Clostridium. The problem of the complete purification of these waste-waters still remains unsolved.
matter).

RAFFINOSE, C ]8H 32
high, rotatory

16

+
3z

power

[a]^

+ 104-5),

C. TRIOSES 5H 2 0, forms pointed

and

crystals and has a very since also saccharose containing

inversion,

and

then (XVII)

F the number of P -= a + V f _
L je
2l

o.c. of
a,
,

two* of these give x

V>

(i

a$

-f

a 32

=P
XVT
r

L'Ooodi
I 2 y -f
l. Az
z.

r/"Ko~

P t - 1-053 a^x -f a 2y + w hih corresponds with

Thus x
15-57?
-

Fchling's solution reduced

rt

by weight p
;

of the substance,

3z

-= & 2 /y -f I 3 z.

The

first

formula Vll.

Then (XVTII)

a tx

and

F, which are analogous to formula

an( l
f

determination of the yalues of y and

to formula
'

~K-.QQQ^
-

y an(l

XV, allow of the we have, in analogy

MSP7UPH- 27.7F
8. )()0

(diminishing the polarisation, P,

and

2M

by the

rotation of the saccharose, 3-839*),

(.r),

inmrt sugar
'

(u)

and

asfltt 6 20-048 grms. of the sugar or mixed sugars are dissolved in a 100 c.c. is added drop flask and, if the solution is coloured, basic lead acetate solution (10 to 30 drops) is made up to 100 e.o. with water, by drop until it forms 110 further turbidity ; the solution filtered through a dry filter and polarised in a 20 cm. tube, a drop of acetic acid being previously added, if necessary, to make the liquid clearer. the liquid is made up to If it is thought desirable to eliminate the excess of lead acetate, volume with saturated sodium sulphate solution instead of with water. In the case of a mixture of invert sugar and saccharose, if the normal weight solution gives 27-0 after inversion, the quantity of saccharose in 100 c.c. a rotation of 4- 24-0 before and 1-254 X 24 3-839 X 27 24 4- 27 , f be will 10-01, and that of invert sugar of the solution

-15-40J'

lactose (z), the

- 185-6P

-568/J ,
-

saccharose

8 500 is arrived at as above,

z

-777^
0-066^

^^
'

, and

and then 243P + 7457^

---

Practical

Kxampk*.

-^93-

-- --

If other sugars are also present, the invert sugar is first determined with Fehling's solution, such quantity of the sugar solution being taken (after a preliminary trial) as contains about 0-2 grm. of invert sugar and the determination being made with 50 c.c. of Fehling's solution to a slight correction, according to a Table by the gravimetric method. The result is subject the Fehling's solution, but this only by Meissl and Killer, for the influence of the saccharose on in cases where the invert sugar is present in relatively small proportion compared with the

saccharose, as, for instance,

when samples

of saccharose are being analysed.

STARCH
raffinose exhibits pointed crystals in Germany as Spitzenzucker or Pluszucker.

585
rotation, raffinose
is

and an increased
It

a hexatriose, and

up 2H 2 0, giving equal proportions of d-glucose, rf-fructose, and By restricting the hydrolysis, most suitably by effecting it with an intermediate stage may be realised, consisting of df-fructose and enzymes,
lysed takes
d-galactose.

is known when hydro-

melibiose (isomeric with lactose), which is subsequently resolved into rf-glucose and rf-galactose. Raffinose is found together with cane-sugar in the sugar-beet, In the manufacture of saccharose, it its amount varying with the season. accumulates in the molasses and often occurs abundantly in the sugar extracted

from beet-molasses by the strontia process in the final syrup from this treatRaffinose does not give it occurs sometimes to the extent of 20 per cent. the reactions of the monoses (reduction of Fehling's solution, etc.), and hence contains no carbonyl group, its rational formula being
;

ment

(C 6

HU

0)

(C 6

H 10
:

C6HU

Galactoso

Glucose

5 ). Fructose

Melibiose, which, like lactose, exhibits the reactions of the monoses and contains So that raffia carbonyl group, is represented thus (C 6 n 5 0) C 6 11 O 5

(lUlactose

Glucose

nose usually decomposes first at the point where a carbonyl group occurs (between ghyeose and fructose) otherwise it would yield a biose without a free carbonyl group. Indeed, Neuberg (1907) has shown that the action of emulsin on raffinose gives galactose and cane-sugar (which does not give the monose reactions), this decomposition thus occurring at the opposite end of the mole cule. This observation supports Herzfeld's hypothesis that in the beet raffinose is formed from saccharose and galactose, the latter originating in the decom;

position of pectic substances, possibly by the action of an anti-emulsin. In presence of saccharose and invert sugar, raffinose may be determined quantitatively

by the

optical

method previously described (Saccharimetry),

or

by the method devised by

Ofner (1907), who extracts the whole of the raffinose with pure methyl alcohol, evaporates the alcohol, hydrolysen the remaining syrup for 3 hours on the water-bath with 3 per cent, sulphuric acid, and then precipitates the galactose as methylphenylhydrazone, which is quite insoluble and can be easily weighed ; the corresponding weight of raffinose can then be calculated. An exact determination of raffinose in sugar, which almost always contains
less

tion in saccharose

than 0-5 per cent, of it, is very difficult. The presence of raffinose in small proporis regarded as probable if the ratio between non-sugar and ash is less
1-5.

than

D.

TETROSES
is

MANNOTETROSE, C 24H 4aO 21

tose, 1 of fructose,

and

1 of

found in manna, and yields 2 on hydrolysis. glucose

,

inols. galac-

E.

HIGHER POLYOSES
Gum, Glycogen,
Cellulose

Starch, Dextrin,

These are not, or but slightly, sweet, and are amorphous and, in some cases, insoluble in water. On hydrolysis they usually give either pentoses alone or hexoses alone, and hexoses being formed together only in rare
instances.

pentoses Their molecular weights are unknown, but their molecules are very n (C6 12 6 ) 1) (n 2 large and are represented by the general formula, where n is very large, this approximates to (C 6 10 5 ) H which represents the

results of analysis.

525)

STARCH, (C 6H 10O 5 )^. It has already been pointed out (pp. 133, 140, and how starch originates in vegetable organisms and how it passes from the
;

leaves,

where it is formed under the influence of chlorophyll and of light, to in cryptogams, which the reserve stores of the plants (tubers, seeds, etc. have no chlorophyll, starch is not formed). It is a carbohydrate, and occurs in white granules insoluble in both cold and hot water, although with the latter it swells up, forming starch paste, which is Coloured a characteristic deep blue
VOL. n.

38

586

ORGANIC CHEMISTRY

by

Starch paste is dissolved by acids, forming glucose and diastase (see p. 532), (see pp. 133, 140, and 201), forming intermediate by polyoses with less complex molecules (dextrins) and then maltose and isoStarch does not give the reactions of the monoses (i.e., with maltose. Pehling's solution, phenylhydrazine, etc.), and hence contains no free carbonyl
dilute iodine solution.

groups, so that (C 6 10 4
.
.

(C 6 10 6 0) (0 C 6 10 5 ), where there is only one dicartwo such linkings are inadmissible, bonyl linking, possibly in the middle since otherwise decomposition should give, together with df-glucose, another substance with two carbonyl groups. Such a substance has, however, never been obtained. The molecular weight has not been established, but it must be very high, and, according to Syniewski, the formula is C 216H3 60 180 the molecule consisting of twelve C 18 nuclei. The shape of the starch granules varies with the plant from which they are
:

its

rational formula (see pp. 523, 538) will be

C 6H 10

4)

obtained, so that it is possible to ascertain the origin of starch by observing see Figs. 378 it under the microscope (with a magnification of 200 diameters to 385). 1 When examined in polarised light, between crossed nicols, potatostarch granules, having a stratified structure and an eccentric nucleus, show a black cross like the multiplication sign ( X ) (Fig. 386), while other stratified starch granules with a central nucleus also behave like doubly refracting this is ) crystals but show a black cross more like the sign of addition ( seen well with wheat starch (Fig. 387). Starch granules show their stratification better under the microscope if they are treated with a dilute solution of chromic acid containing a little sulphuric acid, and in some cases dark radial
;

striae also

appear.

is given to starches from cereals, leguminosesR, acorns, chestnuts, etc., and that of starch to those from potatoes, manioc root, arrowroot, palm stems, sago, etc., but chemically there is no difference. The flour of these plants contains more or less gluten (wheat, 12 per cent. rice, 3 to 5 per cent.), and wheat yields 55 to 65 per cent, of starch maize, 60 to 65 per
;
;

Commercially the n&me flour

cent.

rice,

38 per cent.
1

70 to 73 por cent. beans, peas, and

rye, 45 per cent.

lentils,

oats, 32 per cent. about 38 per cent. 2

;

barley,

Starches of different kinds

may

possess granules of similar form, but

may be

distinguished

by the varying mean magnitudes of the granules, although in most kinds there are a greater or less number of granules much smaller than the average, these being sometimes grouped together in ovoid or bunch-like masses (e.g., rice, oat, starch, etc.). The average sizes of the
granules of the different starches, in micromillimetres
(1) (2) (3)
(4)
(/u),

are generally as follows

;

Wheat
Barley

large granules, 26-29 ju,

20/u, 36/x,

more common

small granules,

7/u

4-5/x
6/u

Rye:
: :

(5)

(6)
(7) (8)
2

Potato 20^ 60-80,*, Rice bunches, 20/u, of several granules ; separate granules, 5/u. Oats: ,, fy 30/u, Maize largo granules, 18- 20/u, more common ; small granules, 5/u
:

Buckwheat

9/u

(polyhedra)

/*

The mean percentage compositions

of potatoes, wheat,

and

rice are as follow

Potato starch in particular purification, 0-165 per cent, of

P2

always contains, as a component resisting elimination by any of ash, and it has been 6 corresponding with 0-35 per cent,
,

suggested that starch consists of the molecular complex, (C

Hj O 5 )n,PO^-Ov

OH

^n

being 200.

VARIOUS STARCHES

587

FIG. 378.

Kice starch.
(a)

FIG. 379.-

Maize starch.
;

FIG. 380.
part.

Buckwheat

starch.

Free granules

(6)

horny

FIG. 38 L

Oat starch.
;

FIG. 382.

Rye

starch.

FIG. 383.

Wheat

starch.

Cellular tissue

(6) free

granules.

FIG. 384.

Barley starch.

FIG. 385.

Potato starch.

FIG. 387.

Wheat

starch in

FIG. 386.

Potato starch in polarised

light.

polarised light.

38 --2

588

ORGANIC CHEMISTRY
when

The specific gravity of potato starch, when air-dried, is 1-5029, and dried at 100, 1-6330. When heated above 160 it is transformed into dextrin.

In Italy starch is extracted principally from rice, maize, etc,, but in should always have a supply exclusively from potatoes. A starch factory -of pure cold water, not very hard and free front iron. contain about 20 per cent, of starch (minimum 18 per cent., Fresh mature

MANUFACTURE.

Germany almost

potatoes 21 per cent.), the proportion being determined sufficiently exactly by a very in 1837 by Berg, applied in 1845 by Balling, and improved rapid physical process, proposed the specific in 1880 Behrend, Marcker, and Morgen. An exact relation exists between

maximum

by

and gravity of potatoes and their starch-content,

it

has been found that the difference

FTG. 388.

FIG. 389.
is

constant (the proportion between the total dry substance (S) and the starch -content (F) of the dry determination Thus a 5-752 on the is N cent.). of non-starch, per average N. Further, if the relation between matter gives the proportion of starch, since F = S 1 F and the specific gravity is determined once for all, a Table can be prepared showing be determined the or from of starch specific gravity, which can the proportion of dry matter from the loss in weight of a given weight of potatoes in air (5 kilos) when weighed immersed is 400 grins., the loss of weight will be 4600 grms. in water if, for instance, this weight
9
;

WASHING OF POTATOES
and the
specific gravity

589

5000 : 4600 1-087, which the Table shows to correspond with of the balance shown 15-4 and matter of 21-2 per cent, per cent, of starch. By means dry can be in Figs. 388 and 389 or of the Reimann or Schwarzer basket steelyard the potatoes in air and in water at 17'5. To calculate the practical yield the value
rapidly weighed

FIG. 390.

FIGS. 391

AND

392.

FIG. 393.

diminished by 1 -5 per cent., since part of the starch is converted, given in the Table should be small extent in potatoes soluble into sugar, which may also exist to a during extraction, which are either not too ripe or too old. The is most washing of potatoes in starch factories out in machines of important, and is carried various types. The first washing, to remove the soil and stones, which arc present to the extent of about 8 per cent., can be done in the machine shown in Fig. 105 (p. 142) or in transused for sugar-beets porter channels like those The potatoes are then (see Figs. 318-320). an inclined Archimedean screw in a raised

by

the washing (see Fig. 321), of water in a being repeated with copious jets bottom long vessel having a concave perforated and fitted with vaned stirrers, which are someperforated channel

FIG. 394.

times furnished with brushes (Siemen's washer, vessel in the opposite direction to that taken by Fig 390). The potatoes pass along the the at extremity where the washed potatoes emerge. the water, which is introduced clean on an average, 20 cu. metres of 40 tons of potatoes per 24 hours requires, The
of

washing water per hour. The rasps used to convert the potatoes into pulp, by rupturing

all

the starch-containing

590
cells,

ORGANIC CHEMISTRY

consist of a number of saw-edged steel plates fixed radially round a drum which has a diameter of 50 to 60 cm, (Figs. 391 and 392) and rotates at a speed of 800 to 1000 revo-

lutions per minute. The Angele rasp (Fig. 393) consists of such a drum working in a cylindrical casing, which in some forms has a saw-toothed inner surface (Schmidt rasp, Fig. 394),

FIQ. 395.

FIG. 396.

FIQ. 398.

the potatoes from the feeder being forced against the drum by means of an adjustable wooden compressor, A, and the resulting pulp drawn between the two indented surfaces. clean and washes the pulp into a tank underpowerful water-jet keeps the saw-edges from which the starch has been removed (100 tons of potatoes give 3 to 4 neath. The

pulp tons of dried residues)

still

contains unaltered starch

cells,

and as a

loss of 2 to 3 per cent.

PURIFICATION OF STARCH
of starch

591

the pulp is passed into ordinary horizontal stone mills like those used in flour-mills, the stones having a diameter of about a metre and making 150 turns per minute. The Champonnois rasp, used in France, is composed of a drum, (iigs. 395 and 396), formed of a number of saw-blades with the teeth turned inwards ; the washed potatoes enter by the feeder, J, and are forced against the saw-edged periphery by the blades, F, which are rapidly rotated by the pulley, H. A water-jet washes the supplied at pulp between the saw-blades into the vessel, JV, below, loss
result,

would thus

spurting being prevented by the casing,

by

factories, however, Uhland has suggested the replacement of the mill by a special machine which completely disintegrates the remaining starch-containing cells without rupturing the fibres* This machine consists of a horizontal cone of cast-iron, either channelled or edged (Figs. 397 and 398) and enclosed in a casing of similar shape by means of a screw regulator, F, the distance between the cone and casing can be Fia. 399. varied. The coarse paste is introduced by a hopper and fed on to the cone, (7, by the blades, ft being subsequently discharged through the channel, R. In order to separate the starch granules from the residual pulp, which holds in solution the vegetable juice and in suspension the cellular residues of the vegetable tissues, epidermis, etc., the pulp is passed immediately (to avoid on to copper sieves of various ^^^^^^-^^^^ types (usually semi- fermentation) cylindrical and several metres in length) ; these retain the residues, while a water-spray, helped by suitable scrapers, carries the starch granules through the meshes
;

For large

(see.

399); the same scrapers, which are arranged helically, carry the exhausted residues to the far end of the sieve and keep the latter clean. When these operations are carried out properly and in large works, the total loss is not more than O3 kilo of dry starch on 100 kilos of washed potatoes; these losses are detected

transverse section, Fig.

by

FIG. 400.

estimating chemically the

residues.

starch in the ultimate exhausted

milky liquid collected under the sieves also contains, in addition to starch, small proportions of colouring and gummy matters, proteins, dextrin, and very fine particles of epidermis, sand, etc. In order to separate these impurities, the starch-milk is introduced into large concrete vessels, where the sand separates in a few minutes. The liquid with the suspended starch is then removed to another vessel, where the whole of the starch separates after a rest of 10 to 12 hours, but in some cases the starch is subjected to levigation with a gentle current of water in a number of vessels, in which the starch forms successive The water and the dissolved impurities are deposits.
readily separated, either during or after standing, by means of a floating syphon consisting of a funnel joined to an india-rubber tube (Fig. 400). The volume
of the deposit tanks is taken^o be about 1 cu. metre per 100 kilos of potatoes treated.

The

In some starch factories the starch from the milky liquid by a kind of

is still

separated

levigation on in-

clined planes, the liquid passing slowly along large wooden or cement channels, 30 metres long, 1 to 3 metres wide, 50 to 60 cm. deep, and with a slope of 3 FIG. 401. to 5 mm. per metre. The coarser starch, together with a little sand, is deposited in the first parts of the channel ; then comes the best starch, while the smallest granules, mixed with a few organic impurities, are the last to settle.

The water which emerges from the end

of the channel is passed through two or three depositing tanks before being rejected. In order that the working may be continuous, two channels are always employed, one being in use while the starph is being removed from the other. The channels are fed from large reservoirs provided with stirrers so that the density of the starch suspension may be kept constant and uniform (3 Be"., the

592

ORGANIC CHEMISTRY

The litres per minute per 2-5 sq. metres of channel surface). being fed at the rate of 6 be channel of the repeating by last first and purified the may from crude starch portions mass composed the levigation, but that obtained from depositing tanks forms a compact intermediate an little a with purer layer, mixed sand, of coarse of a lower layer granules wash the and a grey uppermost layer mixed with organic detritus. It is indispensable to colour. For this starch quickly, as in time the impurities impart to it a pale yellow starch the so-called green starch (i.e., impure, moist starch)-~is purpose the layer of blades (Fig. 401) covered with double its depth of water, a suspended stirrer fitted with long surface the to lowered being then the first more of the starch;
impure layer is thus stirred up so as to form a dense milk of 4 to oV 5 Be., this being deposited in an on the adjacent wooden vat or
inclined

channel.

The

middle

purer layer is then stirred up the suspension removed, and so on. In these wooden vats (see is repeated, Fig. 401) the stirring
this operation

and

._

FIG. 402.

a perfectly white starch

is

obtained, the

it is to be acidified with sulphuric acid until keeping'it under water slightly contains for example, for manufacturing glucose, green starch, which is used, in ce ntrifuges similar to removed be can of this 65 per cent, of water; part retain the coated inside with a fine cloth to for sugar (p. 565), the perforated drum being contain* it as off of the cake of starch is scraped granules. The superficial layer imputes with a ; then discharged below and the remainder (with 35 to 40 per cent, of moisture) tea are The centrifuges in diameter 50 kilos of starch are obtained.

by

drum 80 cm.

dense suspension of the starch of 20 Be.

sedimentation vessels
is

mixed

to

The impure grey starch a dense milk and passed through

^^!?

fine silk sieves,

^^
which

retain the detritus

sieves

and then and to increase the whiteness

to other finer solid proteins, etc., the sieved milk being conveyed action bacteria To vats. prevent to the inclined channels or sedimentation solution calcium of more bisulphite or kilo 0-5 of starch,

and

oases sulphurous acid is used) is soda in small proportions, sulphuric acid or caustic reaction to the final starch and starch in the tanks, but they impart a faint the of deposition of frozen or bad potatoes, where the treatment the in them only it I advisable to employ with dilu e and turns yellow. Bleaching is sometimes effected prSluctTeSy after a few acid ; with sulphuric filtered calcium hypochlorite solution (1 300), together unt,l the water cold of abundant an in supply tTe starch is washed *' reactor, of yellow in the starch may be corrected by slight oTthe chlorine disappears. The last trace ete. Prussian blue, carmine, blueing with ultramarine, indigo cubical or similar cakes, the mass or cereal starch is to be prepared in When

Lie

sometimes added to each cubic metre of

These reagents" as well

he milk facilitate the

fcJLu

Su

eoZt,

potato

DRYING OF STARCH
from the sedimentation tanks

593

above each mould to fill it ; when hopper travelling on a suspended iron rail and stopping and the air-compressor started. With closed are all the moulds are full, they hermetically a suitable machine the smooth cakes are removed whole from the moulds, and as they contain very little water, the time required for drying is considerably shortened. Modern plants make use of another arrangement devised by Uhland (Fig. 404). Here with the moulds are fitted inside with a rubber bag with a perforated base and covered a purer starch, while the moulds can be to the walls and this fits cloth
;

is introduced into moulds of galvanised or tinned iron with 16 cm. in each direction) ; these are either enclosed in are cubes bases (the perforated evacuated cases or, as Uhland suggested, subjected to considerable air-pressure, so as batteries to remove the water as far as possible (see Fig. 402). Fig. 403 shows how the fills a of moulds are arranged in large factories ; the dense starch-cream from the vat

closely

gives

thoroughly cleaned after each operation. The drying of the starch is carried out in hot-air desiccators, which readily reduce the moisture to 20 per cent., which is the customary proportion ; if more moisture is present an allowance is made to the purchaser, but if there is less than 20 per cent, the seller loses, In order to obtain starch of good appearance the temas no allowance is then made. 30 to 35 (at 50 it begins to swell and form lumps) be about should of drying perature and the air should issue from the desiccator almost saturated with moisture after traversing or in cakes. all the frames or gratings on which the moist starch is spread in a thin layer The best arrangement consists of channels or galleries 10 to 12 metres long, 1-2 metre wide, and 2 metres high, through which trolleys carrying the frames pass from one end to the other ; the hot, dry air is injected under slight
pressure in the opposite direction by a large helical fan, gentle suction being applied at the far end if necessary.

Rapid drying depends not

the temperature as on

so

much on

the supply of the proper amount The doors of of pure, dry air. FlG 404. the drying tunnel slide up, and of the trolleys from time to time are opened just sufficiently to allow of the entry and exit
-

driers consisting of a number of It has recently been proposed to employ mechanical while in some cases drying stories fitted with endless bands, or of long revolving cylinders, residues 151, p. 183), time and Fig. (see with as distillery been in a vacuum has practised increased. the output consequently greatly space being thus economised and it is passed first into The dried starch forms friable lumps, and to obtain it in powder mills. For the use of in those to similar employed grooved cylinders and then into sieves 269. Microscopical appearance, see p. 587. ball-mills, see Vol. I., p. 652 ; this Vol., p. of starch present in potatoes, Yield of Starch and Treatment of Residues. Of 20 kilos into the residues. The 17 to 18 are usually obtained in the pure, dry state, the rest going and epidermis the contains parenchyma 0-5 moist pulp, freed from starch (within per cent.), with aqueous juices. of the potatoes, which are composed largely of cellulose saturated is sometimes The pressed pulp (about 16 per cent, of the weight of the potatoes), which and contains 50 to dried (it then constitutes 3 to 4 per cent, of the weight of the potatoes or mixed with bran, chaff, etc. 60 per cent, of starch), forms a good cattle-food, either alone " for (see p. 183) or for beet-pulp (see "grains It is dried in the vacuum apparatus used 0-017 per salts (0-06 per cent. 2 contain waters waste The potash Fig. 335, p. 553). 0-17 per cent, 0-12 cent, gum per 0-24

(every hour).

cent.

and may be used for irrigating pasture land; if it These waters are readily clarified by colloidal fermentation. digested quickly it undergoes aluminium hydroxide. The moist, non-pressed pulp has the following percentage oompou11-2 ; cellulose tion : water, 86 ; protein, 0-7 to 0-9 ; fat, 0-1 ; starch and extractives,
cent, nitrogenous substances)

P2

0-1 per cent, ash

per

sugar

+ +

is

not

to 65 per cent, of Since wheat also contains, in addition to 56 the renders latter the of preparation of the starch, 12 to 16 per cent, of gluten, the separation soluble the fermentation process (Halle) the gluten is rendered starch more difficult.

WHEAT

STARCH.

By

594
and consequently
manner.

ORGANIC CHEMISTRY
lost,

so that only wheats containing

little

gluten are treated in this

The non-fermentation process, in which the gluten is recovered, is the one usually employed, more especially because no large amount of bad-smelling liquor is formed, as is

the cas$ with the other method. In the fermentation process the wheat is cleaned and steeped in water in apparatus similar to that used with barley to be malted (see Fig. 155, p. 195). When sufficiently soft to be squeezed between the fingers, the wheat is passed between a pair of smooth rolls which break the epidermis without crushing it too much. The mass is placed in large tanks and covered with the acid liquid from a previous fermentation, alcoholic fermentation starting in a few days and being followed by acid fermentations (lactic, butyric, acetic, etc.) with evolution of gas ; the fermentation is complete in 10 or 12 days in summer or 20 days in winter, the liquid being then clear, yellow, and covered with mould, but not yet smelling. The acid liquid is decanted off, and the starch separated from the bran in a The solid residue serves as cattle-food, finely perforated drum under a current of water. while the starch-milk is allowed to deposit in the ordinary vats, where it is washed ; it is

then conveyed to the fine sieves and inclined channels (see under Potato The Starch). pure starch separated in this way should, however, contain a small proportion of gluten, since, during the drying, this facilitates the formation of so-called crystals desirable in the commercial product. The crude starch-milk can be purified more rapidly in the Fesea-Decastro centrifuge, which has a non-perforated drum. The purer starch is deposited first in a compact layer on the inner surface of the basket and the less pure starch-milk remaining is discharged
automatically before it deposits its impurities, new starch-milk being introduced and treated similarly until a thick layer of moderately pure starch is obtained. The .centrifuge is stopped, the water discharged from the middle, and the yellowish, superficial portion of the starch, which contains gluten, etc., removed with a sponge. The starch is then
discharged, mixed with water in a vat fitted with a stirring arrangement, and the starchcream, sometimes after a little ultramarine or indigo carmine has been added, introduced into the suction moulds.

The drying of the cakes (see Potato Starch) is carried out immediately (to avoid mouldgrowth), and in winter-time this is done in an oven, the temperature of which is raised from 30 to 75 ; in the summer the drying is begun in the air. When a certain stage is reached in the drying process, the cakes shrivel at the surface ; this less pure portion is removed and the cakes broken into smaller blocks, which are wrapped in paper and dried further. Under this treatment the mass gradually assumes the radiating structure. 1 In the non-fermentation process the crushed wheat is treated with a stream of water,
being manipulated meanwhile in the form of a paste, which is placed on perforated channels or sieves so that the whole of the starch is gradually removed and the pasty gluten left. The starch is then deposited in the ordinary manner, while the gluten is transferred to
rotating cylinders with their inner surfaces covered with points, which retain the pure a the bran is washed away with water. gluten According to a suggestion by Fesca, the dry ground wheat is mixed with water and the paste introduced into a centrifuge with a perforated drum, the starch being
;

by a continuous current
operations are as usual.

of water, while the gluten remains in the centrifuge

separated the further

The Fesca

process

is

very simple and more convenient than that

the flour with ozone, chlorine, bromine, sulphur dioxide, etc., but better results are obtained with nitrogen peroxide (N0 2 ). According to some observers, flours bleached in this way begin to darken earlier, irregular staining taking place. The process which has given the most favourable results and has been largely applied in America and before the War also in Italy, is that of Wesener (Ger. Pats. 209,550 and 232,204), according to which flour is bleached instantaneously in contact with a current of air containing mere traces of nitrosyl chloride (see Vol. I, p. 380) ; 1 kilo of the latter is sufficient to bleach 100 tons or even more of flour. 2 In presence of a little water and at a moderate temperature, the gluten thus obtained undergoes a slight fermentation and becomes liquid when dried in thin layers on metal plates, this is obtained in transparent sheets, which are used as a glue in the manufacture of boots. Or the gluten is mixed with 5 per cent, of powdered salt and made into strings in presses ; the strings are dried in an oven, when they become friable and readily convertible into flour, which is used in the preparation of dough and serves as a foodstuff when mixed with other products.* The gluten contains 75 per cent, of nitrogenous substances, 21 of non-nitrogenous substances, 1 to 5 of fat and 1-5 of ash.
;

Wheat flour attains its maximum whiteness 30 to 60 days after grinding and retains it until about the sixth month, after which it slowly darkens. In America various patents have been filed, during the last few years, for obtaining this maximum whiteness more rapidly by treating

RICE STARCH
described above.
first

The average yields, calculated as percentages on the wheat, are as follow quality starch, air-dried, 54 gluten flour, 12 bran, mixed with a little gluten and
:
;

matters dissolved in the waste water, 14. ; Microscopical appearance, see p. 587. RICE STARCH. On the average, rice l contains 77 per cent, of starch and less gluten (4 to 5 per cent.) than wheat, but the starch is more difficult to separate (for 1 part of gluten about 1 part of starch is lost). Of all the processes which have been suggested, that devised
starch, 19-5
still gives the best results. Use is generally made of waste rice (broken rice, costing 14s. to 24s. per quintal according to the season), which is softened in a large galvanised iron or iron steeping cylinder with a conical base, by means of dilute solutions of caustic soda (0-3 per cent, in winter, 0-5 per cent, in summer). Here it is left for 5 to 15 hours, being mixed every 3 to 5 hours with a vigorous air-jet ; in winter the alkali solution is heated to 20. The duration of the steeping varies with the quality of the rice and with the season of the year Italian rice requires 5 to 6 hours and Rangoon rice as much as 14 hours, the soda solution being changed in the latter case after six or eight hours. After steeping, the rice can be readily crushed between the fingers. The dissolved gluten (20 to 30 grms. per litre) is separated from the alkaline liquid simply by acidification with sulphuric acid (in order to bring the gluten into such a condition that it can be filtered in a filter-press, the temperature is raised to 80 or 1 kilo of lime is added per cubic metre of the alkaline solution). In some cases the gluten is extracted with an
;

by Orlando Jones in 1840

alkaline liquid in an apparatus similar to beet-diffusors (see p. 572), while in others the is carried out in a vacuum with agitation. The swollen and softened rice, cotainirig a little of the alkaline solution, is then ground between horizontal millstone'

extraction

liquid paste with 22 to 26 per cent, of starchy matter being obtained ; this is pu up into large square cement tanks provided with stirrers (see Fig. 401), where it is with more dilute caustic soda solution (0-2 per cent.), care being taken in sum

the temperature does not rise sufficiently to admit of fermentation. In thep separation of the starch from the liquid occupies about 1| hours afte*
stopped. The liquid is decanted and the residual starch mixed with a 0-2 per cent. solution and left for 45 minutes to settle. In some r is repeated a third and fourth time, the thin surface layer of yellow staris
fr

NaOH

etc., being scraped off each time before adding fresh washing w*>* the first and second settlings are ground again in the stone mil other starch. After the final washing, for which water is '1

to other

cement depositing tanks, being previously

p*

through revolving perforated cylinders sj obstruction by impurities or by solid gluten (the gh

1 Hice (Oryza saliva) is an annual plant belongi India and, according to some, to Ethiopia. In E> also in Spain and in the south of Russia, particvf it is grown in the moist soil of warm, rainy regie in Florida and Southern Carolina. In riee-plf almost stagnant water, and, on account of the be at some distance from any habitation ; intense heat of summer. After the harvest t' machines (threshers), but still retains the g separated from the residues by means of con between two light, horizontal, stone discsin this way the husk is remover revolves separated from the rice by means of vertic? the bottom of the mortar filled with the the other, and the husk removed. The means of a simple vertical mill similar making 30 to 40 turns per minute. [ apparatus, the inner cone of which is pi at the rate of 200 turns per minute, a polished rice is discharged at the bott rice, or 67 of commercial rice, or 63 of u The residues consist of about 1-5 per and 8 -5 per cent, of meal, which is ue of fat, 13 per cent, of total protein, 5 i cent, of ash. hectare of good rice L were quoted for rice in October, 1911 Burmese, 15s. per quintal ; Ostiglia ric 28s. ; first quality Japanese, 26*. 6d.
;
*

silk sieves or

596
chalky water).
forated

ORGANIC CHEMISTRY
drum
in the

The deposited starch is mixed with water and centrifuged in a non-permanner employed for wheat starch, the yellow surface layer being
Finally, it is made into a thick paste (24 Be. or about 50 per alkalinity less than 0-2 per cent.) with water and moulded under an airatmospheres or with a suction-pump giving a vacuum of 600 mm. (see

removed with a sponge.

cent, of water
;

pressure of two

the starch has not a very bright appearance if made into cakes ; immediately it leaves the centrifuge. In this way blocks containing 40 to 50 per cent, of water are obtained, and these are subjected to a preliminary drying in an oven at 40 to 45 after 5 to 8 days the mass contains 30 per cent, of water and is shrivelled at the surface, owing to efflorescence of the gluten, etc. This impure, yellow portion, which may
Figs. 402, 403, 404)
;

constitute 15 per cent, of the whole, is sawn off, washed, centrifuged, filter-pressed, and then either treated again or dried arid sold as a lower-grade product. The remaining blocks are dried further in the air or, more commonly, after wrapping in paper, in an oven, where the temperature is raised to 25 in two days, to 28 on the third, and then slowly to 32 or 35. In 15 to 20 days the mass contains 12 per cent, of water and is crystallised completely in long, fragile needles with irregular surfaces ; these blocks are then exposed to the air (sheltered from dust), the normal moisture-content of 15 to 18 per cent, being thus

acquired (the alkalinity is usually below 0-15 per cent.). According to Ger. Pat. 205,763, the formation of needles is accelerated by drying the moist starch rapidly, grinding and compressing in the moulds the cakes are then wrapped in paper arid placed in the ordinary channel ovens, through which warm, moist air is passed. The starch may be bleached in v ordinary way with sulphur dioxide and blued with ultramarine (about 150 to 200 grins,
;

g added per 500 litres of dense crearn before introducing it into the moulds). Difficulties r ten encountered in the manufacture of rice starch, owing to the readiness with which ation occurs, this leading to generation of gas and to trouble in the settling and * the liquids the remedy lies in increasing the concentration of the alkali employed
;

'e

of sulphur dioxide.
's

waters, cannot be used for

Rice gluten, separated from the various residues and making shoemaker's paste. employed largely for making face powder and almost exclusively for the a gloss being obtained in the latter case by the addition of borax (6 to 8

^ered stearic acid (2 to 3 per cent.), etc. ^icroscopical examination, see p. 587. iizc, which has an average starch-content of 62 to 65 per cent., 9 or 4 days and ground coarsely, the germ and bran ining flour treated several times with sulphurous acid, irch-milk treated as usual in sedimentation tanks, the

The form of the granules is shown on p. 587. %rge quantities as a dressing for textile fibres and
'on
^r,

on starch at

different temperatures of

many

caustic soda, sulphuric acid, calcium hypo-

hate,

Tup

hydrogen peroxide, formic acid, gaseous or malt extract, known in Germany as

rch are used as a dressing in the spinning % thickening material, in the manufacture

he laundry and kitchen, as well as for

us vegetable juices, but

pared

artificially

is always from starch by

of a mixture of products interSeveral dextrins of various >se).

brin,
'

amylodextrin, erythrodexthe molecular weights of various their solutions, use being made inclosed in pure collodion. The

ing a mixture of 4 grms. with 50 c.c. nute until it becomes transparent and after shaking and allowing to cool, the
roperties are satisfactory.

DEXTRIN
values obtained were
to 11,700
;
:

597
;

achroodextrin, 8200 amylodextrin, 20,500 to 22,000 ^-dextrin, 950. erythrodextrin, 3000 to 6800 According to some, dextrin has a marked aldehydic character, and hence gives all the reactions of the inonoses, including those with phenylhydrazine and Fehling's reagent, while others hold that the aldehydic character is feeble, and This others, again, that Fehling's solution is not reduced, even on boiling. diversity of view is explained by the great difficulty of separating chemical in any case all the dextrins individuals from the mixtures containing them reduce solution to a greater or less extent. commercially Fehling's prepared Dextrin is not fermented directly, and diastase does not transform it entirely into fermentable sugar (maltose), 15 per cent, remaining unchanged, although this slowly becomes fermentable under the prolonged action of diastase (see
;
;

p. 141).

Dextrin

is

known

gum,

artificial

also by various commercial names (vegetable gum, starch gum, gommeline, British gum, etc.), and forms a light powder

having a slight smell of new it is white, yellowish, or bread even brownish, according to the
;

purity, the method of preparation

and the purpose

intended.
in

It

is

which it is sometimes sold

for

semi-transparent, yellowish lumps. It dissolves completely in water when pure and has a high rotatory power ( [a] it is insoluble in about 194)
L)

iodine solution it gives a reddish coloration, and boiling dilute hydrochloric or sulphuric acid converts it into
alcohol.

With

glucose, while malt transforms it into maltose with concentrated

;

__
F TG>
405,

nitric acid it gives

oxalic acid.

Commercial dextrins often contain a little starch and glucose, so that they then give a violet coloration with iodine and reduce Fehling's solution in the hot the specific rotation varies from 125 to 225.
;

According to the ordinary Heuse process, 1000 kilos of starch are moistened with 2 kilos of nitric acid of 40 Be. diluted with 300 litres of water, the paste being made into loaves which are dried in the air, ground finely, and heated for about two hours at 100 to 120. For this purpose the starch is either spread in thin layers on a number of trays, which are arranged in a suitable oven, or placed in a circular Uhland apparatus the mass is mixed (Fig. 405), the base of which is heated with superheated steam while continually by means of a stirrer fitted with a number of pegs. If the temperature is raised to 130 to 140, the duration of heating is shortened, but yellow and not white dextrin is
obtained.
Dextrinification is complete when the product is entirely soluble in water and gives no longer a blue, but only a reddish brown colour with iodine solution. The preparation of dextrin by torrefying starch is, however, a very simple process, which can also be carried out in the Uhland apparatus, the starch being stirred and heated at 180 to 200 by means of superheated steam until it assumes a brownish yellow colour

MANUFACTURE.

and gives the reactions just mentioned. cold water immediately dextrinification

The steam -pipes

is

are utilised for the circulation of

complete.

Its moisture-content is adjusted to

about 12 per cent, before it is marketed. To distinguish commercial dextrins from gum arabic, the aqueous solution is treated with either oxalic acid or ferric chloride in the cold or concentrated nitric acid in the hot dextrin is not altered in this way but the gum becomes turbid or gelatinises. Further, dextrins are strongly dextro-rotatory, while gums are almost always laevo-rotatory.
:

598

ORGANIC CHEMISTRY
H
,

GUMS. These are also polyoses (C 6 10 6 ).T which are frequently formed in plants and are soluble in water or swell up, giving viscous, sticky liquids ; they are insoluble in alcohol and other solvents of the resins. Gum Arabic is excreted, from December to May, as an
adhesive juice from the bark or, better, from the roots of certain African acacias, 3 to 5 metres in. height after drying, it has the sp. gr. 1487, and the various components vield In Egypt these acacias occupy entire forests, d-glucose and arabinose on hydrolysis. The natives make a especially in the provinces of Kordofan and Gedda (White Nile). number of incisions in the roots, and the liquid which issues condenses in the air into nutlike masses, these being detached before the commencement of the rainy season. The grains have the colour of amber and become white when exposed to the air, so that there are two qualities of the gum. It is used in large quantities by pastrycooks and in textile
;

dyeing and printing, and generally as an adhesive. A similar type of gum, obtained in abundance from Senegal, issues from certain wounds of Cherry- and peach-trees, while Gum Tragacanth is extracted from certain varieties of Astragalus in Serbia, Syria, Persia, etc., and, after being rendered mucilaginous by prolonged contact with water, is used as a thickening material in calico printing, etc. The value of a gum is ascertained by determining the viscosity of its solution (see
p. 91).

GLYCOGEN or Animal Starch is also a polyose (C 6 10 O 5 ),,, found principally in the blood and liver of mammals. It is a white amorphous powder insoluble in cold water, and It is converted into maltose by an enzyme, is coloured reddish violet by iodine solution. whilst on the death of the animal containing it or on boiling with dilute acids it is transformed into d-glucose.

CELLULOSE,
The actual molecular magnitude
is
1
,

(C 6

H 10

5 )W

but

been established it may be regarded as a multiple of Like starch, certainly very great. C 6 10 5 but, while starch is able to undergo transformations (into dextrin, maltose, etc.) in the vegetable organism, cellulose represents a stable complex. Together with lignin, cellulose forms the principal component of the cell-walls
of cellulose has not yet

It occurs, for instance, in wood and cotton, in different degrees of in different vegetable organisms the cells assume distinct and while purity, characteristic forms, readily recognisable under the microscope (see Part III., Textile Fibres). Cotton-wool and Swedish filter-paper consist of cellulose in an of plants.

almost chemically pure state. 2 Pure cellulose forms a white amorphous mass and can be obtained by treating cotton (flocks) successively with hot dilute caustic potash, hot dilute hydrochloric acid, alcohol and ether, and drying at 125 to eliminate the water with which a small part of the cellulose is hydrolysed.
1 In order to determine at least minimum values for the molecular magnitudes of the polyoses, when the latter Skraup (1905) applied to these compounds a reaction given by the bioses are treated with acetic anhydride and dry hydrogen chloride gas, they give chloracetyl-derivatives without undergoing hydrolysis, and the chlorine-contents of these derivatives indicate the
;

molecular weights. In this manner the molecular weight of cellulose is found to be at least 5508, that of soluble starch 7440, and that of glycogen 16,350. 2 From the crude cellulose or woody parts of plants, J. Konig (190(5) separated four components mineral acids (1) hemicellulose, which is hydrolysed by dilute giving the following reactions insoluble in ammoniacal copper oxide solution (2) cutin or suberin, which is soluble in alkali but
:

oxidisable by weak oxidising agents ; (4) true cellulose, insoluble in dilute acid or alkali, soluble in ammoniacal copper oxide, not oxidisable by hydrogen peroxide. The part of the cellulose which enters into the formation of the cell, but gives no glucose on hydrolysis, constitutes the hemicellulose group the hemicelluloses of lupins, certain lichens,
(3) lignin,

which

is

give galactose, xylose, mannose, etc., on hydrolysis. Cross and Sevan divide celluloses into four groups : (1) celluloses which are hydrolysed with or ketonic), the characteristic type difficulty and contain no active carbonyl groups (aldehydic of this group being the cellulose of cotton ; (2) celluloses which contain active carbonyl and, sometimes, methoxyl groups, and give furfural when hydrolysed with hydrochloric acid such are the celluloses of wood and straw ; (3) celluloses (or hemicelluloses} which are easily hydrolysed
etc.,
; ;

The furfural and methylfurfural formed by the celluloses of group (2) may be derived from the pentosea yielded by the pentosans of the celluloses or from the furfuroids which occur in abundance in vegetable organisms, and although they contain no pentosans yet give furfural
(see p. 528),

(4)

complex

celluloses.

CELLULOSE
(sp.

599

Cellulose does not dissolve in ordinary solvents, but is completely soluble in concentrated zinc chloride solution, concentrated sulphuric acid, nitric acid acid (which converts it completely into gr. 1 -52), 41 per cent, hydrochloric

glucose in 48 hours), hydrofluoric acid, phosphoric acid, xanthic acid (C 2 5 CS SH) or, best of all, in an ammoniacal solution of copper oxide (Schweitzer's reagent, prepared by dissolving freshly precipitated, well-washed copper hydroxide in concentrated ammonia solution in the proportion of CuO to 4NH 3 4H 2 0) ; from this solution it is reprecipitated as gelatinous hydrocellulose by acids, alkali salts, or sugar solutions, Hydrocellulose dissolves in

a mixture of caustic soda and carbon disulphide, and

gelatinous state
artificial silk.

by

salts, etc.

These

is reprecipitated in a used for the manufacture of are jellies

for cellulose

solutions of thiocyanates constitute good solvents thiocyanate, for example, gives viscous solutions from which water separates gelatinous cellulose. In dissolving in any solvent, however, cellulose generally dissociates into simpler molecular complexes, which cannot be converted into the original cellulose but give hydro- or oxy-celhilose,
;

Dubosc (1906) found that

ammonium

acids, alkalis, and results in the gradual hydrolysis of cellulose, so that, while before with iodine solution, after the hydrolysis only a brown colour is obtained action of concentrated sulphuric acid a blue reaction is given ; in this reaction

which show more marked reducing properties. 1 The prolonged action at moderate temperatures of
.

enzymes

the cellulose swells and dissolves into a kind of paste, and the action on this of water separates substances similar to starch (amyloids). If the hydrolysis is carried further the reactions of the dextrins may be obtained, dilution with water and boiling then resulting in the formation of monoses (hexoses and
2 Cellulose may hence be regarded as composed of complex anhypentoses). drides of hexoses and pentoses, and recent investigations indicate that the behaviour of cellulose is best explained by regarding it as a colloid containing

basic hydroxyl ions and some groups with acidic hydrogen ions, others with the reactions of cellulose with both basic and acidic non-dissociated groups substances are explainable in this way. Cellulose has alcoholic characters, the hydrogen of each of the hydroxyl
;

groups being replaceable by an acetyl- (see p. 381) or nitro-group, etc. Not more than three or four hydroxyl groups correspond with each six carbon atoms ; with nitric acid three nitrate groups can be introduced, while with
acetic anhydride,
in presence of sulphuric acid, esters (cellulose acetates) C6 are obtainable (Cross and corresponding with four hydroxyl groups per

Bevan, 1905).
According to H. Ost (1906) the ordinary methods of acetylation always yield triacetates
of cellulose, but hydrocdlulose is first formed as an intermediate product, (C 6 10 6 ) , 2 O, and it is this which forms the plastic triacetate, [C 6 7 O 6 (COCH 3 ) 3 ] n, a O, used as artificial 3 If the action of sulphuric acid and acetic anhydride is carried too far, friable silk, etc.
fl

1 Other solvents for cellulose, as given by Denning (1911), are: concentrated aqueous solutions of SbCl a SnCl 4 , ZnBr a , best in presence of a halogenated acid ; OaCl a , CaBr a , BaCl 2 , MgBr a , LiCl, KBr, in presence of formic acid or of formic and hydrochloric acids together. solution of zinc chloride in concentrated hydrochloric acid dissolves cellulose more easily than aqueous zinc chloride. 2 Numerous attempts have been made to convert wood industrially into saccharine substances and so prepare alcohol (see p. 167), but it was only in 1910-1911 that Flechsig, Ost, and Wilkening showed that cellulose can be transformed completely into fermentable glucose by dissolving it in concentrated sulphuric acid, diluting until the solution contains only 1 to 2 per at 110 to 120 (but not to 126, as was done by Simonsen, since cent, of and then
,

a part

acid, heating Cohol (1912) obtained 25 per cent, of reducing of the glucose is thereby destroyed). sawduf.t substances from by heating the latter under pressure at 125 to 150 in presence of 0*5 to 0'3 per cent, of hydrochloric acid. 8 Cellulose Acetate is soluble in chloroform, tetrachloroethane, aniline, pure acetic acid, The less highly acetylated products are soluble in epichlorhydrin, and boiling nitrobenzene. serves for the preparation of celKtefilm* alcohol, giving a solution which, together with camphor, these films are considerably less inflammable than those of celluloid. The for ;

cinematographs

600

ORGANIC CHEMISTRY
H

acetates of no industrial value are obtained, the ultimate product being a crystalline octoacetate of a biose, cellose or celldbioae (C e 10 O 5 ) 2 , 2 0, which can be liberated from the acetate by hydrolysing with alcoholic potash but is of no value industrially. The rotatory power of cellobiose is 33-7, the solubility of its phenylosazone in boiling water 1 : 135,

and the melting-point

of its phenylosazone 198

it is

thus quite different from maltose

(rotatory power, 142-5 ; melting-point of phenylosazone, 206 ; solubility of phenylosazone in boiling water, 1 : 75). The origin of cellulose in plants cannot be regarded as a condensation of starch ; the latter is probably converted into glucose, which gives cellulose

The preparation of nitrocellulose (pyroxylin, guncotton, collodionon condensation. cotton) has already been described in the chapter on Explosives (p. 286). Cellulose Formate (Blumer, Ger. Pat. 179,590) has also been prepared. At 210 cotton begins to decompose with evolution of carbon monoxide and dioxide, methyl alcohol, acetic acid, acetone, hydrocarbons, etc. (see Distillation of Wood, p. 330).

By

the dry distillation of pure cellulose (Swedish filter-paper) under ordinary pressure,
,

ISrdmann and Schacfer (1910) obtained about 5 per cent, of tar, 42 per jcent. of acid liquors, and a residue of carbon, together with gas containing 66 per cent. CO, 19 per cent. CH 4 from the acid liquors, acetone, formaldehyde, furfural, methoxy11-5 per cent. H 2 etc. furfural, mdltol (C 6 H 6 O 3 which, according to Peratoner and Tamburello, has the con, ; ,

CH O
stitution
I!

C CH
||

3N
)
,

and y-valerolactone were separated.

etc., cellulose

With
(see

lapse of time

CH CO C OH
-

'

or under the action of bacteria,

Coal, Vol.
I.,

pp. 443
1

et seq. ;

and Methane,

p.

undergoes various changes 33 of this Vol.).

Peat, Lignite,

per cent, sulphuric acid, pure cellulose yields only traces of formic and which wood, straw, etc., yield as much as 2-8 per cent., the formyl and acetyl groups hence originating in the lignin. The acetic acid formed during the dry distillation of wood has a different origin from that obtained by heating with very dilute

With hot

acetic acids, of

sulphuric acid.

which contains 0-04 per cent, of ash, has the absolute sp. gr. dissolves to the extent of 0-5 to 0-9 per cent, in 16 per cent, sodium hydroxide solution and, after boiling for 6 hours, to the extent of 2 per cent, in 3 per cent, sodium
Pure
cellulose,

1-58,

and

hydroxide solution. When dry it is an excellent electrical insulator, but its insulating power diminishes rapidly as its moisture content increases in the air. Suspended threads of cotton pass to the anode when a current passes. The hygroscopic moisture varies, with the degree of comminution of the fibre, from 5 to 8 per cent. Pure cellulose remains unaltered up to 150, but at higher temperatures begins to turn brown and decompose if contaminated, even with oxycellulose, it decomposes at a lower temperature. When distilled it gives no methyl alcohol the exothermal process during the distillation occurs at about 290 and is characterised by abundant separation of
;
;

water.

Mineral acids, even when very dilute, hydrolyse cellulose more or

less,

and

if

any

traces

of acid remain during the drying of the product hydrolysis proceeds rapidly, causing diminished strength of the fibre and increased reducing power. Concentrated (or even 63 acid cent.) sulphuric acid transforms cellulose into a colloidal solution ; 69 per cent,

per

gives amyloid

and 78 per

cent, acid parchment.

triacetyl-compound is used for making artificial silk (see later), and is prepared by treating hydrocellulose in the cold with acetic anhydride, a few drops of concentrated sulphuric acid, and a little glacial acetic acid or phenolsulphonic acid. More or less successful attempts have also been made to acetylate cellulose in the hot with of a small acetyl chloride and metallic acetates, the reaction being facilitated by the addition quantity of pyridine or quinoline and, in some cases, of a solvent of cellulose acetate (e.g., acetone,
nitrobenzene, naphthalene, etc.). The following method of manufacture (from Fr. Pat. 347,906) admits of the direct acetylation of cotton textiles and may be taken as an example : 10 kilos of defatted cotton, containing 10 to 20 per cent, of moisture, are heated with 40 kilos of acetic anhydride (containing 0-25 per cent, of concentrated sulphuric acid) and 150 kilos of benzene, at 70 to 75, in a reflux apparatus until a small portion of the cotton dissolves completely in chloroform ; the whole mass is then
,

Cross, Sevan, and Briggs (1907) obtain cellulose acetates easily and cheaply, without preparing of 100 parts of glacial acetic acid, hydrocellulose ; cellulose is treated directly with a mixture 30 of zinc chloride, and 100 of acetic anhydride, the whole being heated for 36 hours at 45. " " Cellulose acetate is largely used as dope for aeroplanes and as a coating for the fabric It forms a good electrica, insulator. of airships to render them impermeable to gas.

pressed and dried.

STRUCTURE OF CELLULOSE
H H

601

The action of sulphuric acid on cellulose varies somewhat with the concentration of the acid, the duration of the reaction, and the temperature. The concentrated acid has
a gelatinising action and dissolves part of the cellulose, which is reprecipitable by water If the action is protracted, the very friable Hydrocellulose, C H or ammonia. 12 2 20 11 2 0], is formed, but, in general, hydrocelluloses of diminishing molecular [(C 6 10 O5 ) 2 , see above) are successively formed. The weight and increasing friability (e.g., cellobiose hydrocellulose formed in the preparation of artificial silk is only slightly friable, and has Since also these hydrocelluloses exhibit rather probably the formula (C 6 H 10 O 6 ) 6 2 O. different behaviour towards dyes, it has been suggested that the name hydrocellulose be the increase of given to that resulting from advanced hydrolysis by non-oxidising acids weight during this change, owing to the addition of hydrolytic water, is 3-5 to 5 per cent., this being lost at above 125, whilst the hygroscopic moisture is expelled at 104. This Cross and Bevan, 1909). On the other hydrocellulose reduces Fehling's solution (Ost hand the name cellulose hydrate or hydracellulose is given to that obtained by gentle alkaline hydrolysis, which produces an augmentation in weight of 8 to 10 here, too, per cent. this hydrolytic water is given up at temperatures above 125. Hydrocellulose docs not reduce Fehling's solution. Schwalbe (1907) measured the reducing power of hydrocellulose towards Fehling's solution. 1
;
,

Cross and

Bevan proposed

for cellulose the formula

or

some polymeride

of this, such as

H
O C'
:

\/ c
\C

--OH

OH

\/H c
C

OH
;C

H
I

OH

OH\/
C/ N
/C
C

\/
(!

OH
/H

C'

^C/ X
OH

etc.,

H
On

OH
it)

H \)H
OH, namely
:

H
|

the basis of the formation of the trinitrate and triacetate, Green (1894) suggested for

cellu-

low a formula (or some multiple of

CH(OH)
containing 3

CH

and

for Jiydrocdl-uhw the

CH(OH) CH formula >O CH(OH) CH

I

CH(OH)

CH

>0

CH(OHk

CH a

;>0, /

CH(OH) 2

CH -OH
2

these constitutions explain the

formation of furfural by the decomposition of cellulose and also the formation, under the action of oxidising and bleaching agents, of oxy cellulose containing ketonic groups which react with phenylhydrazine, reduce Fehling's solution, and admit of direct dyeing by basic dyes Two oxycelluloses are, however, distinguished: the one very similar (e.g., methylene blue). to hydrocellulose and insoluble in boiling dilute alkali, and the other possessed of considerable reducing power and soluble in alkali. The hardening of cellulose in the formation of wood is due to its partial transformation into LIGNIN, which is not yet well defined chemically but certainly contains methoxy -groups, whic-h explain the formation of methyl alcohol and acetic acid when wood is distilled. According to Green, lignin is formed by dehydration of cellulose and would be a polymeride of

CH
I

CH:C

>O >O

CH-OH

but Klason

is

CH-OH

of the opinion that lignin is a kind of glucoside with

two

aromatic nuclei containing mothoxy- and hydroxy -groups, also lateral groups, -CH : CH and CH 2 -OH, besides the fundamental cellulose grouping ; it is probably represented by the formula (C4oUOii) w into which there enters a condensation product of coniferyl or isoconiferyl alcohol. wood contains 26 to 30 per cent, of lignin. Schultze, Tollens, and Konig hold the view Dry that the hard part of wood is formed of cellulose, together with small proportions of pentosans and of lignin. The formation of wood in plants has been attributed by Wislicenus to the colloidal character of the plant fluids which, in the initial phase, transport into the tissues the cellulosehydrogel as a superficial, chemically indifferent substance; in a second phase, the latter is lignified by absorption and surface gelatinisation of the colloidal metabolic substances contained in the sap. Lignocellulose is hydrolysed and dissolved by zinc chloride solution and by ammoniacal copper oxide solution, dilute acids and alkalis also exerting a action. hydrolysing Lignin gives a number of colour reactions, e.g. t with aniline sulphate (yellow), with phloroglucinol and hydrochloric acid (red) ; with potassium ferricyatiide it forms potassium ferrocyanide, and with fuchsine decolorised by sulphur dioxide it gives a red colour ; it fixes various aniline dyes VOL. ii. 39
.

602

ORGANIC CHEMISTRY
to 60
sheets of pure, unsized paper are immersed for a few minutes in sulphuric acid B6. and then washed immediately in a plentiful supply of water, they are
artificial

When
of 60

(artificial parchment), amyloids being formed at the surface. parchments are distinguished from the natural ones by the presence of nitrogen in the latter, and from paraffined paper by the extraction of the paraffin from these by ether. Parchment paper is rendered softer and more transparent by immersion in glycerine or glucose solution. If cellulose pulp is well ground ajid beaten in the hollander until it forms an almost gelatinous pulp, a translucent paper can be obtained which is similar to artificial parchment and, under the name of pergarnin, is largely used as a wrapping for foods and fatty materials this may easily be distinguished from vegetable parchment, which is composed of cellulose hydrate (amyloids) and is hence coloured blue by a solution of iodine in potassium iodide, whilst pergamin gives no such coloration.

converted into parchment paper

These

With concentrated zinc chloride solution, cellulose gives compounds similar to those forms with sulphuric acid papers thus prepared and then superposed and compressed form the so-called vulcan fibre ; this is very hard, impermeable to water, and a bad conductor of electricity ,*and is used for making plaques, tubes, and noiseless gearing. When cellulose is treated for a long time with energetic oxidising agents, it is converted into oxycellulose (C 18 26 16 )a;, which lowers the resistance of the tissues and, unlike cellulose, reduces Fehling's solution and fixes, although feebly, basic dyes and alizarine without a mordant. Hydrocellulose reduces Fehling's solution slightly and is not coloured by basic
it
:

dyes.

When cellulose (spun or woven cotton) is treated in the cold with concentrated caustic soda solution (25 to 35 Be. ), it swells and becomes semi-transparent owing to the formation of sodiocellulose, and treatment of this with a large amount of water converts it into hydrocellulose (see above), the original appearance of the cellulose being retained. In the hot, however, sodiocellulose cannot be obtained (see Part III., Textile Fibres and Mercerised Cotton), prolongation of the action then resulting in decomposition into oxalic acid. Hygroscopic water held by cellulose is eliminated by heating at 100 to 105 ; the water of hydration in hydrocellulose is determined by heating in toluene or petroleum or at

130.

The hydration occurring during mercerisation

increases the weight of the cotton

by

8 to 10 per cent.

PAPER INDUSTRY
in the paper industry, use has been and is still made of all the cellulosic fibres obtained from most widely differing plants, 1 linen and cotton rags, straw, wood,

As prime material
etc.

hemp,

Wood is regarded by Cross and Bevan as an ester (e.g., methylene blue, eosin, etc.) directly. of lignocellulose, derived from cellulose (polyhydric alcohol) and lignic acid (lignin). 1 History of the Paper Industry. The origin of paper dates back to the second century B.C., when the first traces of it were evident in China. In early times races marked their
records and writings on stone, wood, and parchment. In the seventh and eighth centuries the Japanese and other neighbouring peoples learnt how to prepare paper from the bark of various In 1190 trees, this industry then becoming known to the Arabs, but only much later in Europe. paper made its appearance in Germany, in 1250 in France, in 1275 in Italy, and in 1430 in Switzerland. In the East, besides bark, cotton and linen rags were also employed for paper-making. In Italy the first important factory furnished' with grinders and pistons for the preparation of the raw material was erected at Fabriano in 1320. With the subsequent discovery of printing, the paper industry underwent an unforeseen and marked development, and grew to enormous proportions in the nineteenth century. About the middle of the eighteenth century, the pistons and grindstones in use up to that time for treating the raw materials were gradually replaced by the so-called hollanders, which led to an increase in the output and an improvement in the quality of the product. The demand for paper increased largely at the end of the eighteenth century, the form being improved and the price lowered. Mechanics and chemistry came to the aid of the paper manufacturer, and as early as the beginning of the nineteenth century the paste of cotton or linen fibres, mixed in large tanks, was transformed into a thin sheet of paper by means of a revolving, perforated drum, through which the water escaped. It was about 1826 that rudimentary continuous machines were first employed, these supplying an uninterrupted strip of paper a metre in width at a rate of 10 metres per minute. The imposing and complex, but very accurate, continuous machines of the present day give paper as much as 4 metres wide at 150 metres per minute. Great advances were also made in the .chemical treatment of the raw materials. In the first quarter of the nineteenth century, the putrefaction to which the rags were subjected so that

PAPER
It is not possible here to review all the wonderful mechanical improve*, endered paper-making one of the most interesting and important industries of t* eenth century. From the arrival of the wood in the factory to the despatch of the ^ r reams of paper, all the operations are carried out mechanically by means of perfected nachinery, which is not only more rapid in its action but more accurate than hand labour. A description cannot be given here of all the varied and ingenious dressings employed ,o obtain different kinds of paper, or of the mineral loading of kaolin, barium sulphate,

rypsum,
>r

etc.,

with which some papers are so impregnated that the mineral substances

exceed the vegetable matter, to the delight of the tradesman

sausages.

who

sells

gypsum

for cheese

What will be attempted here will be simply a brief description of the various treatments which the raw material is subjected to convert it into paper. Paper factories require a plentiful supply of pure water, which must not contain iron ind should be filtered if turbid. The rags, gathered in places of all sorts and in all conditions, are acquired from the ragnerchants, who separate those of wool and silk, which go to wool factories, etc., and often jort the remaining linen and cotton rags into light and dark sorts. The rags arrive at the paper factory in large bundles, some light and others dark. Preference is given to linen rags, since these give longer and tougher fibres and are used also to improve those of cotton. The first operation to which the rags should be subjected .s disinfection, either by heat (great care being then taken to avoid fires) or by gaseous iismfectants (e.g., by introducing the bales into large iron cylinders, which are then evaluated and filled with formaldehyde vapour). In many factories, however, this disinfection is omitted, the health of the sorters being thus jeopardised. Sorting is carried out by workpeople who spread the loose rags on tables and separate carefully those which are more
,o

they might be more easily disintegrated was replaced by heating with soda and lime in open Then came bleaching of the fibres boilers and, later on, in closed boilers under steam pressure. with gaseous chlorine and subsequently with chloride of lime. The yellow cellulose obtained from straw can also be bleached in this way, and since 1830 has been used in large quantities for the commoner papers and for mixing with rags. Sizing of paper by means of resin soap, although suggested in 1800, only later came into general use. With the rapidly increasing consumption of paper, there came a time of dearth of raw materials ; cotton and linen rags were no longer obtainable in sufficient quantities, and straw could not be used alone. It hence became necessary to look for other sources of cellulose, and it is to Keller that we owe the happy solution of this pressing problem. In 1843 he succeeded in utilising wood- cellulose by means of machines which, rotating rapidly against logs of wood the wood into an converted aqueous pulp made up of the separate fibres kept wet, gradually these machines were improved later by Volter, and the first factories of mechanical wood-pulp were erected. This inexhaustible material can be purified by boiling it with caustic soda in digesters under pressure and bleaching the resultant brown mass with chloride of lime ; this procedure gives chemical wood-pulp, which to-day forms the basis of almost all kinds of paper, from the finest to the commonest. In 1884 Dahl effected considerable economy in the manufacture of wood pulp by replacing the expensive caustic soda to a large extent by sodium sulphate ; calcination of the evaporated residue of the exhausted lye yields mainly caustic soda, sodium carbonate, sulphide, thiosulphate, etc., and a solution of this product acts on wood, giving a whiter and more resistant product. Although this process was applicable with advantage to straw cellulose, which gives good results only when treated with alkali or sulphate (the consumption of straw is limited nowadays by its increasingly high price), it was not convenient for dealing with the enormous As early as 1865, Tilgman quantities of wood necessary to meet the growing demands for paper. in America had attempted the chemical purification of mechanical wood-pulp by digestion with acid sulphites, and in 1874 Ekman's large factory at Bergvik was working regularly with magnesium bisulphite. Meanwhile, Professor Mitscherlich of Munich (1872) had suggested the improvement of this process by using calcium bisulphite in large digesters under pressure. From that time, and especially after the improvements introduced by Keller, the use of bisulphite spread gradually in Germany and other European countries and received a fresh impetus on the lapse of Mitscherlich' s patents. At the present time, with rare exceptions these including the treatment of straw, which contains silicates not attacked by bisulphite almost all wood-pulp is transformed into cellulose by the bisulphite process. This process not only effects economy in the digestion of the wood-pulp, but results in an increased yield of a whiter and stronger product. With improvements in the chemical methods and especially by the use of energetic bleaching processes (chlorine, chloride of lime, electrolytic alkali, hypochlorite, etc.), it became possible to utilise the wood of many different trees from the fir to the poplar so that there is now no danger that raw material for paper-making may some day fail. In Canada alone there are still ^forests large enough to supply the whole world with paper for 800 years, even with a much larger
;

annual consumption than at present.

392

ORGANIC CHEMISTRY
and those which are coloured to varying degrees the larger pieces are then having a number of horizontal knives fixed to the periThe A y of a cylinder, the seams, buttons, hooks, etc., being previously removed. different qualities then pass to suitable machines to be cleaned and brushed. Fig. 407 shows a simple form of duster, in which the rags are beaten vigorously by pegs on rapidly
;

,pecial cutters (Fig. 406),

FIG. 406.

FIG. 407.

end of the machine, revolving horizontal wooden cylinders and carried to the opposite while the dust is removed by an air-draught to be deposited in chambers or in large bagfilters of various types (Fichter, Beeth, etc.). After this the rags are washed a little with water in vessels similar to hollanders (see a gauze drum for renewing the pp. 291 and 610) without knives but with a vaned wheel and water. They are next removed to revolving spherical boilers, where the residual dirt is eliminated and any dye, fat, resin, starch, gum, or other impurity destroyed. This is effected by boiling, sometimes with soda or caustic soda, but more commonly with lime (2 to 5 per cent, on the weight of the
rags)

and water.

These boilers

(Fig. 408) hold as much as 2000 kilos of rags and make about two

is

revolutions per minute, while steam passed in through a tube traversing the axis until a pressure of 2 to 3 atmos. is reached. The boilers,
are coated with insulating material, and the boiling lasts for 6 to 12

hours, according to the nature of When the boiling the material. is finished, the steam under pres-

sure

is

released into the adjacent

boiler, in

which the operation

is

just starting, and the rags removed, rinsed well in water, and reduced

to a fine pulp in machines similar to hollanders (see later) with cast-

iron or reinforced concrete tanks,

the knives of the drum not being set too close to those of the fixed

About 20 horse-power is required by the hollanders for a The loss in weight in all the operations up to the present stage charge of 200 kilos of rags. of the material, from 12 per cent, to 40 per cent. In holthe to quality according
FIG. 408.
plate.

varies,

landers or similar vessels holding up to 800 kilos of rags, the bleaching is carried out with a clear solution of chloride of lime, of which 2 to 10 kilos are required per 100 kilos of rags ; a 10 kilos of chloride of lime) is finally added to little sulphuric acid (100 to 200 grms. per In some factories fresh electrolytic liberate all the chlorine from the bleaching agent. solutions of sodium hypochlorite (see Vol I., p. 572) are used. The bleaching must not be.

MECHANICAL PULP
boo prolonged,

605

afterwards washed in large quantities of water until all smell and potassium iodide starch paper is no longer turned blue or as a precaution, 30 to 50 grms. of sodium thiosulphate (antishlor) and soda are added to each vessel. The bleached mass or half-stuff, as it is called, is freed from water and allowed to drain for some days in brickwork chambers with floors
is

and the pulp

chlorine has disappeared blue litmus paper reddened

3f

From these it is taken in the moist state as required for Df absorbent grooved bricks. mixing with bleached wood-pulp. The mixture is beaten in true hollanders, the knives being set more or less close according as more or less fine refined pulp is required. WOOD-PULP (Mechanical Pulp). The treatment of the woody parts of the various
plants suitable for paper-making [fir, pine, larch, poplar (Populus nigra or, better, Populus canadensis), beech, birch, esparto (of which Algeria exports half a million quintals annually), straw, hemp, broom, etc.] varies somewhat, as the cellulose and the surrounding 1 lignin are present in different proportions and in different states of aggregation. Logs containing few knots are cut into

the

required lengths (40 cm.), which, after the knots have been removed by a boring machine, are barked in another machine. The
logs

are then defibred by being pressed against a stone mill, which revolves rapidly and removes the This mill is fibres tangentially.

about \\ metre in diameter and 35 to 40 cm. thick, and it revolves

either horizontally or vertically (at 150 to 180 turns per minute). To

to*

grinder devised

the latter type belongs the vertical by Voith and sub-

sequently improved in various ways (Figs. 409). The three chambers three the with corresponding

toothed rods, B, contain the logs cut to the proper length, and, while the grinder revolves, these are pressed against it by the corFIG. 409. responding covers whrch are forced down by the toothed rods the latter connect with gearing worked by a chain, D, the velocity of which is proportioned to that of the grinder. The pressure is nowadays
;

1 In the disintegrated wo^-L the proportion of cellulose is determined by digesting several times with sodium bisulphite solution and then treating repeatedly with chlorine at 0, by which means almost all the constituents except the cellulose are dissolved. For the determination of the crude cellulose in plants, Weender's older method, modified by Henneberg and Stohmann, 2 grms. of the finely divided has been largely replaced by that of Gabriel (or Lange and Konig) substance is heated in a beaker with 60 c.c. of alkaline glycerine (33 grms. of caustic soda dissolved in a litre of glycerine) at 180, the mass being then cooled to 140 and poured into a basin conThe supernatant taining 200 c.c. of boiling water, with which it is mixed and allowed to settle. liquid is drawn off through a siphon covered with cloth at the end dipping into the liquid, and the deposit boiled with 200 c.c. of water which is siphoned off as before. The boiling is repeated with 200 c.c. of water containing 5 c.c. of concentrated hydrochloric acid, and the residue finally brought on to a tared filter, washed with water, alcohol, and ether successively, dried and weighed as crude cellulose. To determine the pure cellulose, almost free from pentosans, ash, etc., Konig's method is used 3 grms. of the finely divided, air-dried material is treated with 200 c.c. of glycerine (sp. gr. 1-230) containing 4 grms. of concentrated sulphuric acid in a dish which is heated in an oven at 137 for exactly one hour, the liquid being then allowed to cool to 80 to 100, mixed with 200 to 250 c.c. of hot water, boiled and filtered hot through an asbestos filter with the help of a pump. The filter is then washed with 300 to 400 c.c. of hot water, then with boiling alcohol, and finally with a hot mixture pf alcohol and ether. The filter with its contents is next introduced into a platinum crucible, which is dried at 105 to 110 and weighed. The crude cellulose is then ashed by heating to redness, the loss in weight thus produced representing the crude cellulose free from ash. If, in a second estimation, the cellulose is not dried and ashed, but is repeatedly treated for several hours with strong hydrogen peroxide and ammonia, and finally washed, dried, weighed, ashed, and again weighed, the proportion of pure, white cellulose is obtained. The difference between the crude and the pure cellulose represents the lignin,
, :

606
exerted hydraulically
is
;

ORGANIC CHEMISTRY
Fig.

410 shows a series of such vertical grinders in which hydraulic Horizontal grinders (Fig. 411, vertical section; Fig. 412, general view) with hydraulic pressure are now widely used, as they admit of a larger number of logs being ground at the same time. While in operation, the grinder is continually spraye'd with water to prevent heating and to remove the woody fibres as they are liberated.
pressure

employed.

FIG. 410.

more or

According to the pressure of the logs on the grinder and to the speed of the latter a less fine pulp is obtained with a smaller or larger content of splinters, dust, and other irregular and unusable portions ; these are removed by means of sloping sieves, B and C (Fig. 413), on to which the channel, A, conveys the water to carry away the crude wood-pulp, while powerful water- jets carry the splinters (6), the good fibre (c), and the

FIG. 411.

FIG. 412.

dust (E) to various collecting channels. Cylindrical or superposed sieves are also used. When the wood-pulp is to be used immediately for making paper, it is mixed with the necessary quantities of rag-pulp and dressing and worked up as described below, but removed and generally the wood-pulp is placed on the market, hi which case the water is the pulp converted into sheets by sucking it on to drums of metal gauze or travelling planes, through which the water is drawn by suction ; the continuous layer of pulp is cut into
of water). Somelengths and is best dispatched in the wet state (with 40 to 60 per cent, times, however, the sheets are dried on, hot drums, although this renders difficult the subsequent treatment necessary to transform them into pulp in the bollanders, N

CHEMICAL PULP
is yellowish or rather brown, and still contains all the encrusting stf||tance cannot be used as it is for paper, the action of light altering its colouFfmmediately. It cannot be bleached with chloride of lime or alkaline reagents, which intensify 4ts yellow colour, but good results are obtained with sulphur dioxide, which does nt)t,

Wood-pulp
;

(lignin)

it

indeed,
tint

remove the yellow but prevents the browning or reddening which gradually Barked and cleaned logs
about one-half their weight of dry wood-pulp (containing 12 to 15 per cent, of
yield

sets in.

moisture).

CHEMICAL WOOD-PULP.
This is obtained by removing the encrusting matter from the wood or other raw mateFlG 413
various chemical agents.
rials

(straw,
1

esparto,

etc.)

hemp, alfalfa, by means of

It was Payen who first, in 1840, attempted this purification with nitric acid, and who afterwards tried caustic alkalis, sulphurous acid, etc. The preparation of the cellulose in the chemical way can be effected by (a) the soda process, (b) the bisulphite process, (c) the electric process, (d) the chlorine process. (a) The logs freed from bark and knots are converted into sticks 1 cm. thick, which are heated for some hours with caustic soda of 12 Be", under a pressure of 6 to 8 atmos. (160 to 170) in large digesters, 100 to 200 cu. metres in Various types of digester are in use, capacity. Fig. 414 showing the vertical type devised by Sinclair. This consists of an iron cylinder, A, 5 to 6 metres in height, with conical extremities, a charging orifice, C, a wide horizontal discharge tube, C v a tube, &, by which the caustic soda is

introduced, and an inner perforated jacket, which is filled to the extent of four-fifths with the
reservoir, 0, contains a supply of soda solution, and circulation in the digester may be effected with the help of a Kdrting injector, the cocks of the tubes, h t and h, being opened ; the latter conveys the alkali on to the sticks, while that collected between the perforated jacket and the inner wall of the digester ascends through A r The hot gasgs from the hearth, K> heat the digester and pass through E to the chimney. At the end of the operation the highly coloured alkali is discharged from the tap, V, and can be used for several successive treatments, being reinforced each time with a little sodium carbonate. The soda is eventually recovered from this liquor by evaporating in FIG. 414. a vacuum, calcining the residue, extracting the sodium carbonate thus formed with water, boiling with milk of lime, and decanting the resultant caustic soda solution (see Vol. I., p. 554). But for this recovery of the soda, this process would be inapplicable. A method which is more economical and more generally used consists in reinforcing the alkali liquor first used with sodium sulphate, instead of the carbonate, for subsequent operations ; the liquor is then ultimately evaporated in a vacuum and calcined, the sodium sulphate, in presence of carbonised organic matter,
sticks.

The

caustic

being converted partly into caustic soda and partly into sodium sulphide (which exerts
1 JSsparto and alfalfa, which are very similar, are the leaves of Lygeum spartum and Stipa, tenacissima respectively, and are used for making nets, sandals, mats, ropes, paper, etc.

608
process (see Vol.

ORGANIC CHEMISTRY
I.,

on wood the same action as caustic soda), just as

p. 591).

in the preparation of soda by the Leblanc Extraction of the calcined mass with water yields a liquor containing sodium sulphate, sulphide, and carbonate, and is ready to act on fresh quantities of wood in the Cellulose thus prepared is termed sulphate digester. pulp. The concentration of the alkaline liquor is accompanied by the production of pungent and disagreeable odours, which are a source of annoyance to the neighbourhood, so that in certain countries (e.g. t Scandinavia) such concentration is prohibited. It has been suggested to destroy these odours (due to mercaptan) by nitrous tapours, or to condense the noxious fumes or pass them

over metallic oxides.

Use

is

also

made

of horizontal autoclaves arranged

in series like sugar diffusors (see p. 549), while ordinary vertical iron digesters, as shown in Fig. 415, are largely employed. The digesters may be heated with indirect

steam for 24 to 48 hours, or, more economically and rapidly, by direct steam (10 to 15 hours) to 140 to 150 (12 to 15 atmos.), but the yield is then rather lower and the mass slightly more attacked. The residual cellulose is washed, in the digesters themselves or in hollanders, with water and steam, and is then mixed with the Fi. 415. quantity of rag half-stuff necessary for the kind of paper required, the whole being then worked in the hollander into the refined pulp (see later), This (b) Calcium Bisulphite (Mitscherlich) or Magnesium Bisulphite (Ekman) Process. process is the one most largely used at the present time, as it gives a cellulose of better quality than the preceding method. The wood is heated under pressure (115 to 130 or 2-5 to 4 atmos.) in large autoclaves lined inside with cement or brickwork with a
solution of calcium bisulphite, Ca(8O 3 H) 2 or magnesium bisulphite, which dissolves the encrusting matter
,

but does not act on the cellulose ; the liquid is circulated inside, the boiler by means of an injector or by leaving a small upper tap slightly open. The bisulphite solution of 4 to 5 Be. (about 30 grins, of SO 2
per litre, approximately one-third being combined with lime) is prepared in very tall wooden towers (that of Harpf being as much as 35 metres high), usually lined with lead and filled with limestone or dolomite (Fig. 416). A current of sulphur dioxide

ascends from the bottom to the top of the tower, while the trough, b l9 supplied by the reservoir, S, at the bisulphite the top, yields a fine spray of water solution is collected at the bottom. Harpf's tower has ten gratings (I to X), connected by steps not shown in the figure each of these can be charged and attended to independently of the others by means of the door, k. The first six gratings are cleaned every
; ;

FIG. 416.

four weeks, but the others far less often. The sulphur dioxide issues from pyrites furnaces into the iron tube, c, and passes down the earthenware

pipe

b,

BB

being for convenience of cleaning.

its

tion deposits
1

suspended matter in

and

is

The calcium or magnesium bisulphite soluthen discharged into storage tanks, When

dissolved with remarkable ease by calcium bisulphite, giving a stable soluble is neither detectable by iodine, nor capable of being set free by sulphuric acid, nor able to exert reducing action. Sulphurous acid alone does, not act so well as the bisulphite, the lime being necessary for the formation of these sulphonic salts and for the neutralisation of the sulphuric acid always formed.

Lignin

is

compound, the sulphur dioxide in which

BISULPHITE PROCESS

609

the whole of the tower is to be washed, the plug, P, of the cistern is raised. Towers with bundles of wide vertical tubes are also used (Fig. 417). Wood in logs is treated in suitable boilers, either horizontal as in the MitscheYlich proThese are of iron and were cess or vertical (Fig. 418) as in the Hitter- Kellner process. formerly lined with thick lead to resist the action of the sulphurous acid, but now a lining, of acid-resisting brick or special cement is preferred ; the cocks are of phosphor-bronze. To ascertain the completion of the action of the bisulphite on the wood in the digesters, a sample of the liquid is removed now and then and treated in a graduated tube with ammonia when the calcium sulphite occupies one-sixteenth of the volume of the sample
;

the heating

is

stopped, and

when this

fraction

is

reduced to one thirty-second the operation

Fia. 417.

FIG. 418.

is

ing

and the coloured liquor can be discharged. The whole operation, including chargdischarging, preliminary treatment of the wood and action of the bisulphite, lasts 50 to 60 hours. The spent bisulphite liquor is highly coloured and charged with salts, gummy matters, tannin, glucose, pentoses, acetic acid, nitrogenous compounds, etc., and
finished

and

it is

purified

usually forbidden to turn it into watercourses or bottomless wells ; so that it is often by precipitation of the sulphite with lime, the calcium sulphite being then reconverted into the bisulphite by sulphur dioxide. Attempts have also been made, but with little success, to evaporate the residual liquor and so obtain adhesive gummy substances
itilisable in

the preparation of coal briquettes. In a factory with two boilers, each of 120 cu. metres capacity (12 to 15 metres high, 3-5 to 4 metres in diameter, and about 2 cm. hick), each of these is charged with about 200 quintals of wood and 85 cu. metres of bisulfite solution. With a monthly output of 1000 quintals of cellulose, the daily production
if

spenjt Jiquor is

30

cu. metres,

the organic residue amounting to 8 per cent, and the

a.sb

610

ORGANIC CHEMISTRY
;

to 2 per cent. The rational disposal of these spent liquors is always a serious problem, which still awaits solution the attempts made to prepare alcohol from them are mentioned * in the note on p. 169. The yiejd of cellulose varies with the quality of the wood, but is about 40 to 55 per
cent*
(c)

Electric Process.

closed receptacles containing the

This was proposed by Kellner, and consists in passing through wood a solution of sodium chloride at 126, through

FIG. 419

which an electric current passes; the chlorine, _m/J _ , together in the nascent state, dissolving the encrusting substances of the wood and liberating the cellulose. This process has not yet been much used. This has been often attempted without success, but during (d) Chlorine Process. recent years has been again tried on an industrial scale, owing to the large supplies of

by the development of the electrolytic manufacture of caustic The processes now being applied are derived from the analytical method proposed long "ago by^Cross and Bevan to separate cellulose from ligniru
chlorine rendered available
soda.

FIG. 420.

MECHANICAL REFINING OF THE CELLULOSE AND MECHANICAL WOOD-PULP.

of wood, more or less finely divided, extracted from the digesters is coarsely defibred in suitable disintejgrating machines, and the cellulose and the mechanical pulp, either together or sepsSately, acoorcfia^trCiie kind of paper required, are introduced intj> the so -called hollanders, where they are completely defibred and converted into a very

The mass

fine

pulp

carried out in the hollanders, as necessary Iprtne desired paper,

bkftcning with Calcium hypochlorite and the subsequent washing are also is the addition of dressing, colour, size, resin, alum, etc^
"

^
"

The

vessel (A, Figs.

hollander beating machine Consists of a large, oblong wooden or, better, cement fy 419 and 420), in the middle of which is a vertical, longitudinaf
1

FORMATION OF THE PAPER

which does not extend to the ends drum, Z), furnished at its periphery

611

of the vessel. In one part of the vessel is a large revolving with a number of cutters which circulate the water

this part of the vessel is in containing the cellulose or mechanical pulp. The bottom of the form of a ridge (PR, Fig. 420), and at a point, F, on one of the slopes are fitted cutters ; the drum can be moved up or down by means of the lever, HG, and the distance between thus adjusted as required. The movement of the water produced its cutters and those at by the rotation of the drum causes almost the whole of the cellulose and pulp to pass

between the fixed and revolving cutters, and after some time

woody fibres swim separately in the water. As the process goes on, the knives are gradually brought closer tothe
gether until the desired degree
of

fineness

is

attained.

The

mass passes up the plane, P, dowrt*the plane, JR, round the

partition,

B,

again

up the

plane, P,
FIG. 421.

and so on.

The washing water can be changed by immersing in the free half of the vessel a fine gauze drum from which the water can be aspirated by means of a pump. This drum is then raised by the chain and pulley, R (Fig. 419), and fresh water introduced into the vessel. To avoid spurting from the drum, D, it is fitted with a cover, T. In the base of the vessel and in front of the inclined plane is a recess for catching pieces of iron or stone accidentally present in the wood-pulp, the cutters thus being protected from of hollanders, which are also used for guncotton. a damage. Fig. 206 on p. 291 shows battery
SIZING

AND FORMATION OF THE PAPER. The

refined pulp in the hollander,

containing the different raw materials (rags, woodpulp, cellulose, etc.) in the requisite proportions, is blued and sized before being transferred to, the

continuous machines. The blueing is effected by adding, a short time before the end of the beating,

500 to ^000 grms. of ultmrnarine,

aniline blue
;

Prussiajx. blue, or

tfie^izjeTs^J4ed, renders the paper imperviouTfo"water and prevents ink from running on it 4f blotting-paper or filterpaper^^ required, thesizing is omitted. Sizing may
;

little later

which

be carried out oh the finished paper, but

it

is

to usually preferred to add the dressing directly the finished pulp while this is still suspended in water, since in this way all the fibres become c'ojited with the size without losing the power of adhering,

one jbo/ the other, to form a homogeneous, felted mass of paper. Animal size was at one time used, but, even owing to its ready putrefaction or alteration while it is being applied, it has been almost entirely replaced by tesin (colophony) previously rendered
soluble (resin soap)

by means of caustic soda. With water this soap forms very fine, be increased by the homogeneous and persistent emulsions, the efficacy of which may addition of starclUpagte (in amount sometimes equal to that of the resin) or 'of dissolved in ctilute so^a solution. The total dressing added amounts to
7 the dry p^per.^ ^-~ In order to precipitate the resin in a fine state of division on the fibres, a solution of aluminium sulphate {or of potash alum) is added to the homogeneous mixture of pulp and resin soap; as was shown by Wurster, this effects the precipitation of ,the resin, starch resinate* Nowadays one-half of the (or casein); and a very small amount of aluminium the sometimes cheaper ma^esium. sulphate/ The sulphate is replaced by

612

ORGANIC CHEMISTRY
sulphate^

so-called loaded papers are obtained by adding, in addition, a considerable quantity (sometimes 50 per cent.) of kaolin, barium sulphate, talc, or calcium

dyes, lakes, or substantive aniline dyes) are also added directly to the finished pulp, organic dyes being the more commonly used. The lakes are produced by mixing basic dyes with the pulp and then precipitating with tannin solutions ;
for direct dyeing, substantive dyes (see later, Colouring-Matters) are employed. Powdered lakes obtained by precipitating either acid aniline dyes with aluminium hydroxide or basic

The colouring-matters (mineral

dyes with tannin or tartar emetic may also be used. After all these additions have been made, separation of any of the components from the homogeneous pulp is prevented by conveying the latter into two vats, where it is kept 'in motion by stirrers, the resultant milk being more or less dense according to the thickness
of paper required. Before going to the continuous machine to be converted into paper, the pulp is passed through a purifier (Fig. 421) which removes any clots of fibre still preThis purifier consists of two or three slightly inclined, oscillating plates, perforated sent.

with very fine slots ; when the pulp is fed regularly on to these plates, the fine fibres pass through while the lumps are discharged into channels provided for the purpose. The homogeneous pulp collected under the vibrating plates is conveyed to the continuous machine at an almost absolutely regular speed, and on this depends the uniformity in the thickness of the resultant paper the pulp regulator or feeder should hence be constructed with great care. If this homogeneous pulp is placed on a very fine sieve, the water passes through, leaving a thin layer of interlaced, adhering fibres which can be removed in
,

FIG. 423.

the form of a wet sheet.

place in a similar manner.

gauze after concloth then passes the wet sheet to a pair of rolls, which compress it and give it tnore other rolls heated to 130 gradually dry the paper, while others, again, press it sistency and give it a little polish. When it leaves the endless gauze, the paper is sufficiently consistent to be conveyed to the supercalendar (Pig. 422), where it is pressed and polisljpd
;

The preparation of the paper in the continuous machirie takes The pulp is distributed uniformly on a very fine endless copper a good proportion of its water has been removed by draining and suction. A

Other nrachines wind it into rolls, cut it, rule it, etc^y^ cost several thousands of pounds. A general machine the two vats of pulp are seen at a, while b feeder carrying buckets, c the drum sieve which collects the pulp and circular the represents to the metal gauze, d, this transferring it to the cloth at/ and passing passes it as a wet sheet back round the rollers, e, underneath to take up fresh pulp g shows the drying rolls and h
between several pairs of
rolls.

may large modern continuous view of such a machine is shown in Fig. 423

where the cloth returns, the continuous length of paper being drawn
apparatus.

off at i

to the winding

It is not possible here to consider the different kinds of paper now manufactured, or the different pulps required, or the special modern machines devised to meet all the require1 ments of the trade, but a few words may be devoted to the testing of paper, the pulp

is detected by determinjjig, in a 1 Testing of Paper. The presence of mineral loading nondried at 100 to 105 platinum crucible, the ash of 1 to 2 grms. of the paper, cut up and loaded paper contains 0-4 to 2-5 per cent, of ash. To detect the presence of mechanical wood-pulp, the paper is immersed in an aqueous solution of aniline sulphate, which imparts a golden-yellow or use may be made of aqueous pbloroglucinol faintly acidified colour to the crude wood fibre r with hydrochloric acid, this dyeing the crude wood fibre (mechanical is determined by Leonardos method; the or solidity sizing -*y of impermeability
; ;

..

PAPER STATISTICS
are corroded and
characters.

613

used being recognisable under the microscope by the magnitude and form of the fibres (see Figs. 424 et seq.). As will be shown in the chapter on Textile Fibres, the fibres of paper

somewhat

distorted

and resemble the

original fibres only in certain

The fibres of the white fir are shown in Fig. 424 at A and in transverse section at B ; they are brown and are characterised by the pores arranged in concentric circles. Fig. 425 shows at B altered cotton fibres and at L those of linen. Fig. 426 gives an idea of the microscopical appearance of mechanical wood-pulp of the conifers (fir, pine, etc.) with medullary rays, while Fig. 427 shows chemical pulp from the conifers ; in the latter case, the concentric circular pores are less marked and the fibres more homogeneous. Fig. 428 shows straw cellulose with the very thin parenchymatous cells, a, rounded at the ends, and the superficial toothed cells of the epidermis, o, mixed with the bulk of ordinary elongated and striated fibres. Esparto fibres resemble those of straw to some extent but are lacking in thin and terminal cells, while the toothed edges are different in nature and are found in smaller cells than in straw ; esparto contains certain isolated fibres having the form of teeth or elongated pears. Spain exported more than 90,000 tons of esparto in 1872 and about 46,000 in 1900. Algeria now exports 80,000 tons, Tunis 30,000, Tripoli 75,000 and Morocco 4000. Algeria contains 5,000,000 hectares under esparto. England imports about
200,000 tons of esparto per annum. STATISTICS. Books and reviews often contain contradictory and fantastic statistics concerning the output of paper. According to the most trustworthy data, the world's production of paper and pasteboard in 1906 amounted to about 8,000,000 tons, and that of cellulose in 1908 was estimated at 1,600,000 tons of the value of 16,000,000, and in 1913 at 3,000,000 tons. In 1913 the paper industry of the world consumed 38,000,000 tons of
stretched
inclined at 60, a solution containing 1 per cent, of ferric chloride, 1 per cent. and 0-2 per cent, of phenol is allowed to fall drop by drop so as to form a number which are then allowed to dry similar strips, crossing the first and perpendicular to them, are next made with a solution containing 1 per cent, of tannin and 0'2 per cent, of phenol ; the formation of a black stain of tannate of iron at the point of intersection indicates bad sizing^ absence of stain shows perfect sizing, and stains more or less grey denote more or less good sizing" Resin sizing is recognised by pouring a few drops of ether on to the paper and allowing them Or to evaporate ; the formation of transparent rings indicates the probable presence of resin. a few grms. of the paper may be boiled with absolute alcohol containing a few drops of pure acetic acid, the solution being afterwards poured into distilled water; if the latter becomes turbid, the presence of resin is certain. To detect animal sizing, a few grms. of the paper are boiled with a very small quantity of distilled water, the liquid being filtered, highly concentrated and treated with a solution of
of gum arable, of moist strips
;

and

if size is present, whitish grey flocks are formed, which, when observed under the microscope in contact with a dilute solution of iodine in potassium iodide, are seen to be coloured brown, while if starch is present this is coloured blue the test for starch may be made directly on the paper itself. The presence of free mineral acid is ascertained by boiling the paper in a little distilled water and noting if the solution turns Congo-red paper blue or black. For the microscopical examination (see Figs. 424-428), the fibres are liberated as follows 3 to 5 sq. cm. of the paper is boiled and vigorously shaken for two minutes with 3 to 4 per cent. caustic soda solution, the pulp thus formed being poured on to a very fine metal sieve and washed well with tepiol water. The fibres are then tested microchemically with solutions containing (1)6 parts of iodine, potassium iodide, 10 parts of glycerol, and 90 of water, and (2) 100 parts of zinc chloride, 10-5 of potassium iodide, 0-5 of iodine, and 75 of water, the clear liquid being, in this case, decanted from the precipitate formed linen, hemp, and cotton are coloured pale to dark brown by solution (1), the thin fibres remaining almost colourless, while with solution (2) a more or less intense wine-red coloration is obtained. An alcoholic solution of phloroglucinol containing hydrochloric acid does not colour pure cellulose but reddens impure cellulose, the presence of wood-pulp (i.e., impure cellulose) in pa^er being hence detectable in this manner. Further, aniline sulphate or naphthylamine hydrochlonde colours impure cellulose yellow, but does not alter pure cellulose. The bursting strain of paper, called also the degree of elasticity, is determined in the directions of the length and breadth by means of suitable dynamometric apparatus, the elongation which occurs before rupture being expressed as a percentage of the length (this varies from 1-5 to 4 per cent, for different papers). The breaking length expresses the length of a uniform strip if a strip 10 cm. of paper which would tear under its own weight if suspended from one end wide of paper of which 1 sq. metre weighs 70 grms. breaks under a load of 3500 grms. the creaking

tannin

ength

is

T~JQ

X 1000

5000.

The

resistance to folding is

of the paper between the hands ; when different papers are least number of creases is the best.

determined roughly by crushing and rubbing an irregular ball compared in this way, that with the

614

ORGANIC CHEMISTRY

wood, valued at about 32,000,000, the consumption increasing by abJut 5 per cent, each year. In some countries as much as two-thirds of the wood used is converted into cellulose,
90 per cent, of the latter being obtained by the bisulphite process. The following numbers represent the mean annual consumption of paper in kilos per l inhabitant for various countries, these being regarded as a rough indication of progress
:

FIG. 427.

FIG. 428.

United States, 19-3; England, 17-2; Germany, 14; France, 11-5; Austria, 9-5; Italy
7-5
1
;

Spain, 2-5

Russia, 2-3

Serbia, 0-6

China, 0-6

India, 0-13.

Prior to the War about 75,000 new books were published per annum throughout the world, In addition, some 70,000 daily papers are these requiring 30,000 tons of mechanical pulp. published with a total circulation of 11,000,000,000, these requiring 15,000 tons of mechanical

pulp per day. Of the total output of paper, 32 per cent, is for ordinary printing, 10 per cent, consists of paper and writing paper, 10 per cent, of brown paper and cardboard, 6-3 per cent, of fine 5 per cent, of straw paper and card, 3 per cent, of cellulose and rag paper for fine printing cent, paper for placards, etc., 3 per cent, of wall-paper, 0-6 per cent, of drawing paper, 0-5 per 0-4 per cent, of blotting- and of silk paper, cigarette paper, and paper for making flowers
fine
; ;

Although the consumption of paper has increased to an extent that would have been incredible a few years ago, yet the day is far distant when a scarcity of raw material will be experienced. Canada alone, with its 322,000,000 hectares of forest land, can supply the whole world for several centuries. Of other reserves of forest the most important are those of the United States, 200,000,000 hectares; Russia, 184,000,000; Queensland, 86,000,000; Siberia, 38,000,000; British India and Burmah, 26,000,000 ; Finland, Sweden, and Japan (excluding Formosa and Hokkaido), 20,000,000 each ; Germany, 17,000,000 ; Austria and France, 10,000,000 each ; Hungary, Croatia, and Slavonia, 9,000,000 ; New Zealand, 8,000,000 ; Asiatic Turkey, 7,000,000 ; Norway, 6,000,000; Hokkaido (Japan), 6,000,000; Italy, 4,500,000, etc. In Burmah and elsewhere there are immense tracts of bamboo, wjiich will one day be utilised for the manufacture
of paper. It cannot, however, be denied that an immense amount of wood is used for building purposes, and in Italy, for instance, many of the forests have been destroyed, so that the imports of wood, which in that country amounted to 840,000 in 1871, increased to 2,000,000 in 1900, to '2,840,000 in 1905, and to still greater extents (mostly from Austria-Hungary and America) in recent years (see Vol. I., p. 223).

filter-paper, etc.

CORK
CORK

615

This forms the principal component of the bark of the cork oak (Quercus suber), cultivated in Spain, Portugal, Prance, Italy, Algeria, Tunisia and Morocco. The corky bark may attain the thickness 25 to 45 cm., but in order to prevent it from deteriorating and
cracking owing to excessive age, its collection is commenced after the tree is 15 to 20 years old. From each tree about 6 kilos of cork may be obtained every 10 years. The best qualities are golden-yellow, the poorer ones greenish-yellow. The density of cork varies between 0-215 and 0-24, and increases with age. It consists
of suberin,

which

is

ing phellonic and other acids composition of air-dry cork is

soluble in alcoholic potassium hydroxide, and of other substances yieldwhen hydrolysed with alcoholic potash. The percentage crude cellulose, 22 to 23 ; fats and resins, 4-6 ; water, 8
: ;

various non-nitrogenous substances, 58 ; nitrogenous materials, 6 ; ash, 1-3. From 8 to 12 kilos of cork 1 kilo of cork stoppers is obtained, the waste being utilised, either by agglomerating with pitch or chalk to make insulating material for the refrigerating industry, or for making linoleum (see p. 496), or for packing fruit, etc.

PAKT
(e.g.,

III.

CYCLIC COMPOUNDS

aliphatic series contains various groups of closed- chain compounds lactones, uric acid derivatives, anhydrides of dibasic acids), which are readily opened by simple reactions giving ordinary open-chain compounds of

the fatty

series.

Numerous substances are, however, known containing a closed-chain nucleus which is composed of 3, 4, 5, or more commonly 6, carbon atoms united in a special manner and is resistant to the most energetic reagents. These compounds form the important group of isocyclic compounds. Other groups of cyclic substances are also known with nuclei composed, not of carbon atoms alone, but of several elements, e.g., pyridine, C5H 5N, in which the nucleus contains 5 carbon atoms and 1 nitrogen atom pyrrole, C4H5N, with C4 and N in the nucleus furan, C4H4 0, with a C4 nucleus pyrazole, C 3H 4N 2 with the nucleus thiophen, C4 H 4S, with a C 4S nucleus C 3N 2 etc. These compounds are called heterocyclic. There are also many substances derived from more complex nuclei formed by the condensation of two or more of the nuclei mentioned above, e.g., naphare condensed two benzene nuclei held together by thalene, 10H 8 in which 2 carbon atoms common to the two nuclei, and quinoline, with a nucleus analogous to that of naphthalene but composed of one benzene and one pyridine
;

nucleus.

AA, ISOCYCLIC
These contain
1 or several

COMPOUNDS

homogeneous carbon atom rings, and can be subto the divided, according type of linking, into (1) Polymethylene Compounds, which contain singly linked carbon atoms and are less resistant to chemical reagents than (2) Benzene Derivatives, where the carbon atoms are linked very Compounds of the first group approach those of the differently (see later). in their chemical properties and are hence intermediate to
aliphatic group

methane and benzene

I.

derivatives.

CYCLOPARAFFINS AND CYCLO-OLEFINES OR

POLYMETHYLENE COMPOUNDS
TRIMETHYLENE
(Cyclopropane),

CH,/

XCH
|

2
,

is

\CH 2

obtained by the action of sodium

CH 2 Br CH 2 CH 2Br, the bromine being eliminated as NaBr and the chain closed. It is a gas which liquefies at a pressure of 5 to 6 atmos. and combines so that it is very slowly with bromine or hydriodic acid giving open-chain compounds, CH 2 CH CH. 3 Its heat of combustion is much easily distinguished from propylene into which it is partially converted at 400. greater than that of propylene, Its derivatives are obtained from ethylene bromide by means of the ethyl malonate
on ay-dibromopropane,
:

synthesis (see p. 369).

Trimethylenedicarboxylic Acid,
action of ethylene bromide

^>Cv

CH/

XJO2H

was obtained by Perkin by the

inter.

and ethyl sodiomalonate.

616

POLYMETHYLENES
TETRAMETHYLENE
are obtainable

617
it

by syntheses

(Cyclobutane) is not known similar to those used for trimethylene compounds.

in the free state, but derivatives of

CH 2 CH 2v

PENTAMETHYLENE

(Cyclopentane),

CH 2 CH 2/
\

)>CH 2

is

a liquid boiling at 50

its

derivatives are prepared by the ethyl malonate synthesis. According to Baeyer's tension hypothesis (see p. 107 and Fig. 252, p. 366), it is easy to understand why pentamethylene is the most stable of the preceding compounds, a ring of five carbon atoms being the only one which can be formed without tension of 'the Unkings.

Indeed, while trimethylene combines with Br or HI with rupture of the ring, pentamethylene does not unite with bromine and resists the action of nitric or sulphuric acid like a saturated hydrocarbon, the properties of saturated open- and closed-ch&in compounds

hence differing but

little.

KETOPENTAMETHYLENE
tion of calcium adipate
:

(Cyclopentanone), C 5 H 8 0,

is

obtained by the dry

distilla-

CH 2 CH 2 COCK
|

CH 2 CH 2 COO/
-

)Ca

CaC0 3

CH 2 -CH 2X
|

CH 2

CH/

)>CO

by reduction and subsequent treatment with HI

it gives pentamethylene, whilst oxidising Ketohexaconstitution. agents convert it into glutaric acid, these reactions proving its and C Calcium Ca, is obtained Pimelate, higher 4 7 10 distilling methylene similarly by Calcium homologues by distilling the corresponding calcium salts of higher dibasic acids ;

Suberate,

C8 12 4 Ca, for example, yields Ketoheptamethylene (suberone). diminishes with increase of the number of carbon atoms.

The

yield

CH CH^
:

CYCLOPENTADIENE,
first distillate of

CH CH/
:

j>CH 2

is

a liquid boiling at 41, and

is

found in the

crude benzene and also in illuminating gas ; it combines with iodine and with hydrogen sulphide. The presence of two double Unkings in the nucleus is deduced from the fixation of four atoms of halogen. The two hydrogen atoms of the CH 2 readily react, e.g., with acetone, giving intensely red hydrocarbons
:

/CH 3 CH CH 3 CH:CHX = C:C H 0-H + >CH >CO > < \CH 3 CH CH/ CH 3/ CH:CH/
,
:

CHx

this

compound
:

is

known
:

as Dimethylfulv^ene, fulvene being

an isomeride

of

benzene of the

CH CH.
structure
|

\C CH
:

2.

CH CH/ HEXAMETHYLENE
81, m.-pt.

pentamethylene and also by liquid, b.-pt. see and Senderens to Sabatier nickel of in benzene (according presence hydrogenating in Russian and GaUcian petroleum. p. 35), platinum, or palladium. It occurs Numerous less hydrogenated derivatives, and also some with ketonic groups, are an oil with the smell of mint, boils at 155, is found in wood oil, known.

C H (Cyclohexane, njiphthene, hexahydrobenzene), 6 12

is

a colourless

6, and

is

obtained similarly

.to

Cyclohexanone, converted completely into adipic acid on oxidation. in the decomposition products of cocaine and atropine.

and

is

Some

of its derivatives occur

CYCLOHEPTANE
is

obtained by reducing suberone (see below) ; bromine and aluminium bromide conan,d tract the ring, pentabromotoluene being formed. SUBERONE (Ketoheptameihykne), (CH 2 ) 6 CO, is formed by the ketonic intramoand lecular transformation of the calcium salt of suberic acid. It is a liquid, b.-pt, 179, on oxidation gives pimelic acid and on reduction suberane (see above).
:

(Heptamethylene, suberane), (CH 2 ) 7 ,

is

a colourless Uquid,

b.-pt.

117,

CYCLOHEPTATRIENE, CH 2<
of leeks,

/CH CH CH
:
||

is

a liquid,

b.-pt.

116, with the odour

N:H CH CH
:

and occurs among the products

of the decomposition of cocaine

and atropine.
40

It

VOL.

IT.

ORGANIC CHEMISTRY
is

compounds

obtained from suberone by complex reactions, and resembles olefines and not aromatic thus it unites energetically with hydrobromic acid. ;

CYCLO-OCTANE, (CH 2 ) 8 , is a liquid, b.-pt. 147, and was obtained by decomposing an alkaloid, N-methylgranatonine, derived from the bark of the pomegranate tree and having
the constitution

CYCLO-OCTATETRENE, C 8 H8

is

a yellow liquid which behaves

its

and not^as an aromatic compound, although

constitution

is

CH CH CH CH
:
|| ||

like the cyclo-olefines analogous to that of benzene.

CH-CH:CH-CH.
octarfe.

With hydrogen
in

in presence of spongy platinum

it

yields pure cycloof valency.

Such compounds are not

harmony with Baeyer's tension theory

II.

BENZENE DERIVATIVES OR AROMATIC COMPOUNDS

It was observed by several chemists about the middle of last century that a whole series of compounds, in aromatic besides nature, mostly exhibiting certain common physical and chemical characters, showed on analysis proportions of hydrogen very low in comparison with those of carbon and also very low compared with those of hydrogen in saturated or unsaturated comCW ,, CW ^ etc. pounds of the methane series, e.g., C n 2

In general the hydrocarbons of these substances correspond with the fundamental formula, C H 2n _ e and the various transformations of the aromatic substances often yield Benzene, C 6 H 6 from which they can again be prepared.^ If the^constitutional formula of jo-assume the presence of .double bejizej^werej^jape^ or triple linkings between carbon and carbon which would lead to ready addition of bromine and to_reaclgL.QxidatiQiL These reactions do no^ how^y^gr^^mTr^ruj _the great stability ofthe compounds of this group and of benzene in particular, can be' expKmecTorily'TJy nucleus~ of carbon atoms, probably joined in tne form of a closed t|ie existence^a^stable rt

ring.

benzene forms only one monosubstituted product (nitrobenzene, all the hydrogen atoms of benzene exist under similar conditions ; three isomeric disubstituted products (e.g., dinitro- or dibromo-benzene) are, however, known. With the empirical formula C 6 H 6 correspond the three rational formulae (a) C4 (CH3 ) 2 , C3 (CH 2 ) 3 , and (y) (CH) 6 Formulae (a) and (ft) would give only two isomeric disubsti(ft)
later that

It

was found

bromobenzene,

etc.),

and that

H^
2,

2,

~~

buted products, whilst in the case of groups were joined in the form not (y), if the six of an open-chain but of a closed ring, the six hydrogen atoms would be under the same conditions, and the formation of a single monosubstituted and of three isomeric

CH

product

disubstituted products would be explained. It was Kekule who, in 1865, first advanced the ingenious hypothesis that the fundamental compound of aromatic substances is benzene, the constitutional formula of which
single

must be represented as a closed, hexagonal chain of carbon atoms united alternately by and double linkings, the fourth valency of each carbon atom being united to a hydrogen atom. Such an arrangement is figured in the scheme

SCH
C

H
FIG, 429.

STRUCTURE OF BENZENE
or, if
: ;
: :

619

the six carbon atoms are represented by tetrahedra, in the diagram shown in Fig. 430. The carbon atoms combined with the substituents in the three disubstituted derivatives would then be (a) I and 2 (c^o-derivatives), (6) 1 and 3 (meta- derivatives), and (c) 1 and 4 (para-derivatives) the 1 5- and 1 6- compounds would be identical with the 1 3:

and 1:2- compounds

tracted to o-,

respectively. shortness, the terms ortho-, meta-,

For the sake

of

m- and

p-, these

and para- are conbeing prefixed to the

6

names

of the

compounds.

The constitutional formula given for benzene by Kekul6 and also those of Claus (1867), Baeyer (1868), Korner (1869), and Ladenburg (1870) would seem to indicate the possible
existence of 2 ortho-substituted derivatives, since the 1 and 2 carbon atoms are joined by a double linking and numbers 1 and 6 by a Hence Claus and Korner prosingle linking.

posed the hexagonal formula with the fourth valencies of the carbon atoms joined diagonally (para-linking) (Fig. 431, A), while Ladenburg preferred the prismatic formula (Fig. 431,
J5 2 ,

FIG. 430.

15 ), and Armstrong and Baeyer the centric formula, with the fourth valencies in a latent (or potential) state and directed towards the centre

and

B3

(Fig. 431,

(7)

see also Fig. 432.

In order to obtain a better interpretation of the formation of the disubstituted isomerides of benzene, Kekule (1872) developedjiis theory further on the assumption that
A
B,

FIG. 431.

be regard nd a. yiKrnf,inn gj ar> linking het.wpon thn nn.rhrm and 6 of the Kekule" formula are in identical conditions, -Tfreae oscillations would ejfelam whyJbenzene do^jiotjmite readily with halogens or ozone (aee-p. 107), or give Baeyer s permanganate rjac^onJ^j^.JLOT), t-hns ^^^ yjng almost like a saturated fiorn^ Even.Kekul6's oscillatory formula does not, however, explain completely the pound. optical
ff

q tojns_2
i

andtnermal behavioulF^oTTEe~~aTomaliu uumpOKiidsr^ work on the hydrogenated derivatives of benzene~siibsequently to 1 886J Indeed, when two or four hydrogen atoms
are adHeoTtoTieiizene so as to form dihydro- or tetrahydrobenzene, the latter are found to be quite different from true

results of
~~

~~

Baeyer

s~

aromatic compounds and to resemble olefine compounds ; it must, then, be assumed that where the hydrogen has not been added, true double linkings are formed capable of combining with halogens or ozone and of giving Baeyer's permanganate reaction. Baeyer's centric formula would harmonise with this behaviour, since each of the valencies FIG. 432. directed towards the centre is kept in equilibrium with all the others, stability being thus conferred on the molecule ; if, then, two or four of the central valencies are used in the addition of hydrogen or other groups, the remaining central valencies becomes true, olefinic, double linkings. There are, however, aromatic compounds, especially those with several condensed benzene nuclei, with which Baeyer's centric formula alone cannot be assumed. In 1899 Thiele attempted to harmonise all the chemical and physical phenomena observed with benzene and its derivatives on the assumption that when two carbon atoms are united

402

620

ORGANIC CHEMISTRY
=

by a double linking the two affinities are not completely utilised, parts of the unsatisfied valencies (partial valencies) remaining. These are regarded as bringing about addition C, etc., but processes, and are represented by dotted lines, e.g. 9 C

C=C C=C,

when, as in the latter formula, a conjugated system of double bonds is present, the addition of hydrogen, halogens, etc., occurs only at the two extreme carbon atoms, the partial valencies of the two middle atoms forming a new inactive double bond, C = C C= C;
:

after the addition at the

extreme carbon atoms, the central inactive bond becomes

Q
again, the constitution then being,

_C= C_C H

active

In Kekule's benzene formula, we

may assume

the existence of three conjugated double bonds with three inactive bonds,

HC
thus,
||

CH
|

it

would then be clear why benzene, being without partial valencies,

HC

CH

H
would not readily form additive products, and why, when even a single inactive double bond is broken down, true active olefinic double linkings would appear (see Theory of Double Linking, Note on p. 107). A plausible explanation of the constitution of benzene is also arrived at by means of the ideas of motochemistry, according to which double or single linkings arc represented

by double or single vibrations of blows per unit of time (E. Molinari, Gazzetta Italiana, 1893, Vol. II., p. 47, and Journal fur praktische Chemie, 1893, p. 113).

Chimica

ISOMERISM IN BENZENE DERIVATIVES

is

been seen already that when one of the hydrogen atoms of benzene by a halogen or an organic residue, the same monosubstituted is always obtained, no matter at what point of the molecule the compound
It has

replaced

If two substituent groups, either similar or different, substitution occurs. are introduced, three disubstituted derivatives are obtainable. If the benzene molecule is represented simply by a hexagon, each angle of which indicates

a carbon atom united with a hydrogen atom, replacement of the latter by another atom or group (#, y, z, etc.) may be shown by .placing the symbol *of the substituent at the angle of the hexagon. With disubstituted compounds, if one group is assumed to occupy the position 1, the other may go to either 2 or 6 (ort/w-position), 3 or 5 (meta), or 4 (para).

/\
Benzene

/\ \/
Monosubstituted benzene

X
.

/\ r

,/\

/\
1:3- and

/\
'

/\
X
Para-derivative

Ortho-compounds 1 2- and 1:6:

Meta-derivativea
1
:

5-

(identical)

(identical)

trisubstituted derivatives, three isomerides are possible when the three substituents are similar (1:2:3- or vicinal, identical with 1:6:5-; the symmetrical, 1:3:5-, identical with 2:4:6-; and finally, the unsym-

With the

metrical,

1:2:4-,

identical with

1:4:5-):

J* X
Vicinal (**

Symmetrical (-)

Unsymraetrical (cw-)

CHARACTERS OF BENZENE DERIVATIVES

When
one of the three substituents isomerides are possible
:
'

021
six

is

different

from the remaining two,

\/ V
Vicinal

Unsymmetrical

Symmetrical

With four similar substituent groups, it will readily be seen that three isomerides are possible. The number of isomerides may be further increased in cases where one or more of the substituents form lateral chains capable of isomerism, e.g., saturated in these compounds, hydrocarbon or unsaturated alcohol or acid groups further replacement of hydrogen may occur either in the benzene nucleus or in the side-chain, fresh cases of isomerism being thus possible. It was Korner (1869-1874) who first showed how it is possible to determine experimentally the positions of the various substituent groups in the benzene nucleus examples will be given later.
; ;

GENERAL CHARACTERS OF BENZENE DERIVATIVES

While the saturated hydrocarbons of the aliphatic series offer considerable resistance to oxidising agents and to concentrated sulphuric or nitric acid, those of the aromatic scries readily give nitro-derivatives with nitric acid, and derivatives, having an acid character, with sulphuric acid

H 2 + C 6H

S0 3 H (benzenexulphonic acid). In the latter, the sulphur is 5 united directly to a carbon atom of the benzene nucleus, this being confirmed of oxidisby the fact that benzenesulphonic acid is also obtained by the action is known to be the in which C on SH, sulphur 6 5 thiophenol, ing agents joined to carbon. Oxidation of aromatic hydrocarbons containing side-chains leads to the C0 2 H, the benzene nucleus replacement of the latter by carboxyl groups, various aromatic acids are obtained remaining unchanged in this way the

C 6H 6

sulphonic

+ HN0 3 = H 2

C 6H 5

N0 2

(nitrobenzene)

C 6H 6

+ H

S04

/~^CH + 30 = H + <^
3
2
'

)C0 2H;
C0 2H

Toluene

Benzole acid

CH 2 -CH 3

/
The halogen

\
CH 3

+90 = 3H 2 +

_
-

<" ~

y
CO,H aeid

+C0

Nthyltoluene

Isophthalic

substitution derivatives, which are readily obtained by the direct action of the halogens, have less reactive properties than the halogen resistant to substitution. compounds of the aliphatic series and are more The hydroxyl-derivatives (e.g., phenol, C6 5 OH) are more decidedly acid for. 6 5 in character than the alcohols of the fatty series, the plienyl group, their resistance to oxidisexample, being more negative than the ethyl group the tertiary alcohols, to which they are analogous ing agents is similar to that of in constitution, the group being present in both cases. nitroare which The amino-derivatives, readily obtainable by reducing the C6 5 6H 2H 2 aniline) with interderivatives (C 6 5 2 2 are easily converted by the action mediate formation of

>C OH

H N0 +
-

+ H NH
-

azo-compounds of nitrous acid into diazo-compounds

(q.v.),
;

the latter are formed oqiy seldom and

with difiiculty in the case of aliphatic compounds. In their last investigations Korner and Contardi (1908) show how, with the

622

ORGANIC CHEMISTRY

substitution products of benzene, the formation of one isomeride rather than another sometimes depends on minimal differences in the physical conditions under which the reactions take place. Thus, in the nitration ol aniline or of

halogenated derivatives, a very slight difference in the concentration (even in the second decimal place of the specific gravity) is sufficient to alter the yield very considerably or even to give entirely different products.

FORMATION OF BENZENE AND

When
vapours of aliphatic

ITS

DERIVATIVES

compounds

are passed through red-hot tubes,

:

the products formed contain aromatic compounds.

At a red heat acetylene 3C 2 2 C6 6 gives benzene (the reverse reaction is also possible) Another source of aromatic products is the distillation of lignite tar or petroleum residues (see Cracking Process, p. 87).

H = H

When allylene, C 3H4 is distilled with dilute sulphuric acid, mesitylene, C6H 3 (CH 3) 3 (1:3: 5), is obtained, while under similar conditions crotonylene, C4H forms hexamethylbenzene, C 6 (CH 3 ) 6
,
, .

In presence of concentrated sulphuric acid, several aliphatic ketonos undergo condensation to aromatic hydrocarbons thus, acetone forms 1:3: 5-

3H 2 C 6H 3 (CH 3 ) 3 trimethylbenzene, 3C 3 6 Acctoacetaldehyde, CH 3 CO CH 2 CHO, when liberated from its sodium derivative, is transformed immediately into triacetylbenzene, C 6 H 3 (COCH 3 ) 3 Various aromatic compounds may also be obtained by the action of sodium on ethyl bromoacetoacetatc or ethyl succinate, by heating ethyl sodiomalonate and by certain other syntheses. From the tar obtained by distilling coal, wood, or lignite, many aromatic compounds can be separated 5 to 10 per cent, of naphthalene, 1 to 1-5 per

cent, of

benzene and toluene, besides quinoline, anthracene, etc. Benzoic and salicylic acids, bitter almond oil, e.tc., occur naturally
A.

in the

vegetable kingdom.

AROMATIC HYDROCARBONS.

teristic

Those with saturated side-chains are colourless, refractive liquids of characodour, insoluble in water, but extremely soluble in ether or absolute alcohol they are lighter than water (0-830 to 0-806). General Methods of Preparation. (1) Alkyl chlorides and aromatic hydrocarbons in presence of aluminium chloride give mono- and poly-substituted CII 3 Cl hydrocarbons, which can be separated by fractional distillation C 6 H 6 HC1 C 6H5 CH 3 (Friedel and Craft's synthesis) intermediate aluminium
;

compounds are first formed. Ferric chloride, zinc chloride, or zinc turnings act in the same way as aluminium chloride. The latter salt also brings about tho decomposition of the higher hydrocarbons into more simple ones.
(2) In presence of sodium, monobromo-substitution derivatives of aromatic hydrocarbons and alkyl bromide or iodide give higher aromatic hydrocarbons (Fittig's synthesis, analogous to that of Wurtz for the aliphatic series)
:

C 6H 5Br

+ C H I + Na
2

= NaBr + Nal + C H6
6

C 2H 5

calcium salts with soda lime (analogous to the synthesis of aliphatic hydrocarbons)
(3) Distillation of
:

(C H C0

6 5 Calcium benzoate

2 ) 2Ca

+ Ca(OH) = 2CaC0 3 + 2C H
2

6.

(4) Aromatic sulphonic derivatives give the hydrocarbons when heated with C 6H 5 S0 3 tL sulphuric or hydrochloric acid, best in presence of steam C 6 6 On this reaction is based the method used for 2O 2 S0 4 separating aromatic hydrocarbons from those of the aliphatic series, the former with concentrated sulphuric acid giving soluble and the latter (paraffins) insoluble sulphonic acids.

=H

+ H

COAL TAR
(5)

623

When an
:

of zinc chloride at

formed

C6H 6

+ H U OH = H 2 + C H
5
6

aromatic hydrocarbon is dissolved in an alcohol in presence about 3(K), water separates and a higher hydrocarbon is
5

C5H n

COAL TAR
tion nf lar^e

.The cheapest and moat abundant hydrocarbons used as raw material for the preparanpmhpra ojf important aromatic ^ompoundT(from artiticiai perfumes to aniline

d^caX^ie.obtaincd by the distillation _of tar. While at one time this product constituted an nnplpnggnf. anrl inconvenient residue of the illuminatinjjTgas industry (see^ppTlO et tieq.), now an mimh, in ^feynand liyjajge manufacturers of chemical product sj^afj jt 13. s \\, ja scarce, and attention has been turned to the utilisation of the tar produced in
factories, this haying been formerly discarjJecT Westi)halian coal gives, on an average 2-5 per. cent, of tar, that of Saar as 4 per cent., and that of Silesia even more than 4 per cent.
1

much

as

COMMONEST AROMATIC HYDROCARBONS WITH A SINGLE BENZENE NUCLEUS.

1 The first attempt to utilise tar dates back to 1834, when, in a works at Manchester, it was distilled out of contact with air in primitive retorts, the liquid products being collected and the residual pitch employed for making black varnish. Bethell subsequently patented a process for obtaining from tar creosote oil for the impregnation and preservation of wood. illuminant Still later the more volatile products of the distillation of tar were used both as an and as a cleaning liquid. Nitrobenzene was then prepared from it to replace essence of mirbane, but it became possible to develop an. industry for the regular utilisation of tar only after the wonderful discovery by Perkin (1856), who prepared synthetically the first artiticiai coal tar the foundation of one of the most important industries for which the nineteenth thus

dye,

laying

century
for

is

famous.
utilisation of tar
distillation,

Numerous

industries then arose for the more complete and more rational the various products of its fractional employing to the best advantage

Since

624

ORGANIC CHEMISTRY

After separation from the ammoniacal liquors of gas manufacture (by centrifugation), tar forms a dense, somewhat viscous, blackish (since it contains 10 to 30 per cent, of suspended carbon particles) liquid of sp. gr. 1-1 to 1-3. It'coiitains many varied acid, basic, and
indifferent products

the first can be extracted by agitating with aqueous alkali solution, ; the second with acids, while the neutral compounds, consisting principally of aromatic hydrocarbons, form the residue. The composition of tar varies, however, with the nature of the coal, the typo of furnace, and the temperature of distillation. It seems that tar contains at least 300 different substances, of which 150 have been
established cither directly or indirectly and 90 have been isolated with certainty and studied, although only four have wide application in the pure state : benzene, phenol,

toluene,

is tar used as it is for varnishes, coal briquettes, bitumenised 1 paper, lampblack, treating roads to render them less dusty, etc., but for such purposes tho residue from the distillation of tar can also be used. A little tar is used in preparing the basic lining of Bessemer converters for the manufacture of steel.
:

and naphthalene. Only to a small extent

OTHER TARS. These include (1) Lignite tar, which consists mainly of paraffinoid hydrocarbons, both saturated and unsaturated, but contains also phenol, cresol, various bases, sulphur compounds, benzene and its homologues, naphthalene, naphthencs, paraffin wax, etc. It is dense and yellowish -brown or black with a greenish fluorescence, its sp. gr. being 0-82 to 0-95 at 45 and its m.-pt. 25 to 35. When distilled it yields various light
and heavy oils, creosote oil and hard and soft paraffin waxes (see pp. 95 et seq.). (2) Wood tar or Vegetable tar (see pp. 128, 333, 335) has the sp. gr. 1 -06 at 15 and is of less value than coal-tar ; its most important constituents are those soluble in alkali, these consisting of methyl ethers of polyhydric phenols (pyrocatechol, pyrogallol and
homologues, forming
that lime a continuous aeries of mechanical improvements in the plant and chemical ones in the processes have been introduced. Improvement in the coke furnaces to admit of the collection of tho whole of the products of distillation and of the rational recovery of the heat have been dealt with in Vol. I. (p. 451). 1 Lampblack is prepared by the incomplete combustion of tar, colophony, vegetable oils, the pitch or heavy oils from tar, etc. The liquid or fused substance of the receivers, a, is passed through pipes to the long pans, A (Fig. 433), in which it is heated while a carefully regulated minimal air-current is passed over the surface of the liquid so as to burn the vapours incompletely and separate the greater part of the carbon in a free and finely divided state. This is carried away by the air into the first arched chamber, B, where it is partly deposited, then into the second arched chamber, r, and finally into (before the chimney, O),-in which the final traces

FIG. 433.

lampblack are deposited on a thin cloth in front of the mouth of the shaft. This operation continued for five days, the sixth day (Sunday) being occupied in cooling down and the seventh A very tine lampblack is obtained by burning paraffin oil in a kind of lamp with in restarting. a wide thin jet and allowing the flame to impinge on an iron cylinder inside which water circulates ; the cylinder thus cools the flame and the lampblack deposited on it is removed from time to time by an automatic scraper. With more or less intense cooling the lampblack has a lower or higher 100 kilos of tar 25 kilos of lampblack, while 100 kilos of resin residue specific gravity. yield give 20 kilos. Lampblack contains, in addition to free carbon, tarry impurities and oily distillation products. Attempts have been made, apparently without success, to prepare lampblack by exploding acetylene with a measured proportion of air in closed vessels. The Frank process seems to be more advantageous ; in this, acetylene is burned with a certain proportion of carbon monoxide or dioxide : C 2 2 -f- CO = H 2 O 4- 3C. Before the War Swedish lampblack cost 16*. to 20$. per quintal, that from resinous wood It is used for making black varnishes, printers' 40a. to 52s., and that from lamps 8 to 20. Boot polish is made by mixing lampblack with wax, molasses, turpentine, ink, boot jjolish, etc. and sometimes also sulphuric acid or a little chestnut tannin extract to preserve the skin or
of
is

leather.

DISTILLATION OP TAR
cresoste

625

Wood-tar is distilled in a vacuum, the oil), which are used for making guaiacol. gases which do not condense being utilised for power or heating purposes, as they have a calorific value of 6000 to 9000 cals. per cubic metre: (3) Peat tar gives, when distilled, the following products (percentages) : aqueous liquid, about 50 ; this contains 1 -5 per cent, of
acetic acid

2,

and about 2 per cent, of ammonia ; coke, 33 gas, 8 to 10 (28 to 38 per cent. 20 to 25 CO, 6 to* 10 C0 2 32 to 38 CH4 8 to 12 of hoavy hydrocarbons) ; tar, 8.
;
,

DISTILLATION OF TAR
tar is mostly subjected to distillation for the extraction of the following products (1) Indifferent substances, in which benzene hydrocarbons predominate (benzene, toluene, xylene, tri- and tetra-methylbenzene, and, to a still greater extent, naphthalene,

Nowadays
:

anthracene, etc.), those of the methane series being small in amount (these occur abundantly in the distillation products of lignite or peat tar and of bituminous shale, see pp. 95-100). Small quantities of nitrogen compounds occur, such as acetonitrile, beuzonitrile, carbazolo, and pyrrole derivatives, and also traces of carbon disulphide, thiophene,

cumarone, etc. (2) Acid substances, among which phenol (carbolic acid), cresol, xylenol, and the naphthols abound. (3) Basic substances, which are found in small amount and contain small proportions of pyridine and quinoline compounds and a trace of aniline. In order to prevent bumping and frothing over during distillation, tar must be completely freed from water, which it holds tenaciously. In gas works the wet tar passes continuously into a small tank C (Fig. 434) where the ammoniacal liquor overflows into
;

A, while the tar is syphoned into B. Gypsum or cement is also used for removing the
water. 1

Treatment of the wet tar with water removes a large proportion of the ammoniacal liquor, this being especially

advantageous

subjected to continuous distillation owing to the removal of ammonium compounds liable to obstruct the cooling coils and to prevention of corrosion by the
tar
is

when the

-::i

hydrogen chloride produced by dissociation

of the

ammonium

chloride.

Application of

to the upper part of the boiler, and only later to the lower, is suggested for preventing aqueous tar from frothing over.

heat

first

The ammonia water may also be largely FIG. 434. removed by centrifuging the tar. In largo distilleries the dehydration and distillation of the tar are carried out simultaneously. The old type of boiler is shown in Fig. 435, but preference is now given to horizontal locomotive boilers, in order to obtain more stills, which are sometimes multitubular, like 2 It will be seen in the figure that direct-fire heat is homogeneous and more rapid heating. used (at 6) the mass is mixed at intervals by means of a stirrer or of a steam-jet introduced
;

is not easy, since when the tar is heated in a dish it readily and overflows. Beck and Rispler (1909 and 1904) allow 200 grms. of the tar to fail drop by drop from a separating funnel on to about 500 grms. of water-free heavy tar-oil contained each drop of tar, as it falls, is instantly evaporated, and the water in a flask of about 2 litres with the flask and collected, together distilling over is condensed in the refrigerator connected the temperature is finally raised to 300. The with a little tar-oil, in a graduated cylinder from the oil its volume cylinder is kept at a moderate temperature, so that the water separates is then read. If much naphthalene also distils over, it is difficult to read the volume of the water in this case, the whole of the distillate is poured on to a small filter-paper steeped in benzene, so that water allowed to pass into only the tar-oil filters. The filter-paper is subsequently pierced and the a graduated cylinder. Ott, on the other hand, heats 400 grms. of tar in a copper retort, the heating orifices in its lower side. being carried out from the top by means of an annular gas-pipe with 2 The rapid wear of the iron vessels and coils is due especially to HOI, NH 3 H 2 S, HCN, etc., formed by the dissociation at high temperatures of chlorides (e.g., ammonium chloride, dissociating The base at 360), etc., and perhaps also by certain electrolytic processes.
1

Estimation of water in tar

froths

of the
iron,

sulphides, cyanides, Cast-iron coils last better than those of wrpughtoften 18 to 20 mm. in thickness. of superposed straight tubes connected at alternate ends by semicircular pipes of cast iron.
still is

and are composed

626
at x
at r t

ORGANIC CHEMISTRY

and subdivided on the arched base of the still by a number of pipes, z. The tar enters and at the end of the operation the pitch is discharged through a much wider oriiice than that marked a. A thermometer or pyrometer is inserted at v, while t serves as exit for the vapours, which are condensed in a coil surrounded by cold water in the case of the first products and by hot water in that of the last
products
;

number
to

of small receivers,

large batteries under light roofs open at the sides so that the damage in case of fire or explosion may be mini-

these are collected in'order of density in a from which they are passed The stills arc arranged in store-tanks.

mised, the further precaution being taken of placing the fire hearths outside in the open. When the products formed at 270 are distilled over, the yield is
increased

and the pitch rendered more liquid, and so prevented from charring, by introducing a current of superheated steam, this removing various substances (anthracene oil) which would otherwise remain in the pitch. The latter is then discharged, while hot,
into old, disused stoam boilers so as to avoid contact

with the air, which might ignite the mass when almost cold but still fluid, it is run into shallow vessels Fid. 435. or pits dug "in the earth and allowed to solidify. With a still holding 300 to 400 quintals, each distillation (including charging and discharging) lasts about four days. Distillation in a vacuum saves time, lessens repairs, and gives an improved yield of oil, better pitch, and a smaller deposit of coke, so that it suffices to clean the retorts after 25 or 30 charges. In large tar distilleries, after the temperature in the still has reached 270, the distillation is completed by passing into the mass a current of superheated steam at 275, the
;

FIGS. 436-437.

a harder pitch products boiling at higher temperatures being thus distilled unaltered and obtained ; if a soft pitch is desired, heavy oil is introduced into the boiler at the end of the
distillation.

fuel

Various systems of continuous distillation have been introduced to economise plant, and labour. In the Lenhard process the washed and dried tar, heated to 100, is forced metres in length, slowly (70 tons per 24 hours) through a weldless iron coil about 800 heated in a furnace by means of producer gas. The temperature of the tar may reach 350

TAR PRODUCTS
successive coils.

627

and, as the mass passes from the coil to a separating vessel, the hot pitch separates arid the remainder is transformed instantly into vapours, which are condensed in several

In the Hirzel system the whole distillation is effected continuously in a current of superheated steam, only the final products being distilled by direct fire heat from a still

438-439.

connected with the first one. In this way the different oils distil at temperatures lower by 125 to 150 than in the ordinary apparatus, and, hence, are not only less highly coloured, but are also obtained in better yields. In the Ray system, five or more cylindrical iron retorts are arranged parallel, but alternately, with one extremity high and the other low (Figs. 436- -439). The tar from a raised tank enters at the bottom of the first boiler and passes out at the top to enter the second boiler at the base, and so on. The furnace gases heat the last boiler first, so that this attains the highest temperature and the first boiler the lowest The vapours temperature. from the different boilers are condensed in separate coils.

Werneoke (Ger. Pat: 301,372, 1907, and 237.823, 1911), has proposed the use of a conical,
stepped still, A* fitted with a number of superposed peripheral channels, E, inside (Fig. 440). The cover, B, is fitted with a vapour outlet, I,' and a pipe, a, for the continuous introduction of the tar (which first passes through a heater, where the water and light oils are distilled). The latter enters the uppermost channel, E, and overflows into the lower channels, gradually diminishing in volume owing to the distillation of various products the more or less liquid pitch is discharged at d. The vapours of the medium oils pass through the upper orifice, 6, to refrigerators, but those of the heavy oils from the lower channels are collected by the perforated FTG. 440. pipe, DF, which is provided with a cap, Q, and is surrounded by metal gauze, and carries them through c to refrigerators. The still is heated by the gases from the hearth, r, which circulate in the flues, e. The distillation is interrupted only once in 4 to 8 weeks to allow of the removal of the coke deposited on the inner surface of the still. Although the total capacity of the channels is only 600 kilos of tar, the daily output is equal to that of a still of the old typo holding 2500 to 3000 kilos. Such a still also serves well for the distillation of lubricating oils from petroleum residues.
;

PRODUCTS OF THE DISTILLATION OF COAL TAR. The products

which

distil

below

628

ORGANIC CHEMISTRY
(3 to 5 per cent.) which that distilling between 110 and 170, this forming the so-called light tar-oils (fp. gr. 0-910 to 0-950). From 170 to 230 the phenols or medium oils or creosote oils (6 to 9 per cent.) are collected.
is

110 at ordinary pressure (sp. gr. 0*900 to 0*910) are somewhat similar to the ammoniacal liquor of gasworks, and consist of a more or less coloured liquid on which floats an oil containing a little benzene and toluene.

The second portion

is

collected

The next
and the

of heavy oils (up to

final one,

fraction (25 to 30 per cent.) consists 270 ; sp. gr. 0-980 to 1-030),

the anthracene,

oil (7

to 9 per

270 to 320 (sp. gr. 1-050 to 1 -095) and forms a buttery mass composed of
cent.) passes over at
oils

and crystalline substances. constitutes the pitch.

The

final residue

The percentage amounts of the different products obtained from tar arc, on the average, as follows benzene, about 0-6 ; toluene, 0-4 ;
:

homologues of toluene, 0*5 crude phenol, 1 higher phenols, 4 to 5 pyridine bases, 0-2 naphthalene, 7 to 10 heavy oils, 23 to 26
; ;

anthracene, 0-3

phenanthrene, 0-6 pitch, 55 to 60 ; ammonia liquor, 4 ; gas, about 1 -5. 1 The various fractions obtained in the first
;
;

distillation of tar are treated as follows

FIG. 441.

brownish-yellow Their comand darken in the air and light. position varies with the quality of the tar, as is shown by the following results obtained in
actual practice
:

(A)

The

LIGHT OILS*

are

Gasworks
tar.

Coke-o\on
tar.

Crude benzene

Phenol oils Residue (medium Water and loss

36-12 per cent. 11. (distilled at 135 to 165) 15-59 per cent. 18-01 per cent. (165 to 195)
I.

(distilled

up

to

135)
.

12 -66 per cent. 16-42 per cent.

oils)

.26-51

per cent.

3 '67 per cent.

18-47 per cent. 49-36 per cent. 3-09 per cent.

The light oils are distilled and rectified in a column apparatus (Fig. 441) with stills holding 100 to 200 quintals and heated by direct -lire or by superheated indirect steam ; the first three fractions (up to 195) are collected separately. The crude benzenes I. and II.
can bo purified from the small amount of phenols they contain by washing with caustic soda solution ; the remaining benzene is then rectified again in order to remove the toluene, of which it may contain as much as 25 per cent, (see later, Benzene). The phenol oils (disand 195) contain appreciable quantities of naphthalene, and are tilled between 165 therefore worked up with the medium oils.
(B) MIDDLE or CREOSOTE OILS vary in amount from 5 to 10 per cent, according to the type of tar used and to the temperature of distillation (110 to 180), They are brown, and at the ordinary temperature become pasty owing to the separation of naphthalene
crystals.
1

They darken

in the air

and on

distillation give the following

components

In a large Cermari coke-tar

distillery,
:

where retorts holding 350 quintals were used, the

4-27 per cent. ; light oils, 4-06 ; The pitch, 60-49; loss, 0-98. tar distilled contained on an average 24 per cent, of matter (carbon) insoluble in benzene, and the mean cost of distilling 1000 kilos of tar was as follows : Labour, 7-7c/. ; coal (at la. Id. per quintal), 144e?. ; steam, 4-8^. ; various materials, l-4rf. ; repairs, 3 -8d. ; depreciation, 11 -5d. ; total, 43- Orf. In a large distillery fitted with retorts holding 180 quintals and working at reduced pressure a larger annual output was attained, while the mean cost per ton distilled was 36-5rf, ; the yields were as follow : Ammoniacal liquor, 3-86 per cent. ; light oils, 1-24 ; medium oils, 12-02; heavy When tar free from water is distilled oils, 8-50 ; anthracene oil, 18-68 ; pitch, 54-56 ; loss, M4. the consumption of coal is diminished from 7-6 to 6 per cent.

mean yields of several years were as follows Ammoniacal liquor, medium oils, 10-38; heavy oils, 6-11; anthracene oil, 13-71;

HEAVY TAR-OILS

629

and form a semi-solid, blackish (C) HEAVY OILS constitute 25 to 30 per cent, of the tar mass, that obtained from gas (metallurgical coke) tar containing about 28 (30) per cent, of naphthalene and 16 (10) per cent, of phenols. They are fractionally distilled, the main 1 middle fraction being either used directly for various purposes or distilled in a vacuum.
1 Heavy tar-oil, when not redistilled in a vacuum to recover the anthracene, is used as an To illuminant, or for the manufacture of lighting gas, or as fuel, or for impregnating wood. obtain illuminating gas the oil is run in a thin stream into heated iron retorts (as in the cracking of petroleum, see p. 87), carbon and an oil still containing a considerable proportion of benzene being formed in addition to tho lighting gas. When these oils are used directly for heating purposes, they are pulverised under the furnaces by means of ft steam-jet which introduces the necessary quantity of air. At the Deutz gas-engine works (near Cologne), heavy tar-oil has been applied in Diesel engines, i Tar itself may be used in these engines, especially that from vertical furnaces, which contains far less naphthalene (2 to 3 per cent.) than that from horizontal or inclined gas retorts; the at which coal is distilled the greater is the proportion of paraffin lower the

considerable amount of heavy tar-oils is used for the disinfection and dcodorisation with water may be replaced with advantage by brushing of urinals ; continuous rinsing of these on a thin layer of a mixture of tar-oils of various compositions (heavy tar-oils mixed with heavy sp. gr. 0-990 mineral oil, soap, etc.). This mixture should answer the following requirements and should not separate into different at most ; b.-pt. 105 at least ; it should remain liquid at or free alkalis or mineral acids ; at layers on standing ; it should not contain soap, alcohols, least 75 per cent, should distil at 350 ; it should contain at least 7 per cent, of cresol. the preservation of wood. Timber, Very large quantities of heavy oils are now used for when in contact with the ground, are injured railway sleepers, telegraph poles, etc., especially and become unusable in a few years owing to the attacks of various moulds and micro-organisms

temperature hydrocarbons obtained.

when hard wood is used it gradually (Merulius lacriman*, Polyftorus vaporarius, etc.). Even becomes considerably attacked. Telegraph poles and railway sleepers have been successfully treated by jsmearing with pitch or bitumen the parts which come into contact with the earth, and superficial charring of the wood at the points most subject to attack has also been tried. wood. Concentrated and more Formerly much use was made of the method of mineralising or less hot solutions of various salts (ferrous or copper sulphate, zinc chloride, etc.) are forced or the wood is heated in a large autoclave, which is into the pores of the wood under pressure then evacuated to remove all -the air and water from tho pores and subsequently filled with the salt solution, which thus impregnates the wood completely. The process which gives the best results and has become widely used in recent years is, however, that of Bethell, which consists in tho complete impregnation of tho timber with heavy tar-oils (crude creosote oil) these contain phenols, cresols, etc., which have a marked disinfecting action. In Italy this not in autoclaves, but in open vessels, process has been applied for some years, and is carried out, such as are used in America, the treatment being completed in zinc solutions according to the immersed for 5 to 6 hours in improvements of the Giussani patents. The beams are first a bath of fused inasut (sec p. 86) kept at 160 to 170, by which means the wood is deprived medium of its ah? and water and sterilised they are then passed into a cold vessel containing cent, due to various tar-oil (the portion distilling at 210 to 240 and having an acidity of 25 per the oil penetrates the pores to a depth of 1 cm. phenols) where, after 20 to 30 minutes' cooling, The wood is finally left for 3 to 4 hours in a cold, concentrated solution of zinc or more thin superposed layer in the pores (the wood chloride, which forces the oil further in and forms a the absorbs as much as 15 per cent, of the zinc chloride solution). Thus treated, wood resists as hard. action of weather, water, and soil for 15 to 20 years, soft wood being as resistant The German railways require that every sleeper, 2-7 X 0-26 X 0-16 metres, shall contain In order to economise tar-oil, Ruping's process is often used. This 7 kilos of creosote oil. the wood and then consists in creating an air pressure of 5 atmos. in the autoclave containing When the pressure in the autoclave subseintroducing the creosote oil at 10 atmos. pressure. air compressed in the pores, the latter quently falls off, the excess of oil is forced out by tho In this way 2 kilos of creosote oil give the same remaining coated inside with a thin layer of oil.
; ; ;

sterilising effect.

Tar-oils freed
,

from the phenols have a bactericidal

effect three times

,.

thatjrf

ziiw chloride,

especially if they are emulf

630

ORGANIC CHEMISTRY

(D) ANTHRACENE OIL or green oil, obtained in the direct distillation of t*r, is a dense, almost buttery, greenish-brown mass of specific gravity 1-09 to 1-125, fluid at 60. It contains 6 to 10 per cent, of crude anthracene (40 per cent, of anthracene), besides naphthalene, methylnaphthalene, phenanthrene, acenaphthene, diphenyl, methylanthracene, pyrene, chrysene, retene, fluorene, fluoranthrene, benzerythrene, carbazole, acridine, about 6 per

and /2-naphthols, and various basic substances. usually collected in two fractions, I. and II. Anthracene oil I., with specific gravity ^p to 1-100, is used for the preparation of anthracene, and anthracene oil II. either for making oil gas (see p. 64), or lamp-black, or for removing the^naphthalene
cent, of higher phenols, a-

The anthracene

oil is

from coal gas (see p. 47), or for making carbolineum, which is used to preserve and stain wood. (E) TPITCH is the final residue of the direct distillation of coal tar (or peat or lignite tar) and forms about 50 to 55 per cent, of the tar. According to whether the pitch (residue) is required to be more or less liquid or solid, the distillation is. suspended after the third or fourth fraction has been collected to render
;

the pitch shiny, it is mixed in the still with the heavy oil remaining after the crystallisation of the anthracene. Soft pitch melts at 50, medium pitch at about 70 (used in making briquettes from
coal residues

and hard pitch, of sp. gr. 1-25 to 1-275, at 90. interrupting the distillation of the tar when tho light products have been eliminated and passing a current of air through the liquid at 100. To
;

see Vol.

I.,

p. 459),

Artificial pitch is

made by

render the pitch more readily fusible, it is fused with sulphur. The percentage elementary composition of pitch is C, 85 to 92 H, 4-6 to 4-8 ; 8, 3 to 7 ; ash, 0-5 to 2-5. Pure carbon remains undissolved when pitch is extracted with tar phenols, but benzene extracts from pitch a pure litmtien used in electrotechnics, the insoluble part being employed
: ;

+N+

either to

make lamp-black

or as retort graphite for

making

electrodes.

Perkiii calculated the value of the final products of the complete and rational treatment of 9,000,000 tons of coal (costing 5,400,000) to be as follows : dyes, 3,350,000 ; ammo-

nium sulphate (195,000

(1,125,000 hectoK),
2,400,000. carbonised.
Total,

tons),

1,960,000;

pitch (325,000

tons),'

365,000;

creosote oil

208,000;
8,503,000,

carbolic acid (45,000 hectols.), 220,000; coke exclusive of the 30 cu. metres of gas per ton of coal

crude

BENZENE (or Benzol), C 6H 6 This was discovered by Faraday in 1825 in the liquid obtained on compressing illuminating gas, but the more abundant
.

source, tar, was found by Hofmann in 1845. It is obtained pure by the dry distillation of benzoic acid with lime, and then forms a colourless, mobile, highly refractive liquid of sp. gr. 0-8841 at 15, b.-pt. 804 (a mixture of 60-65 parts of benzene with 39-35 of methyl alcohol boils unchanged at 58-35), and 54 it burns with a luminous, m.-pt.

smoky

flame.

The calorific value of benzene is 10,050 cals. per kilo, the latent heat of evaporation being 94-4 cals,, and the vapour pressures at different temperatures
as follows
:

Mm.

Temperature - 10 of Mercury 14-8

10
20-5

20
74-7

30
118-2

40
181

454

50 209

GO
388-6

70
547-4

80
753-6

90
10-16

100 1344

The commercial product contains thiophen and traces

which
be eliminated in various ways, e.g., with moist Ger. Pat. 133,761) which separates insoluble oil drops, or

of carbon disulphide,

may

ammonia (Schwalbe, by boiling with mer-

their weight of water less than 1 kilo of tar-oils results have also been obtained with
;

is thus sufficient for a railway sleeper. Good heavy petroleum oils heated to 200 with 2 per cent, of sulphur and then mixed with 40 per cent, of creosote oil. According to Friedmami and Heidenstam, wood is preserved well by impregnating it with calcium cresolate (soluble in water) and then precipitating calcium carbonate and cresol in the pores by simple exposure of the wood to air or, better, to fumes rich in carbon dioxide (Danish

Pat. 12,419 of 1909). Injection of a hot solution of zinc 0-naphthalenesulphonate, .which insoluble in the cold, has also been suggested.

is

KUBIERSCHKY COLUMN
curie acetate, sulplmr chloride, or -5 per cent, of ing to Uer. Pat. 211,239, formaldehyde,
;

631

aluminium chloride accordacetaldehyde, or phthalic anhydride

may also be used, all these substances combining with thiopheri. Benzene dissolves resins, fats, sulphur, rubber, gutta-percha, camphor, etc., it mixes with alcohol, ether, acetone, etc., and is almost completely insoluble in water.
on

The preparation of artificial benzene, starting with petroleum, was described Benzene forms the prime material for many varied syntheses of p. 87. aromatic compounds, such as nitrobenzene,^ aniline, phenol, etc., and of dyes In presence of A1C1 3 it is rendered more (also nowadays of artificial indigo). active chemically, as though it contained a true double linking. It is used as a solvent for fats and for purifying many organic compounds the addition of 15 per cent, of benzene to the alcohol used with an Auer mantle for lighting
;

purposes results in a saving of 27 per cent, of the alcohol. Large quantities of 90 per cent, benzene are now used for carburetting illuminating gas to which It is also employed for dissolving rubber water-gas has been added (see p. 58).

and

lacs for making linoleum, for removing fat from bones, and for automobile engines, but should contain toluene to prevent it from freezing in winter.

was obtained exclusively from gas-tar, this yielding also larger quanthe uses of which were limited. After 1880, when the tendency was to obtain increased yields of illuminating gas by raising the temperature of carbonisation of the coal, the quantity of tar diminished, as also, in still greater proportion, did the amount of benzene. In 1882, the price of benzene, then in great demand by dye manufacturers, exceeded 12 per quintal. It was then that attention was turned to the recovery of the tar from metallurgical coke factories, but although this tar is obtainable in large amounts, it is very poor in benzene, most of wljich escapes with the gases and is wasted in the furnaces. Darby was the first to suggest the recovery of the benzene from the gases of the coke furnaces and nowadays these gases, before being burnt, are either strongly cooled to condense the benzene or washed with slightly volatile tar-oils, in which the benzene dissolves and from which it is recovered by subsequent beating (see Note, p. 58). 1 As a
it

At one time

tities of toluene,

1 Benzene is now recovered from its solutions in heavy mineral or tar-oils by means of the f Kubierschky rectifying column ((j|er. Pat. 194, >G7, 1906), which works continuously and gives a sharper separation of the components of a mixture than other systems. The action of this column is based on the displacement of a vapour or the two layers do gas by superposition of another lighter vapour or gas not mix if the velocity of movement is less than 0-75 metre per second, and usually the velocity in such an apparatus is ()3 metre per second. In the ordinary rectifying column (we p. 158) the mixed vapour (for instance, of alcohol and water) passes upwards and has to overcome the resistance of the liquid layers in the chambers above further, the lighter, hotter and less concentrated vapours below do not merely displace the cooler, heavier and more concentrated vapours of the upper chambers, but mix with them to some extent and render the rectification less perfect. vEri the Kubierschky column, however, the lighter vapour passes from the lower part of one chamber to the upper part of the chamber above and settles gently on the heavier and colder vapour contained therein, this being thus forced to the upper part of the chamber above (see Fig. 442). The dilutp alcoholic liquid enters half way up the column by the pipe a and descends as a spray through the perforated plates of chambers 6, 5, and so on. At the same time steam at slightly above 100 enters by b into chamber I and descends along with the spray of alcoholic; liquid from the perforated base of chamber 2. This liquid gives up to the steam any traces of alcohol it still contains and is discharged from the perforated bottom of chamber 1 through the pipe (?., The steam passes into the upper part of chamber 2 and there forms a layer above the slightly more alcoholic (and hence heavier) vapour therein and forces this into the top of chamber 3, and so on. The ascending vapours are not subjected to friction, since they fall with the liquid spray and never bubble through liquid layers. At the top of the column, in chamber 14, the vapour rich in alcohol rises through the
;

to the dephlcgrnator, B (acting as a prcheater for the dilute alcoholic column at a), where a little water and a very little alcohol condense and fall as spray into chamber 14 and the lower chambers. The i alcohol-rich vapour not condensed in the dephlegmator issues through tha. netroleum 11 pipe c. and is condensed in a coil a short distance away. The col Further J benzene is composed of a number of flanged cast or wrought-iron rings or f attack fl tt n ,.i/ trnloiim 4 es not P etrolcum Communication between the lower part of one chamber and[V

pipe

liquid entering the

'

632

ORGANIC CHEMISTRY

result of this process, the production of benzene became more than ten times that of toluene, the price, which was 2 to 3 per quintal in the period 1885-1896, falling to 20s. to 245. Pure thiophen-free benzene cost before the War in 1898-191Q, and to below 16s. in 1913. about Is. 6d. per kilo and the puriss. product, obtained from benzoic acid, 325. per kilo. Various forms of apparatus are used for distilling and rectifying crude benzene, all being heated by means of indirect steam. Use may be made of Hirzel's apparatus (p. 88), or of the similar one of Heckmann (p. 165), but having a still with a smaller base in the form of a short, horizontal cylinder and with a dephlegmator in the upper part of the

column. 1 above
or
is effected by means of various arrangements, for example, by tubes, as shown in Fig. 443, by means of a central tube and a peripheral annular space (Fig. 444). The liquid collecting bottom of each chamber passes into the chamber beneath through hydraulically sealed on the * The fall ses of the chambers being thus prevented. bells passage of the vapour through the bases
<

Fro. 444.
or of the spray may be rendered slower by the insertion in the chambers of perforated plates metallic gauze (Fig. 444). For the recovery of benzene from its solutions in heavy oils use may be made of two such columns superposed. In the lower one the solution, falling as a spray, comes into contact with

steam which removes the benzene, the mixed water and benzene vapours then passing upwards benzene. The mixed water and through the upper column, where they meet a spray of crude benzene vapours issuing from the top of this column are condensed and the water separated by
_ __ , ., v* commercial 90 per cent, different fractions obtained on rectification are as follows : (1) and 100 cent, at 120 ; 100 at distils this of cent, per at 15 0-885 (90 per benzene I. of sp. gr. 120 is termed the dry -point of the benzene) ; (2) 50 per it contains about 20 per cent, of toluene ; at 100 and 90 per cent, at 120 ) ; 0-880 with (50 per cent, of this distils cent benzene sp. gr. or solvent naphtha with sp. gr. 0-875 (20 per cent, of this distils at 130 and (3) 'heavy benzene it serves as a good solvent for rubber). cent, at 160

decantation.
i

The

90 per

tmw

The

testing of
it
'

commercial benzene is carried out by determining its density and by fractionally 100 c.c. are distilled in an ordinary flask with a side-tube (see p. 75) and heated the flame th a flame so adjusted that two drops distil over per second before changing the cylinders in which the separate fractions (100, some cases a nitration test is made, note being taken of the The later t Nitrobenzene). by steanv and then rectified (see
;

TOLUENE, XY^ENES
f uKE BENZENE, now
tries,

633

required in considerable quantities for various chemical indussuch as the manufacture of synthetic phenol (see later), the manufacture of nitrobenzene for making pure aniline, etc., is obtained from purified 90 per cent, benzene. This is washed several times with a total of 2 to 3 per cent, of 96 to 98 per cent, sulphuric acid or of 2 per cent, of oleum. After standing for some time, it is washed first with a little water and then with 18 per cent, caustic soda solution (04 per cent, of NaOH calculated on the weight of the benzene), and afterwards subjected to careful fractional distillation, being heated by indirect steam. The fraction boiling at 80 to 85 is further rectified, and then yields 1)9-5 per cent, be-iizene, b.-pt, 80-2 to 80-8 at 760 mm. pressure ; a variation of I mm. in the pressure alters the boiling-point by about 0-05. The final purification of small quantities of benzene may be offected by cooling the from the liquid until it freezes and then squeezing or ceiitrifuging away the toluene, etc.,
crystals.

When shaken with an equal volume of pure concentrated sulphuric acid, pure benzene should not turn the acid yellow. If traces of thiophen are present, the benzene will give blue colour of indophenin when treated with isatin and concentrated sulphuric acid t)*e TOLUENE (or Methylbenzene), C C H 5 CH 3 , is formed by the dry distillation of balsam of Tolu and of various resins, and is obtained in appreciable quantities by the distillation 28, and has the sp. gr. of tar (see about). It boils at 110-4, does not solidify even at 0-87 at 15. It occurs to the extent of 10 to 16 per cent, in crude benzene L and of 25 per
:

cent, or

more

in crude benzene Tf.

is purified from the hydrocarbons of the fatty series which always accom(ami are, not eliminated by rectification) by washing it with hot sulphuric add decomcontaining a little nitric acid, the olefines being thus polymerised and the thiophen posed, ft may also be purified by heating with sodium. Commercial puro toluene gives 99 per cent, of distillate below 1 12 and 95 per cent, between 108 and 110 (two drops per second). It does not colour on protracted sliaking with concentrated sulphuric acid, and if 90 c.c. of toluene and 10 c.c. of nitric acid (44 the nitric acid Be.) are shaken together for some minutes in a tall glass-stop|>ered cylinder, should become only a transparent red and not a greenish black and should not thicken. Toluene is used hi the manufacture of dyes, pharmaceutical products, perfumes, etc., and, during recent years, of trinitrotoluene (see later), which is used in largo quantities as

Crude toluene
it

pany

an explosive.

XYLENES (Dimethylbenzenes), C H 4 (CH a ) 2 Xylene obtained from tar contains the three isomerides, o-, m-, and p-, metaxyleiie being present to the extent of 70 to 80 per rent. They cannot be separated by fractional distillation owing to the small differences
.
fl

m- 139 between their boiling-points (o- 142 p- 138). Treatment with concentrated sulphuric acid in the cold, however, converts the o- and m- compounds into the corresponding sulphonic acids, the p-xylenc remaining unchanged. The sodium salt of o-tolucnosulpkonic acid crystallises more readily than that of the w-compound, so that the three hydrocarbons can be separated. With oxidising agents,
;

the xylenes give phthalic acids

It is

(see later).
is

used in the manufacture of dyes. is obtained by Fit-tig's synthesis benzole acid on oxidation (difference from the xylenes).
mostly w-xylene which
fi

ETHYLBENZENE, C H5 C 2 H5
known

(see p. 622)

and gives

TRIMETHYLBENZENES, C 6 H 3 (CH 3
arc
:
:

)3

(see

Table, p. 623).

The

following isomerides

3 5-) is a liquid of pleasant odour boiling at 165. Its (a) Mesitylene (symni. 1 constitution is proved by its synthesis from acetone or allylene, by the faet that it does not form isomeric compounds by further substitution in the nucleus, and by its oxidation nitric acid oxidises the three side-chains successively and chromic acid simulproducts
:

taneously.

Pseudocumene (asymm, 1:2:4-) is prepared from bromo-p-xylene (1:4:2) or It is bromo-w-xylenc (1:3:4) by Fittig's synthesis, which indicates its constitution. obtained in small proportion from the distillation products of tar, and is separated from
(6)

mesitylene by conversion into the slightly soluble sulphonic acid (see Xylenes).
addition of petroleum spirit to benzene is detected by the lowering of the density ; also petroleum does not dissolve tar-pitch or picric acid, which are readily soluble in benzene. Further, tho latter reacts vigorously with concentrated nitric acid, which does not attack petroleum
spirit
Bpirit. k

VOL.

II.

41

634
(c)

ORGANIC CHEMISTRY
n-Propylbenzene, facts that
(Fittig)

C 6 H6
it

CH 2 CH 2 CH3

shown by the
thetically

from

yields benzoic acid propyl iodide and

The constitution of this compound is when oxidised and that it is obtained syn.

C 6 H 5 CH 2C1, and
(d)

bromobenzene or from benzyl chloride,

zinc ethyl.

Isopropylbenzene (or cumene), <

CH(CH 3

)2,

also gives benzoic acid

on

oxidation,
(in
is

and is formed from benzene with either isopropyl iodide or normal propyl iodide the latter case aluminium chloride is necessary to cause molecular rearrangement) ; it obtained also on distilling cuminic acid, C 6 4 (C 3 7 ) CO 2 H, or by the interaction of

benzylideno chloride,
ing
:

CHC1 2 and zinc methyl. TETRAMETHYLBENZENES, C H 2 (CH 3 ) 4 The best known

6
,
.

H5

of these are the follow-

durene, in tar

Durene (1:2:4:5) or s-tetramethylbenzene, which is found, together with isoit is a solid, has a smell resembling that of camphor, and is prepared synthetically from toluene and methyl chloride. (6) and (c) Isodurenes, two isomerides being known (1:2:3:4 and 1:2:3:5) (see
(a)
;

Table, p. 623).
(d)

p-Methylisopropylbenzene

or

cymene,

CH 3<^

CH(CH 3

)2,

is

a liquid of

pleasant odour, b.-pt. 185. It occurs naturally in cumin oil (from Cumiwum cyminum) and in various essential esters, and it can be prepared by heating camphor with phosphoric

anhydride or by the interaction of

various acids.

oil of

turpentine and iodine.

On

oxidation

it

yields

(e) m-Isocymene is found in resin oil. Hexamethylbenzene (mellithene), C 6 (CH 3 ) 6 m.-pt. 164, is a stable compound and can bo neither nitrated nor sulphonated, owing to the absence of hydrogen atoms from the nucleus. When oxidised with potassium permanganate, it gives Mellitic Acid, C 6 (C0 2 H) 6
,

HYDROCARBONS WITH UNSATURATED SIDE-CHAINS

tives, whilst

compounds behave like true benzene derivaby means of the unsaturated side-chain they give all the reactions of unHaturated methane derivatives. STYRENE, C 6 H 5 CH CH 2 occurs in storax and is formed on heating cinnamic acid,
: ,

As

far as the nucleus is concerned, these

which

loses

CO 2

C 6 H B CH CH CO 2 H
-

= C0 +
2

C 6 H 5 CH CH 2
:

It

is

a liquid of

C 6 H 6 CHO CH 3 N0 2 -= C 6 H 5 CH CH NO a H 2 O. aldehyde and nitromcthane Styrene serves for the synthesis of anthracene (q.v.). PHENYLACETYLENE, C 6 H 6 C CH, is a liquid of pleasant odour boiling at 142, and is prepared by converting acetophcnone, C 6 H 5 CO CH"3 by means of 1'C15 , into the dichloro-derivative, C 6 H 5 CC1 2 CH 3 and eliminating 2HC1 from the latter by the action
:

pleasant odour boiling at 146, and tends to polymerise to Metastyrene. Styrene combines with bromine, iodine, hydrogen, etc., in the same way as olefines do. When it is treated with nitric acid, a nitro-group is introduced into the side-chain, giving Nitrostyrene, C 6 5 CH CH 2 the constitution of this being shown by its formation from bcnz-

NO

C 6 C C CO 2 H. Like acetylene, it forms metallic compounds ; treatment with concentrated sulphuric acid results in the addition of 2 O, subsequent dilution with water giving acetophonone.
:
fl

of potassium hydroxide. It is also obtained by the cautious distillation of Phenylpropiolic acid,

B.

HALOGEN SUBSTITUTION PRODUCTS OF BENZENE

Halogens act on benzene and its homologues, replacing one or more atoms hydrogen and forming colourless liquids (sometimes crystalline substances) which are heavier than water, distil unchanged, and dissolve in alcohol and in
of
ether.

In aromatic hydrocarbons, a halogen in the benzene nucleus is held much firmly than one in a side-chain and cannot be replaced by hydroxyl by the action of silver hydroxide or by the amino-group by treatment with ammonia only by sodium or sodium alkoxide at about 200 can the halogen be eliminated.

more

AROMATIC HALOGEN COMPOUNDS

*

635

The chlorine? in the nucleus of chlorotoluene benzene, whilst the chlorine in benzyl chloride is readily replaceable, just as is the case with that in methane derivatives. To ascertain whether the halogen is present in the nucleus or in the side-chain, the oxidation products are studied thus, chlorotoluene gives chlorobenzoic acid, C 6 4 C1 C0 2 rl, whilst benzyl chloride yields benzoic acid. For distinguishing isoraeric halogen derivatives, the same methods are used as for the xylenes, etc. In order to be able to name aromatic derivatives the more readily, the following names are given to the more common of the different groups or
is

united as firmly as in chloro-

aromatic residues (known as aryl radicals and denoted generally by Ar) Ce H 5 phenyl O CH 3 methoxy C0 2H, carboxyl OH, phenolic S0 3I1, sulpho CH 2 C6H 5 benzyl ; CO C6 5 benzoyl ON, nitrile
:

or sulphonic

C C6H5
;

benzenyl
6

C6H4<^
,

/C^

/ 0,

phthalyl

Oil

C61I5

benzylidenc or benzal

and bromine act on benzene, giving additive products, e.g., C6II 6 C1 6 and C6H6 Brg, but in diffused light (best in presence of traces of iodine, aluminium chloride, antimony trichloride, etc.), substitution products are formed. With homologues of benzene, if the reaction is carried out in the cold and in the dark (or in diffused
enters only light) or in presence of iodine (which acts catalytically), the halogen the bonze'ne ring (even in the hot, if iodine is present), whilst in the hot or in direct sunlight, the substitution takes place principally in the side-chain. (2) By heating halogenated acids with lime
:

C6H4 diphenylene. GENERAL METHODS OF FORMATION. (1) In

H4

direct sunlight, chlorine

C 6 H 4 C1 C0 2H
(3)

= C TI 01
6 5

-f

C0 2

By

withdrawing
alcohols,

oxygen

from

oxygenated

aromatic

C6 H 5

OH + PC1 5 = POCI 3 + HCl + C6II5C1.

boiling
:

ketones,

acids,

aldehydes)

compounds (phenols, f?.//., by means of PC15

;

with cuprous chloride or potassium iodide the diazofrom the corresponding nitro- or umino-compounds obtained compounds N 2 ^ll.l. KC1 NCI KI C 6II5 NCI C 6 5C1 C6H 5 2 iodic add of action the obtained be Iodo-de,rivatives iodine, by may (5) is formed. which acid the oxidise are, added to however, They being hydriodic usually obtained by process (4). unites with two atoms of chlorine, forming iodoso(6)" lodobenzene, C 6 5I, benzene chloride, C 6 5IC1 2 digestion of which with alkali yields iodosobenzene, C 6 51 0, the latter, when heated or oxidised (with chloride of lime) giving
(1) ]iy
:

= H

+N

iodylbenzene,

206H5IO

- H I + C H I0
6 5

or

C6H5IO

+ - C II I0
6
5

(an

explosive, crystalline compound). Chlorination or bromination of toluene yields the para- and ortAo-derivatives the weto-derivative is obtained indirectly (from diazoin equal quantities
;

compounds).
C 6 H B -CH 2C1, is a colourless liquid with a pungent odour, molting 49 and boiling at 178 ; its specific gravity at 15 is 1-113. It was first prepared by Cannizzaro in 1853, and is obtained by chlorinating boiling toluene. With potassium acetate this chloride gives the acetyl-derivative, with potassium hydrosulphide a mcrcaptan, and with ammonia amino-bases. On protracted boiling with water it is transformed into benzyl alcohol, while boiling with lead nitrate converts it into benzaldehyde ; when heated with finely divided copper, it loses chlorine and condenses to dibenzyl, C 5 CH2 -CH 2 C 6 6 It is used for the preparation of oil of bitter almonds and for numerous aromatic syntheses

BENZYL CHLORIDE,

at

fl

its

chlorine

atom being readily replaceable. Benzyl bromide, when treated with potassium iodide, gives Benzyl iodide.

These

412

636

ORGANIC CHEMISTRY
PRINCIPAL HALOGEN DERIVATIVES OP BENZENE

products are also formed from benzyl alcohol, C 6 H 5 OH 2 OH, and halogen hydraeids they may be converted hack into the alcohol by boiling with water or potassium carbonate
;

solution.

BENZAL or BENZYLIDENE CHLORIDE, C 5 CHC1 2 and Benzotrichloride, (1 H 5 (XM 3> are obtained either by protracted ehlorination of boiling toluene or by the action of PC1 5 or benzaldehyde or benzole acid.
,

at --

Benzal chloride boils at 204 and has the sp. gr. 1-295 at 16, while the trichloride melts 22, boils at 213, and has the sp. gr. 1 -380 at 14'
J

Mixed halogen derivatives are known, as also is Hexachlorohexahydrobenzene, B H Cl 6 Numerous halogenated derivatives of unsaturated aromatic hydrocarbons have likewise been prepared, e.g. a-Bromostyrene, C 8 H 5 OBr CFT 2 and /2-Bromostyrene, 6 H f GH OHBr.
fl

C.

3ULPHONIC ACIDS

These are formed directly from the aromatic hydrocarbons by the action fuming sulphuric acid or of chlorosulphonic acid, Cl S0 3II. Improved yields are obtained in presence of mercury or ferrous sulphate, which exerts a catalytiq action.
of concentrated or

PHENOLS

637

They are crystalline substances, readily soluble in water and even hygroscopic, and are separated from the excess of sulphuric acid either by means of their calcium or barium salts, which are soluble, or by saturation of the aqueous
solution with sodium chloride and subsequent cooling in the latter case, the sodium sulphonate separates, this being decomposed with the calculated quantity of a mineral acid and the free sulphonic acid extracted with ether. When treated with superheated steam or with hydrochloric acid, they lose the sulphonic group, the aromatic hydrocarbon being thus regenerated. With PC1 5 they form the acid chlorides, c.g. C6 H5 S0 2 Cl, whic^, with ammonium On energetic carbonate, yield the sulphamidcs, C6 H5 SO 2 NI1 2 (see. later). reduction, Ihioplienol -(phenyl hydrosulphide), C 6H 5 -SH, is formed. BENZENESULPHONIC ACID, C H5 SO 3 H, is obtained by the direct action of concentrated sulphuric acid on benzene H 2SO4 H 2 -f 6 H6 -SO S H. Its barium and C6H6
; 9
:

}-

CBH6

lead salts being soluble, it can bo readily separated from the excess of sulphuric acid. It is very stable and is not decomposed on boiling with alkali or acid (as is ethylsulphonic acid), but if heated with hydrochloric acid at 150 or with superheated steam in presence of concentrated phosphoric acid, it takes up water, giving benzene : SO ,H -f H 2 () -~ 6Hr ,

H SO When distilled with potassium cyanide, it forms benzonitrile, + KON = K SO + C H ON. When fused with alkali it forms phenol, C H -SO K + KOK -= K.,SO + while with PC1 it yields Benzene sulphochloride, H -SO H f PP1 P()(
-{-

4.

(- 8 tL 5

S() 3

:I

C1

(! 6

6 H a -OK, f H( 1 f
1

or primary or secondary amines, beii/ene sulphochloride gives inoro or less substituted Benzenesulphonamides, e.g., C 6 rf 5 SO 2 2, C 6 ILpSO 2 NHR, 6 6 SO 2 2 , which crystallise well. As the tertiary amines do not give this reaction, they can be separated from other amines. Owing to the highly acid character of the SO 3 group, the amino-group does not form

O 8 H 5 'HO aOl (decomposable by water). With ammonia, ammonium carbonate,

NH

NR

hydrogen can be replaced by metals, e.g., by dissolving in sodium hydroxide Sulphur trioxide converts benzene into Sulphobenzide (sulphone), (C- G H 6 ) 2 S<) a Nitration of benzenesulphonic acid yields mainly M-nitrobenzenesulphonic acid, but small quantities of tho ortho- and para-derivatives are also formed. Reduction of ^w-nitrobenzenesulphonic acid yields Sulphanilic acid (p-attiinobtnzenefw Iphonic acid), NH., C H 4 SO 3 H (discovered by Cerhardt in 1845), which is also obtained on heating aniline with fuming sulphuric acid or on heating aniline sulphate at 200'J This acid and also the corresponding meta-acid are used in the manufacture of artificial dyestuil's, and both of them can be diazotised (see later).
salts,
its

but

solution.

Sulphonic compounds and their salts are of importance in the dye industry as they give dyes soluble in water and readily applicable to the dyeing of textile
fabrics.

of

them

Polysulphonic acids of benzene and its homologues are also known, some serving for the separation of isomeric aromatic hydrocarbons (see

Toluene).

D.

PHENOLS

Phenols contain hydroxyl groups in place of one or more hydrogen atoms of the benzene nucleus. They have a characteristic odour (phenol, thymol),

and certain of them are partially soluble in water, while all of them are soluble in alcohol and in ether ; they distil unchanged and have a more or less marked
antiseptic action.

Their properties resemble, to some extent, those of tertiary alcohols and those of weak acids. Thus, ethers are formed by the action of alkyl halogen compounds on the sodium derivatives of the phenols, anisole, C il5 OCH 3 and phenyl sulphate, C 6 S0 3H, being obtained in this way the latter
,

compound is readily hydrolysed. They are, however, stable towards oxidising The hydroxyl group is agents, nitric acid forming substitution products. with some difficulty replaced by chlorine by the action of PC1 5 They act as weak acids, but with alkalis form stable salts, which are soluble in water, are
.

decomposed even by carbonic

acid,

and show only

slight electrical conductivity.

638

ORGANIC CHEMISTRY

Halogens and nitric acid replace the benzene hydrogen of phenols more easily than that of benzene itself or its honiologues, so that even in dilute solution phenol can be precipitated quantitatively as tribromophenol by the action of bromine water. If the hydroxyl group is joined to a side-chain and not to the benzene nucleus directly, the compound is an aromatic alcohol and not a phenol.
Oxidation of honiologues of phenol yields hydroxy-acids, the side-chain being oxidised while the phenolic groups remain intact. When distilled with zinc dust, phenols give the corresponding aromatic
hydrocarbons.

In aqueous neutral solution, phenols give a violet, green, or other coloration with ferric chloride, calcium hypochlorite, or, in some cases, iodine. In general, they exert a reducing action.

With nitrous acid, phenols form isonitroso-derivatives (oximes), and, in presence of concentrated sulphuric acid, intensely coloured solutions are formed which are turned blue by potash (Liebermanns reaction). The sodium or potassium derivatives of the phenols (phenoxides), with carbonic acid (or C01 4 -f- KOIT) give aromatic hydroxy-acids
:

C 6H5

OH + C0 2 - OH

C 6H4 C0 2H.

Wiih chloroform and sodium hydroxide, they yield the corresponding aldehydes. They react with diazo-compounds and various other compounds forming colouring-matters (we later). The action of zinc chloride (or calcium chloride) and ammonia on phenols results in replacement of the OH by NH 2 With formaldehyde they yield characteristic resinous condensation products The commoner phenols are obtained from coal- or (see Baekelite, p. 641).
.

wood-tar.
(a)

MONOHYDRIC PHENOLS
,

and partly in These are found alone or together with polyhydric phenr J tar the form of ethers (e.g., guaiacol,OH -C 6H 4 OCH 3 cresol, ,c.) in the obtained by the dry distillation of wood or coal. They are separated from the tar-oils by moans of caustic soda, which renders them soluble, and, after
"j

separation, are set free by mineral acid and subjected to fractional distillation. They are also obtained industrially by fusing salts of sulphonic acids with alkali (in iron vesesls ; in the laboratory silver vessels are used)
:

C6H5 S0 3K
If

+ 2KOH = C H OK + K S0 + H
6

2 0.

the nucleus contains chlorine atoms, these are also substituted by hydroxyl groups by this reaction. Phenols are formed by boiling diazo-compounds (see later) with water in dilute sulphuric acid solution
.

Also,

when

N 2C1 + H 2 = N 2 + HC1 + C 6H5 OH. benzene is oxidised with H 2 2 or with oxygen

C 6H5
,

in presence of

aluminium

chloride, phenols are obtained.

Chlorine atoms or amino-groups joined directly to the nucleus may be replaced by hydroxyl-groups by the action of sodium hydroxide, but only when the nucleus contains also strongly negative groups, e.g., 2

N0

PHENOL

(Carbolic Acid),

C 6 H 5 OH, was

first

discovered by Runge in tar and occurs, to

a small extent and in combination, in urine.

from tar-oils (see pp. 628, 629) by treatment with caustic soda solution and agitation by a current of air steam is passed through the decanted The phenol is then alkaline solution of phenol, this removing the naphthalene, etc. liberated by H aS0 4 or C0 a (e.g. 9 flue gases) and washed several times with water, crude
It is separated
(sp. gr. 1 -09)
;

PHENOLS
O
-

639

00
1

OO
+>-*c<3

O
18

-4-2

-4->

p
CO TH CO

OJ
|

03

SO

rH |>

poo

O5 <M

O5

CO CO <N CO <N r 00 OS <N rH <TJ <M 5^1 <N

i

OO

5 a *|
1 1

I
i
-1-

w
fl

PH

1 (
(r-

ecylph
Amylpheno

Heptylphenol

Octylphenol

Hexadecylphe

W
.8
E
eo

ww

5s

wwrf w

640

ORGANIC CHEMISTRY
H OH +
-

40 per cent, of phenol, the rest creosote, etc.) of sp. gr. 1 -05 to 1-06 1 obtained. being thus Borck (Cer. Pat, 322,242, 1919) proposes to extract all the phenol from tar-oils by treating H 2 ; since water is not 2C 6 6 ONa 2Na them with metallic sodium, 2C 6 5 formed in the reaction, inversion of the latter does not take plaee as when sodium hydroxide
carbolic acid (containing

is

used.

reetifieation Phenol is purified by repeated distillation between 175 and 185 or, better, turns red in the air. To free until it crystallises at the ordinary temperature and no longer 12 to 16 per cent, of water and the hydrate it from final traces of cresol, it is diluted with

- 8 to - 10 (cresol hydrate crystallises at - 20), centrifuged and distilled crystallised at the operation and of the distillation until a strength of 99 per cent, is attained ; repetition of Minimal quantities of water prevent (in earthenware vessels) gives chemically pure phenol.
the ordinary temperature. crystallisation at Phenol. This is economically possible Synthetic Preparation of

when benzene is cheap. the Boer War, but after the with during Britain Great phenol synthetic Germany supplied war the price of phenol became normal again and its manufacture in this way ceased. enormous quantities of phenol were consumed, During the European War (1914 to 1918) acid to be used as an more but an particularly for making picric not only as antiseptic, insufficient to supply the demand, the manufacture Coal-tar quite being phenol explosive. countries on an enormous scale. of synthetic phenol from benzene was carried out in various the Pure benzene is introduced slowly into a steam- jacketed cast-iron boiler containing acid, the mass being at first mixed without concentrated of sulphuric amount necessary to 115 so as to form benzenemoncwnlphomo acid. To heating and afterwards heated the excess of sulphuric acid, the acid mixture is poured into a from latter the separate solution, slow cooling then rt suiting in the separation hot, almost saturated sodium sulphate which is centrifuged and added in small of a crystalline mass of sodium benzenesulphonate, The the and finally raised to 320. temperature sodium fused to hydroxide, quantities thus obtained is poured into a fused mixture of sodium pheiioxidi- and sodium sulphate out and the phenoxide remaining dissmall quantity of water, the latter then crystallising sufficient dilute sulphuric acid to with treated is solution After filtration the solved. which floats on the sodium bisulphate solution, and is decanted off liberate the
phenol,

and

distilled in

a vacuum.

with very dilute may be obtained also by heating chlorobenzene 191 1 ). and under Meyer, 300 at (Bergius alkali solution pressure and boiling unaltered at Pure phenol crystallises in colourless needles, melting at 42-5 J and 1 -070 It has the sp. gr. 1 -084 at it liquid. to suffices water little keep but 1 81 very in all proportions and at in 8 IT, at water of 16", parts at 25 and it dissolves in 20 parts It is readily soluble in alcohol of water. at 84 ; 100 parts of phenol at 9 dissolve 23 parts with synthetic phonal It JH marked less this being or ether and has a characteristic odour, cause death ; calcium sucrato or Tioisonous and 1 grin, on a wound or 8 grm. ingested may of its great antiseptic power it IB largely sodium sulphite serves as antidote. On account 2 in many cases it is, however, replaced by used as a disinfectant in medicine and surgery ;
Synthetic phenol
1

^^^^
carbolic acid is as follows
:

melts at 39', other pure forms Testing of Carbolic Acid. Commercial pure phenol should dissolve Completely When to 186. 183 at phenol pure, and 35 to at 30 boiling melting no residue on evaporation. Phenol a clear solution in 15 parts of water and should leave contains at least 10 per cent, of higher whk-h does^notTystallisc at the ordinary temperature The exact quantitative estimation bf pure phone, (not containing crenels, Xiol io

sitsass s
ta

Uquors

time with 90 vols. of 10 vols. of the product are shaken for a long

**

to

scats t)ST^the
toe

this having varying affinities towards Afferent plasma of the living cells,

t-r

BAEKELITE
otlior antiseptics (corrosive sublimate, cresols, etc.)

641

which have not the unpleasant odour

The maximum antiseptic action of phenol is exerted in aqueous solution and of phenol. 1 and H" ; according in presence of acid, owing to its partial dissociation into the ions to Pflugge, when dissolved in pure alcohol or in oil, it has no antiseptic action, since it is

Cg^O

then not dissociated.

It is used for making picric and salicylic acids and dyes. It dissolves in caustic alkali solutions (forming plienoxides, e.g., C H 5 -OXa),

those of alkali carbonates.

(Baekelite
;

With formaldehyde

it

but not in forms resinous condensation products

see below).

pine splinter, moistened with hydrochloric acid, is coloured bluish green by phenol. As little as 1 part of phenol in 40,000 of water gives a white, liocculent turbidity of tribromophonol on addition of bromine water. With hydrogen in presence of nickel phenol is converted quantitatively into cyclohexano

Phenol coagulates proteins. or into cyclohexanonc at 230. Tn 1913 Great Britain exported 8,000 tons of crude phenol (160,000) and during the in European War manufactured and exported enormous amounts of synthetic phenol ; 1919 the exports were only 6500 tons, and in 1920, 9,000 tons. Before the war the price of commercial dark carbolic acid (25 to 30 per cent.) was about 100 per cent., 15 to 20 ; 6 Ss. to 8 per ton ; the 50 to 60 per cent, product, 10 to 12 the pale acid, 17 to 28 pure redistilled crystals, m.-pt. 35, 55 ; chemically pure crystals, 14 respectively per ton for the 20 cost 8 and Cakittm 74. 68
at 160
; ;

synthetic,

phenoMe

During the war the prices rose to very high values. in appearance Baekelite, obtained by condensing phenol with formaldehyde, resembles, and behaviour, certain resins and plastic materials. It was prepared and patented in 1907 direction were by L. H. Baekelaiid in the United States. Previous experiments in this made by a number of investigators, but Backeland carried out an exhaustive theoretical and technical examination o the question and found that, according to the temperature

and 50 per

cent, products.

conditions

and

to the nature of the condensing agent employed, three distinct products

agents, the so-called sealing
alkali, etc., are
-

are obtainable.
1.

wax

OH ( 6 H.i CH 2 OH, phenol replaced by a phenolic alcohol, such as saligenin, and the heating is carried out at 150 in presence of sulphuric acid, a resinous mass, ttalirelin, is formed which is almost insoluble in solvents and softens but does not melt when heated ;
2.

substitutes, easily fusible

From phenols and formaldehyde with acid condensing and soluble in alcohol, acetone,
is

formed.

If the

a polymerised anhydride of saligenin. of phenols with formaldehyde in presence of alkali (less than one-fifth condensation By form the sodium phenoxide) three important products may be obtained ; to of that necessary
this represents
3.

Baekeliles A, B and (\ Baekelite A, obtained

hot, solid

and

brittle

when

in the by protracted heating below 100, is viscous or liquid it results from partial cold, and soluble in various solvents
;

with formaldehyde. anhydridisation of the condensation product of phenols Baekelite B, formed by keeping baekelite A slightly above 100, is a resinous product insoluble in solvents, but sometimes swelling in them ; it softens without melting when then be moulded. It may be regarded as the complete anhydride of heated and

may
C

backelite A.

Baekelite

is

obtained by heating baekelite

at 160

to 180, but in order that the

their fix the whole of the metal of the antiseptics (e.g., copper or mercury from the solution does not then react with hydrogen sulphide, while the cells of the microdoses of different antiseptics organism do so. The following Table shows the approximate 30 per cent,, i>., 3 grins., of dry matter), necessary to kill 10 grms. of beer-yeast (containing but these numbers would doubtless require considerable modification in the disinfection of other materials

micro-organisms
;

salts)

Jn some

cases

more concentrated

solutions are less active than the

more

dilute

the activity

depends also on the nature of the solvent used.

642
mass may bo
air or

ORGANIC CHEMISTRY
free

is carried out under pressure of used as source of heat. The mixture used to make baekelite may consist, for example, of 100 parts of phenol, 60 to 120 of concentrated formaldehyde and 4 to 12 of commercial aqueous ammonia. The hot mass becomes first liquid and then viscous, a layer of water separating at the surface and afterwards evaporating ; the reaction may be arrested at the A, B or C stage. Baekelite C has sp. gr. 1 -25, is so hard that it cannot be dented by the finger-nail, and is not plastic even when hot ; it resists pressure, shock and heat, and does not soften even at 300 ; at higher temperatures it chars, burning with difficulty and without flame. It is resistant to the action of moisture, acids and alkalis, but is attacked slightly by hot concentrated sulphuric or nitric acid. It forms an excellent insulator for heat and electricity, and is readily turned or sawn. When pure it is transparent and pale yellow, but during manufacture it may be coloured with alcoholic solutions of aniline dyes. It is almost as elastic as ivory and hence serves for making billiard balls it also forms a good substitute

from

air

CO 2

and non-spongy, the heating

superheated steam
is

at 6 to 8 atmos.

for amber, celluloid, gallalith (from casein), etc., for

making cigar holders, umbrella handles, combs, brushes, tooth-brushes, buttons, gramophone records, etc. The moulds are made
of glass, copper or highly polished bronze. Alcoholic solutions of baekelite may be used as varnishes for wood, metal, rendered hard and coils, etc., the last

dynamo

paper,

being

dielectric (48,000 volts per

mm.).

Compressed and baekelised abrasive powders form very

hard grindstones.
Various products, similar in character to baekelite, are known. Invelite, patented by is obtained from phenol, paraformaldehyde, water and phenolsulphonic acid. Raschig (1912) obtained similar resins by varying the proportions of phenol and formaldePollak,

hyde and using also cresols, and regards all such products as condensation products of diphenylmethane derivatives. According to Wohl (1913), however, resite is a polymerised
product of methylene derivatives of the form

CO

Phenol forms phenoxides with many metals (Na, K, Hg, Cu, etc.). when heated with alkyl iodides, give ethers, e.g., ANISOLE, C 6 H5

The alkali phenoxides,

O CH3 (sp.
b.-pt.

gr. 0-991

at

15, b.-pt. 132) PHENETOLE, C 6 H 5 These ethers are neutral, very stable
;

O 2 H5

(sp. gr.

0-9822 at

liquids, and, as is

172). the case with the corresponding

0,

compounds, boil at lower temperatures than the phenols. They are decomposed only in energetic reactions. For instance, hydriodic acid at 140 acts on them with formation of methyl iodide, this reaction serving for the estimation of
aliphatic

methoxy-groups in phenolic ethers

1

(Ziesel)

C 6 H5 -OCH3

'

HI

--=

CH 3 1

-f

CeHg-OH.

Estimation of Alkoxy-grou'pa by ZeiseVn Method. When the apparatus (Fig. 445) has been found to bo air-tight, 0-2 to 0-3 grin, of the substance is introduced into the flask, A (30 to 35 c.c.), 50 c.c. of alcoholic; silver nitrate (2 grms. fused nitrate -f- 5 c.c. water -f- 45 c.c. absolute alcohol)

FIG. 445.
into the
is

two flasks, C, and then 10 c.c. of pure hydriodic acid (sp. gr. !?) into A. The latter then attached to the condenser, K, through which water at 40 to 50 circulates ; the Cleissler bulbs, /?, which are kept at 50 to 60, contain water with red phosphorus (0-3 to 04 grin.) in suspension to retain hydrogen iodide. The flask, A, is heated in a glycerine bath until its contents The boil, carbon dioxide being passed slowly -(2 bubbles in 2 seconds) through the flask. operation requires about 15 minutes and is complete when the precipitate formed in A separates sharply from the supernatant clear liquid. The total contents of the two flasks, C, are diluted in a beaker with 500 c.c. of water and concentrated to about one-half the volume on a water-bath.

HOMOLO CUES OF PHENOLS

Phenol also forms Acid Derivatives,
e.g. 9

64

phenylsulphuric acid,

C 6 H6

8O3 H, which is

stable only as gaits, these being obtainable, for instance, by the action of aqueous potassium pyrosulphato on potassium phenoxido. They are formed in the urine by the putrefaction of proteins, and are estimated by determining the amount of sulphuric acid liberated in the hot by dilute hydrochloric acid. Carbonic and acetic acids also form analogous

compounds.

PHENOLS. The hydroxyl group of phenol facilitates the replacement of the hydrogen atoms of the benzene nucleus by halogens ; even in the cold, bromine water forms Tribromophenol. Chlorination can be effected by the direct action of chlorine or by sulphuryl chloride, while replacement by iodine is facilitated in alcoholic solution, or in presence of mercuric oxide (which oxidises the hydriodic acid as it is formed), or in an aqueous alkaline solution. The halogen usually assumes the orthoor para-position with respect to the hydroxyl. While o- or p-cresol combines with only two^atoms of bromine, the action of chlorine
on
anisole,
6

HALOGEN DERIVATIVES OF

5
-

CH3

,
.

at 60

cMaroanisole,

C a Cl 5 OCH3

in presence of a little iodine, yields tetm- or even pentaHalogen derivatives of phenols may also be obtained by

diazotising halogenated aminophenols. In general, they are colourless crystalline acid character (trichlor&phrnol

compounds of pungent odour and decidedly decomposes carbonates) when they are fused with potash, the halogen atom gives way to another hydroxyl group, which, however, often enters partly in a position different from that occupied by the halogen. Under the further action of
;

chlorine, tri-

and peiita-chlorophenols
-

yield additive products, the

-

OH

the same time converted into CO.

group being at

PHENOLSULPHONIC ACIDS, OH C 6 H4 SO3 H, are obtained by treating phenol with concentrated sulphuric acid, the o- and p -compounds being formed with equal ease the o- is converted into the p -compound by heating with water. The 7/1 is obtained
;

-compound

indirectly

Oxidation of the side-chains in these leads to aromatic hydroxy-acids. The Cresols are not oxidised by chromic acid mixture, but arc completely decomposed
(see

HOMOLOGUES OF PHENOL

by fusing benzene- w-disulphonic acid with

Table, p. 639).

alkali.

by permanganate

if,

however, the hydroxylic hydrogen

-

is

replaced by an alkyl or by

The three isomeric Hydroxytoluenes, OIL, C 6 H 4 OH, bear the generic name of cretolfs. They are present in wood-tar and in the middle oils of ordinary tar, and may also be prepared from the corresponding amino-derivatives or sulphonic acids. The cresbls react with bromine water. The crude cresols mixed with soap solution form creoline and lysd, which
serve as convenient antiseptics

acetyl, oxidation proceeds in the ordinary way.

and are

1 largely used. jj-Cresol,

CH 3 <^

NoH, is formed
by

in the putrefaction of proteins. Crude cresols contain the o-,

m- and/j-isomerides, which cannot be

191, 203

fractional distillation, the respective boiling-points being

easily separated arid 204. 2

OH
\

/ THYMOL, CH 3 <Q
action.

^CH< CH CH

'\

is

found in
is

oil

of

thyme and has an

antiseptic

One

of its ioclo-derivatives, Aristol,

used as a substitute for iodoform.

little water and a few drops of nitric acid are then added and the liquid heated until the silver iodide separates, this being then filtered, dried, and weighed in the usual manner. Various modifications of thin method have been suggested for volatile substances and especially for those

containing sulphur (the substance is hydro lyseci with concentrated NaOH and the products absorbed after first passing through a U-tube containing pumice moistened with CuS0 4 ; a current of air and not of CO 2 is used in this case). 1 Mixtures of creosote oil and concentrated soap solution were used as Creoline. disinfectants as early as 1874. Creoline is obtained by protracted heating on a water-bath of a mixture of 1 part of concentrated resin soap solution with 4 parts of medium tar-oils (creosote oils, best with b.-pt. 200 to 210), the mixture being stirred for several hours and allowed to stand, and the water then separating removed by decantation. 8 The components may, however, be separated as barium salts. Orthocresol serves for making coumarin perfume and m-cresol for making artificial musk, while p-cresol is the raw material for preparing anisaldehyde, a delicate perfume sold as nubepine. When a mixture of p- and w-creaols ia treated with sulphuryl chloride, only the w-creaol reacts, forming p-chloro-m-creeol, which is an excellent odourkss disinfectant, only slightly soluble in water, but readily emulsified by soap (see Creoline) ; it is sold as lysochlor.

644

ORGANIC CHEMISTRY
OH
\

/ CARVACROL, CH a^

OH 3
,

^>CH<,iiT
:

occurs in Origan-urn hirtunt,

and

is

formed by

heating camphor with iodine or by the action of phosphoric acid on carvone (see Terpenes). ANETHOLE, CH 3 O C 6 H.- CH CH CH 3 , is a colourless solid melting at 22, boiling at. 233, and having the sp. gr. 0-986 at 21-5" it has a pleasing odour and occurs in Anise oil (from the seeds of Pimpinella anisum, or the fruits of Illicium venim or star-anise),
;

from which
it is

its

it is obtained by repeated fractional distillation or by freezing. Synthetically prepared from anisaldehyde and sodium propionate by Perkin's reaction (we p. 352), constitution being thus proved. In the pure state it cost 20.v. per kilo before the war.
(b)

DIHYDRIC PHENOLS

These contain two hydroxyl groups united to the carbon of the benzene nucleus. They are analogous in their chemical behaviour to monohydric phenols, and are prepared by similar methods certain of them show marked reducing properties. With lead acetate, pyrocatechol gives a white precipitate, hydroquinone is precipitated in presence of ammonia, while resorcinol is not precipi;

tated.

PYROCATECHOL
at

(Catechol),
;

C 6 H 4 (OH), (1:2), forms crystals melting at 104, boiling

alcohol, or ether,
It is

240, and subliming it dissolves readily in water, salts in the cold and Fehling's solution in the hot.

and reduces

silver
is

found in various resins and

obtained by distilling catechu (Mimosa catechu) ; it is now prepared by fusing o-phenolIt is usually synthesised from osulphonic acid (see p. 643) with caustic potash. bromo- or o-chloro-phenol, which is readily obtained by passing bromine vapour or chlorine into phenol heated at 150 to 170 in a reflux apparatus and purified by washing Avith alkali and distilling in a vacuum, and is stirred and heated for 8 to 10 hours in an autoclave at 180 to 250" with about its own weight of caustic soda dissolved in one and half times its weight of water. The mass is afterwards dissolved in a little water, acidified with sulphuric acid, and extracted with ether. It is used as a photographic developer and serves for the preparation of its dimethyl
11

ether, veratrole. m.-pt. 22-5, b.-pt. 205. Its alkaline solution is unstable, and is coloured first green and then black by the oxygen of the air ; it reduces silver salts, and by ferric; chloride is coloured green or violet if a little ammonia is present (characteristic, reaction of oriho-dihydrojcy compounds). With

bromine water

it

gives trilromoresorcinol, which melts at

18", is soluble in water,

and turns

brown
Its

in the air.

OH
monomethyl
;

Ether,

,OCH 3

is

called

GUAIACOL and

occurs abundantly

used in medicine as an expectorant. Ft is obtained by shaking the creosote oil (fraction boiling at 200 to 250) from the distillation of the above tar with ammonia, treating with alcoholic potash, washing with ether, crystallising the potassium compound from alcohol, and decomposing it with dilute sulphuric acid. It is obtained
in beech-tar
it is

by allowing its light petroleum solution to evaporate slowly. Synthetically prepared by diazotisingo-anisidine, acidifying with dilute sulphuric acid, and distilling in steam. 1 It melts at 29, boils at 205, and dissolves in about 60 parts of water at 15 ; it is readily soluble in ether or alcohol. With ferric chloride its alcoholic solution gives a blue coloration, changing rapidly to green and then to yellow. It yields o-chloroanisolo with PC1 5 catechol when fused with alkali, anisole when distilled with zinc dust, and veratrole on methylation ; it forms an orange-red picrate, m.-pt. 80. Guaiacol is used in the synthesis of vanillin and is employed in medicine as an expectorant and, especially in the form of various salts, in the treatment of pulmonary tuberculosis. 2 Before the war it cost 10$. to 130. per kilo. RESORCINOL, C 6 H 4 (OH) 2 (1:3), is formed on fusing various resins, such as yalbanum and asafcetida, with potash, and also from w-phenolsulphonic acid or w-bromobenzenecrystalline
it is
,

at

According to tier. Pat. 30.5,281 synthetic guaiacol may bo obtained by heating caterhol 00 to 180 with alkali salts of methylsulphuric acid in presence of a diluent and slowly adding sodium carbonate or bicarbonate.
1

JJCH 3
OUAIACOL CABBONATE
(duotal),

OCH 8
O-CO-O
<^

<^

m.pt. 78 to

84,

is

odourless

PYROGALLOL

645

sulphonic acid ; it is prepared industrially from m- or p-benzenodisulphonic acid (prepared from toluene-free benzene) by fusion with potash. It forms rhombic crystals molting at

110, and boiln at 270 with partial decomposition. It turns brown in the air, is soluble in water, alcohol, and ether, and slightly so in benzene, and reduces silver nitrate. It is a less energetic disinfectant than carbolic acid.

With nitrous acid or diazo-compounds it forms dyes and, like all wi-dihydroxy benzenes, with phthalic anhydride at 200 it yields fluorescein. Before the war commercial resorcinol cost 4. to 5*. per kilo and the pure compound 2()a. It is largely used in dyeing and
printing cotton.
(Quinol), C 6 H 4 (OH) 2 (1 4), is obtained by oxidising aniline in the and chromic acids, or by reducing quinone witli sulphurous acid. It forms dimorphous crystals melting at 169, and with ammonia gives a reddish brown coloration. Oxidising agents convert it into quinono. Owing to its strong reducing proper-

HYDROQUINONE

cold with sulphuric

ties it is

used as a photographic developer.

cost, before the war, 8s. per kilo.

The chemically pure compound

OH
ORCINOL
(Dihydroxytoluene),

CH 3 C

^>,

does not form miorcscein with phthalic

OH
anhydride. Its ammoniacal solution oxidises in the air, giving Orceine, is the principal component of natural archil and is related to litmus.
('2 8

jO 7 N 2 which
,

OH

HOMOPYROCATECHOL

(Homocatechol),

CH 3 /

\>H,

gives

monomctliyl

OH
ether, Creosol, f-H a

OOH 3
The unsaturated
derivative,

Eugenol, ("H 2

('FT

OH 2

/OTI,

is

the principal

component (90 per cent.) of clove o?7, from which it is extracted with aqueous potash, being then liberated with acid and rectified in a stream of C0 2 . It is a liquid boiling at 247-5"

and has the

p. gr.

1-073 at 14.

Hot

alcoholic potash displaces the double linking of

__OCH,
ougcnol, giving Isoeugenol,
teristic

CH 3 OH

CH<^

yOFI,

which

also has

a pleasant, charac-

odour.
(r)

TRIHYDRIC PHENOLS
:
:
:

(Trihydroxybenzenes)

constitutions of the three isomeric. trihydroxybonzenes have now boon 2 3 fixed with certainty Hydroxyhydroquinone, 1 2 4 Pyrogallol, 1 (as), and Phloroglucinol, 1:3:5 (s). PYROGALLOL (1:2: 3-Trihydroxybenzene also improperly called Pyrogallic acid), C 6 II 3 (OH) a is prepared by heating gallic acid (see Inter) for half an

The

hour in an autoclave at 200 to 210 with 2 to 3 times its weight of water the solution is decolorised by boiling with animal charcoal, filtered, concentrated, and crystallised. The pyrogallol thus obtained is purified by sublimation and then forms shining, white, poisonous scales or needles, melting at 132 and boiling at 210. It may also be prepared by distilling a mixture of 1 part of gallic acid with 2 parts of powdered pumice in a current of C0 2 It dissolves in 1-7 part of water or ether, or in L part of alcohol. In alkaline solution it is an energetic reducing agent and absorbs oxygen from tHe air with it is used in gas analysis in all cases in which oxygen is to be avidity absorbed (see Orsat Apparatus, Vol. I., p. 463). By fresh solutions of ferrous sulphate it is coloured blue, by ferric chloride brown, and by silver nitrate black.
;
.

and almost

tasteless, insoluble in
p/tosp/iate,

Uuaiaeol

water and soluble in hot alcohol. PO(O-C H 4 -OCK 3 3 has rn.-pt. 98.
)
,

OCH 3

Potassium guaiacol-o-,mlp/ionatc
in alcohol.

(ttyocott), <f

"/OH,

is

soluble in water

and

slightly so

S0 3K

646

ORGANIC CHEMISTRY
hydroxylamine

It does not react with

ether (Dimethyl pyrogallate), homologous ethers, in beech-tar.

It
is

OH

C6H 3 (OCH 3

(see Phloroglucinol).
)

Its

dimethyl

2,

is

contained, along with other

When pure it

used in photography, in electro-plating, in medicine, and in hair dyes. cost, before the war, 1 26-. to Us. Qd. per kilo.
,

HYDROXYHYDROQUINONE (1:3: 4-Trihydroxybenzene), CJI 3 (OH) 3 is obtained by fusing hydroquinone with caustic soda and has not been very closely studied. It crystallises from ether in plates melting at 140 -5, readily undergoes change in aqueous solution, and does not react with hydroxylamine
(see Phloroglucinol).

PHLOROGLUCINOL, C 6H 6

3,

is

obtained by fusing various resins with

of ethyl sodio:

Baeyer prepared it synthetically by condensing 3 mols. malonate in the hot, 3 mols. of alcohol being thus eliminated

KOH.

COOC 2H5
TT

~~
Na

C 2H5 C0 2 (Na)C
:

CJ

IIC
Na

C(Na)
:

C0 2 C 2 FI5

+30

A "OH;

COOC 2H5

C-C0 2 C 2H5

acidification of this product results in the substitution of the sodium by hydrogen with formation of pUoroglucinoltricarboxyUc acid, which, when fused with loses its carbethoxy-groups and gives phloroglucinol. The latter caustic

potash,

should, therefore, have the constitution

CO<^ ~^>CII

which contains no

double linking and corresponds with trikelohexcrnwlhylene ; in accord with this structure, it reacts with 3 mols. of hydroxylamine, giving a trioxime. On the other hand, it behaves also as a trihydroxy benzene or trihydric so that it is able to phenol, giving a triacetyl-derivative with ae.et.yl chloride, exist in two tautomeric forms. This explains why, when it is treated with alcoholic potash or with an alkyl iodide, the alkyl groups unite with carbon and not with oxygen (as they would with a triphenol), giving, e.g., hexamethylphloroglucinol. Pure phloroglucinol cost, before the war, about 1 6 per kilo.
(d)

POLYHYDRIC PHENOLS
is
6 H 2 (OH) 4 (1:2:4:5), formed by the oxidation of the

From
which

dinitroresorcinol

is

obtained a Tetrahydroxybenzene,

boils at

220, while

chloranilic acid (see later)

dichloro-deri vative.

HEXAHYDROXYBENZENE,
in the manufacture of potassium
.

C 6 (OH) 6

is

obtained as potassium derivative,

:

SCO f- 2 by reduction of its carbonate K./JO^ -f- 2 and 6K -f 6CO - C 6 O 6 K 6 These reactions represent a further example of the synthesis of organic substances from inorganic matter. Hexahydroxy benzene is a white, crystalline substance which oxidises readily in the air and yields benzene when distilled with zinc
dust.
*

C 6 O 6K 6

Of the additive products formed by polyhydric phenols with hydrogen,

inositol

quercitol

and

may be mentioned. QUERCITOL (Pentahydroxycyclohexane

or

Acorn Sugar)

OH CH/
is

/CH(OH) CH(OH)v

>CH 2
;

\CH(OH) CH(OH)/
found in acorns and
is

similar to mannitol

it

prisms melting at

234,

its specific

rotation being [a]'D

has a sweet taste and forms monoclinic 24-16. When heated to 240
fi

QUIN
in
;

NES

647

a vacuum or fused with alkali it loses water yielding various aromatic derivatives (hydroon reduction with HT, it gives benzene, phenol, pyroquinone, quinone, and pyrogallol) and hexane. When oxidised with nitric acid it forms mucic and trihydroxygallol, quinone, it yields malonic acid, the presence of the methylene glutaric acids, while with permanganate group, CH 2 being thus confirmed. It forms a pentacetyl-derivative, an explosive pentathe formation of these comnitrate, and a pentachlorohydrin, C Q 7 C15 melting at 102
,

pounds demonstrates the presence of

hydroxyl groups. INOSITOL (Hexahydroxycyclohexane or Muscle Sugar), C 6 H 6 (OH) 6 is similar to qucrOH group in place of the OH 2 It has the appearance and, to citol, but contains a CH some extent, the sweet taste of the sugars, with which it was for long confused. That it is a cyclohexane derivative is shown by the formation of phenol, benzene, and tri-iodophenol on reduction with HI, and that of quinone and some of its derivatives on treatment with The presence of six hydroxyl groups is proved by the formation of a hexa -acetate PC1 6 (m.-pt. 212) when it is treated with acetic anhydride and zinc chloride, and of a heranitrate, C 6 H 6 (NO 3 ) 6 (m.-pt. 120), under the action of concentrated sulphuric and nitric acids
,
. .

five

the hexariitrate is highly explosive and reduces Fehling's solution. Four optical isomerides are known: (1) inactive ; (2) dextro-rotatory, [a],, -\- 68-4, crystallising with 2H 2 O and U 65, m.-pt, 247 (4) racemic, melting at 250. melting at 247 ; (3) Iscvo-rotatory, [a] h indicate eight possible isomerides, according to the Baeyer's stereochemical conceptions and H above or below the plane of the hexagon. Inositol, especially arrangement of the the inactive form, occurs in beans, lentils, peas, the muscles of the heart, the brain, etc.
;

OH

The inactive modification crystallises from water with 2H 2 O at temperatures below 50, and in an anhydrous form, m.-pt. 225, at higher temperatures it boils unchanged in a vacuum at ,'U9 and is not fermented by yeasts. It does not combine with phony Ihydrazine
,

it forms or reduce Fehling's solution, but it reduces ammoniacal silver nitrate solution a basic lead salt, (C 6 11 O 6 ) 2 Pb, PbO. It does not yield quercitol when reduced, so that the
;

hydroxyl groups are symmetrically distributed.

The monomethyl ether

dimethyl ether, or dawhonitot,

of i-inositol, or bornexitol, is found in Borneo rubber, and the C 6 H 6 (OH) 4 (OCH 3 ) 2 , in Gabon rubber. The monomethyl

ether of rf-inositol, or jrinitol, which occurs in many plants and plant- juices, molts at 186, 67-5. The monomethyl ether of Z-inositol, or sublimes at 200, and has a rotation of qwhracMtol, melts at 186, boils at 200 in vacuo* and with HI forms Z-inositol ; it occurs

in

quebracho bark.

E.

QUINONES

These may be regarded as derivatives of phenols obtained by elimination of hydroxyl groups, with consequent displacement and partial elimination of the double linkings of the benzene nucleus. They are usually yellow and of pungent odour and possess oxidising properties: they are volatile in steam, with partial decomposition. Oxidation of meta- and ortho-diphenols does not yield quinones.

BENZOQUINONE or simply Quinone, C 6 H 4 O 2 can be obtained by oxidising cither SO 3 H), or ^-phenolsulphonic acid, 2 'C 6 H 4 jj-aminophenolor sulphanilic acid (1:4 or hydroquinone, or aniline (on a large scale) with chromic acid. On sublimation it forms fine yellow crystals which melt at 116, giving a characteristic odour. It is soluble in alcohol or ether and slightly so in cold water. It fixes hydrogen, which transforms it into hydroquinone, while the halogens give addition or substitution With HC1 it forms monochlorohydroquinono, products according to the conditions.
,
-

NH

C 6 H 3 C1(OH) 2 With amines and with phenols it forms dyes which but are only slightly soluble. With hydroquinone it forms a condensation product, Quinhydrone, C H 4 2 C 8 H4 (OH) 2 , which consists of green prisms with a metallic lustre, and may be regarded as an
U 6 H4
2
.

+ Hd=

crystallise well

fi

intermediate product in the oxidation of hydroquinone or in the reduction of quinone,

OH O O CH/
-

>C!

O.

Constitution.

with hydroxylamine

That quinone contains two carbonyl groups is deduced from the it yields quinonemonoxime and quinonedioxime :

fact that

648

ORGANIC CHEMISTRY
CO
HC,//
HC'v

NOH

NOH

\CH
>CH
CO
Qninonomonoximo
(nitrosophcnol)

CO

C:NOH

It contains two double linkages, since in benzene solution it absorbs four atoms of bromine, while ozone is also fixed quantitatively (see pp. 107 and .359).

OH
The transformation
of hydroquinone,

CO
||

\> <|, into quinone,

/\\ \l/
OH

/\ \/ CO

||,

is

an evident

example of the convertibility of the centric form of benzene into that with two double
linkages.

Tetrachloroquinone (Mora nil), C 6 C1 4 2 prepared by oxidising triohlorophenol with dichromate and sulphuric acid, serves for the manufacture of coal-tar dyes. Toluqiiinone,
,

C 6 H 3 O 2 CH.,, xyloquinone tJiymoquinone, etc., are known, C H 4 O NH) and quinonediimides [e.g., C 6 H t (NH) 2 ].
F.

as also are quinoneiwides

(e.y. 9

NITRO-DERIVATIVES OF AROMATIC HYDROCARBONS

nitric acid, best in presence of concentrated sulphuric acid,

:

These are readily obtained by treating the hydrocarbons with concentrated which fixes the water as it is formed

C61I 6

+ IIN0 - II
3

+ C H N0
-

2.

With the hydrocarbons homologous with benzene, nitration is still more easy, but not more than three nitro-groups can bo introduced directly totranitro;

Aromatic nitro-compounds cannot be derivatives are prepared indirectly. obtained by the action of silver nitrite on chlorobenzcnes, as is the case with those of the fatty series, but this method serves for the introduction of nitrogroups into side-chains. The nitro-compounds are liquid or solid and usually more or less yellow, they are heavier than water and dissolve readily in although some are red alcohol, ether, or acetic acid, but are mostly insoluble in water. They distil unchanged and are volatile in steam. The nitro-group is united very firmly to the nucleus, especially in mononitrobenzene, and is not directly replaceable. It can be reduced to the amino1 reduction in alkaline group by means of nascent hydrogen in acid solution solution results in the formation of azoxy-, azo-, and hydrazo-conipoirnds, whilst in neutral solution or with hydrogen sulphide, the nitro-group becomes a
;
;

hydroxylamino-group. amino-phenols.
;

On

electrolytic

reduction,

nitro-derivatives

yield

Polynitrobenzenes are easily obtained by the. action of fuming nitric acid in the hot the meta-derivative is formed first, and this, by further nitration with
nitric

and fuming sulphuric acids at 110, gives symm. trinitrobcnzene. The polynitro-compounds react more readily than mononitro-derivatives
are oxidised, a phenolic

when the former

group

is

formed, while the nitro-

groups remain intact.

ortho-dinitrobenzenes, sodium alkoxide replaces one nitrogroup quantitatively, whilst with m-dinitrobenzene no reaction occurs

With para- and

C6H4(N0 2 ) 2
1

+ H ONa = NaN0 + N0
2

C6H4 OC 2H5
is
is

The nitrogen

of aromatic derivatives in

which the nitro-group

united directly to the

suitably modified.

benzene nucleus

may

be determined by the Kjeldahl method only when this

NITROBENZENE
By boiling o-dinitrobenzene with caustic
soda, o-nitrophenol
is

649
formed
:

N0 2
>N0 2
while boiling with alcoholic

OH

+ NaOH = NaN0
ammonia

yields o-nitraniline

N0 2

N NH 2
,

x
tive liquid

,*

NH -HN0 + </
a
9
,

Vo

is an almost colourless, faintly yellow, refracwhich has the sp. gr. 1-209 at 15 and, after solidification, melts at 3 and boils at 206. Owing to its pleasant bitter-almond smell, it is used in perfumery under the name of artificial essence of mirbane, but its vapour is somewhat poisonous. It is insoluble in water, but it mixes in all proportions with

NITROBENZENE, C 6H 5 N0 2

alcohol, ether, or benzene. It is of considerable industrial importance, as it forms the raw material for the manufacture of aniline, benzidine: quinoline, azobeiizene, various explosives, etc. On a large scale it is prepared in wrought- or cast-iron vessels, employing precautions and methods similar to those used in making nitroglycerine (t>ee
p. 278).

The

and 180

kilos of

Be), nitre-sulphuric mixture, consisting of 120 kilos of 3 (42 i 2 80 4 (66B6.)> poured gradually (in 8 hours) into 100 kilos

HN0

The mass is kept mixed by means of a stirrer, and during the first 5 to 6 hours is maintained at 25 by means of cold water circulating outside the apparatus. In the final phase of the reaction the temperature is raised by external steam to 70 to 90, the heating being then stopped, while the stirring is continued for a further 6 hours. The. mass is then forced by a suitable elevator into a tank with a conical base. The acid mixture gradually settles to the the former is then drawn off through bottom, while the nitrobenzene floats and the after repeated washing with nitrobenzene, taps (see Nitroglycerine), water, distilled in a current of steam from a vessel with a jacketed bottom heated with steam at 2 to 3 atmos. pressure. second distillation yields moderately pu,re nitrobenzene. According to Ger. Pat. 221,787 of 1907, nitrobenzene can al/so be obtained by running benzene into a mixture of sulphuric acid and sodium nitrate at 70 to 90. It was sold at 36 to 52 per ton before the war.
of benzene.
;

DINITRO BENZENES. By the action of fuming nitric acid or of a suitable nitrosulphuric mixture on benzene, w-dinitrobenzene is formed along with small proportions of the ortho- and para-compounds. The meta- derivative crystallises from alcohol in pale yellow rhombic plates, m.-pt. 90, b.-pt. 297, and is insoluble in water, but readily soluble
in alcohol or ether.
Its heat of combustion is 4103 cals. per grm. When boiled with sodium hydroxide it is converted into m-dinitroazoxybenzene NO 2 C 6 H 4 NO N C 6 4 NO 2 It is often mixed with other explosives, e.g., trinitrotoluene, to lower the melting-point. It is used on a large scale, not only for explosives, but for making dyes and w-phenylenediamine and
'

M-nitraniline.

and para-isomerides, melting at 117 and 172 respectively, are not of indusimportance, and are obtained either from the mother liquors of the mcta-compound or, indirectly, from the corresponding dinitroanilines. TRINITROBENZENES, C H 3 (NO 2 3 The three possible isomerides are known. The symmetrical, 1:3: 5-compound, is obtained by protracted heating of wt-di nitrobenzene with a concentrated mixture of nitric and sulphuric acids. The asymmetric, 1:2: 4-compound, m.-pt. 62, is formed similarly from p-dinitrobenzene. The vicinal, 1:2: 3-eompound, m.-pt. 127-5, was obtained by Korner and Contardi only in 1914 by diazotising
orthotrial
)
.

The

6-dinitroaniline.

s-Trinitrobenzene, m.-pt. 121 *o 122, dissolves sparingly in water, to a somewhat greater extent in methyl or ethyl anohol, and readily in acetone, ether or benzene. Its explosive properties are superior to ti ose of trinitrotoluene or picric acid, the equation 42 VOL. ii.

650

ORGANIC CHEMISTRY

S H

NITROTOLUENES
)

651

~ 9CO + 3H a O -f 3N -f 30. H representing the theoretical decomposition being 2C 6 3 (NO 2 3 2 It readily forms additive compounds with organic bases and hydrocarbons. With a view to the use of this compound as an explosive, attempts have been made, but with unsatisfactory results, to prepare it either by nitrating dinitrobenzene, or dehalogenating chlorodinitrobenzene by means of reduced copper, or by oxidising trinitrotoluene chromic acids (Ger. Pat. 127,325) and decomposing the resultant (see later) with sulphuric and
trinitrobenzoic acid

by

heat.

NITROTOLUENES
Nitration of toluene by nitric acid either alone or mixed with sulphuric acid, under conditions yielding mononitrotoluenes, gives always a mixture containing about 57, 40 and 3 per cent, of the o-, p- and m- compounds respectively. Further nitration of m-nitrofblueno yields the 2:3-, 3:4- and 3 6-diriitro-compounds ; the 3 5-compound, when
:
:

obtained otherwise, does not give trinitrotoluenes when further nitrated. Direct nitration of toluene or mono- or di-nitrotoluenes yields only 2:4:6- (a), 2:3:4and 2:4:5- (y)-trinitrotolueiies, but the other three isomerides, 3:4:5- (8), 2:3:5- (c)
(/?),

and 2:3:61917).

have been recently prepared indirectly by Korner arid Contardi (1914(7;), Tetra- arid penta-nitrotoluenes arc unknown. MONONITROTOLUENES. The three isomerides may be separated to some extent by

fractional distillation

and

crystallisation.
:

obtained pure by reducing 2 4-dinitrotoluenc by means of ammonium the 2-mtro-4-toluidine formed and decomposing the diazo-compound diazotising sulphide, 10 and with boiling alcohol. It exists in two morphotropic forms, solidifying at 4, and is used for making o-nitrochlorobenzil, o-nitrobenzaldehyde, o-hydrazotoluene and o-toluidine. m-Nitrotoluene is obtained similarly from the diazo-compound derived from 3-nitro-4-toluidine, and occurs in the liquid portion of the dinitrotoluene prepared indusof trinitrotoluene ; it has few practical applications. p-Nitrotrially in the manufacture
o-Nitrotoluene
is

toluene serves for making ^-nitro- and 2>-amino-benzaldehyde and, especially, ^-nitrofast yellow and toluene-o-sulphonic acid, which is used in the manufacture of amino Mikado orange 4R. With alcoholic sodium hydroxide it gives an orange coloration of dinitroazostilbeiie (Green) or dinitroazoxystilbene (Giua). DINITROTOLUENES, C 6 H 3 (CH 3 )(NO 2 ) 2 , exist in six isomeric forms, which are prepared

and named in various ways. Denoting the methyl group by (always in position the nitro -group by N, the isomerides have the following configurations
:

1)

and

M
N

M
N
,-N

N
w-dmitrotoluene ordinary dinitrotoluene
o p-dinitrotoluene -dinitrotoluene : 4-dinitrotoliR-ne rn.-pt. 70-5
:

^-dinitrotoluonc
e-/j-dinitrotoluene 2 : ft-dinitrotolncno

1:2:

dinitrotoluene 3-diuitrotoluenp m.-pt. 6:i

:

a,

m.-pt. 52-5

M
IN

M
N
m

M
N
: p-dlnltrotoluene dinitrotoluene : 4-dinitrotolucne m.-pt. 60

o o-dinitrotoluene. 0-dinitrotoluono 6-dinitrotolucnc m.-pt. 655

:

tn-dinitrotoluenu
initrqtoluene

fi-d

3 : 5-dinitrotoluene m.-pt. 02

Of the various names, the last given in each case is the simplest and clearest. 4-Dinitrotoluene is prepared similarly to nitrobenzene and is the one in most
:

common

industrial use, while* it serves also for making ordinary (2:4:6) trinitrotoluene. It is purified by crystallisation from alcohol or carbon disulphide and forms monoclinic crystals

-^ melting at 70

it is

insoluble in water, slightly soluble in cold alcohol or ether,

still less

422

652

ORGANIC CHEMISTRY
and
readily soluble in benzene.
It dissolves in

so in carbon disulphide (2-2 per cent.),

alkali, giving

a red solution, from which acids precipitate a reddish brown substance. .In acetone solution it is coloured blue by caustic potash. It decomposes at 300, but distils unchanged in a vacuum. Fuming nitric acid oxidises it slowly, and in the hot gives the

With hot, concentrated nitrocorresponding o p-dinitrobenzoic acid, C 6 a (CO 2 H)(NO 2 ) 2 Ammonium sulphide sulphuric mixture, it forms ordinary trinitrotoluene (see below). reduces it in the cold to o-niiro-p-tduidine (m.-pt. 105), while in the hot, p-nitro-otoluidine (m.-pt. 78) is also formed. By zinc and hydrochloric acid it is reduced to
:
.

is obtained along with the 2 4-isomeride and accumulates in the mother-liquors, when mononitrotoluene (ortho) is nitrated further. It is prepared in the .pure state by eliminating the amino-group from dinitro-p- toluidine (m.-pt. 168). It form shining needles, m.-pt. 65-5, dissolves to some extent in alcohol, and with ammonium
:

tolylenediamine. 2 : 6-Dinitrotoluene

sulphide gives o-nitro-o -toluidine. 2 3-Dinitrotoluene is obtained

:

With acetone and alkali it gives no coloration. by heating o w-dinitro-jp-toluic acid with dilute hydro:

chloric acid for 6 hours at 265

being pressed or centrifuged

m.-pt. 63. 2 5-Dinitrotoluene
:

it

a current of steam, the crystals formed separates from light petroleum solution in yellow crystals,
distilling in
:

and

is

obtained together with the 2

nitric acid
;

4-deri votive

when

toluene or

iiitrotoluene is

run into fuming

it crystallises

m.-pt. 52-5. Alcoholic ammonium sulphide reduces it to o-nitro-w -toluidine. 3 5-Dinitrotoluene is formed by eliminating the amino-group by diazotisation
:

from alcohol in yellow needles,

(see

Aniline)

from

From it crystallises in needles, m.-pt. 92. it soluble slightly in light petroleum, more so in cold alcohol or in carbon disulphide, and readily in chloroform, ether, or benzene. It distils easily in a current of steam, and with
168).
is

dinitro-o -toluidine (m.-pt. 208) or water, in which it is sparingly soluble,

from

w-dinitro-p -toluidine (m.-pt.

benzene forms the crystalline double compound, C 6 H 3 (CH 3 )(NO 2 ) 2 4- C 6 6 3 4-Dinitrotoluene is obtained by protracted agitation of m~ iiitrotoluene with concentrated nitric acid (sp. gr. 1-54). From carbon disulphide (which dissolves 2-19 per cent.), it crystallises in long needles melting at 60
.
:

tJ

TRINITROTOLUENES. The

following six isomcricles arc possible, all being

known

M
N

M
N

M
N

\y
N
(2
:

\
jB-(2
:

.-

N
3
:

fi-)trinitrotoluenc
80.-fi''

4-}trinitrotoliioiio

molts at

m.-pt. 112

5-)trimtrotoluentj

m.-pt, J04"

M
N

N
r,-(2
:

N
8-(3
:

5-) trinitrotoluene

2:3:

fi-trinitrotoluenc

m.-pt. 137-5"

m.-pt. 07-2

0-) trinitrotoluene w m.-pt. lll

:

a-TJ*INITROTOLUENE (ordinary or 2 4 : 6-Trinitrotoluene) forms long, pale yellow, prismatic crystals, m.-pt. 80-65 (corrected), deflagrating above 260 but distilling unpressure of 2500 atmos. increases the density of the crystalline changed in a vacuum. mass to 1-59, whereas a pressure of 3 to 4 atmos. on the material during
:

crystallisation,

combined with shaking, gives a density of 1-61. This compound is slightly Sluble in water or light petroleum, more so in alcohol or carbon disulphide, and readily so in acetone, ether, benzene, toluene or chloroform. The action of sunlight and air turns it brown and lowers its melting-point. By concentrated nitric acid at 110, or concentrated sulphuric acid and chromic acid at 50 to 60, it is turned into 5-trinitrobenzoic acid, whilst fuming nitric acid at 200 converts it into trinitrobenzene..

TRINITROTOLUENES
With
caustic alkali, alkali carbonate or

653

potassium cyanide

it

gives a deep reddish-brown or

violet coloration.
it forms red additive compounds. poured into an alcoholic solution of trinitrotoluene, a double compound C 6 H 2 (CH" 3 )(N0 2 ) 3 -f C 6 H5 NH 2 separates in red acicular crystals melting at 84. Whilst forms with metals picrates dangerous to handle, trinitrotoluene (see picric acid readily react with metals and can be manipulated safely even in the hot, since it p. 304) does not it is not hygroscopic and does not form a bitter and burns slowly without exploding

With

various organic bases

When aniline is

poisonous dust like picric acid. It is highly stable to shock, and when compressed is exploded with a mercury fulminate cap, but when fused and then solidified it is exploded only by a detonator of moderately compressed, crystalline trinitrotoluene, which in its turn is exploded by a fulminate cap. The velocity of detonation in a charge 50 mm. in diameter and

with a density

of 1 -55 is

7500 metres

(picric acid,

8000 metres) per

:

sec.

2C 6 2 (CH 3 )(NO 2 ) 3 -= 12GO -f 2CH 4 theoretical decomposition is expressed by 3N 2 , 1 kilo giving 778 litres of gases, which are incompletely burnt owing to lack -f2 -fIf the gases formed are free from methane (see Note, p. 259), the equation of oxygen. 20. 12CO -f 6H 2 -|- 3N 2 would be rather, 2C 7 6 (NO 2 ) 3

The

was suggested in 1891, and attempts were of oxygen by addition of ammonium nitrate, but it has been largely used, mainly as a result of Bichel's investigations, only since 1904, and in the crystalline state it now forms a very important military explosive. In the com-

The use of trinitrotoluene as an made to compensate the deficiency

explosive

etc. (it does not serve pressed or solidified state it is used for charging projectiles, grenades, for propelling projectiles, owing to its shattering power and to the abundance of fumes it forms on explosion). Different firms produce it under various names (trotyl, trolite, trilite,
trinol, tritole).

by determination of

or di-nitrotoluene, and its purity is cheeked melting-point. During the European War it was manufactured in enormous quantities in the various combatant countries. For some time a plastic product called pkvttrotyl (Bichcl, 1906) was prepared from

Industrially

it is

made by nitration of monoits

trinitrotoluene, resin, collodion -cotton,

and crude

liquid dinitrotoluene, but this

is

is

no

longer manufactured.

when m-nitrotoluene is boiled for a day with nitric and sulphuric acids, and may be obtained also by nitrating 2 3- or 3 4-dinitrotoluenc. With hot alcoholic ammonia it gives ft-dinitrotoluidine, m.-pt. 94.
a large proportion of the y-isomeride
(see below)
: :

^-TRINITROTOLUENE

or 2

4-Trinitrotoluene

formed in small proportion with

above),

slight solubility in alcohol or carbon at 104. Its physical and chemical disulphide. It forms yellowish, shining crystals, melting are similar to those of its isomerides.

y-TRINITROTOLUENE
from which
it

or 2 4 5-Trinitrotoluene can be separated in virtue of its

: :

ia

formed with the /?-isomeride

(see

properties

The

8-,

and ^-compounds
83,
.

also exhibit similar properties.

ZENE

(m.-pt. 32-5, b.-pt, 246) and /,-NITROCHLOROBEN239), are obtained together by nitration of chloro benzene. The chlorine atom in these compounds is very mobile and is readily replaced by OH, OCFT 3 , H5 The meta-isomeride, m.-pt. 444, b.-pt. 235-6, is of less importance. 2 or NHC

o-NITROCHLOROBENZENE
(m.-pt.
b.-pt.

NH

All are very poisonous.

4-DINITROCHLOROBENZENE

dinitrophenol,

and

di-,

is an important product, being used in making and hence Sulphur Black T, dinitroaniline, picric acid, nitroaminophenol, It may bo obtained in almost theoretical tetra, and hexa-nitrodiphenylamines.

yield by suitable nitration of chlorobenzene. It forms rhombic crystals, sp. gr. 1-697, m.-pt. 51, b.-pt. 315 (slight decomposition), with an irritating action on the skin, this being apparently due and is a

poisonous product
:

to the presence of the 2

6-isomeride.
side-

BUTYLXYLENE has an odour of musk and is used as a perfume. PHENYLNITROMETHANE, C 6 H 5 CH 2 NO 2 contains the nitro-group in the
TRINITROtert.
is
,

chain, as

shown by

its

method

of preparation
H-

C 6 H 5 CH 2C1
Benzyl chloride

AgN0 2 -

AgCl

H 5 CH

W) 2

It is obtained also by heating toluene with nitric acid (sp. gr. 1-12) under pressure. This compound ex *ts in two isomeric (or tautomeric) forms, one being known as a pseudo-

654
acid
:

ORGANIC CHEMISTRY
(1)

not react with

CH : (2) C 6 5 (pseudo-acid) ; the former does while the latter gives a coloration. Modification (1) is a liquid, and its aqueous solution gives, with sodium alkoxide, the sodium salt of the pseudoacid ; when the acid is liberated by means of a mineral acid it forms a crystalline product, which has the same composition as the original compound and gradually changes into
2

C 6 H 6 CH 2

N0

and

NO OH

ferric chloride,

becoming liquid. The presence of a hydroxyl group in the pseudo-acid is demonstrated formation of the characteristic dibenzhydroxamic (or dibenzoylhydroxamic) acid by the by treatment with benzoyl chloride
this,
:

C 6 H 5 CH

NO ONa +

H 5 CO

Cl

NaCl
6

->

-f

C H CH NO O CO C 6 H CO C H H 5 00 NH
8 6
:

Dihonzhydroxamic acid

That these isonitro-compounds contain hydroxyl

is

shown

also

by the

fact that they

react in the cold with phenyl isocyanate, while the nitro-compounds do not.

Similar behaviour

is

shown by ra-Nitrophenylnitromethane,

<^

the

passage from the yellow pseudo-acid to the colourless nitro-compound is clearly shown by the change both in colour and in electrical conductivity, which is very high for the pseudoacid (as for acids in general) and almost zero for the normal nitro-compound, into which
it is

gradually converted.
;

These nitro-derivatives of the side-chain can hence yield metallic derivatives of the treatment of these derivatives with acid yields the normal form, and the pseudo-acids
latter in presence of alkali is only slowly neutralised, this being characteristic of the pseudoacids.

ammonium

In benzene solution the true acids combine rapidly with ammonia, forming insoluble salts, while pseudo-acids combine only slowly or not at all with ammonia.

G. AMINO-DERIVATIVES OF AROMATIC HYDROCARBONS When the hydrogen atoms of benzene are replaced by amino-groups or
of

the

or of a primary aliphatic amine by phenyl groups, the hydrogen resulting products are mono-, di-, or tri-amines in the first case and secondary and tertiary amines in the second. Some of the aromatic amines are similar to but weaker than the aliphatic
bases, the phenyl group being somewhat negative in character compared with the positive alkyl groups. Aromatic amines form salts with acids and double salts with platinum chloride. In contact with the vapours of volatile inorganic acids they form white fumes in the air in the same way as ammonia they distil undecomposed. The diamines are more highly basic than the monamines. Isomerides of the amines are formed when the ainino group enters side-chains.
;

ammonia

1.

PRIMARY MONAMINES
;

Primary, secondary, and tertiary aromatic monamines are distinguished by the same reactions as are used for aliphatic amines (by nitrous acid, etc. see p. 240). FORMATION, (a) Mono-, di-amines, etc., are usually obtained by reducing the nitro-derivatives with tin or stannous chloride and hydrochloric acid, or 6H with iron and acetic acid, or with ammonium sulphide, etc. C 6H 5 N0 2 C6H5 NH 2 The reduction may also be effected electrolytically (see 2H 2 In the electrolytic reduction of organic compounds in later, diazo-compounds). an acid medium, electrodes of lead containing a small proportion of copper
:

are mostly used in place of pure lead electrodes, the resulting products being then purer (Ger. Pat. 252,759, 1911). or naphthols) with ammo(b) By heating phenols (or, better, nitrophenols niacal zinc chloride at 300, primary amines are readily obtained with small

C6 5 2 3 proportions of secondary amines and tertiary bases (substitutt (r) By heating secondary
:

H OH + NH = H

+ CeHg NH
L

2.

amines) with

AROMATIC AMINES
ooo
1
s
o3

655

212
^
(3

S3
cd

SI

oJ

08

c3

cd

g
^H

CO OS 00 cs os

PH CD os r-

00 <N O -H i> oo t-

66

IH

6666

oo

"tososoococoioiocoio^co^ioaO' OOOSOSOS<MMpHf i(Ni ir-<COCO(!Ni-H<

ling-poi

oooooo

SS
10

l
<

<N

"

S
S?

N
S?
s

,Q

S
'

1 o
.9

?
. "

'

isij~i li
^--'2*'4>
c! "r<
..
flJ

,t
^5
r

-SLl?^ S
r

1ll ^11
w -H T?

ft

r 8

U
'

^t
"^
3

-3

^<N co^ 3
rt-^t^s

S^
me

'

'(NCNcococo^^S^Sl ^T.
. .
.

^U4 o
l
.

<

5T*

hy
be

--S B

C^d-^ % ^SS^o^S i3rNn' ^^a-

3rHd^'<y$S

3"S5

'

i
s

IF S
<g

| ^3
r

s-ia-sii

f^llfjit|ltlflli-l S Sflga-aisEftSflftSflopb
|.|&.9J

'

S S s^a,

\&MSlt
ffi

>to

Sw
!w ,o
w

,w

w
rJ'O

C?O Q

656

ORGANIC CHEMISTRY
H

2HC1 C6 5 concentrated hydrochloric acid at 180, C 6 5 N(CH 3 ) 2 2 2CH 3C1 at higher temperatures the alkyl chloride reacts with the nucleus, C 6 5 -NH 2 -f CH 3C1 the original one giving homologous amines higher than C6 4 (CH 3 ) -NH 2 HC1. In the same way, trimethylphenylammonium iodide HI (the methyl groups of the 2 yields mesidine hydriodide, C 6 2 (CH 3 ) 3 nucleus never assume the weto-position). PROPERTIES. The primary monamines are liquid or solid and turn brown in the air. With acids they form crystalline salts soluble in water, but with carbonic acid they do not give salts, so that they may be liberated from their salts by means of sodium carbonate. With platinum chloride they form double salts (platinichlorides), e.g. (C 6 H 5 -NFT 2 HC1) 2 PtCl 4 which are only slightly soluble and serve for the separation of these bases.
;
:

= H NH + = H

NH

With methyl iodide they form secondary, tertiary, and quaternary compounds C 6H5 NH CH 3 HI -> C 6 H5 N(CH 3 ) 2 HI *-> C 6H5 N(CH 3 ) 3I the base can easily be separated from the acid by caustic soda.
:

C 6H5

Benzaldehyde reacts with

NH

*H 2
:

+ C H CH N
6 5
:

aniline,

forming benzyl ideneaniline C 6 5 CHO C 6 5 while acctaldehyde gives ethylidene:

H
2

diphenyldiamine

2C6H5

KH + CH 3 CHO = H
2

6 6

Jf5
(wianilides,

The action of the organic posable by alkali

:

acids

on amines gives

which are decom-

'

C 6 H5

NH + CH 3 COOK - H 2 +
2

C 6 H5

NH

C 2H 3 O.

Acotanilide

When heated with chloroform and alcoholic potash, the primary amines form isonitriles (carbyla mines), which have most unpleasant odours. With carbon disulphide they give thiotireas, which with P 2 5 give mustard oils of the aromatic series. With nitrous acid (or nitrites) in acid solution, amines yield diazo- or diazoamino-compounds, these giving phenols when boiled with water. Where the ammo-group is in the side-chain, no diazo-derivative is formed.
Aniline, see
later.

These are basic in but only when they contain also aliphatic radicals. These mixed derivatives are obtained from primary amines by treatment with methyl iodide and, if the acetylated primary base is employed, the simultaneous formation of tertiary
base is avoided the acetyl group
:

SECONDARY MONAMINES character, not when they are purely aromatic compounds,
2.

C 6H 5

NH COCH + CH 3I - HI + C6II5 N(CH 3 )(COCH 3

-

may be removed by subsequent hydrolysis. The secondary bases may be separated from the tertiary by means
-

of
:

nitrous acid (potassium nitrite), with which the former yield nitrosamines C 6 5 N(NO) CHg! which are neutral C 2
6

When these nitrosamines are heated with in water. the acid group passes into the benzene nucleus (alcoholic), hydrochloric C 6 4 (NO) C 6 5 N(NO) 3 3 gives Pure aromatic secondary monamines are obtained by heating the primary
compounds, insoluble

H NH CH + NO OH = H
5
3

+ H
-

NO
-

CH

NH CH
:

bases with the corresponding hydrochlorides

C 6 H5

NH 2 + C 6H NH
-

IIC1

= (C H NH + NH C1.
6 5) 2

3.

TERTIARY MONAMINES

aniline:

2KBr + (C6H ) 3tf. 2C6H5Br + C?H6 NK 2 The purely aromatic tertiary monamines are not basic

These ara formed by alkylating primary or secondary bases. Triphenylamine is obtained from bromobenzene by the action of dipotassio-

in character,

and

ANILINE
hence do not form salts. mustard oils with CS 2
.

657

They do not

give isonitriles with chloroform, or

With alkyl iodides they form quaternary compounds. When they are treated with nitrous acid, the NO group enters the benzene nucleus, this reaction distinguishing these bases from the tertiary bases of the fatty series.
4.

QUATERNARY BASES

These are analogous to the corresponding aliphatic compounds. hydroxide, N(OH 3 ) 3 OH, for example, 6 5 is and and bitter, decomposed on heating. alkaline, colourless,

phenylammonium

is

Trimethylstrongly

5.

DIAMINES, TRIAMINES, TETRAMINES, ETC.

These are obtained by reducing the corresponding nitroamino- or polynitrothus tetraminobenzene is formed from dinitro-w-diaminobenzene. The polyamines give various reactions with nitroso- compounds of tertiary amines, with certain azo-dyes, etc. The diamines and polyamines are solid substances, which distil undecombrown in the posed and are soluble in hot water. They are colourless, but turn air with a rapidity increasing with the number of amino-groups they give characteristic colorations with ferric chloride. The ORTHODI AMINES form Anhydro-bases or Benziminazoles, e.g.,
derivatives
;
;

C 6 H4<^

;>C \N/

CH 3

Further, aldehydes react with the hydrochlorides of

diamines, forming Anhydro-bases or Aldehydo-bases. Glyoxal yields Quinoxaline, etc., while nitrous acid gives Azimino-com-

pounds,

e.g.,

Aziminobenzene (aminoazophenylene), G 6H 4 <^

^S.

give, with nitrous acid, yellowish brown colouring-matters With diazobenzene chloride they yield sensitive reaction). brown: (Bismarck

w-DIAMINES

a azo-dyes (cbrysoidine). When oxidised together with ^-diamines, they give blue colour which becomes red on boiling. C6 4 2 2 S0 4 yield quinone, ^-DIAMINES, when oxidised with Mn0 2 and a homologuc with a peculiar odour some of them give colouring-matters when treated with solutions of hydrogen sulphide and ferric chloride.

+H

ANILINE (Aminobenzene, Phenylamine), C 6H5 NH^. 1

Industrially it is prepared by treating nitrobenzene with nascent hydrogen produced by the action of hydrochloric acid on iron filings or, better, turnings, as was proposed in 1864 by Bechamp, who first used acetic acid in place of hydrochloric H 5 NH 2 + SFeOL, -| 2H 2 O. C 6 H 5 N0 2 -f 6HC1 f 3Fe =
:
-

of HC1 consumed is, however, only one-fortieth of the theoretical amount, so that after a certain point the reduction is perhaps continued by the action of the iron 2Fe CC 5 on water in presence of ferrous chloride 2Fe(OH) 3 -f 2 -f 4H 2 O cast-iron cylinder, A of a consists aniline C 5 for The manufacturing 2 apparatus and is replaceable, as (Fig. 446), the lower half of which is furnished with a discharge tap it corrodes rapidly ; it is provided with a cover, through which pass a vertical stirrer, B,
:

The quantity

NO

fl

NH

was discovered in 1820 by Unverdorben among the products of the dry distillation and was called crystalline, since with acids it readily formed crystalline masses. It was then found also by Runge in 1834 in coal-tar, and he named it kyanol or blue oil, since with hypoohlorite it gave a blue coloration and its salts a violet coloration. In 1841 Fritsche obtained it by distilling indigo with potash, and he termed it, after the '* native name of the plant, ami" aniline. In 1842 Zinin gave the name benzidam to the product obtained by reducing nitrobenzene with ammonium sulphide. The identity of these various substances antf their true constitution was proved by Hotmann in 1843,
1

Aniline

of indigo

658

ORGANIC CHEMISTRY

'worked by toothed wheels, and a direct-steam coil. The cover is also fitted with a reflux condenser, NOG, and a hopper, F, with a wooden plug for the introduction of the iron turnings. A tube fixed laterally to the lower part of the reflux condenser carries off the aniline distilling with the steam to a condensing coil, 0, and a receiver, R. The operation is carried out as follows 300 litres of water, 180 kilos of iron turnings, and 60 kilos of concentrated hydrochloric acid are kept stirred in the cylinder while 750 kilos of nitrobenzene are introduced. The reaction is started by a jet of direct steam, and is afterwards maintained by gradually adding moist iron turnings up to a total quantity of 650 kilos these additions are made over a period of 6 to 7 hours and are arranged so that the mass is kept hot (90 to 95), but the reaction is allowed to calm down before fresh iron is introduced. If the reaction becomes violent, benzene and ammonia are formed instead of aniline. ^A further quantity of 100 to 150 kilos of iron turnings is added. The nitrobenzene evaporatAt the end of the operation ing with the water is condensed in the reflux condenser.
:

the vessel contains aniline, aniline hydrochloride, ferric oxide and o- and ^-toluidines, together with a little unaltered nitrobenzene and some impurities such as azobenzene, etc. Thick milk of lime is then added until the reaction is strongly alkaline, and the mass dis-

FIG. 446.

condensed in R separates into two water containing 2 to 3 per cent, of used in the reduction of subsequent quantities of nitrobenzene. The decanted aniline is purified by distillation in vacuo from an iron still. The decomposition of the aniline hydrochloride by milk of lime takes place
tilled

with superheated direct steam.

The

distillate

layers, the lower one of aniline and the upper one of aniline in suspension or solution ; this lower layer is

according to the equation

2C 6 H 5

NH

2,

HC1

+ Ca(OH)

- CaCl 2

+ 2H

{-

2C 6 H 5

NH

2.

It has also been proposed (Ger. Pat. 184,809) to reduce nitrobenzene by means of sodium bisulphite in the hot. At one time the nitrobenzene employed was obtained from crude 90 per cent, benzene containing toluene, the resultant product being a mixture of aniline and toluidine, which

served well for the preparation of certain dyes, but nowadays it is regarded as preferable to start from pure benzene and pure toluene separately and to mix the aniline and toluidine subsequently in the required proportions. Aniline can also be obtained by other processes which have not yet been applied on

a large

vapour with excess of hydrogen the copper acts as 300 to 400 a catalyst and remains unchanged (Ger. Pat. 139,457). Some importance is now being
scale, e.g.,

by passing a mixture

of nitrobenzene

(or water-gas) over reduced copper turnings heated to

ANILINE HYDROCHLORIDE
t

659

assumed by the electrolytic process, according to which nitro-derivatives can be converted into amino-derivatives in presence of metallic salts (e.g. copper salts), which also separate at the cathode (see Diazo-compounds). Kunz's process, based on reduction of nitrobenzene by means of sodium bisulphide, Na2 S 2 C6 6 Na2S 2 3 , gives a good yield and allows of the C6 5 2O 2 2 separation of pure sodium thiosulphate by concentration of the residual aqueous

H N0 +

+H

H NH +

solution.

Aniline is a liquid which boils at 1844 (92 at 33 mm. pressure), has the sp. gr. 1-026 6-3 (or at 16, and solidifies at 20 if impure). It is colourless and refractive (refractive index, 1-585 at 20), but becomes brown in the air at a rate increasing with the proportion of impurities present. It is soluble in alcohol, ether, benzene, fatty oils and, to a
slight extent (3 per cent., whilst aniline dissolves

5 per cent, of water) in water, and

it

dissolves sulphur (in the hot), phosphorus, camphor, indigo, a little water (in the hot), etc. ; it is readily oxidisable. It distils easily and completely in steam, and its vaopur is some-

what poisonous * and combustible. As a base it is weaker than ammonia in the cold but stronger in the hot, but its aqueous solution does not react with litmus or turmeric paper. Although it is a weak base, it precipitates salts of zinc, aluminium, and iron, and in the hot it displaces ammonia from various salts.

With formaldehyde
sation product (C 6
5

it
:

H N CH
;

gives a characteristic (for aniline and for the aldehyde) condenWith chloride of lime a solution of aniline 2 ) 3 , melting at 40.

becomes intensely blue if pure or \iolet if impure (sensitive reaction), the colour rapidly if the aniline solution is very dilute this coloration does not changing to brown appear, but a red colour will then form on further addition of a few drops of ammonium hydro sulphide, minimal traces (1 250,000) of aniline being thus detectable. Aniline or one of its salts forms ^-aminobenzenesulphonic acid with concentrated sulphuric acid, but in presence of a drop of potassium dichromate solution a fine blue colour is produced which disappears very rapidly ; in dilute solution a green and then a black colour (aniline black) is formed. Different methods of oxidising aniline give varied products azobenzcne,
: :

and nitro-benzene, ^-phenylhydroxylamine, jp-aminophenol, quinone, ^-aminophenylamine, violaniline (with arsenic acid). Oxidation of a mixture of aniline and toluidine yields fuchsine, while a mixture of aniline and ^-toluylenediamine gives safranine. 2
nitroso-

Chlorine transforms dry aniline into a tarry substance, while in presence of water trichloraniline and trichlorophcnol are formed. The action of calcium hypochlorite on a solution of aniline in chloroform yields azobenzene.

8ome
as follow
:

of the

more important

salts

and derivatives

of aniline

and

its

homologues are

ANILINE HYDROCHLORIDE (Aniline salt), C 6 5 2 , HC1, is obtained pure and dry in white crystals by passing a current of dry hydrogen chloride into an ethereal solution of aniline. It melts at 198 and partly sublimes, and boils unchanged at 245 ; it dissolves
readily in water or alcohol, but
is

NH

insoluble in ether.

Tt is prepared industrially by neutralising aniline at 100 with concentrated hydrochloric acid, free from chlorine. After standing for some days, crystalline aniline salt

separates out, this being centrifuged and dried at 50 ; the mother-liquors are then evaporated and crystallised. In the air the white scales assume a reddish or greenish tint. In presence of HC1 its aqueous solution imparts a yellow colour to pine- wood or elder-pith.
Aniline acts on the nervous system, and even when its action is slight the edges of the turned bluish and an effect similar to drunkenness is produced, but the face becomes pale and the appetite fails ; in such cases Epsom salts are administered as purgative, alcoholic Clothes soaked in aniline may produce serious poisoning and giddiliquors being harmful. ness so acute as to cause collapse, the lips becoming dark blue or even black. When this happens, recourse should be had to excitants or ablution or to small doses of ether administered Benzene and nitrobenzene vapours are also injurious to health. internally. 2 For the making of aniline black and other dyes, the following qualities of aniline are placed on the market aniline oil for blue, which is almost pure aniline, b.-pt. 182 to 186, sp. gr. 1-034 to 1-036 ; aniline oil for red, consisting of about 1 part of aniline and 2 parts of o- and p-toluidines and boiling at 190 to 198 ; aniline oil for safranine, sp. gr. 1-032 to 1-034, containing 35 to 50 per cent, of aniline and 50 to 65 per cent, of o-toluidine. Aniline oil is tested commercially by measuring the fractions distilling at different temperatures from 100 grms. of the oil in a suitable distilling flask fitted with a thermometer graduated in fifths of a degree from 150 to 225, the heating being carried out on a sand-bath. The best qualities of aniline oil give 95 to 98 per cent, of distillate between 182 and 185. It is also advisable to make small dyeing iiests with aniline black in order to ascertain which of the different aniline oils and salts on the market gives the finest and most intense black (see later. Dyeing Processes).
1

lips are

660

ORGANIC CHEMISTRY
, ,

(C e H 5 NH 2 ) 2 H 2 SO 4 is only slightly soluble in water. Various other salts of organic and inorganic acids are known. ANILINE PLATINICHLORIDE, (C 6 H- NH 2 HC1) 2 ,. PtCl4 forms yellow leaflets dissolving readily in water and, to a less extent, in alcohol. METHYLANILINE, C 6 H5 NH CH 3 is obtained by heating 100 parts of aniline hydrochloride with 30 parts of methyl alcohol (free from acetone) at 180 in an enamelled iron autoclave. It is a colourless liquid, sp. gr. 0-972 at 15, b.-pt. 193-8, with an odour resembling, but stronger than, that of aniline. With chloride of lime it gives first a violet and then a brown coloration. The corresponding NITROSAMINE, C 6 H 5 NO CH 3 is obtained by methylating phenylnitrosamine or by treating methylanilinc with nitrous acid. It forms, a yellow oil which distils unchanged only in a current of steam and gives Liobermann's reaction, characteristic of the nitrosamines and of various nitroso-derivatives ; this reaction consists in the formation of a dark blue coloration when the nitroso-compound is heated with phenol and sulphuric acid and the liquid then diluted with water and neutralised with potash. DIMETHYLANILINE, C 6 H 5 N(CH 3 ) 2 is a mixed tertiary amine and is obtained by heating aniline hydrochloride with methyl alcohol, methyl chloride being formed as an intermediate product and reacting with the aniline. If, however, dirnethylaniline hydrochloride is heated with gaseous hydrogen chloride at 180, methyl chloride and aniline are formed. When dimethylaniiine is heated to a high temperature, the alkyl groups pass into the nucleus. The hydrogen in the para-position of these dialkylamines is readily replaceable by different groups thus, the action of nitrous acid yields p-nitrosodimeihylaniline, which forms green crystals and gives a yellow hydrochloride. Permanganate converts the NO group into NO 2 giving nitrodimdhylanili'ne (m.-pt. 162), while boiling with caustic soda results in the elimination of dimethylamine and the formation of nitrosopJienol, NO C 6 4 OH. It gives a straw-yellow coloration with chloride of lime and reacts with

ANILINE SULPHATE,

aldehydes and various other compounds. Dimethylaniiine, which is of importance owing to its use in the manufacture of various dyes, is a colourless, oily liquid, solidifying at 2-5, b.-pt. 192-5, density 0-962 at 15. The pure compound falls in temperature when mixed with an equal weight of acetic anhyis present the temperature rises. obtained by heating aniline with its hydrochloride in an autoclave at 220 to 230 for 10 hours

dride,

whereas

if

aniline or monomethylaniline
fi

DIPHENYLAMINE, C 6 H 5 NH C H 5
C6 H5
-

is

NH

HCl

+ CH

NH - NH
2

C1

|-

NH

Ca H 8

Contardi (1918) developed a method which requires no autoclave and may be rendered almost continuous. Diphenylamine melts at 54 and boils at 302, and forms a very sensitive reagent for the detection of traces of nitric acid, with which, in presence of concentrated sulphuric acid, it gives an intense blue coloration (also given with nitrous acid and various oxidising agents ; see Detection of Nitrates in Water, Vol. I., p. 234). It is also largely used to stabilise smokeless nitrocellulose powders ( 4 to 6 per cent.) and gelatine dynamites, and serves also in the

manufacture of orange IV., metanil yellow, diphenyl C6H

blue, etc.

4\

DIPHENYLCHLOROARSINE, NH<

;>AsCl,

known

as

Adamsite

or

DM,

forms a yellowish, crystalline mass, m.-pt. 193, and was largely used in poison shells during the war, 0-012 grm. rendering 30 cu. m. of air irrespirable. It is prepared by heating either diphenylamine with arsenic trichloride for 24 hours at 160 to 190 in a reflux apparatus or

diphenylamine hydrochloride with arsenious anhydride.

which

Various nitro- and nitroso-derivatives are known, as well as triphenylamim, N(C 6 H 5 ) 3 , crystallises in large plates melting at 127 and distils unchanged. BENZYLANILINE (Benzylphenylamine), C 6 H 5 CH 2 NH C 6 H 5 is obtained either
,
'

C 6 H 5 CS

by heating benzyl chloride

NH

C6 H 5

mol.) with aniline (2 mols.) or by reducing thiobewanilide, It forms crystals melting at 33 and boils at 310.
(1

HEXANITRODIPHENYLAMINE, NH (<( /NO 2 /a / \ \ N0 2 {aurantia is its ammonium derivative, NH 4 N[C 6 H 2 (N0 2

)
,

a yellow colouring matter

) 3] 2

quantities as a shattering explosive

fpjr

charging torpedoes.

but is prepared in large In its manufacture 2 4:

ACETANILIDE
dinitroehlorobenxene
is

661

aniline, giving dinitorodiphenylamine, 6 5 m.-pt. 157. Nitration of the latter yields telranitrodiphenyla.niine, m.-pt. 180 to 190, and nitration of this hejcanitrodiphenylatnine, m.-pt. 240 to 250 (decomp.) ; this compound is turned brown by sunlight, is somewhat sensitive to shock, and inflames the skin and irritates the mucus of the eyes.

treated with

NH

C 6 H 3 (NO 2 ) 2

C 6 H 5 NH SO 3 H, is obtained by the action of sulphur very unstable except in the form of salts. ANILIDES are derivatives of aniline in which one or both of the hydrogen atoms of the in amiiio-group of aniline are replaced by one or two inorganic or organic acid residues the latter case, compounds of considerable interest are formed. FORMANILIDE, C 6 H 6 NH CHO, obtained by heating aniline with formic acid, melts at 46 and is used for making p-nitroaniline. ACETANILIDE (Antifebrin), C 6 H 6 NH COCH 3 is obtained by boiling a mixture of aniline and glacial acetic acid for a couple of days in an earthenware vessel fitted with a reflux condenser

PHENYLSULPHAMINIC ACID,
on the amine, and
is

trioxide

C H5
it is

NH + CH
2

(JO

OH - H O +
2

C6 H5

NH COCH 3

in thick, seamless, aluminium vessels placed in iron vessels to Industrially protect them from direct fire heat. It is purified by repeatedly crystallising or distilling, best in vacua. Jt melts at 115 and boils at 303-8, with partial sublimation at 95. It
dissolves in 174 parts of cold or 18 parts of boiling water or in 3 parts of alcohol ; it is The hydrogen atom united to nitrogen can be readily soluble in ether or chloroform. replaced by metals (Na, K, etc.). It causes considerable lowering of the temperature of

made

animal organisms, and

in

is

hence used as an antipyretic.

is

It

may

be used to replace camphor

making

celluloid,

and

employed

also to adulterate certain perfumes (vanillin,

musk,

piperonal, etc. ). Di- and Tri-acetanilides have analogous properties, and Methylacetanilide, (' 6 H 5 N(l'H 3 ) OOCH-, is used under the name of exalgin as a specific against headache. Diacetanilide melts at 37.

CHLORACETANILIDE, C 6 H 4 C1 NH COCH 3 exists in three isomeric forms the and the para-, at 172. The chloroortho-compound, melting at 88" ; the mcta-, at 72-5 and bromo-derivatives of acetanilide and other anilides are obtained by the action of chlorine or bromine on the anilide or by the interaction of acetyl chloride and the substituted anilines. Another scries of isomerides is that in which the substitution is in the acid group, e.y., Phenylchloracetamide, C 6 H 5 NH CO CH 2 C1 (m.-pt. 134), which is obtained from chloracetyl chloride and aniline. 1'hcnyldicblor- (m.-pt. 118) and phenyltrichloracetamide (m.-pt. 82) are also known. NITRACETANILIDE, NO 2 C H 4 NH COCH 3 The three isomerides are obtained by the action of acetyl chloride on the corresponding nitranilines ; the o -compound melts at 92 (yellowish crystals), the w- at 142, and the^- at 207.
,
:

PHENYLACETANILIDE (Diphenylacetamide), (C 6 H5 ) 2N CO treating a benzene solution of diphenylamine with acetyl chloride

BENZANILIDE
chloride
alkali.

CH 3
;

it

is obtained melts at 99-5.

,

by

(Phenylbenzamide), C 6 H 5

NH COC 6 H

5,

is is

and
It
is

aniline

and melts at 162.

It

is

very stable, but

prepared from bcnzoyl decomposed by fusion with

acid),

PHENYLGLYCOCOLL
C0 2 H,
is

insoluble in water, but dissolves in alcohol. (Phenylaminoacetic or Anilidoacetic

C6H5

NH CH 2

obtained by protracted heating of chloroacetic acid (1 mol.) and aniline (2 mols.) with water. It forms crystals melting at 127, gives characteristic mercury and copper salts,

and when heated at 150 gives up water and

at 263.

yields the anhydride

/CH C 6 H 5 N<^
*
|

melting

\CO

HOMOLOGUES OF ANILINE, POLYAMINES, AND THEIR DERIVATIVES

(see

Table, p. 655).
,

C 6 H 4 NH 2 are obtained by reducing the corresponding nitro-compounds. Since the three isomerides are formed simultaneously in the nitration of toluene, reduction yields a mixture of the three toluidines (m-toluidino in small amount). In order to separate them, the mixture is poured into a solution of oxalic acid containing hydrochloric acid and the liquid heated to boiling ; thejp-toluidine oxalate, which is only slightly soluble in water and insoluble in ether, is then separated,

ORTHO- and PARA-TOLUIDINES, CH 3

662

ORGANIC CHEMISTRY
+

the filtrate containing the soluble hydrochlorides of the other toluidines. Also Wiilfing has shown that only amines which have the para-position free can be converted (by HC1 NaN0 2 ) into the corresponding aminoazo-derivatives, the unaltered jp-toluidine being then separable by distillation in steam. p-Toluidine can also be separated by cooling, since

The toluidines are distinguished from aniline by the different solubilities it freezes first. of the nitrates, hydrochlorides, and acetyl-derivatives. #-Toluidine, like the meta-compound, costs double as much as the ortho-isomeride. o-Toluidine, which is also found in
a liquid (sp. gr. 1-09) boiling at 199 and turning brown in the air. p-Toluidine a solid melting at 43, and boils at 198 ; it is sparingly soluble in cold water, but dissolves readily in alcohol, ether, or benzene. The toluidines are used in the manufaccoal-tar, is
is

ture of dyes.

w-TOLUIDINE
pound

is

obtained indirectly by nitrating acctylated p-toluidine, the com3

CH 3<^

yNH COGH
~~NO 2

being thus formed

the acetyl-group

is

then eliminated

by

boiling with hydrochloric acid and the ammo-group by diazotisation. Reduction of the resultant w-nitrotoluene yields wi-toluidine, which is a colourless oil (sp. gr. 0-998 at 25)
boiling at

197.
;

XYLIDINES. Six isomeridcs are known (see Table, p. 655), and all are formed together by nitrating crude xylene and reducing the resulting nitro-compounds the most important is ra-xylidine. Various methods of separating the different xylidinca are known, almost all of them being patented and based on the varying solubilities of the acetates and hydrochlorides of p- and ra-xylidines. The separate isomerides are prepared pure from the

corresponding pure nitro-compounds.

the amines of the aliphatic
isomeric with the toluidines and behaves like obtained together with di- and tri-benzylamine by heating benzyl chloride with ammonia. It is a colourless liquid of ammoniacal odour and boils at 185 ; it has an alkaline reaction and is a more energetic base than aniline, the amino-group being further removed from the benzene nucleus, which has a somewhat
,

BENZYLAMINE, C 6 H 6 CH 2 NH 2
series.

is

It

is

negative (acid) influence.

o-PHENYLENEDIAMINE, C 6 H4 (NH 2
o-nitroaniline with caustic soda

and

) 2, m.-pt. 102, b.-pt. 257, obtained by reducing zinc dust, is of little practical importance.

m-PHENYLENEDIAMINE, m.-pt. 63, b.-pt. 287, is made by reducing ni-dinitrobenzene with iron turnings and hydrochloric acid. With a trace of a nitrite and hydrochloric acid it gives the characteristic brownish-yellow coloration of Bismarck brown. It is used as a developer in dyeing and printing cotton, but more especially for making numerous azo and other dyes, e.g., Bismarck brown, anthracene acid brown B, Columbia black FB, FT, vesuvine, azo bordeaux, chrysoidine, diamine brown V, neutral violet. ^-PHENYLENEDIAMINE is obtained by the reduction of aminoazobenzene (dissolved in aniline) with hydrogen sulphide, or hydrochloric acid and iron turnings, or, more easily, by heating _p-dichlorobenzene or ^-chloraniline with ammonia in presence of a copper salt (Ger. Pat. 204,408), or by reducing jp-nitroaniline with hydrochloric acid and iron
turnings. It melts at
;

147, boils at 267, and is soluble in alcohol or ether, and to a less extent in water in the air it browns slightly. Addition of a trace of its hydrochloride and then a few drops of ferric chloric solution to dilute hydrogen sulphide solution gives a characteristic
violet coloration (Lauth's violet). It is used in making many dyes
:

ethyl acid violet, azidine orange,

violet, etc.

azoalizarin black, direct

brown B, paraphenylene blue and

with boiled, milk it gives a violet coloration. It colours woody fibre been proposed as an accelerator of the vulcanisation of rubber. It is frequently employed for dyeing hair by oxidising it with hydrogen peroxide, but its use for this purpose should be
prohibited owing to
i.e.,

brown and black, With raw, but not brick-red, and has

its

poisonous properties.
.

The most common of these is the o :p)2 one the in the 2 and 4 positions and the methyl with the amino-groups compound, group in the position 1. It is obtained by reducing the corresponding dinitrotoluene (see p. 651) with iron and hydrochloric acid and is used for making dyes and, together with sodium sulphite, for dyeing hair, as it does not seem to be injurious to health, as
jp-phenylenedianiine
is.

TOLYLENEDI AMINES, C 6 H 3 (CH 3 )(NH 2

It costs about 16$. per kilo.

NITROPHENOLS
NITROANILINES.
and
aniline,

663

Concentrated nitric acid acts very energetically on may be introduced into the benzene nucleus without the amino-group being attacked, either the amino-group is acetylated or the nitration is carried out in presence of a large proportion of concentrated sulphuric acid.
in order that the nitro-groups

o-NITROANILINE, N0 2 C 6 H4 NH 2 forms orange-yellow crystals, m.-pt. 71-5, and obtained by heating o-ehloronitrobenzene with concentrated ammonia solution under pressure. It is of little industrial importance. w-NITROANILINE, prepared by reducing m-dinitrobenzene with sodium polysulphides, forms yellow crystals, m.-pt. 114, dissolves in water to the extent of 7-12 per cent., and is used for making alizarin yellow GG and dimethylnitraniline orange. p-NITROANILINE is made either by heating ^-nitrochlorobenzene with ammonia under pressure, or by nitrating acetanilide to jp-nitroacctanilide and hydrolysing the latter. It forms yellow crystals, m.-pt. 147, dissolves to the extent of 0-08 per cent, in water and 5-84 per cent, in alcohol, and is used for making alizarin yellow K, p-nitraniline red and
,

is

jp-phenylenediamine.

trated
violet

4-DINITROANILINE, obtained by heating 2 4-dinitrochlorobenzene with concenammonia under pressure, forms yellow crystals, m.-pt. 188, and serves for making G for wool and permanent red 2G. The presence of the two nitro groups attenuates
:

the basic character of the acid solution.

-

ammo

group, which

is

diazotised only in concentrated sulphuric

(2:4:

6-)

picryl chloride diazotised.

TRINITROANILINE (PICRAMIDE), NH 2 C 6 H 2 (N0 2 ) 3 and ammonia, forms orange-red needles, m.-pt. 186
;

it

obtained from has not been

2:3:4: 6-TETRANITROANILINE, m.-pt. 210, prepared by nitrating 7/i-nitroaniline, a more powerful explosive than other aromatic nitre-compounds but less so than nitroglycerine. Characteristic is the mobility and hence the ready replaceability of the nitrois

group in position

3.
,

(Tetryl), C 6 H 2 (NO 2 ) 3 N(N0 2 ) CH 3 prepared by nitration of dimethylaniline, forms yellow crystals, m.-pt. 129, and is an endothermic compound ( 40-8 cals.). It is a highly stable compound but is more sensitive to shock than picric acid, and is used as a secondary detonator.

TRINITROPHENYLMETHYLNITROAMINE

H.

NITROPHENOLS, AMINOPHENOLS

The ortho- and para-compounds are obtained mixed with dilute nitric acid, a larger proportion of the paraby treating phenol derivative being formed in the cold and of the ortho- in the hot. The latter is volatile in steam, and can hence be readily separated from the former. m-Nitroamline gives m-nilrophenol only by passing through the diazocompound, but o- and ^-nitroanilines give the corresponding nitrophenols when simply fused with potash. Nitrophenols are more markedly acid than the phenols and decompose the
alkali carbonates,

NITROPHENOLS.

forming Nitrophenoxides.

free from the para-isomcride, is obtained by distilling o-nitro-pphenolsulphonic acid in steam superheated to 150, or by heating o-chloronitrobenzene with sodium carbonate solution, or by boiling o-nitrobenzene with caustic soda. It forms yellow crystals with a peculiar aromatic odour, sp. gr. 1-447, m.-pt. 44-5 to 45, b.-pt. 214. It forms orange-red salts when heated at 200 with methyl sulphate and methyl alcohol, the sodium salt gives o-nitrophenol methyl ether, which, on alkaline reduction, yields dianisidine, this being used for making azo dyes. 7/i-NITROPHENOL, prepared from w-nitraniline and nitrous acid, forms yellow crystals, m.-pt. 96, b.-pt. 194 (in vaciw), and is not volatile in steam. jp-NITROPHENOL, colourless needles, m.-pt. 114, is used especially in making phenacetin (q.v.), and is obtained by heating p-nitraniline with caustic soda solution. ^-NITROPHENETOLE, which is the ethyl ether of ^-nitrophenol, NO2 C 8 4 OC2 Hg, forms crystals, m.-pt. 58, b.-pt. 283, and is used in making jp-phenetidine (q.v.). It is prepared by mixing jp-nitrophenol, alcohol and 50 per cent, caustic soda solution, allowing to cool overnight, and heating under pressure with ethyl chloride and alcohol

o-NITROPHENOL,

664
pound
is

ORGANIC CHEMISTRY
.
:

Various isoinerides are known. The 2 4-eom* )2 used for making colouring matters, especially sulphur black, and was made in large It is quantities during the war for mixing with picric acid to lower its melting-point. obtained by nitrating chlorobenzene and treating the resultant dinitrochlorobenzene with sodium carbonate. It is used also for preserving timber. It melts at 1 14 and has the sp. Tin and hydrochloric acid convert it into 2 4-diaminophenol (amidol), while gr. 1 -683. with ammonium sulphide it gives 4-nitro-2-aminophenol, and with toluene-o-snlpho:

DINITROPHENOLS, OH C 6 H 3 (N0 2

chloride l-chloro-2

4-dinitrobenzene.

PICRIC ACID

(Trinitrophenol),

N0 2/

JN0 2

\)H,
NO 2

was discovered

in 1771

^y Amato

di Welter, but was used first as a dye and much later as an explosive, jt is formed by the action of concentrated nitric acid on various substances, such as silk, wool, indigo, certain resins, etc., and by the oxidation of s-triiritro-

benzene with potassium ferricyanide. duced directly into picric acid.

Further nitro-groups cannot be intro-

The first tests on its explosive properties were made by Sprengel in 1871, and on Turpin's representations it was applied by the French Government under the name melinite (see p. 303) for charging grenades. Before the war it was prepared industrially as follows equal weights of sulphuric acid (66 Be.) and pure phenol were heated at 120 in a cast-iron vessel and continually stirred until a small portion of the mass dissolved in water without separation of phenol. The phenolsulphonic acid thus obtained was poured into two parts of cold water and the solu:

tion introduced gradually into earthenware jars containing 65 per cent, nitric acid (sp. gr. 1400) in the proportion of 3-5 parts per 1 part of phenol. The jars were surrounded by a water- bath and were covered over so that the nitrous fumes, which wore at first freely

evolved, could be
boiling.

drawn

off.

Towards the end

of the reaction the water- bath

was heated
:

to

The

stages of the process are represented

by the following equations

-

(1) (2)

C 6H 5

OH + H S0 - H
a 4

+ OH
=it

C 6 H4
-f

OH
this

C6H4
is

S03 H'-f 3HNOa

it solidifies,

2H 2

H0 3 H SO4 -f-

OH

C 6 H 2 (NO 2

)3.

When
water
;

the mass

cool

and

by

means the

picric acid crystals

was then centrifugcd and washed with a little can be efficiently separated from the mother-

liquor.

During the European War it was prepared on a large scale by treating pure synthetic phenol with sulphuric acid, and nitrating the resultant phenoldi- (and Iri-) sulphonic acid by

means

of

sodium nitrate and

:

nitric acid.

suggestion has been made to prepare picric acid in the cold, as follows (Fr. Pat. 1 part of crude phenol is stirred into a mixture of 10 parts of nitric acid (sp. gr. 345,441) 1 -4) with 3 parts of denatured alcohol, the mass being poured into hot water at the end of

the reaction
is

the yield
is

dear, aniline

When phenol is good, but part of the alcohol is oxidised and lost. sometimes used, being converted into the sulphonic acid, diazotised, and

treated with the theoretical quantity of nitric acid (Ger. Pat. 125,096).

PROPERTIES. Picric acid forms yellowish, very bitter, and somewhat poisonous leaflets, which melt at 122-5 and have the sp. gr. 1-7635 or, in the fused state, 1-62 to ] -64. It burns without exploding, but if it is heated in a closed vessel, or if its vapour is superheated, it may explode with great violence. In the open, mercury fulminate is not able to explode it, a detonator of dry guncotton (or lead picrate) with a mercury fulminate cap being necessary. When it is exploded in a closed vessel, its shattering effect is double that of
dynamite.

One hundred parts of water dissolve 0-626 part of picric acid at 5, 1-161 part at 15, 1-225 part at 20, or 3-89 parts at 77. It is readily soluble in alcohol or benzene. In aqueous solution it is dissociated to some extent and shows a marked acid action. The yellow colour of its aqueous solution is due to the anion ; in light petroleum it gives a colourless solution and is hence non-ionised.
,

PICRIC ACID
non-volatile in steam. Its hydroxyl-group is highly reactive, It owing to the presence of the three nitro-groups. The potassium and ammonium salts
is

are exploded

whilst with ammonium sulphide or sodium hydros ulphide, or on electrolysis (in presence of vanadium salts) it gives 4 G-dinilro-2-aminophenol (picramic acid). With potassium cyanide it gives a characteristic and sensitive red coloration (isopurpuric acid). With nitron acetate it gives a precipitate of nitron picro:

by percussion, whilst the free acid requires a detonator. With many aromatic hydrocarbons it forms well-crystallised, molecular compounds which serve for the identification and separation of the hydrocarbons picric acid is eliminated from these compounds by ammonia. When reduced with tin and hydrochloric acid it yields 2:4: 6-triaminophenol,
;

nitrate,

C 20H

1(?

N4

C 6 H 3 0(N0 2

) 3,

which

is

insoluble in extremely dilute aqueous

filtered off,

solutions acidified with sulphuric acid, water, dried at 110, and weighed.

and can be

washed with

Nitron has the structure

N
CRH, -N

C6 H5

>N

5,

and

in presence of

CHwhen
nitrites

acetic acid precipitates are also present.

N0 3

ions from very dilute solutions even

With calcium hypochlorite picric acid forms chloranil (p. 648) and chloropicrin (p. 23G), the yellow stain of the acid being removable from fabrics or the hands in this way.
The decomposition
investigated, but
is

of picric acid

on explosion has not been thoroughly

represented approximately

by the equation
2

C 6 H 2 (OH)(N0 2 ) 3
the acid

= 6CO + H

+ 3N + II

is hence too poor in oxygen to give the maximum monoxide and hydrogen not being oxidised.

effect,

the carbon

USES. Picric acid is employed in the preparation of certain organic compounds and was at one time used for dyeing silk and wool yellow, but the colour is not very stable it
;

has also been used for colouring foodstuffs. It is now mostly used as an explosive, either as acid or in the form of ammonium or potassium salt, these exploding at 310 or on percussion (see Explosives, pp. 258 et seq.). Melinite, a very powerful explosive suggested by Turpin for filling grenades, is merely picric acid which has been fused in a tinned vessel it A cold saturated is poured into the empty grenade, the interior of which is also tinned.
;

aqueous solution of

picric acid is

used for alleviating the pains of burns.

From ammonium
of potassium nitrate,

picrate

and ammonium salts of trinitrocresol, sometimes with addition powerful and stable explosives are obtained, these bearing various
,

names

(lyddite, ecrasite, etc.).

has also been proposed as an explosive. )3 OH, forms colourless crystals which o-Aminophenol, 2 6 H4 turn brown and resinify in the air ; it melts at 174 and sublimes. Its acid properties are weak and it forms salts only with acids. With ferric chloride it gives a red coloration, turned blue and then green by addition of stannous chloride. It is obtaint'l by reducing C 6 rf4 OCH3 2 o-nitrophenol and is used for dyeing furs. Its methyl ether, o-anisidine, prepared by reducing o-nitroanisole, is used in the preparation of synthetic guaiacol (see p. 644), and hence of synthetic vanillin (see later), and of various important azo dyes (fast

TRINITRORESORCINOL, C 6 H(OH) 2 (NO2

AM1NOPHENOLS.

NH

NH

chrome yellow G T G 2 azoeosin, azocochineal, diazo-scarlet). m-Aminophenol, m.-pt. 122, is prepared by heating resorcinol, aqueous ammonia and ammonium chloride under pressure and is used for making dyes. The corresponding dimethyl- and diethyl-amino compounds serve for making rhodamines. 2?-Aminophenol, m.-pt. 184, is readily oxidisable, and is prepared by reducing jo-nitrophenol, or by the electrolytic reduction of nitrobenzene. It is used for making various
,

VOL. n.

43

666
dyes, for dyeing hair 1 (see Vol. I., p. 714).

ORGANIC CHEMISTRY
and
furs,

and as a photographic developer under the name rodinal

2>-Methylaminophenol Sulphate, developer under the name metol, and pressure ; it melts at 250 to 260.
,

OH
is

C 6 H4

NH CH 3 H 2 SO4 is largely used as a prepared from quinol and methylamine under

, ,
'

AMINOANISOLES (Anisidines), NH 2 C H4 OCH 3 and Phenetidines, NH 2 C 6 H4 OC2 H 5 are used in making azo-dyes and are similar to aniline. Glacial acetic acid yields, for example, phenacetin (Acftyl-p-phenetidine), CH 3 CO NH C 6 H 4 OG 2 H5 phenetole Phenacetin is used as an antipyretic and antineuralgic and forms bsing C 6 H 5 OC 2 H 6
, ,
.

colourless

and

tasteless white crystals, m.-pt.

135, which are soluble in alcohol and

slightly

so in water.

^-PHENETIDINE
dukin
(sticrol),

(ethyl ether of p-aminophenol) is used in

etc.),

making various dyes

(stable

acid blue, alizarin yellow 5CJ,

and

its

hydrochloride,
2,

when heated with

C 2 H 5 O C 6 H4
is

NH CO NH

as sugar (saccharin

500 times as sweet).

Phenetidinc
is

m.-pt. 173, which is is used also in pharmacy.

urea, forms 200 times as sweet

PHENACETIN

(see above), in

doses of 0-5 grin.,

no disturbance in the system. heating together p-phenetidine and acetic acid. In

antineuralgic, causing

an excellent antipyretic and a specific It melts at 135 and is obtained by its manufacture use is found for the
f

p-nitrophenol obtained in large quantities as a waste product in making blue a /o dyes. 2 : 4-DIAMINOPHENOL is used as a photographic developer as sulphate (amidol) or

hydrochloride (diamol), and

is

employed

also for dyeing hair

is

and

furs dee]) chestnut.

the product prepared by Ehrlich and Bertheim as hydrochloride and placed on the market in 1910 under the name salmrsan or 606. It is a straw-yellow powder, dissolving in water to an acid solution, and it contains 34 per cent, of arsenic. It also bears the name Hata, since it was 13r. Hata, of the Elirlich
Institute, who first injected it into animals and found it to be highly efficacious in cases of syphilis in rabbits, which were able to withstand a certain dose of the preparation. It was applied to man by Alt in the case of a syphilitic paralytic, and was subsequently largely used with success by Fversen.

DIHYDROXYDIAMINOARSENOBENZENE

remedy for syphilis, the spirochotes being killed in 24 to 48 hours symptoms disappearing rapidly even where treatment with mercury or iodine is without effect. The cure seems, however, to be very painful, relapse and secondary effects sometimes occurring. The firm of Meister, Lucius und Briining Hochst, near Frankfort), who make salvarsan, sold a million pounds' worth of it in 1911.
Salvarsan
is

specific

and the

syphilitic

Salvarsan has the constitution

O H/
*l

^>
2,

As

As-

<

(
^
I

OH
2,

NH
so that
it is

HC1

NH

HC1,

'-diaininoarsonobeiizeno dihydrochlorido. Salvarsan cannot be injected as such into the veins, but must first be transformed into the sodium salt, the two phenolic hydroxyl groups being salified. The solution for injection
:

//-dihydroxy-w?

in

should be prepared a few instants before use in order to avoid the formation of the highly poisonous salvarsan oxide. Neosalvarsmn ,

As As
:

OH

2H 2 0,

NH CH
is

S0 2Na

may deposit the base of 606, which the feeble alkalinity of the blood may be unable to dissolve ; to avoid this inconvenience neosalvarsan may be mixed with various salts (neosalvarsan, 1914) which, however, lower the arsenic content
resistant to oxidation, but
is

more

21 per cent. Besides being used for curing syphilis (90 per cent, of cures), salvarsan also in cases of sleeping sickness, tertiary malaria, etc.

from 30-6 to 20 to

administered

THIOPHENOL
1

(Phenyl hydrosulphide), C e H 5

SH,

is

obtained by heating phenol with

Aromatic photographic, developers should contain several hydroxyl- or ami no-groups, or at least one group of each kind ; if the hydrogen of the hydroxyl- and amino-groups is partly replaced, the compounds lose their developing properties, unless some of these groups remain
unchanged.

AZO-

COMPOUNDS
-

667

phosphorus pontasulphide or by reducing benzenesulphonic chloride, C 8 H 5 8O 2 C1. It is a liquid of very unpleasant odour and exhibits the characters of the mercaptans. It readily forms salts, that of mercury, (C 6 H 6 S) 2 Hg, for example, crystallising in needles. When oxidised in ammoniacal solution, thiophenol yields Phenyl disulphide, (C 6 H 3 ) 2 S
,

melting at 60.

Phenyl sulphide, (C 6 has an alliaceous odour.

6 ) 2 S, is

obtained from thiophenol and diazobenzene chloride, and

-

AMINOTHIOPHENOLS, NH 2 C 6 H 4
densation products of the type
line (a

SH.

The ortho-compound

readily forms con-

X C 6 FT 4 <^

/CH,

or of greater complexity, such as primu-

yellow dye diazotised on the fibre), which is obtained by heating /j-toliiidine with sulphur and then sulphonating. When heated with sodium sulphide and sulphur, ju-aminophenol yields Vidal black, which colours cotton in an alkaline and reducing bath of sodium sulphide. The black thus obtained is brilliant and stable, like most of these sulphur dues. PHENOLSULPHONIC ACIDS, OH C G H 4 S0 3 H, are obtained from phenol and concentrated sulphuric acid or, better, from benzenesulphonic acid. The ortho- and paracompounds are preferably formed, and the former is transformed into the latter on heating. The meta-derivative is prepared indirectly. The ortho-compound is used as an antiseptic

under the name

I.

sozolic acid or aseptol.

AZO-, DIAZO-,

AND DIAZOAMINO-COMPOUNDS AND

HYDRAZINES
1.

AZO-DERIVATIVES

These are intermediate reduction products of mtro-compounds and contain a characteristic group of two nitrogen atoms, each of which is united to an aromatic group. In acid solution hydrogen reduces nitro-derivatives directly to aromatic amines, but in alkaline, solution two benzene nuclei condense and become joined by two nitrogen atoms. Tn this way the following compounds can be obtained C G II5 (2) Azobenzene, .H5 from nitrobenzene (1) Azoxybenzene,
:

N N
:

II

CpHg

N N
:

C 6H 5

(3)

Hydrazobenzene, C II 5

NH

NTT

C G H5

Reduction

of nitrobenzene with zinc dust in neutral solution yields Phenylhydroxylamine,

C 6H 6 Nil OH.

When aliphatic amines are oxidised, the alkyl groups are detached in the form of acids and ammonia is generated, but the aromatic amines yield important intermediate compounds, e.g., azoxy-derivatives.
Azo-compounds are crystalline, indifferent, more or less yellowish red compounds. They are soluble in alcohol, but insoluble in water, and some of them distil unchanged. Halogens replace the hydrogen in their aromatic nucleus, oxidising agents convert them into azoxy-compounds, and reducing agents into hydrazo- and amino-compounds. They are obtained, together with azoxy-compounds, also by oxidising amines with permanganate 2(J 6 II5 NH 2 + 2 C6H5 N N C6 H5 + 2H 2 0. AZOBENZENE Benzeneazobenzene), C H N N C 6 H 5 is obtained by reducing
:

fi

r>

nitrobenzene with a solution of stannous chloride in excess of potassium hydroxide or by It forms orange-red crystals melting at 68 and distilling azoxy benzene with iron filings. it is insoluble in water and is volatile in steam. On boils at 29,3 without decomposition reduction in acid solution it yields benzidine
;
:

Higher homologues, such as Azotoluene, are also known. Azoxy-derivatives are neutral compounds obtained by reducing the corresponding nitre-compounds with alcoholic sodium hydroxide or by oxidising azo-compounds by means
of hydrogen peroxide.

AZOXYBENZENE

is

formed by oxidising aniline with potassium permanganate in

432

668

ORGANIC CHEMISTRY
HYDROXYAZOBENZENE
C6
:

alkaline solution or, bettor, by boiling nitrobenzene with alcoholic potash. It forms pale When heated with concentrated sulphuric acid, it is conyellow crystals melting at 36. verted into

H N-N
5

C 6 H5

->C 6 H5 N: N
-

C 6 H4 OH.
-

\0/
Hydroxyazo-compounds are formed also by the action of diazo-compounds on phenols
(especially resorcinol

and the naphthols)

in presence of alkali

C 6H 5
insoluble in water.

Cl

+ G H OK =
-

C 6 H5

N N
:

OH + KC1.

crystals, readily soluble in alcohol but are azo-dycs (tropceolims). AMINOAZO BENZENES are obtained by the following methods, which introduce the Aminoazobenzene itself is formed by nitrating azoamino-group into the para-position

These compounds form yellow,

red, or

brown

They

benzene and reducing the mononitroazobenzene thus obtained or by transposition of the diazoamino-compounds (see p. 672), and hence indirectly from diazobenzene and a primary or by coupling diazo-compounds with tertiary amines, in which case or secondary amine the aminic hydrogen of the aminoazo-compounds is substituted. If the aminic group cannot enter the para-position, owing to this being occupied, the reaction becomes more difficult and o-aminoazo-derivatives are formed. The interaction of diazo-compounds with
; ;

w-diamines yields diaminoazobenzenes, which are yellow, red, or brown dyes and are termed Chrysoidines, C 6 H 5 N 2 Cl + C 6 H 4 (NH 2 ) 2 - HC1 + C 6 H 5 N N C 6 H 3 (NH 2 ) 2 The amino-group of p-aminoazobenzcnes can also be diazotised, giving (chrysoidine). diazo-compounds, which again react with amines to form a group of substances called
-

C6 4 N N 6 4 bisazo-compounds or tetrazo-compounds, e.g., C 6 H 5 for making Biebrick are used These substances known. are also trisazo-compounds

N N
:

H NH

scarlet,

croceine, etc.

G6 4 2 , forms yellow needles /;-Aminoazobenzene, or aniline yellow, 6 5 it boils without decomposition also or scales, m.-pt. 127, b.-pt. 225 at 12 mm. pressure at the ordinary pressure. It dyes woollen fabrics yellow but the colour is not fast as it to dye lacs, fats, butter, cheese, etc. It forms slowly sublimes ; it is used as alcohol yellow C6 4 : two hydrochlorides, the yellow having possibly the quinonoid form, C 6 5 It is used in making HC1. G N the flesh-red structure, the and 2 4 6 6 5 G1,
:

H N N
;

H NH

NH N

NH

H N

H NH

many

diazo colouring matters, acid yellow or stable yellow (mono- and di-sulphonic acids as
salts),

sodium

^-phenylenediamine, indulines,
:

etc.

Di- and tri-aminoazobenzenes and aminoazotoluenes are also known.

Dimethylaminoazobenzene, 6 H 5 N N G 6 H 4 N(OH 3 ) 2 obtained by coupling diazobenzene chloride with dimethylaniline, forms yellow scales, m.-pt. 117, and its hydroThe sodium salt of its monosulit is used for colouring butter. chloride, violet needles
,

phonic derivative,
sulphide.

S0 3Na C 6 H 4 N

G 6 H 4 N(GH 3

)2,

is

the indicator methyl orange

(or tropceoline II. or orange III.),

which

is

insensitive to carbonic acid

and to hydrogen

HYDRAZO-DERIVATIVES

are colourless, crystalline substances of neutral reaction

;

which are decomposed on boiling hydrazobenzene, for instance, gives aniline and azobenzene. They are obtained by reducing azo-compounds with ammonium sulphide or sodium hydrosulphite, or zinc dust and alkali. Oxidising agents (e.g., FeCl 3 or, slowly, energetic reducing agents, such as sodium the air) convert them into azo-compounds molecular transpositions (especiamalgam, give amino-compounds. Strong acids produce is free) with formation of diammodiphenyl comthe NH to the if group para-position ally
;

benzidine pounds, hydrazobenzene giving

(see

Mow).
,

is obtained by reducing azobenzene or nitrobenzene with zinc dust and alcoholic potash, and forms colourless crystals melting at 131. With energetic reducing agents it gives aniline, while oxidising agents (FeCl 3 or atmospheric oxygen) convert it into azobenzene. Under the action of a strong acid it undergoes transformation, even in the cold, into

HYDRAZOBENZENE,

C 6H5

NH NH

C 6H6

Benzidine (diaminodiphenyl)

-NH NH- /

">

->

NH /

^ -<

p>NH

(benzidine)

which forms a sulphate only slightly soluble in cold water. The formation of benzidine in this way shows that it contains the amino-groups in the para-positions, and this is con-

DIAZO-COMPOUNDS

669

firmed by the fact that this transformation does not occur with a hydrazobenzene in which the para-hydrogen is replaced by another group. Electrolytic Reduction of Nitro -derivatives. This has been studied more especially by Gattermann, Haber and Elbs, who found that, in the electrolytic conversion of nitrobenzene to aniline in acid solution, various intermediate products are formed, the primary ones being
:

C 6 H 5 -N0 2
Nitrobenzone

-> C 6 H 5 -NO _> C 6 H 5 -NH-OH

Nitro*obonzene

>

C6H 5
Aniline

NH

2,

Phonylhydroxylamine

whilst in alkaline alcoholic solution

two secondary reactions occur, the nitrosobenzene formed reacting with the phenylhydroxylaminc formed later, giving azoxybenzene
:

first

C 6H 5

NH OH + C H
6

NO

--=

C.H 5

N-N

C8 H 6

\0/
this being subsequently reduced to hydrazobenzone,

which reacts with the excess of

nitro-

benzene, forming azobcnzene and azoxybenzene. The reduction of hydrazobenzene to aniline requires a tension at the cathode greater than suffices for the formation of nitrosobenzene and phenylhydroxylamine 147 volts, only traces of aniline are formed.

much
;

with

2.

DIAZO-DERIVATIVES
aromatic series (discovered by P. Uriess in is united to only one aromatic radical 2 This group therefore forms two series of (X)".

In the diazo-compounds

of the

1859) the characteristic group, (aryl, Ar) and to an acid residue

compounds. (1) Diazonium

ammonium

salts.

salts, in which one atom of nitrogen Hantzsch showed their structure to be

is
:

Ar

pentavalent as in N.

X
True diazo-compounds with two trivalent nitrogen atoms, Ar N N X these exist in two stereoisomeric forms (see p. 22), the somewhat unstable syn-dfiazo-compounds, Ar N, and the stable an^'-d&zo-compounds, Ar N.
(2)
:

X-N

II

N-X

II

The two groups Ar and X are far apart in the an/i-compounds, so that they cannot The cyanide of easily react, these compounds hence being the more stable. antidiazo-p-chlorobenzcne, Cl C 6H4 N, is not decomposed by powdered copper
II

N-CN
and, on the other hand, cannot have the constitution of a diazonium salt, Cl C 6 4 N, which, like ammonium salts, should be colourless (whereas

CN
the cyanide is yellow) and should have an alkaline reaction and conduct the electric current in aqueous solution neither of these properties is shown by this cyanide, although they are found with the analogous diazoanisole cyanide, CH 3 0-C 6 6 -N: N.
;

CN
behave partly like acids and the corresponding pseudoIndeed, antidiazo -hydrate gives the reaction for hydroxyl and forms a conducting aqueous solution it is unstable and is converted by acids into the nilrosamine (pseudo-acid), which no longer gives the reactions for hydroxyl, does not conduct, has a neutral reaction, and in dry ethereal solution does not form the ammonium salt with ammonia (as, for example, Phenylnitromethane does). By alkali the nitrosamine is immediately reconverted into the antidiazotate
anlidiazotates
acids.
;
:

The

670

ORGANIC CHEMISTRY
Ar-N-H
Ar-N

N O
:

N OH
Antid iazotate

Nitrosamino

PREPARATION.

The gradual addition

of

sodium
:

nitrite

(1

grm.-mol.)

solution to a solution of the salt of the amine (1 grm.-mol.) cooled with ice results in the formation of the soluble diazonium salt

C 6 H5

NH HN0 3 + NO OH - 2H
2,
-

+CH N
6

NO,.

Aniline nitrate

Phenyldiazonium nitrate
2,

C 6 H5

NH

HC1 h

NO OH = 2H 2 + C6H5 N 2
C 2IL

01.

Aniline hydroehlorido

Phenyldiazonium chloride
is

When
2

and a primary alcohol formed

aliphatic amines are treated with nitrous acid, nitrogen

:

NH + NO OH = N --r +H
2

evolved,
-

-OII.

+ T

These diazonium salts are highly explosive when dry, so that they are always used in aqueous solution, when they are completely harmless. In these compounds the group C .H5 behaves like the ammonium 2 cation and with strong mineral acids gives neutral salts, while the salts formed with carbonic acid have alkaline reactions, since, like the alkaline carbonates (see Vol. T., pp. 271 and 546), they readily undergo hydrolytic dissociation. These salts have extremely high conductivities, and hence are dissociated
(

ammonium chlorides, and like these, too, they form diazoThe hydroxide, C 6 5 platmidiloride, (C 6 5 Cl) 2 PtCl 4 2 2 (from the chloride -|- AgOH), is known, although it has not yet been isolated it is soluble, colourless, and strongly alkaline. All these reactions indicate the existence of a pentavalent nitrogen atom in the Two constitutional
like

potassium and

nium

H N

H N
-

OH
;

f orniukB

are hence possible

C 6 H5

NX and

C 6H5

group
|

N
;

N
;

various reactions

indicate the latter to be the

more probable (see above). There are various ways of eliminating the nitrogen from diazo-compounds in the free state, union taking place between the benzene nucleus and the other group joined to the N 2 complex (a) By heating the aqueous solution of a diazonium salt a phenol is formed C 6H 5 N 2 01 C 5 OH N 2 HC1. 2 (6) When a diazonium salt is heated with alcohol the benzene nucleus unites with the alkoxy-group

PROPERTIES.

+H

= H
fl
:

C6H5

N 2 HS04 + C H5 OH = C 6 H 5
2

C 2 H5

+ N + H S04
2 2

under certain conditions, however, the alcohol along with the nitrogen
:

is

oxidised and aldehyde liberated

N0 a

C 6H 4

N2

Cl

+ C,H

OH

=CH
6

NO,

+N +
2

HC1

+ CH

OHO.

2>-Nitrodiazobenzene chloride

Aeetaldehydo

(c) When a diazonium chloride is treated with either cuprous chloride dissolved in concentrated hydrochloric acid (Sandmeyer) or finely divided copper (Gattermann), the chlorine (or other halogen) is introduced into the nucleus C6 5 C 6 H 5 Cl or C 6 5 CuBr Cud C6 5 Br. 2 C1 2 2C1 2 Azo-derivatives may, however, also be formed 2C 6 5 2 C1 2CuCl 2CuCU

H N
-

+N
2 .i

H N

+
:

+CH
6
1

.N 2 .C6 H5

HN

+N

+N + H = +
less

Oontardi (1022) found that in many reactions, especially anilines, cupric salts give results as good as, or even better than,

with more or

halogenated

cuprous

salts,

the formation of

DIAZOBENZENE SALTS
N 2C1 + KCN = KOI + N 2 + C6H5 CK
Benzonitrilo

671

(d) Hydriodic acid, potassium iodide, and hydrogen sulphide often act in an analogous manner, whilst by means of cuprous cyanide it is possible to replace an amino group by a cyanogen group by passing through the

diazo-compound

C6H5
This
is

(e)

a general reaction for obtaining (by subsequent hydrolysis) arwmtic acids. of Dry diazobenzene chloride, when treated with benzene in
presence
chloride, gives diphenyl
:

aluminium

C 6H5N 2C1

+ C H = N + HCI + C6H
6
6

C 6H5

(/) Treatment of a diazo-compound with a primary or secondary amine (or treatment of the amine with nitrous acid without other acid) yields diazoaminocompounds (see later), which arc then easily converted into aminoazo-compounds. With tertiary amines, diazonium salts condense in the para-position, giving

aminoazo'deriwt lives

C 6H5N 2C1
Diazonium

+ C H tf(CH - HCI + C
6 5

3) 2

H 5 N N C6 H4 (CH 3
:

)2

salts also

form hydroxyazobenzenes

(see p. 668).

(Phenyldiazonium chloride), C 6 H 5 N 2 Cl, forms colourwater and is obtained by the action of moist AgCl on the corresponding bromide ; the bromide is obtained in nacreous scales by the interaction of ethereal solutions of bromine and diazoaminobenzene (tribromoaniline remains in the solution). In solution, as usually employed, it is obtained by diazotising aniline hydroehloride.

DIAZOBENZENE CHLORIDE

less needles soluble in

(Phenyldiazonium nitrate), C 6 H 5 N 2 NO 3 is the salt obtained by passing nitroso-nitric fumes into a eold ethereal solution of diazoaminobenzene or into an aqueous paste of aniline nitrate until this is dissolved ; to the filtered liquid are added the triple volume of alcohol and then ether until the nitrate separates in colourless needles, [t is readily soluble in water but insoluble in ether, benzene, chloroform, etc. It has a strong acid reaction and is easily
,

DIAZOBENZENE NITRATE
is

which

most widely used, and

is

exploded by shock.

DIAZOBENZENE SULPHATE (Phenyldiazonium sulphate), C 8 H 5 N2 HS0 4 , is best obtained by treating a concentrated solution of crude diazobenzene nitrate with moderately concentrated sulphuric acid, precipitating several times with excess of alcohol and with ether, and allowing to crystallise in a desiccator. It forms crystals which are readily soluble in water and deflagrate at 100. DIAZOBENZENE PERBROMIDE, C 6 H 5 N 2 Br3 is prepared by the action of hydrobromic acid and bromine water on diazobenzene salts, and when treated with ammonia
,

gives
F

DIAZOBENZENEIMIDE
;
F

(Benzeneazimide),

C 6 H 5 N 2 Br.,

-{

NH 3

3HBr

-j-

C6H5

this is

more

easily obtained

by the action

of nitrous acid

on pheiiylhydrazine and

may

be regarded as the phenyl derivative of azoimide (Vol.

I.,

p. 376).

DIAZOBENZENESULPHONIC ACID, C 8 H 4 <;

C 6 H4<f

yN 2 OH
-

is

known

as the anhydride

/N2
|

and

is

obtained by adding a mixture of sodium sulphanilatc and sodium

azo-compounds being then impossible.

for cuprous salts holds
:

For euprio
C'uCl

salts the interpretation

given Ly Hantzsch

C 6H 5

N N+
:

Cu01 2

=CH N
fl

&

NCI

-H*

Cud 2

C6 H 5

NCI

* C a H 5 C1

+N

N.

Cl

Cl

Some nitrohalogenatcd amines, after conversion into diazonium salts, undergo further nitration in the nucleus when treated with sodium nitrite in acid solution ; thus, with 2 6-dichloro-4-nitroaniline : : > 2 C 6 H 2 C1 2 -N(NO 3 ) 2 C1 2 N(N0 3 ) 2 2 C a C 2 Cl 2 -N : 2
:

N0

N0

NH N0 -> NO

fl

N N0

G72

ORGANIC CHEMISTRY
It forms white needles readily soluble in water,

nitrite to dilute sulphuric acid. to prepare azo dyes.

and
:

is

used

With KOH, phenyldiazonium hydroxide forms a potassium compound, C 6 H 6 N 2 OK, and hence behaves as an acid besides as a base, but as it cannot be assumed that these two functions are exhibited to such marked extents by one and the same substance, Hantzsch
supposes that, in aqueous solution,
it

C6H6

N
HI

forms a mixture of phenyldiazonium hydroxide,

OH,
and syn-diazobenzene hydroxide, C 6 H5

N N
:

N
6

OH,

so that the general

reactions mentioned above

N
Cl

N + H OH =

would be explained thus

HC1

+ C H N N OH ->
6 5
:

C6 H 5

OH + N

N.

of the reactions referred to above can be explained well without assuming the passage of diazonium salts with pentavalcnt nitrogen into true diazo-compounds with -~ trivalcnt nitrogen ( ) (see above).

None

N
3.

DIAZOAMINO-DERIVATIVES
,

These contain the aminodiazo-group, and are yellow, N N NH crystalline substances which do not combine with acids. They are obtained by adding to diazo-salts (freshly formed in solution) primary or secondary
is

amines, e.g., aniline hydrochloride the separation of the yellow crystalline mass hastened by addition of concentrated sodium acetate solution
; :

C 6H 5
To 2

N2

01

C 6 H5

NH a - HC1 + C6H5 N 2 NHC6H5

mols. of aniline and 3 mols. of hydrochloric acid, kept cool with ice, is slowly added 1 niol. of sodium nitrite, the liquid being then precipitated with concentrated sodium acetate solution. They are also formed directly from free aniline and nitrous acid, in which case diazobenzene hydroxide must be regarded as an intermediate product
:

(a)
(b)

C 6H5 C 6H 5

NH + HN0 = H + C6H N OH N OH + C H5 NH = H + C II N NHC6H5

-

With nitrous acid in acid solution, diazoamino-compounds are converted into diazonium salts, the remaining aminic residue, diazo6 5 being tised

NHC H

C 6H5

N N NHC6 H5 + HN0 2 + 2HC1 = 2II 2 + 2C 6H5 N 2C1.

:

When heated with aniline hydrochloride, diazoaminobenzene solution yields aminoazobenzene, which is a colouring matter from which others are derived. In this transformation, which is common to all diazoamino-compounds, the aniline hydrochloride acts catalytically and takes no part in the reaction the amino-group is carried to the para-position with respect to the diazo group, or,
;

if

this is occupied, to the ortho-position

C6H5

-N:N-NHC6H5

->

C6 H5

Diazoaminobenzene

: 6 4 Aminoazobenzene

N N

H NH

It has been shown by H. (jroldschmidt that the velocity constant of this transformation increases with the amount of the catalyst (aniline hydrochloride), and the catalytic powers of the different amine salts are proportional to their

degrees of dissociation in water.

4.

HYDRAZINES
salts

These compounds are obtained by reducing diazonium chloric acid solution of stannous chloride
:

with a hydro-

C 6H 5N 2C1

+ 4H = C H NH NH

6 5 2, Phenylhydruziue hydrochloride

HCL

PHENYLHYDRAZINE

673

The use of sodium sulphite in place of stannous chloride gives first the diazosulphonate, which, when treated with zinc dust and acetic acid and subsequently boiled with hydrochloric acid, gives phenylhydrazine hydrochloride this salt separates out, being only slightly soluble in water and less so in acid. The three stages of the reaction are as follow
;
:

(a)

C6H5N 2C1

+ Na

S0 3

=CH N
6

S0 3Na

+ NaCl.

Diazobenzcnc chloride

Sodium diazobenzoncsulphonate
6

(b)

C6H6

N 2 S0 3Na + 2H = C H5 NH NH S0 3Na.
Sodium phpnylhydraKincRiilphonate

(r;)

C u II 5

NH NH

S0 8Na

-]-

= NaHS0. + C H NH NH
4

6 Phenylhydrazine

2.

PHENYLHYDRAZINE, C 6 H 5 NH NH 2
and has a
at 243

is

the most important

member

of this

group

basic character, forming well-crystallised salts. It is a colourless, oily liquid which turns brown in the air ; it dissolves only slightly in water, melts at 19-6, and boils

with slight decomposition ; it distils unchanged in a current of steam. With energetic reducing agents it forms aniline and ammonia, and with oxidising agents (e.g., chloride of lime) it can form diazonium compounds, but usually nitrogen is eliminated with forma-

tion of water'and benzene.

and

ketones (see pp. 246

and

It gives characteristic reactions with lactones, sugars, aldehydes, 253), and reduces Fehling's solution in the cold.

With diketones it forms jthenylosazones (see p. 524), and with acetoacetic acid it forms phenylmethylpyrazolone, from which, by methylation, antipyrine is obtained. With nitrous acid phenylhydrazine gives the highly poisonous nitrosophenylhydrazine,

C6 H 5
The
by
of

N(NO)

NH

2.

C 6 H 5 N(CH 3 )
the

constitution of phenylhydrazine

NO

action

C 6 N 5 N(CH 3 )
metallic
:

NH
6

is proved by the fact that nitrosomethylaniline, CH 3 , (obtained from the secondary amine, methylaniline, C 6 5 of on reduction, yields as-phenylmethylhydrazine, nitrous acid), be obtained from phenylhydrazine by the action 2 , which can also

NH

sodium

(this

replaces

the

iniinic

hydrogen) and subsequently of methyl

iodide

H 5 -NH-NH

-> C 6 H 5 -N-NH 2 ->

Na

CH

N NH 2
-

CH 3

Replacement of the aminic hydrogen by an acid residue yields hydrazides (a and ft), which give a reddish violet coloration with sulphuric acid and potassium dichromate. The hydrazides are insoluble in water and may hence be used for the precipitation of soluble
acids.

DIPHENYLHYDRAZINE,
samine, (G 6

H N
5 )2

NO,

is obtained by reducing diphenylnitro(C 6 N 5 ) 2 N 2 in alkaline solution with zinc dust and acetic acid. It is a base
,

NH

boiling at 34 almost without decomposition, and oxidising readily in the air ; its salts are unstable. It is insoluble in water and hence reduces Fehling's solution only slightly, With concentrated sulphuric acid it gives a blue coloration. The even in the hot.

action of oxidising agents distinguishes it from the isomeric hydrazobenzene ; the latter gives azobenzene, whilst diphenylhydrazine yields in the cold tetraphenyltetrazone, (C 6 6 ) 2 N N N N(C 6 H 5 ) 2 and in the hot diphenylamine and violet colouring-matters with abundant evolution of nitrogen. With nitrous acid, hydrazobenzene forms nitroso-

derivatives, whilst diphenylhydrazine, like other secondary hydrazines, gives diphenylnitrosamine and nitrous oxide. BENZYLPHENYLHYDRAZINE, C 6 H 5 CH 2 N(C 6 H 6 ) NH 2 is obtained from phenyl2 boiling at 135 hydrazine and benzyl chloride. Benzylhydrazine, C 6 5 CH 2
-

NH NH

(in vacuo), is also

known.
jp-nitraniline,

^-NITROPHENYLHYDRAZINE,
and
is

obtained from a useful reagent for aldehydes and ketones.

forms yellow crystals

/J-PHENYLHYDROXYLAMINE, C 6 H 6 NH OH,
colourless crystals melting at 81. With acids benzene and with dichromate nitrosobenzene.
it

of aniline or the cautious reduction of nitrobenzene with zinc dust

obtained by the gentle oxidation and water, and forms gives jp-aminophenol, with oxygen azoxyis

The

a-isomeride,

NH OC H
2

6 , is

of little

importance.

674
J.

ORGANIC CHEMISTRY
ROMATIC ALCOHOLS, ALDEHYDES, AND KETONES

In these compounds the primary alcohol group, the aldehyde group, or the ketonic group forms a side-chain to the benzene nucleus and shows all the general properties of these groups. Di- and trihydric alcohols are also known, e.g., Phthalic alcohol (ortho) Xylylene alcohol (para), C6 4 (CH 2 OH) 2
:

Phenylglycerol,

with the cresols, GH3 C 6 H4 OH, and is obtained by tho interaction of benzyl chloride and potassium acetate and subsequent hydrolysis of the acetyl-derivative thus obtained, or, better, by the action of aqueous potassium hydroxide on benzaldehyde
:

C 6H5 CH(OH) CH(OH) CH 2 OH. BENZYL ALCOHOL, C H 5 CH 2 OH (discovered by Cannizzaro

fl

in 1853), is isomcric

20 6 H 6

OHO + KOH =

C 6 H 5 CO 2K

-f C 8

H5 OH 2 OH.
.

alcohol readily gives benzyl chloride when treated with PC16 On oxidation it gives first benzaldehyde and then benzole acid, its constitution being thus proved. It forms simple and mixed ethers and esters. It differs from aliphatic alcohols by resinifying

The

with sulphuric acid.

It has the characters of a true alcohol

It is slightly soluble in alcohol
:

and

is

hence insoluble in

alkali (unlike the phenols).

and

boils at

206.
;

Various higher homologues are

Cumyl alcohol

(p.).

Styryl alcohol,

known Tolylene alcohols, CII 3 C 6 H i GH 2 OH C3 H 7 C 6 H4 CH 2 OH, ete. C 6 H5 CH CH CH 2 OH, containing an unsaturated side-chain, is
: ;

found as ester (styrarin) in storax

it

forms acicular crystals with an odour of hyacinth.

With alcoholic potash aronwtic aldehydes are partly oxidised and partly reduced, benzaldehyde, for instance, being converted into potassium benzoate and benzyl alcohol
:

2C6 H5
phenylmethane
-

CHO + KOH

-C H
6

CO 2K

+ C H5
6

CH 2 OH.
-

With dimethylaniline
:

or phenol these aldehydes give derivatives of

tri-

C6H5 CHO
BENZALDEHYDE,

+ 2C H5 OH - H
-

+ C H CH<
-

r>

Nyi, OH
C20 H 27 NO n
,

C 6 H5

Cf

occurs in the Amygdalin,

of

bitter

\H
;

almonds in the form of a glucoside. It is a liquid of pleasant odour and dissolves slightly in water it boils at 170, has tho sp. gr. 1 -05 and constitutes bitter almond oil. When pure it forms crystals, m.-pt. 26. It oxidises easily and forms crystalline products with bisulphites, while it combines with hydrogen, hydrogen cyanide, etc., forming an oxime, a hydraWith ammonia it gives hydrobenzamide, 3C 6 H 5 CHO + 2NH 3 =- 3H 2 O + zone, etc. (C H 5 CH) 3 N2 It is formed by distilling a -mixture of calcium formate and benzoate and
.

also

oxidising benzyl alcohol. Until recently it was prepared industrially

by

by heating benzylidenc
:

chloride under

pressure with milk of lime

-

and calcium carbonate

C 6H 5 CHC1 2 f Ca(OH) 2

CaCl a

+ G H5 CHO + H O.
-

By using catalysts (finely divided iron, etc.) Schulze found that this reaction could be rendered complete at low temperatures in open vessels, very pure hydrochloric acid being recoverable. Benzaldehyde may also be obtained by treating benzene with a gaseous mixture of carbon monoxide and hydrogen chloride in presence of Cu 2 Cl2 or AlBr3 (Ger.
Pat. 126,241).

A method now largely used is that discovered by Poner of tho Badische Anilin-und Soda-Fabrik (1887) and kept secret for some years but published in 1898 in the French Patent No. 276,258. It consists in shaking toluene vigorously with sulphuric acid (52 Be.)
and gradually adding precipitated manganese dioxide, the temperature being kept at 40. The benzaldehyde formed is free from chlorine and may be separated from the toluene by a current of steam, or, better, by diluting the toluene- benzaldehyde mixture with four

AROMATIC KETONES
times
its

675

water and treating the liquid with sulphur dioxide until about 26 weight i>er cent, is absorbed. In this way all the aldehyde passes into solution (improvement on the use of sodium bisulphite) and can be decanted from the undissolved toluene. It is then J sufficient to heat the sulphurous solution slowly from 30 to 100 to eliminate all the sulphur dioxide, which is passed into a further portion of the aldehyde mixture. After cooling the solution, almost the whole of the benzaldehyde is obtained in a pure state and the motherof

liquors are utilised in succeeding operations so that the small

amounts

of aldehyde remain-

ing dissolved

may

not be

lost.

Commercial benzaldehyde and that for industrial uses cost before the war about 3*., the pure product about 4,9., and the chemically pure about 9$. 6d. per kilo. For industrial purposes, it should have a specific gravity of 1-052 to 1-054, and should distil completely in a current of hydrogen between 176 and 180. Its solution in concentrated sulphuric acid should be only slightly brown and it should dissolve completely in ammonium bisulbeiizoic acid phite. Any present can be titrated with phenolphthalein as indicator. It is used mainly as oil of bitter almonds and in perfumery, and also for making dyes of the trip heny line thane series.

HOMOLOGUES OF BENZALDEHYDE are obtained by treating aromatic hydrocarbons with gaseous hydrogen chloride and carbon monoxide in presence of Aid 3 or Cu 2 C1 2 The first product obtained under these conditions is probably formyl chloride, which then reacts thus
. :

C 6 II 6

+ Cl OHO - HC1 + X
,

C 6H 4 CHO.

and aromatic hydrocarbons in presence of A1C1 3 the ketonic ester obtained being hydrolysed and the acid subjected to dry distillation in order to expel C0 2
:

Aldehydes are also obtained from ethyl chloroxalate

C 6H

fi

CO COOC 2H 5 - HC1 f X C 6H 4 CO C000 2 H5 + x c 6H 4 co oooc aH 6 - x cyi 4 CHO + co 2

Cl
-

of H(J1 and 1ICN on aromatic hydrocarbons also yields alde(Mines hydes, being formed as intermediate products
:

The action

+ HCN + HC1 = C,H CII Nil, HOI. C H CH Nil, HOI H = C H CHO + NH C1.
C 6H6
B
:

lieiizaldine h>drochloride
-

(-

CINNAMALDEHYDE,
it is

C 6H5

CH CH CHO, is an
:
-

oil

by means

steam and is separated from cinnamon oil, sodium bisulphite. NITROBENZALDEHYDES, N0 2 C 6 H t CHO, are prepared in various ways. The ortho- compound is obtained either from o-nitrobenzyl chloride or by oxidising o-nitrotoluene. It forms colourless crystals melting at 4ti and with acetone and caustic soda leads to the synthesis of indigo.
volatile in

of pleasant odour, boiling at 246 ; of which it is the chief constituent,

of

Nitration of benzaldehyde yields mainly the ro-compound, together with 20 per cent,
of the o- derivative.

CUMIN ALDEHYDE Roman cumin oil.

(Cuminol,

Isopropylbenzaldehyde),

C.,H 7

C 6 H,

CHO, occurs

in

AROMATIC KETONES
ACETOPHENONE, C 6 H 6 CO CH 3 is obtained by distilling calcium acetate with calcium benzoate or, better, by treating benzene with acetyl chloride in presence of A1C1 3 It forms crystals melting at 20 and boils at 200 it dissolves only slightly in water, has a pleasant smell, and is used as a hypnotic under the name of hypnone. On oxidation it gives either benzylformic acid or benzoic acid and carbon dioxide ; halogens give products
,
.

substituted in the side-chain.

BENZOPHENONE
distillation of

of AlClg.

(Diphenyl ketone) t C B H 5 CO C 6 H 5 is obtained either by the dry calcium benzoats or by the action of benzoyl chloride on benzene in presence Its behaviour is similar to that of aliphatic compounds, and with hydrogen it
-

forms Benzhydrol,

C 6 H5 CH(OH) C 6H 5 and
,

Benzopinacone, (C 6

H5

)2

---

-C-

(C 6

5 )2

OH OH

676

ORGANIC CHEMISTRY
fused with potassium hydroxide,
it

When

gives benzene

and potassium benzoato:

an unstable form,

C 6 H 5 CO C 6 H 5
m.-pt.

+ KOH --

C 6H 6

-|-

C 6H 5 COOK.
differ physically
:

Benzophenone exists in two modifications which 27, and a stable form, m.-pt. 49. C 64 6 H4
|

DIPHENYLENEKETONE,
methane
(see later),

H/
|

j>CO,

is

the ketone corresponding with diphenylene-

and is obtained by heating phenanthraquinone with lime. With nascent

C 6 H4\

hydrogen

it

gives Fluorene alcohol,

^>CH

OH

(colourless scales, m.-pt. 153), and,

O.H/
when fused with

potash, Diphenylcarboxylic acid, 6 5 C 6 EI 4 C0 2 H. Polyacetones, such as Benzoylacetone, C 6 5 CO CH 2 CO CH 3 and Acetophenoneacetone, C 6 5 CO CH 2 CH 2 CO CH 3 are also known. Condensation of benzaldehyde with acetophenone or acetone in presence of NaOH Benzalacetone, C 6 H 5 CH CH CO CH 3 (m.-pt. 41) gives unsaturated ketones

Benzalacetophenone (chalkone),

C 6 H 5 CH

CH CO C 6 H 5
two forms

(m.-pt. 58).

AROMATIC OXIMES
253).

present interesting cases of isomerism (see pp. 22 and

is

Thus, Benzaldoxime
boils unaltered,

known

in

which

and

solid syn-benzaldoxime,

C6H5 -C-H-:H 2 04-0 6H 5 -C;N.

1 1

which readily

liquid anti-benzaldoxime, loses water

(with acetic anhydride), forming benzonitrile

N-OH

Under these conditions the anti-aldoxime gives an acetyl-derivative, so that the two aldoximes may be distinguished in this way. With ketoximes two isomerides are formed only when the two groups united
to the carbonyl group are different
:

X - C - X'
ancl

N-OH
syn

II

X - C - X' OH - N
II

anti

C 6H 5
Thus, Benzophenonoxime,

-C-C H N-OH
6
||

5
,

does not form isomerides,

which
is

however, obtained if a hydrogen atom of one of the benzene groups replaced by a halogen, alkyl group, etc. The ketoximes show Beckmann's transposition, 1 in which the isomeric
are,

ketoximes, which have different melting-points, give rise to two different substituted amides according as the transposition takes place with the group or X' (see Note).

1 The Beckmann transposition is that obtained with ketoximes in general by treating them with acetyl chloride or concentrated sulphuric acid or, in some cases, merely by fusion. The oxygen of the oxime changes places with a radical united to the ketonic carbon giving a substituted amide, an unstable, tautomeric, hydroxyl compound being probably formed as an intermediate product :

C
I

x-o-x'
II

rx-c-oH-i
I
I

^.

N-OH
The
structure of the isomeric synis
:

N-X'J

||

>.

TT

N <X'

Thus, if the above oxime be as follows

and anti-oximes can be determined by Beckmann's reaction. the anti-compound, the transposition with the syn-isomeride would

O C X'

C X'
|l

>

TT

OH-N

V>N

AROMATIC HYDROXY-ALDEHYDES
BENZALAZINE, C 6 H 5 CH N N CH C 6 H6
-

ETC.

677

2 mols. of benzaldehyde with melting at 93.

crystals melting at 132

: is obtained by the condensation of , mol. of hydrazine (sulphate), and forms yellow crystals -

BENZALDEHYDEPHENYLHYDRAZONE,
and forms

C 6H 5

CH N NHC 6 H 5>
:

forms colourless

stereoisomerides.

K.

AROMATIC HYDROXY-ALCOHOLS, HYDROXYALDEHYDES, AND KETONIC ALCOHOLS

I

C 6PI4 < ril r

_

OH
-

~ sa ^9en n
^
j

OH 2 nTT OK m\ hydroxybenzyl akohols

C 6H 4 < r)TTr^J
CIIO

/~)TT

= salicylaldehyde
\

^
*

hydroxybenzaJde-

UH <X UI
4

= (mitaldeh'fde
'

G 6 H^OGH 3
4
3
vanillin

4 3 vanillic alcohol
1

\CH, OH

C,

6ll a(

/OH OCR 3 OCH

^CIIO

The three isomeric hydroxybenzyl alcohols are known, their melting-points o~, 82 m-, 67 being as follows p-, 110. The most common of these is
:

SALIGENIN

(o- Hydroxybenzyl

alcohol, see above),

it

the glucoside salicin, from which dilute acid (Piria, 1845)

:

OH C 6 H 4 CH 2 OH, occurring in can be obtained by the action of emulsin, ptyalin or

-

<

Hn

C 6 H4 CH 2

OH + H

- OH

ft

H 4 CH

OH +

C 6 H 12

(glucose). ferric

It

is

soluble in alcohol, ether, or boiling water

and gives a blue coloration with

chloride.

AROMATIC HYDROXYALDEHYDES,
action of chloroform

or phenolic aldehydes, are obtained (1)

caustic potash on phenols : C 6 5 CHC1 3 3KC1 C6 4 3H 2 -f or (2) by the action of hydrocyanic and hydrochlor| ; acids on phenols in presence of aluminium chloride or zinc chloride, alditn hydrochlorides being formed as intermediate products.

and

by the

CHO

H OK

OH + 4KOH +

With difficulty by oxidising agents, but readily by fusion with alkali, these aldehydes give the corresponding hydroxycarboxylic acids. They reduce ammoniacal silver solution but not Fehlintfs solution. With alkali they give soluble alkali phenoxides which form the
alkyl derivatives of the phenols

when

treated with alkyl iodides.

(o-Hydroxybenzaldehyde), OH C 6 H 4 CHO, is found in the volatile oil of Spircea ulmaria. Its synthesis by means of chloroform is indicated above and it is separated from the p-aldehyde formed at the same time by distillation in steam. It is a liquid, b.-pt. 196, sp. gr. 1-172 at 15 ; it dissolves to some extent in water and gives

SALICYLALDEHYDE

a violet coloration with

yellow.

ferric chloride.

Like

all

o-hydroxy-aldehydes

it

colours the skin

is obtained by the cautious oxidation of Anethole, with dichromate and sulphuric acid, the aldehyde being distilled in steam and purified by means of sodium bisulphite. It boils at 248, has sp. gr. 1-123 at 15, and, owing to its strong odour of hawthorn, is used in perfumery. VANILLIN, C 6 H 3 (OH)(OCH 3 )(CHO) 4:3:1 (w-Methoxy-^hydroxybenzaldehyde), is found (about 2 per cent.) in the pods or fruit of vanilla ( Vanilla planifolia) l and as a gluco-

ANISALDEHYDE
:

(see

above)
,

CH 3 CH CH C 6 H4 OCH3

a climbing, herbaceous plant growing well in Mexico, Reunion and elsewhere. and cylindrical (15 to 25 cm. long) and contains a number of round black seeds with a pleasant odour. The fruit is gathered before it is quite ripe, as otherwise the pods open and the seeds are lost. Their vitality is destroyed by steeping them in water at 80 to 85 or placing them in an oven at 50 to 70 or in the sunlight. The capsules thus turn dark brown and after being allowed to sweat for 20 to 30 days at 30 to 40 they become covered with a
Vanilla
is

The

fruit is fleshy

678

ORGANIC CHEMISTRY
2H

side (coniferin, 2 0) in the sap of the conifers (Coniferin, C lfl 22 O 8 C^H^O,, -f in asparagus, in beet-juice, in certain woods, in asafsetida, etc. ; it is also formed by

+ 2H20),

oxidising

the resin of olives.

Jt is readily obtained artificially by treating clove oil with dilute alkali, which dissolves the eugenol and transforms it into Isoeugenol, C CH CH3 ), which is 3 (OH)(OOH )(CH then oxidised by ozone or permanganate. It forms slender white crystals which melt at
fl

:1

to 81-5, and sublime, and it boils at 285. ft has a strong odour of vanilla. Considerable quantities of synthetic vanillin, are now made by various processes, the details of which are kept secret.

81

By HC1

at 200

it is

transformed into protocatcchu aldehyde, the mcthylene ether of

CH:CH-C-(X
which constitutes Piperonal (heliotropin or artificial heliotrope),
(rn.-pt.
|

||

CHO C CH
:

C (K

/OIL,,

37

b.-pt.

purity.

Formerly

it

263), costing before the war from 16*. to was obtained by oxidising piperinic arid

28-?.

per

kilo,

(see Piperidiiio),

according to its but it is now

made by

oxidising isosafrole, prepared

by the action of

alkali

on

safrole,

BENZOYLCARBINOL, C 6 H 5 CO CH 2 OH, obtained from Phenacyl bromide, C 6 H5 CO CH 2 Br, forms stable, shining scales, and possesses strong reducing properties The corresponding acetonaldehyde is Phenylglyoxal, C 6 H 5 -CO CHO, analogous to pyruvic
;

aldehyde.

L.

AROMATIC ACIDS

Like the aliphatic acids, these form salts, anhydrides, esters, amides, etc., end give in addition other products by substitution in the benzene nucleus. Here, too, the characteristic group is the carboxvl, COOI1, and the acids may be either mono- or poly-basic, according to the number of carboxyl groups, this being indicated in the name
:

C6H5 -COOH
Benzole acid
or

C,.II 4 (OOOH) 2 Phthahr adds

(liriiiu'nwlfrnrhoxylfc or bonaeni'dimcthaiioic ariita)

H 3 (COOH) 3
also

C S(COOH) 8
Mdlit.ic acids

IJciizenftricarbo\.\lir acids

(brnsenetrimethanoic acids)

nemethanoic acid) PrnprnrlioxYlir

(IxMi/riiohexncarboxylie OP bt'iiXfMichcxaint'thanoic'adds)

Aromatic acids with unsaturated side-chains are

like

known, these behaving

unsaturated aliphatic compounds

C 6 H5

CH CH C0 2 H
:

C CO 2 H

Clnnanur acid

PhiMi>lproiilnlic acid

There are also various acids derived from the hydrobcnzenes, with characters resembling those of aliphatic compounds. Aromatic hydroxy-acids with a hydroxyl group in the nucleus behave partly like phenols and partly like acids, and are analogous to the aromatic alcoholacids containing acid groups and true alcoholic groups in the side-chains.
perfumed powder. They arc then tied up in bundles of 50 and sold in boxes holding 3 to 10 kilos. Of inferior quality arc the smaller fruit arid those from the Antilles, Brazil, and Guiana. They are used for pistry, liquors, perfumes, and chocolates. 1 Contfirin, m. pt. 18.T, isaglucoside of the larch having the constitution OH CH 2 CH CH
crystalline,
:

(~ N

,O

CH 2 [CH OHJ 4

(110

+ 2H

2 0.

It is lavorotatory

and yields glucose and oonifcryl

OCH 3
OH- CH 2 -CH:CH /
it

alcohol,

V>H, when

treated with a dilute acid

or

emulsin.

On

OCH 3
reduction
gives eugenol

and glucomnittyl

alcohol, whilst

on oxidation

it

forms fiTatglHcovanittin,
acid.

\ O CH
OCH 5

[CH OH

CHO, which gives vanillin on hydrolysis with dilute

AROMATIC ACIDS
H CH

679

In each of the aliphatic acids a hydrogen atom can be replaced by a benzene residue, giving aromatic acids of the acetic acid series (e.g., PhenyJacetic Acid, ' C0 2II) and of the glycollic and succinic series, etc. C6 5 2 In general, aromatic acids are crystalline and only slightly soluble in water,
while they are often soluble in alcohol or ether. The more simple ones sublime or distil unchanged and lose C0 2 only on distillation with vsoda-lirne, this occurring with the more complex acids simply on heating. Their alkaline salts are soluble in water, but the acids are precipitated in the free state on addition of a mineral acid.

METHODS OF FORMATION. (a) When hydrocarbons with benzene are oxidised, each side-chain, no matter what its homologous length or nature, yields only a single carboxyl group attached directly to the benzene nucleus. When several lateral chains are present, dilute nitric acid oxides them gradually, whilst with chromic acid they are all oxidised
GENERAL
-

C 6 H 5 CH 3 gives C 6II, C0 2 C 6 H 5 C 2 5 gives C0 2 together 5 C 6 5 CII CH C0 2 'gives C 6 H 5 CO 2 C 6 4 (CH 3 ) 2 gives C 6 4 (CO a H) a Of the disubstituted derivatives, the o/Y/jo-compounds are oxidised very easily and do not give carboxyls unless the oxidation is carried out with great care, nitric acid or permanganate e.g., with dilute jwra-derivatives are readily oxidised by chromic acid and the meta- less readily. Compounds containing a negative group, even Oil, in the or/Ao-position are not oxidised even by chromic
:

H H

CH

acid.
(b)
(c)

By oxidising primary alcohols and aldehydes in the usual way. By hydrolysing nitriles C 6 H6 CN + 2H 2 O _- NH 3 + C 6H5 COOH.
:

fcrrocyanide Cg^s S0 3K -f- KCN = K 2 S0 3 -fC 6 H5 CN (benzonitrile) or from the chlorides of compounds with side-chains C 6H 5 CH 2 C1 + KCN = KC1 MJ 6 FT 5 CH 2 CN (benzyl cyanide). Nitriles

The

nitriles

potassium

are formed cyanide or

by

distilling, e.g.,
:

potassium phenylsulphonate, with

'

can also be obtained from primary amines by diazotising and subjecting the diazo-compounds to Sandmeyer's reaction (*ee p. 670) also from the aldehydes by way of the oximes (t>ee p. 246). (d) By the action of C0 2 on monobromobcnzene in presence of sodium (Kekule), or by treating benzene or its homologues with phosgene (COC1 2 ) in presence of A1C1 3 (Fricdel and Crafts)
;
:

C 6H 5 Br + C0 2 + 2Na = C 6 H5 COONa f NaBr C 6H 6 + C()C1 2 - HC1 + C H5 CO Cl (which, with

;
-

2 0,

gives the acid).

(e)

Phenolic acids are obtained

:

by the action

of

C0 2

or CC1 4

and

alkali

on

sodium plienoxides

OH + C0 = H 4 <^ONa OH C H ONa + CC1 4 =- C,H 4 <Jyj + Nadl, and + 4NaOH = 3NaC1 + 2ll2 + C H < COONa
C 6II5 ONa
6

If chloroform is used in place of carbon tetrachloride, ortho- and parahydroxyaldehydes are obtained. acetoacetate or ethyl malonate are analogous (/) The syntheses with ethyl to those of the fatty series (see pp. 368 and 397) and are carried out with phenols, derivatives with halogens in the side-chain, etc. complex ketonic acids are obtained which undergo both the acid and the ketonic decomposition. Aromatic acidb with unsaturated side-chains are obtained by the methods used for aliphatic unsaturated acids, or by Perkin's reaction (see p. 352) between fatty acids and aromatic aldehydes in presence of acetic anhydride, which removes the water formed
;
:

680
6 5

ORGANIC CHEMISTRY
H CHO + CH 3 C0 Na = C H5 CH CH
2 6
:

COONa

+H

2 0.

Sodium acetate

With substituted benzaldehydes a varied

can be obtained.

series of

unsaturated aromatic acids

:

Also benzal chloride and sodium acetate give unsaturated acids

C H5
G

CHC1 2

CH 3 COOH

= 2HC1 + C H CH CH
6
5
:

COOII.

Cinnamie acid

Ethvl acetoacetate and also malic acid act on phenols in presence of concentrated sulphuric acid, giving anhydrides of unsaturated phenolic acids, e.g.,

CH CH
:

CO
(a)

MONOBASIC AROMATIC ACIDS

is

The isomerism among these compounds

derivatives of aromatic hydrocarbon?.

similar to that of the halogen

resins
(e.g.,

sublimation or by heating with milk of lime. It is formed in the urine of herbivorous animals as Hippuric acid, which gives glycocoll and benzoic acid on putrefaction or when heated with acid or alkali. It forms white leaflets, sp. gr. 1 -292, melting at 121 4, It has an it sublimes at 100 to 12(3 and distils in steam. and boils at 249-2 in boiling water ; its alkali salts crystallise well irritating odour and is soluble C0 2 |H 2 0) and dissolve in water. (C 5 It is prepared industrially by converting toluene (from light tar oils), by means of chlorine, ID presence of a little powdered iron, into benzenyl trichloride, C 5 CC1 3 and heating this with milk of lime under pressure 2C 6 5 CC1 3 4H 2 (with traces of chlorobenzoic 3CaCl 2 (C 6 5 COO) 2 Ca 4Ca(OH) 2 the with treated of Instead lime, benzenyl trichloride may be oxibeing acid).
; (

BENZOIC ACID, C 6H 5 COOH, is found naturally in various gum benzoin) and in balsam of Tolu, from which it is obtained by

K+

dised directly with dilute nitric acid, in vessels fitted with stirrers, as long as then distilled, allowed to hydrogen chloride is evolved, the benzoic acid being Jessnitzer (Ger. Pat. sublimation. and by purified crystallise, centrifuged, 236,489 of 1910) proposes to oxidise with calcium hypochlorite instead of with
nitric acid.

Bcnzonitrile, C 6 5 CN, found in the middle tar oils, gives pure benzoic acid when hydrolysed (Ger. Pat. 109,122). and phthalic acids are readily According to Ger. Pat. 136,410, benzoic obtainable heating naphthol or other naphthalene derivative with fused

the or dissolved alkali in presence of metallic oxides (Mn0 2 CuO, Fe 2 3 ) benzoic acid is separated from the mixture by distillation. USES. Benzoic acid is used in medicine, in making certain aniline blues of the anthraquinone dye group, in the seasoning of tobacco, in printing textiles, 1 and for preserving foodstuffs, although it has not been shown to be harmless when used in this ; experiments made in the United States in 1910 showed
,

by

that doses of
effect.

or sodium benzoate have no injurious grm. per day of benzoic acid It cost about 3s. to 4s. per kilo before the war, and as much as 32.9.
1

way

during the war.

BENZOIC ANHYDRIDE,
benzoyl chloride
:

(C 6

H5

CO) 2 O,

is

obtained by heating an alkali benzoate with

C 6 H 5 C0 2Na
L

C 6H6 CO

Cl

NaCl

(C 6

CO) 2 O,

Of the various methods for detecting benzoic acid in foods, the following may be mentioned. benzoic acid in milk may be shown by converting According to Jonescu (1909) the presence of diluted ten times, and then testing it into salicylic acid by means of 3 per cent, hydrogen peroxide for salicylic acid with ferric chloride solution (sp. gr. 1-28) diluted ten times (as in the examination In the case of butter or margarine this is acidified with sulphuric acid and distilled of beer). with steam, the distillate being tested as above (see also Salicylic Acid),

BENZOYL CHLORIDE
MONOBASIC AROMATIC ACIDS

681

or,

Cl

according to Cer. Pat. 146,690, by heating nearly 2 parts of sodium chlorosulphonate, SO 3Na, with 3 parts of sodium bcnzoate ; by changing these proportions, benzoyl chloride (see below) may be obtained. In the cold it is not decomposed by water, but on boiling it gives bcnzoic acid. BENZOYL CHLORIDE, C 6 H 5 CO Cl, is formed by the action of PC1 5 or POC1 3 on benzoic acid, and is obtained industrially either by the action of chlorine on benzaldehyde or from sodium chlorosulphonate (see above, Benzoic anhydride). It is a colourless liquid

C 6 H5

which boils at 194, and has a very pungent odour. Water decomposes it very slowly in It the cold (distinction from acetyl chloride), giving hydrochloric and benzoic acids. reacts readily with many compounds in alkaline solution, introducing into them the benzoyl group (Schotten and Baumann's method). For instance, a mixture of benzoyl chloride with a little potassium hydroxide acts in the cold on aniline, forming Benzanilide,

NH CO

C6 H 5
it

hydroxylamine coloration with

(white compound, melting at 158, gives Benzhydroxamic acid, C 6 5 CO

and

boiling unaltered).

With

NH

OH, which

gives a violet

ferric chloride.
is

Benzoyl chloride

ETHYL BENZOATE,

used in the preparation of benzaldehyde and of various dyes. C 6 H 5 C0 2 C 2 H 5 has an odour of mint, and is obtained by heating
,

benzoic acid with alcohol in presence of sulphuric acid. BENZAMIDE, C 6 H 5 CO NH 2 , is obtained by the action of

ammonia

(or

ammonium

carbonate) on benzoyl chloride, or by the interaction of sulphuric acid and benzonitrile. It forms nacreous crystals melting at 128, and is soluble in boiling water. It forms metallic derivatives more easily than acetamide. Dibenzamide, (C 6 5 C0) 2 NH, melts at 148. 44 VOL. n.

682
benzoic ester

ORGANIC CHEMISTRY
C 6H5
-

BENZHYDRAZIDE,
;

CO NH NH 2
-

is

obtained from hydrazine hydrate and

with nitrous acid,

it

gives

BENZAZIDE

(Benzoylazoimide),

C 6 H5

CO N/

N
||,

which

is

readily

hydrolysed,

giving hydrazoic and benzoic acids.

HIPPURIC ACID, C 6 H 5 CO NH CH 2 CO 2 H, is obtained by heating benzoic anhydride with glycocoll. It occurs in the urine after ingestion of benzole acid or toluene, and is found in considerable quantities in the urine of horses and other herbivorous animals. It forms rhombic crystals melting at 187, and is soluble in hot water.

CHLOROBENZOIC ACIDS,
1

position,

and

nitric acid (in presence of

2 2

benzoic acid,

NO

C 6 H4
6

benzoic acids,
acids

NH
;

H4

The halogen enters preferably the metaconcentrated sulphuric acid) gives mainly m-NitroOO 2 H, 2 which, on reduction, yields Azobenzoic acids and AminoCO 2 H. The latter, like glycine, exhibit the functions of both
C 6 H,C1
-

CO 2 H.

and bases

with nitrous acid, they form Diazobenzoic acids,

(Cl,

C 6H 4

<N
(-H 3

: '

]>.
,

Poly substituted benzoic acids, having the substituents

Br,

NO

2,

CO 2 H,

etc.)

in the ortho-position with respect to the carboxyl, give no esters when treated with alcohol and hydrochloric acid, such acids being hence separable in this way.

ANTHRANILIC ACID

(o-Aminobenzoic

acid),

NH 2

C 6H4

CO 2 H,

serves for

making

synthetic indigo and many azo colouring matters, drugs and perfumes, especially thio3 It has m.-pt. 145 and sublimes readily ; it has a salicylic acid and methyl anthramlatc. very sweet taste and, when distilled, decomposes into CO 2 and aniline. Its formation by the intramolecular transposition of o-nitrophenol is of interest, although It is best obtained by treating phthalimide with the theoretical it is not of practical utility.

proportions of sodium hypochlorite and caustic soda

/ H4^

co

\C(K
forms

\ />NH + NaOCl
an internal

-f-

3NaOII

H.,O

|-

Nad

-f

Na 2 CO 3

+
C0
|

NU.>
.

L\K

CO,Na.

it

anhydride,

termed anthranil, C 6

/ Hj/ \NH
is

Of the dibasic Sulphobenzoic

interest,

acids,

C 6 H 4 (SO 3 H)(CO 2 H),

forms

the ortho-isomeride

is

of

since

its

imino-derivative

SACCHARIN

(o-Benzoicsulphimide),

C 6 H 4 <;

SO 2
r

>NH,

which

a white crystalline substance exhibiting marked phosphorescence

It

when

its crystals

are fractured.

unaltered in a vacuum,
alcohol

ft dissolves slightly in

melts at 224 with partial decomposition, and sublimes cold water and to a greater extent in cold
is

its heat of combustion is 4751-3 cals. ; Saccharin is about 550 times as sweet as sugar but

rapidly eliminated unchanged from

1 o-Chlorobenzoic acid, m.-pt. 140, b.-pt. 287, is formed in appreciable amount as a byeproduct in the manufacture of bcnzaldehyde (sec p. 674), one works alone accumulating 30 tons A few years ago Mettler succeeded in transforming it into an excellent^olouring in a few years.

matter, rriochronwjlavine A,

H 4 C1 CO 2 H +
-

HNO 3 > NO /
2

^>C1

> NH 2

C0 2 H, C'0,H which on diazotisation and coupling with salicylic acid gives an azo dyestuff of little value, N2 namely, Cl ( ^>OH ; when the latter is heated at 135 with potash and )>

<^

__/Ul,

CO 2 H

C0 2 H

\
")

a little copper oxide, it gives eriochromojlarin or azosalicylic acid, OH'^

/ ___ \
2

OH.

C0 2 H~~

C0 2 H

2 m-Nitrobenzoic acid, m.-pt. 144, sp. gr. 1-494, gives, on reduction with iron and acetic acid, m-aminobenzoic acid, m.-pt. 174, sp. gr. 1-5 1, which is used in making azo dyeatuffs. s-Trinitrobcnzoic acid melts at 210 with evolution of OO 2 and formation of trinitrobenzene, and is obtained by oxidising trinitrotoluene with either nitric and sulphuric acids, or nitric acid and potassium chlorate, or chromic and sulphuric acids. When boiled with water it is converted completely into trinitrobenzene. 3 Methyl anthranilate. has m.-pt. 24-5, b.-pt. 135-5, occurs in neroli and jessamine oils, and has a pronounced odour of orange blossoms and mandarins. CH 3 , m.-pt. 19, b.-pt. 130, occurs in mandarin Methyl methylanthranilate, CO 2 CH 3 C 6 H 4 oil and has a feebler odour than the preceding ester.

NH

C|INNAMIC ACID
the animal system.
It behaves as

683

an

energetic acid, being able to decompose carbonates

;

and
-f

acetates, forming salts, all of

is

which are very sweet

the sodium

salt, (' 6

H 4 <^ Y>NNa
CO

o/~\

used as a sweetening agent owing to its solubility in water. It was discovered accidentally by Fahlberg and Remseii in 1879, being obtained by the oxidation of o-tolueneSO 2 C H 4 Me. Its manufacture was gradually improved by Hempel sulphamidc, 2 and especially by Heyden, and the price fell to 12*. per kilo before the European War. 1 Paul (1920) found that the sweetening power of saccharin may be increased by admixture with certain other substances, such as dtdcin, NH 2 CO C 6 4 OC 2 H5 rn.-pt. \ 73, which is obtained by heating urea with ^-pheiietidine and is itself 200 times as sweet

2H 2 O,

NH

NH

as sugar.

In large doses saccharin has an antifermeutative action, but it is harmless in. the small amounts usually introduced into foods. In some countries its use has been prohibited for
fiscal

or supposed hygienic reasons. An International Convention at Brussels in 1909 passed a resolution that all countries should prohibit the use of saccharin in foods and beverages and place severe restrictions on its sale.

TOLUIC ACIDS, CH 3 C 6 4 COOH. The three isomerides are obtained by oxidising the corresponding xylenes with dilute nitric acid (see Table, p. 681). y-Toluic acid is formed also by the oxidation of turpentine. C0 2 H, is isomcric with the Phenylacetic acid (a-Toluio acid), 2 6H5 toluic acids, but it gives benzoic acid on oxidation, whereas the toluic acids give

CH

phthalic acids.

XYLIC ACIDS, C 6 H 3 (CH 3

CO 2 H

various isomerides are

known

(see

Table, p. 681).
(^-Isopropylbenzoic acid), C 3 H 7 C 6 H 4 CO..H, is formed in animal organisms by the oxidation of cymene, and is obtained by oxidation of Roman chamomile oil with permanganate. It melts at 117 and yields eumene when distilled with lime.

CUMINIC ACID

is found in storax and in certain balsams (Tolu, Peru, etc.), and remains as sodium salt when these are distilled with caustic soda. It is prepared according to Perkin's synthesis (p. 352) by heating benzaldehyde with sodium acetate in presence of a dehydrating agent or by heating benzylidene chloride (benzal chloride) with (acetic anhydride) or by the malonic synthesis from sodium acetate in an autoclave at 200
:

CINNAMIC ACID, C 6H 5 CH CH CO 2H,

benzaldehyde and ammonia

C 6H B

CHO + CH 2 (COOH) 2 - H 2 + C0 2

H 5 CH CH COOH.
*
:

Cinnamic acid melts at 133 and boils at about 300. It readily forms additive products owing to the double linking in the side-chain, and on this account also reduces permanganate in presence of sodium carbonate (Baeyer's reaction,
p. 107).

According to theory, the presence of the double linking should result in the
existence of

two stereoisomerides

C 6 H5

H
and

C 6TI5 C

II
-

C C0 2H
-

II

C0 2 H C

||

H,

but, in addition to these, two others, Allocinnamic (m.-pt. 68) and Isocinnamic acids (m.-pt. 58 to 62), are known and have been studied by Liebermann,
1 The method now used for making saccharin is as follows : pure toluene is treated in the eold with chlorosulphonic acid, a mixture of toluene ortho- (35 per mit.) and para- (65 per cent.) The mixture of sulphochlorides is cooled to a low temperature flulphochlorides being obtained. and centrifuged to separate the crystalline para-compound (m.-pt. 69) from the liquid orthocompound, which distils unaltered in a vacuum at 126 and has tho sp. gr. 1-3443 at 17. By

be effected by means of dichromate and sulphuric acid.

442

684

ORGANIC CHEMISTRY
Previous failures to separate the three crystalline forms were difficulty of excluding minute crystals of the common form from the this was finally overcome by the use of cotton-wool plugs.
16s. per kilo,

Michael, and Erlenmeyer, jun. Biilmann (1909) shows allocinnamic and the two isocinnamic acids to be merely trimorphous modifications of one and the same chemical individual the cis-acid so that they are identical in the fused or
dissolved state.

due to the
solutions
;

Cinnamic acid cost before ]913

and

it is

used in medicine and

in the synthesis of various perfumes.

PHENYLPROPIOLIC ACID, C 6 H 5 C C C0 2 H,
of ethyl cinnamate with alcoholic potash
:

is

obtained by heating the dibromide

C 6 H 5 CHBr CHBr CO 2C 2 H 5 f

HO=
2

2HBr

C 6H 5 C C CO 2H
|

C2H5 OH.

It forms shining needles which melt at 137 and readily sublimes. Its sodium salt is used in 1 to 3 per cent, solution as an inhalation in cases of tuberculosis, and cost 4 per kilo prior to the European War. o-Nitrophenylpropiolic acid, obtained in a similar manner

from ethylo-nitrocinnamate,

is

used in the synthesis of indigo.

(6)

DIBASIC

AND POLYBASIC AROMATIC ACIDS

dihalogenated

The basicity of these acids is given by the number of carboxyl groups, and the phenomena of isomerism are similar to those of the derivaThe carboxyl groups may be united directly to the benzene nucleus or to side-chains, and by means of them esters, amides, acid chlorides, etc., can
tives.

be formed.

PHTHALIC ACID

(Phenylene-o-dicarboxylic

acid),

C 6H 4

<2!J!

is

vxOC/rl^J! j,

obtained by oxidising compounds with two lateral chains, but not by chromic acid, which would partially destroy the benzene nucleus. At one time it was prepared industrially by chlorinating naphthalene and then oxidising (Laurent), but for some years it has been obtained more conveniently by oxidising naphthalene with fuming sulphuric acid in presence of mercury salts or, better, rare earth salts (thorium, etc.), which act as catalysts. This catalytic process, which is due to Sapper, allows of the recovery of the whole of the mercury, while the sulphur dioxide evolved is converted again into sulphur trioxide, so that the oxidation of the naphthalene may be regarded as taking place at the expense of the oxygen of the air. This economical process has rendered possible the industrial preparation of artificial indigo. The process of fusing naphthols with alkali in presence of metallic oxides also seems to give good results and yields benzoic acid at the same time (see According to Ger. Pat. 152,063, the electrolysis of naphthalene in above). presence of an acid solution of a cerium compound yields naphthaquinone and
phthalic acid. When phthalic acid is substituted in the ortho-position, that is, adjacent to one of the carboxyl groups, only one of the latter can be esterified. It is a white, crystalline substance soluble in hot water, alcohol, and ether.
It melts at 213

and

is

then transformed into Phthalic anhydride, C 6

H4 <^>0, CO

which melts at 128

temperature
;

when

and boils at 277, but sublimes considerably below this the anhydride has a characteristic odour and gives phthalic acid boiled with water.
,

With PC1 6

phthalic acid gives Phthalyl chloride,

C 6 H4

<^ >0,
2

which gives Phthalide'

C 6H4

on and Phthalophenone, C H < < CH >0, with benzene CO >0, reduction, C()
2 6

+ A1C18

).

PHTHALICACIDS
When
heated with phenols and sulphuric acid, phthalic anhydride forms phthaleins,

685
e.g.,

C 6H4

m + 2C H <r>0
L>U
g

OH = H2 + C 8H4 < LU >0 (phenolphthakin).

C(0 6

H4

OH)2

Phenolphthalein is a yellow powder and, being a phenol, dissolves in alkali, the solution having a violet-red colour (it forms an excellent indicator, see Vol. I., p. 100). When heated with resorcinol in presence of zinc chloride at 210, phthalic anhydride yields
Fluorescein (resorcinolphthalein),

~C

(OH)

which, even in very dilute alkaline solution, shows an intense greenish yellow fluorescence, while by transmitted light the solution appears reddish (see Triphenylmethane Byes). 1 Tetrabromofluorescein, or eosin, gives alkaline solutions showing a marked reddish
effect

green-yellow fluorescence, and is used for dyeing silk red, producing a beautiful fluorescent the colour is, however, not very stable, especially towards light. ;

With dry ammonia

in the hot, phthalic anhydride gives Phthalimide,

C 6 H4

< CO >NH, L/O

ri

which is of importance since the iminic hydrogen can be replaced by metals and the latter, under the action of alkyl halides, by alkyl groups. The compounds thus obtained, when heated with acid or alkali, yield phthalic acid and a primary aniine free from secondary or tertiary amine (important general synthesis of primary amines, discovered by Gabriel)
:

H 5 Br - KBr + C 6 H4
2H 2
C.H 4

<>N0
2

2 II5 ,

and

25
Phthalic acid
is

<

+ C H NH
-

2.

group, and

is used in the synthesis of indigo and of dyes of the pyronine usually placed on the market as the anhydride (although called chemically pure, acid) at a pre-war price of 60 per ton (65 per cent, strength) it cost 4s. per kilo.
;

ISOPHTHALIC ACID, C 6 H 4 (C0 2 H) 2 (1

nitric acid, or, in general, salt is soluble in water.

3), is

obtained by oxidation of colophony with

by the oxidation
:

of meta-derivativos of benzene.

The barium

4), is formed by oxidising oil of turpentine by oxidising p-toluic acid with permanganate. It is almost insoluble in water and alcohol and sublimes unchanged. It gives a sparingly soluble barium salt, but does not form an anhydride. POLYBASIC ACIDS. The tri-, tetra-, penta-, and hexa-carboxylic acids are known, but

TEREPHTHALIC ACID, C 6 H 4 (CO 2 H) 2 (1

oil,

or chamomile

or

are of

practical importance. Trimesic acid (1:3: 5), derived from mcsitylcnc ; Benzenetricarboxylic Acids are Trimellitic acid (1:2:4), obtained from colophony ; Hemimellitic acid (1:2:3). The Benzenetetracarboxylic Acids are Pyromellitic acid (1:2:4:5), melting at 264 ; Prehnitic acid (1:2:3:4), melting at 237 and forming an anhydride ; Mellophanic acid

little

The

(1:3:4:5), which
which
is

melts,

and

is

converted into anhydride, at 280.

acid),

MELLITIC ACID (Benzenehexacarboxylic

C 6 (COOH) 6

is

obtained from mellite,

a kind of mineral found in deposits of lignite, and consists of yellow, quadratic 18H 2 0. octahedra of aluminium mellitate, C 6 (COO) 6 A1 2 Mellitic acid may also bo obtained by oxidising wood charcoal with alkaline permanand loses 2H 2 ganate. It forms needles insoluble in water and alcohol and, when heated,

4
2

2CO 2 forming
,

Pyromellitic anhydride,

O<^>C 6H
2

<^>O, which
5

give,* Pyromellitic

acid,

C 6 H 2 (C0 2H) 4 with

,

water.

1 This property is sometimes utilised to ascertain if underground watercourses communicate with one another and to detect infiltrations into wells.

686
Mollitic acid

ORGANIC CHEMISTRY
cannot form substitution products, since all the benzene hydrogens are sodium amalgam it readily yields Hydromellitic C 6H e (COOH) 6 which gives benzene when distilled with lime.
,

already substituted, but on reduction with

acid,

(r,)

HYDROXY-ACIDS OR PHENOLIC ACIDS

SALICYLIC ACID (o-Hydroxybenzoic acid), OH C 6H 4 COOH, is the most important of the hydroxy-acids, and was discovered by Piria in 1839 and prepared in 1885 by treating salicylaldehyde with alkali. Kolbe established its constitution in 1853 from its ready decomposition into C0 2 and phenol, and in 1860 synthesised it from these products in presence of metallic sodium. It is derived from salic.in (glucoside of willow bark), which, when hydrolysed,
first

These are formed by the methods given on p. 679 or by oxidising homologues of phenol or fusing them with alkali. The basicity is given by the number of carboxyl and phenolic groups, both of these leading to salt-formation, but the basicity towards sodium carbonate is determined by the carboxyl groups alone. When both the carboxyl and hydroxyl groups are etherified, only the former can be subsequently hydrolysed.

gives glucose

and Saligenin

Halicin

Snligenin

Glucose
is

the saligenin giving salicylic acid on oxidation. ester in the essence of Gmiltlierui procumbent*.
in

The acid

found as methyl

It is prepared industrially by heating sodium phenoxide with carbon dioxide an autoclave at 140, according to Kolbe's process from the resulting sodium salicylate the acid is liberated by treatment with a mineral acid. In Marasse's method a mixture of phenol and potassium carbonate is heated in presence of C0 2 at 1 40 to 160, but the yields arc very low. Only later, when the conditions of the reaction were studied, were the yields and quality of the product improved. By the action of C0 2 in the hot, sodium phenoxide is converted, to the extent C0 2Na, whereas potassium of one-half, into the salicylate, NaO 6 H4 phenoxide yields the para-compound, p-KO C 6 4 C0 2K. In the first case the reaction begins at 100 and the yield increases up to 180, no further increase with the potassium compound, the ortho-dipotasoccurring even up to 300 sium salicylate is formed at 100 to 150, the para-isomeride being formed as the. temperature is raised and constituting the sole product at 220. At the latter temperature monopotassium salicylate is transformed into the para-dipotasC0 2 C 6 H 5 OH |- OK C6 H 4 C0 2K, sium compound, 20H C 6 4 C0 2K whereas under no conditions does monosodium salicylate give the para-isomeride. The monosodium para-salt may be obtained otherwise, and at 290 gives phenol, 00 2 and disodium salicylate. According to Schmitt, phenol may be converted wholly into salicylic acid by the action of C0 2 at the ordinary temperature on sodium phenoxide, the sodium phenyl carbonate, C 6 5 C0 3Na, thus formed yielding sodium salicylate when heated out of contact with the air. S. Tymstra, jun., showed, however (1905 1912), that the final product formed in this process is o-Oxysodiobenzoic acid, ONa C 6 H4 C0 2H, which arises by simple addition of C0 2 On the basis of these results the more economical and rational method of manufacture now in use has been developed, the various phases of the reaction being carried out in an autoclave provided with a stirrer and with either a double jacket or coils through which steam or water may be passed. Salicylic acid forms white crystals melting at 156-8, subliming at 200, and It is readily soluble in alcohol or in distilling in superheated steam at 170. ether, and 1 part dissolves in 444 parts of water at 15 and in 13 parts of hot
;

ASPIRIN
water.
It has a sweetish astringent taste.

687

When heated with POCI 3 it gives the

Internal anhydride,

C 6H4<(

/
|

which forms a white powder softening at 110

and melting at 261. With bromine water

it gives a precipitate, C 6 II 2Br 3 OBr, and with ferric chloride it gives a violet coloration even in alcoholic solution (phenol is coloured only in aqueous solution). With lime-water in the hot it forms a basic salt,

C 6H4

<QQ>Ca,

and can thus be separated from

its

isomerides, which do not

give this reaction. It is used as an antiseptic for preserving foodstuffs, 1 and in the manufacture of dyes and perfumes. Its sodium salt is largely used as a medicine. When heated to 200 it loses C0 2 giving Phenyl salicylate (salol)
,
:

20H C 6H4 C0 2H
-

- C0 + H
2

+ OH
;

C 6H 4 C0 2C 8 HB
-

which is used as an antiseptic for the intestines it melts at 42 and boils at 172 in a vacuum. Industrially it is obtained by heating a mixture of sodium salicylate, sodium phenoxide and phosphorus oxychloride (or phosgene) at 125, the product being washed with water, decolorised with animal charcoal and crystallised from alcohol. ACETYLSALICYLIC ACID, C 2 H 3O O C 6H 4 CO 2 H, prepared by heating salicylic acid with acetic anhydride and sulphuric acid, is largely used under the name ASPIRIN as an antipyretic, antineuralgic and analgesic. It has an acid taste and forms lustrous, white crystals, molting at 135 and solidifying at 118. Unlike salicylic acid and salol, it gives no coloration with ferric chloride, and it passes unchanged through the stomach but undergoes decomposition in the
-

intestines.

m- and

^-HYDROXYBENZOIC ACIDS
;

coloration with ferric chloride

tho ra-acid

CH 3O C 6 4 00 2 H, resembles the monobasic acids more than the phenols obtained from ^-hydroxybenzoic acid, methyl alcohol, potassium hydroxide, and methyl iodide, the dimethyl ether obtained being then partially hydrolysed. OO 2OH3 forms 90 per cent, of oil of Oaultheria, and is 6 4 Methyl salicylate, OH prepared artificially by the interaction of salicylic acid (2 parts) and methyl alcohol (2 parts) in presence of concentrated sulphuric acid (1 part). It boils at 224 and is used as a perAnisic acid,
is

give insoluble basic barium salts and yield no is more stable to heat than the o- or 2)-aeid.

and

fume.

^-HYDROXYPHENYLACETIC ACID, OH C H4 CH 2 CO 2 H,
fl

formed during the putre-

faction of proteins chloride.

and occurring

in the urine, gives a dirty green coloration with ferric

Of the Dihydroxybenzoic acids, PROTOCATECHUIC ACID (3 4-Dihydroxybenzoic C 6H 3 (OH) 2 CO 2 H, forms shining scales or crystals soluble in water in solution it is coloured green by ferric chloride, the colour being changed to blue and then to red by a little soda. It can be obtained synthetically, together with the 2 3-dihydroxy-acid, by heating catechol with ammonium carbonate, and is prepared by fusing various resins with
:

acid),

alkali.

Like catechol,

it

exhibits reducing properties.

Its

monomethyl ether (3-OCH 3 )

;

is

VANILLIC ACID, which is formed by the oxidation of vanillin (p. 677) its dimethyl ether [(OCH3 ) 2] is VERATRIC ACID, found in the seeds of Veratrum Sabadilla, and its Methylene ether, (X) 2 H C rI 3 <*?>CH 2 is PIPERONYLIC ACID, which is also obtained
fl

by

oxidising piperinic acid.

1 Tho examination of foods for the presence of salicylic acid is carried out in the same way as with beer (p. 212), but baked starchy substances (bread, etc.) contain malfol, which gives the same reaction as salicylic arid and is, like the latter, volatile. In this case Jorissen's method must be used in testing for salicylic acid : 10 c.c. of the liquid distilled with steam is treated

with 5 drops of 10 per cent, potassium nitrite solution, 5 drops of 50 per cent, acetic acid, and The liquid is then boiled, and in presence of 1 drop of 10 per cent, copper sulphate solution. even less than 0-0001 grm. of salicylic acid a reddish coloration forms, which rapidly becomes
blood-red (H. C. Sherman, 1910).

688

ORGANIC CHEMISTRY

GALLIC ACID (3:4: 5-Trihydroxybenzenecarboxylic acid), C 6H 2 (OH) 3 -CO 2 H, occurs naturally as glucosides in various plants and in tea, gall-nuts, etc. It is formed by the action of mould on solutions of tannin or by boiling the latter with dilute acid or caustic soda. It reduces gold and silver salts and becomes oxidised and turns brown in the air. With ferric chloride it gives a black coloration, and, on this account, l it is used in its reducing properties are utilised in making ink photography. When pure it forms colourless needles (+ 2 0) which at 120 lose the water of when distilled it decomposes into crystallisation and melt at 220 to 240 carbon dioxide and pyrogallol. ft is only slightly soluble in ether or cold water but dissolves readily in alcohol or hot water. It reduces Fehling's solution, gives a bluish-black coloration with ferric chloride, and in alkaline solution absorbs
;

atmospheric oxygen and becomes brown. It is used in making pyrogallol, dyes of the anthraquinone (anthracene brown, etc.) and gallocyanin and galloflavin groups, inks and drugs airol, C G 2 (OH) 3 C0 2BiI OH, used on wounds instead of iodoform, is odourless and non-irritant
:

dcrmatol,

C 6H 2 (OH) 3 C0 2Bi(OH) 2

serves as

an antiseptic

for

wounds, intestinal

and stomach maladies, and for perspiring feet. Gallic acid is made by treating gall-nuts with water and yeast at 38 to 40, the mass being afterwards extracted with a mixture of 4 parts of ether and 1 part of alcohol, and the alcohol and ether carefully distilled off through a rectifying column. The crude gallic acid separating from the resulting aqueous solution is purified by treatment with albumin, decolorised by means of hydrosulphite and animal charcoal, and crystallised. Gallic acid may be obtained also by treating tannin (or the mother liquors from its preparation) with dilute sulphuric
acid or with a pure culture of Aspergillus gallwnyces. There are a number of hydroxy-acids with hydroxyl and carboxyl groups in he side-chains mention may be made of
;
:

(1)

COUMARIC ACID

(o-Hydroxycinnamic

acid),

OH C 6 H 4 CH CH CO 2 H,
:

fhich does not give an anhydride owing to its f umaroid structure (see Fumaric -cid), while the malcic stereoisomeride, Coumarinic acid, is known only as salts,
ince in the free state it immediately forms Coumarin,
itter

C 6 H4<^

/0-^CO
|

XCH CH
:

the

may

also be obtained
:

by heating

salicylic acid

with sodium acetate

Perkin synthesis

see Aldehydes).

C0 2 of the various stereo(2) MANDELIC ACID, C 6 5 CH(OH) iomerides, that occurring naturally is laevo-rotatory, whilst that obtained ynthetically (from bcnzaldehyde and hydrocyanic acid, with subsequent
;

INK is made by adding to aqueous gallic acid or tannin ferrous sulphate solution slightly with acetic or hydrochloric acid in order to prevent oxidation and the formation of a lack precipitate. To this brownish solution is added a solution of indigo-carmine or logwood ) render the When the ink is exposed on the paper to the air, it becomes black writing visible. nd insoluble, owing to the evaporation or neutralisation of the acid by the sizing of the paper
1

jidified

Jbumen,

colour to a deep black. the ink adhere without spreading, a little gum is added, and to preserve it, a little fienol (1 litre of this normal ink may be obtained from 23-4 grms. of tannin, 7-7 grms. of gallic jid, 10 grms. of gum, 7-5 grms. of concentrated hydrochloric acid, 30 grms. of ferrous sulphate, grm. of phenol, and the rest water the liquid is left at rest for four days and then decanted oin the deposit and coloured with indigo-carmine or logwood extract). 20 grms. of dry logwood extract or 30 grms. hgwood ink may be obtained as follows the paste (haematem) are dissolved in 800 c.c. of water, and to the hot solution are added ^ 5 grms. of soda crystals (7 grms. of Solvay soda), and then, drop by drop, and with shaking, X) c.c. of a solution containing 1 grm. of normal potassium chromate ; this process gives a fine -,ue-black tint, arid the ink, which does not attack steel pens and dries easily, can be preserved by a trace of phenol. Coloured inks are aqueous, gummy solutions of aniline dyes. Copying inks' are similar to ordinary writing inks, but are more concentrated, and contain also glycerine, sugar, dextrin, calcium chloride, etc., by which the writing is kept moist for some time f

etc.), le original blue

and the consequent ready oxidation by atmospheric oxygen, which changes

To make

TANNIN
is

689

the racemic form. In solutions of the latter, certain hydrolysis) Schizomycetes destroy the d- and leave the Z-isomeride, whilst Penicittium glaucum destroys the Z- and leaves the d-compound. Also, if the cinchonine salt of the racemic form is prepared, the rf-salt crystallises out first.

The Dihydroxycinnamic
transformed into
its

FERULIC ACID and UMBELLIC ACID

CAFFEIC ACID (see Chapter on Glucosides), (^-hydroxy-o-coumaric acid, which is readily anhydride, umMliferone) ; a similar acid is PIPERINIC ACID,
acids include
:

CH
which
is

<>C H
6

CH CH CH CH C0 2 H,
:
:

formed in the decomposition of piperine. derivatives of the Trihydroxycinnamic acids are dealt with in the Chapter on Glucosides (cesculin and daphnin from horse chestnuts and

The

respectively).

Mention

may

<
synthetically.

CO
,
|

Daphne mezereum, etc., be made here of ^ESCULETIN (a Dihydroxycoumarin),

and

of the isomeric

H:CH

DAPHNETIN, which have

also been obtained

TANNIN
Pelouze,

and

(Gallotannic or Tannic acid), C 14 H 10 9 , was studied originally by Berzelius, Liebig. According to Hlasiwetz (1867) and to U. Schiff (1873), tannin is

loss of 1 mol. of

probably a partial and mixed anhydride of gallic acid, 2 mols. of which are condensed with water from a carboxyl and a hydroxyl group and formation of a Digallic
acid (or ether of 3-gallolylgallic acid)
:

OH
2

C0 2 H

=H

OH/ \ O
2

-f

OH

OH

OH

OH

OH

OH
and and

According to the investigations of Nierenstein (1908) on the acetyl-derivativcs hydrolysis, commercial tannin would seem to be a mixture of digallic acid Leucotannin (or ether of %-hydroxygallolylgallic acid) :

OH/ V-CH(OH)

/ \C0 2 H

OH

OH

OH

C 14 H 10 9 (mol. wt. 322), whilst Walden (1898), by the ebullioscopic method, obtained numbers between 760 (about C 35 .) and 1560 (about C 70 ....), which are sharply 1 distinguished from that of digallic acid (332).
.
.

There appear, however, to be various more or less highly polymerised tannins with widely varying molecular weights. Some uncertainty still prevails as to the true molecular magnitude of tannin. Paterno (1907, 1913) found that in aqueous solutions tannin acts as a colloid and by cryoscopic measurements on acetic acid solutions arrived at the formula,
.

P. Biginelli (1911),

on the basis of the property shown by tannin

WilVlO

of forming additive

previously
WVU/AUV/U.
25 6C 2 5 -OH; and C 41 32 O 25 5H 2 OJ, and also on the loss pf C0 2 and 2 C) with formation of Hexahydroxybenzophenone, C 13 H 10 7 , when tannin is heated in aqueous solution " ~ with lead dioxide (the C0 2 liberated was estimated), holds that tannin has the formula C d and that it is probably a glucoside. It was, indeed, observed by Liebig and also by Hlasiwetz that when tannin is boiled with dilute sulphuric acid it decomposes into gallic acid and dextrin or gum (reacting with 6H 2 O), but Etti (1884) and Lowe found that tannin purified with ethyl acetate does not yield saccharine substances (dextrin, etc.). Strecker and also Feist (1912) hold that tannin contains glucose. Lloyd (1908) maintains that the tannin molecule comprises
, ,

C 41 H 32

^jr

JL.

I/AVSLUJV,

C*.tAU

WV/

VJL

JJlfclll^lH O

UUU1L/WU1I.U.CI,

HCHHC"l V ,

V/J 1-lA 32^-'2B

^-^Ht/vOl

/-~
sjx molecules of
allip

acid condensed round the bexavalent nucleus,

/ \G(

690

ORGANIC CHEMISTRY

The nature and mode of condensation of the tannins varies with the nature of the vegetable organisms from which they are derived, two fundamental groups being recognised: (1) The former comprise esters of phenolHydrolysable tannins; (2) Condensed, tannins.
carboxylic acids combined with phenols, carbohydrates and polyhydric alcohols, also ethers of phenolcarboxylic acids formed either among themselves or with other

hydroxy-acids

and glucosides formed by union of semi-acetals of sugars (glucose, rhainnose, etc.) with alcohols, phenols and their derivatives. All tannins of this first group have gallic acid for their fundamental component and are hydrolyscd by emulsin and by tannases. The tannins of the second group contain as fundamental component the phloroglucinol residue, which may be isolated by treating with alkali, whilst treatment with strong acids or oxidising agents or bromide yields amorphous compounds of low molecular weight (sometimes red tannins). One class of this group comprises tannins with a basis of phloroglucinol (or catcchol) combined with a benzene nucleus, a second class including those
(the latter are as depMes),
1

known

with a basis of hydroxycinnamic acid. Tannin is widespread in nature and occurs in abundance in the wood or bark of various plants and in oak-galls (gall-nuts), which are pathological excrescences caused by incision of the oak branches by insects. 2 To extract the tannin, the gall-nuts are ground to a coarse powder, which is treated with hot water in a battery of diffusors similar to those used for extracting beet-sugar (see p. 549). The crude aqueous solution of tannin thus obtained is filtered through a battery of filters and extracted, in a closed copper (or bronze) vessel fitted with a stirrer, with crude ether (aq noons or not free from alcohol). After the liquid
results of the last investigations of Fischer and his pupils (1909-1919) have cast new on the constitution of tannin. Fischer and Freudenberg (1912) hydrolyscd a pure tannin and concluded that it is formed by the condensation of 5 molecules of digallic acid with 1 molecule of glucose, free carboxyl groups being absent. Indeed, Fischer prepared synthetically a compound

The

light

similar to tannin

and havinir the constitution

H(OR) OH(OR) OH(OR)

-

___ ___OH
|

CH(OR) OH, OR

in

which the

five

groups
'

R united

with the glucose are formed of 5 residues of pentamethyl-m'

CH 3
digallic acid,

00 H, O '

_
"

OOH, ^
OOFT 3
.

0(X

Hence

this derivative of glucose will be- a

CO
penta-(pentamethyl-M-galloyl) -glucose, which consists of a mixture of two stereoisomerides corresponding with o- and 0-glucoses and is similar to Ilcrzig's mclhyllannin (1905), obtained by treating natural tannin with diazo me thane. According to Procter, tannins may bo classified in two fundamental groups catechol tanninx (those of pine, quebracho, oak, gambier, mangrove, etc.) and pyrogaJlol tannins (chestnut, sumac, When distilled with zinc dust, the former yield myrobolan, divi-divi, valonia, gall-nuts, etc.). catochol, the latter pyrogallol (sometimes phloroglucinol). 1 Jn the vegetable kingdom there occur three allied groups which contain phloroglucinol, anthocyanine, the favone colouring matters, and phenyl styryl Icetonc : all of these arc derived from (ry-diphenylpropane, O 6 H 5 OH 2 OH 2 OH 2 ( 6 H 5 and are more or less oxidised in the three carbon atom chains joining the two benzene groups, which in their turn contain hydroxyl groups in various positions. 2 Tannin and tanning extracts are mostly obtained from the following plants
:
1

Per cent, of tanning substances.

P<T cent,
of sugar.
... ... ...
. .

gall-nuts Divi-divi (fruit of Cawalpiiria coriana) Sumac (leaves and branches of Rhus coriaria
I

n J Uak
,

bark of Qnerctm
. . .

10-12
and
.
.

rot in UN)
.
I

, of Quercus (ryilops Valomft (cupola

.

|oupolftoOiTfiifiabiifa Quebracho (wood of 8chinoj)sis

Jjorentzii)

30 35 40 45 26 30 on QK 30-35

2-53 0-71
8 4 9 5
re

...

> * Q 2-5-3-5

or

Quebrachfa
. .

(fleshy fruit of Myrobalanus) . Algarovilla (beans of (Itesalpinia hrevifolia)

Myrobolans
.
.

Actt(!ia

(bark of Acacia decurrens [extract of wood of A. catecnu.

Ohestnut

or bark of Costarica wsca ^extract of wood of Catttanea iv*ta

.

wood

(bark of Abies canaden sis t extract of bark Mimosa (barks of various Australian acacias, especially , A, decurrens, the so-called black wattle-bark)

.... ....
. .
.

1624 2540 4050 3035

45
8

...

0-20-5

... ... ...

...

56
8

0-8-1

55
12

20
10

40
12

... ...

2 3

3-5

2326
30
45

...

78
J.

,..

TANNING EXTRACTS
present
is

691

has been left at rest in vats for eight to ten days, the dense lower layer containing the tannin is decanted and freed from ether by distillation. The evaporation of the water
effected in heated, rapidly rotating drums, or
is

on zinc plates placed in

desiccators.

then subjected to short and gentle treatment with steam a very soft, pale, ethereal tannin being thus obtained. Tannin solutions are also concentrated under reduced pressure in multiple-cffet apparatus (see Sugar, p. 560). Aqueous or Alcoholic Tannin, which is extracted by water or alcohol without being
purified

The dry mass

by means

of ether,

is less

pure.

Pure tannin forms a pale yellow light powder or sometimes crystals. It is darkened in colour by light, turns brown in the air, and dissolves in its own weight of water, double
its

weight of alcohol or eight times its weight of glycerol or ethyl acetate. It is almost insoluble in ether, benzene, chloroform, petroleum ether or carbon disulphide. With iron salts it forms a bluish black precipitate, and with albumin or starch a gelatinous precipitate.

In aqueous solution it is dextro-rotatory (-f- 15 to -{- 20). Tannin is used mainly, in conjunction with antimony salts, as a mordant in the dyeing of cotton with basic dyes. It is employed also in making ink and, along with gelatine, in clarifying beer and wine, forming, together with gelatine, a gummy precipitate which gradually settles and carries down with it the suspended matter of the liquid. TANNING EXTRACTS. Powdered barks or woods are used, either before or after extraction, in

tanning hides. Those tanning extracts [from oak bark (containing 10 to 20 per cent, of tannin), mimosa (30 per cent.), leaves and twigs of sumac (15 to 30 per cent.), valonid (20 to 45 per cent.), Asiatic gall-nuts (55 to 75 per cent.), European gall-nuts (25 to 30 por cent.), divi-divi (40 per cent.), myroMans (30 per cent.), quebracho wood (22 per cent.), horse-chestnut bark (2 to 3 per cent.), catechu or witch (40 or 50 per cent.), etc.] aro now rationally prepared on an enormous scale by extracting the finely divided material with hot water in batteries of diifusors. The exhausted material is centrifugod and then burnt as fuel. From the diffusors the liquid issues at about 5 to 6 Be. (about 6 per cent, of tanning materials), whilst the exhausted wood contains less than 2 per cent. The dilute solutions are filter-pressed, evaporated under reduced pressure in a double-effet apparatus to about 15 Be, and then filtered hot, first through coarse and then through fine filtering cloth, the liquid being sometimes mixed with infusorial earth or bone-black so as to give a clear liquid. This is further concentrated in vacuum pans to 28 to 32 Be. or, with extracts required to solidify when cold, to 45 Be. For some years these extracts have been purified and decolorised, either before or after concentration, by many different materials, but principally by sulphites, bisulphites,
1 hydrosulphites, alkali sulphoxylates, etc. The most important extract is that of quebracho wood, which is still crudely prepared in the country of origin (Argentine), and contains about 65 per cent, of tanning material,

1 Formerly use was made of aluminium sulphate and barium hydroxide, aluminium thiosulphatc, blood albumin or blood itself, casein and soda, etc., but better results arc obtained with compounds of sulphurous acid. Bisulphite renders the extracts much more soluble, as it converts part of the tannin substances into soluble sulphonic compounds, while in the resinous extract of quebracho it also causes decomposition of a glucoside present, giving the product the Decoloration is, property of imparting a yellow colour to skins with an aniline mordant. however, due more especially to the hydrosulphite either added directly (Lcpetit's patent) or produced by reduction of the bisulphite added to the extract (1) by zinc or aluminium dust (Eng. Pat. 11,502 of 1902); (2) by treating the crude extract- with aluminium sulphate and sodium bisulphate and then heating under pressure at 120 to 130 (U.S. Pat. 740,283) ; (3) by treating the extract with a mixture of formaldehyde-bisulphite and formaldehyde-sulphoxylate (Fr. Pat. 362,780) ; or (4) according to the recent patent of L. Dufour ((Jenoa), by reducing

the sulphite with thiosulphate, and then with formaldehyde. Use has also been made of the waste sulphite liquors from the manufacture of cellulose (Uer. Pat. 132,224 and 152,236 ; U.S. Pat. 909,343, January, 1909), of aluminium amalgam (Ger. Pat. 220,021), and of chromous

quebracho extract and rendering it soluble even in the The paste that of A. Redlich, L. Pollak, and tt Jurcnka ((Jer. Pat. 212,876 of 1908) deposited from the crude, cooled extract is shaken for six to seven hours with 1 part per thousand of soda at 50 to 100, 50 litres of the red solution thus obtained being mixed with 1000 litres of the crude extract previously decanted and the whole left to stand. A flocculent deposit is thus obtained and a pale solution of pure extract which is decanted off and can be concentrated ; the flocculont precipitate can he dissolved again in dilute soda and used to clarify further quantities of crude extract. Any excess of red alkaline solution may be employed for clarifying
cold
is
:

salts (chloride, sulphate, acetate, etc.). interesting method of clarifying

An

extracts of sumac, etc,

692

ORGANIC CHEMISTRY

5 per cent, of non-tannins, 18 per cent, of water and 12 per cent, of insoluble matters. It is refined in European works to obtain a product poorer in phlobaphenes and more readily soluble in the cold. The price of tanning extracts is roughly proportional to their content of tanning or tannin substances, 1 which may vary from 20 per cent, to 50 per cent., but for a given content of tannin, extracts rich in red or orange colouring-matters have the greater value ; these matters are estimated in special colorimeters or in the spectroscope. A. Gansser (1909) suggested the replacement of the direct test on hide by one on strips of animalised cotton (the latter being immersed in a bath of gelatine and then in one of formaldehyde) ; the resultant colour on the textile is similar to that obtained on hides. During recent years use has been made for tanning of certain artificial compounds
as syntans, and prepared by Stiasny (Gor. Pat. 262,558. 1913), by condensing phenolsulphonic acid with formaldehyde, or by similar means. Neradol D, first made by is made by the Badische Anilin- und Soda-Fabrik, is one of these com pounds; neradol treating naphthalenesulphonic acid with formaldehyde, and similar products are prepared from amino- and hydroxy-naphthalenesulphonic acids. On analysis these artificial extracts correspond with an extract containing 30 per cent, of tanning material and before the war

known

ND

were sold at about 44 per ton. They produce a very pale tanning of the hide but give no increase in weight, so that they are used either for fine goat and sheep skins, etc., or for mixing with ordinary tanning extracts, of which they increase the solubility. TANNING OF HIDES. The hides of oxen, horses, sheep, etc., even when freed from hair and flesh (i.e., in the form of cerium), do not keep and readily putrefy during drying
or in presence of moisture. When dressed (this was carried out as early as 2000 B.C.), and, more especially, when tanned, the hides are more tenacious and resistant, do not putrefy, and do not gelatinise with boiling water, since the fibres on which the tanning material is
fixed (to the extent of 30 per cent, or even more) hence remain fibrous and do not become compact

do riot agglutinate during drying, and and horny. The corium or derma, i.e.,
leather. 2

the fibrous substance of the skin,

1

is

converted by tanning into

"

Rational tanning
II.,

Analysis of tanning materials.

See Villavecchia's

Applied Analytical Chemistry," Vol.

p. 331.
2

THEORY OF TANNING. In the first half of last century, Davy, Si'guin, Dumas, and Berzelius regarded the absorption of tannin by hides as a chemical reaction. In 1858 Knapp defined leather as an animal skin the fibres of which do not adhere during drying owing to the pores separating the fibres being filled with the tannin tanning would hence be a simple .Reiner (1872), Heinzerling (1882), physical phenomenon. Similar views were expressed by Schroder and Passler (1892). Th. Korner (1898-1903) also regarded it as a physical process, since neither the tanning material nor the fibres constituting the hides are electrolytically dissociated, and therefore cannot combine to form a kind of salt. Hcrzog, Adler, and Wislicenus (1904) also supported the physical
;

As it has been established that the hide is capable of absorbing at its surface like a colloidal solution, Stiasny (1908) holds that tanning consists simply of a physical absorption, since tannin Just as colouring-matters reacts with scarcely any of the known hydrolytic products of hides. are fixed by carbon, silica, and alumina without there being any special groups to effect combination, so also in tanning all the known phenomena support the physical absorption hypothesis. According to Stiasny, every tanning process consists in the atisorption of a dissolved colloidal substance by the gel of the hide and in simultaneous secondary transformations (polymerisations, oxidations, etc.), to which the absorbed matter is subjected by the catalytic action of the hide, and which render the absorbed tannin insoluble and the process irreversible. This is more a
physico-chemical than a physical theory. Konnstein (Vienna) also regards the phenomenon as a physical one, owing to the absence of stoicheiometric relations. On the other hand, Miintz (1870) and Schreiner (1890) hold that tanning must be due to a chemical phenomenon, since the same hide always absorbs the same maximum amount of a given tanning material, but Schroder arid Passler advance the objection that below the limit of maximum absorption the quantity fixed varies with the concentration of the bath, there being no stoicheiometric relations characteristic of chemical combination. N. O. Witt (1891) maintains that leather should be regarded as a solid solution of the tanning substances in the animal fibre (the hide), in which they are more soluble than in water. Suida, tlelmo, and Fahrion (1903-1908) revert to the chemical theory, and assert that, as tanning is preceded by treatment with acid or mordant, slight dissociation or hydrolysis may occur (as is the case in the dyeing of wool). Further, hide powder fixes substantive dyes better than wool itself, and that the combination does not exhibit stoicheiometric proportions is explained by the fact that the hide consists of compact fibres and not of separate molecules as in solution, so that the tanning liquor penetrates only slowly into the interior of the mass, and is gradually impoverished and exhausted. Fahrion (1908-1919) points out that in tanning with formaldehyde there can be no question

theory.

TANNING
was introduced only when the anatomical structure of the skin became exactly known and the effects of tanning materials on the different parts of the hide were studied. A clean cut in a fresh ox-hide shows the following layers the thin exterior layer of epidermis or cuticle (Fig. 447) ; the thicker layer I immediately below is the corium or derma, which constitutes the leather after tanning ; below the corium is the fatty layer /. In the unhairing of the hide, the hairs and also the epidermis are removed, the corium being exposed with a papillary surface covered with a fine membrane, p, surrounding the hair-orifices and giving the natural lustre of the tanned hide ; its sinuosities form the socalled natural grain, which serves to distinguish the hides of different animals. The dry hide contains 50 per cent. C, 25 per cent.
:

O, 7 per cent. H, 17-8 per cent.

of mineral matter.

and

traces

(a)

Various methods of tanning are in use Mineral Tanning or tawing, by means of

:

alum and sodium chloride

(b) Oil
;

Tanning
(c)
;

or chamoising, with fatty materials

Ordi-

(d) nary Tanning with tannin substances Chrome Tanning, using chromium salts (tanning with formaldehyde, proposed by Trillat and Payne with quinone by Mcunier and Seycwctz ; with naphthols by Weinechenck ; with rare earths by Garelli ; with fatty acids by Knapp, or with the corresponding
;

ammonium

soaps by Garelli and Corridi, 1909). Garelli (1914) obtained a pseudo-tanning with bismuth nitrate, mannitol (or glycerol) showed that hides being added to prevent separation of basic compounds. Apostolo (1914)

absorb suspended substances and effected pseudo-tanning with precipitated sulphur (or fats). Knapp obtained distinct tanning with fatty acids. of colloidal material (as with tannin), and with regard to the elimination of alum or tannin from leather by the mere action of water, this is due to pswt do -tanning, *.., to the formation of labile, distributed between the hide and readily hydrolysable compounds, the tannin of which becomes

may

the water. With reference to the non-stoicheiometric relations, he observes that the fixation of more tannin from concentrated than from dilute solutions is in accord with the law of mass action for reversible chemical reactions. the tanning According to Heidenhain, Zacharias, and Fahrion (1908), both the dyeing and of the tanning substance and the processes occur in two phases, the absorption and penetration from subsequent chemical combination of this substance with the hide. Garelli (1907-1910), the results of his tanning experiments with rare earths (ceria, thoria, zirconia), supports this solution can undergo hydrolysis forming theory, and holds that all substances which in aqueous basic hydroxides or salts (like chromium, iron, and aluminium salts) are capable of tanning hides (>., the hide hydrolyses and decomposes the salts, which thus deposit hydrates or basic salts on the fibres of the corium or derma, the fibres and the salts combining to form leather). Thus, Garelli effected tanning with the rare earths, >., with compounds of the trivalent (cerium, lanthanum, and didymium) or tetravalont elements (cerium, thorium, and zirconium Zacharias had used stannic salts in 1903), and the tanning, as when alum is used, is facilitated by sodium The most effective chloride (this was not used with eerie salts, which would generate chlorine). metals pass from the higher to the tannings are those in which an oxidation plays a part (the lower valency) and those with alum, which cannot give salts of lower valency but are^not very Chromium stable, and do not resist even the prolonged action of cold water (pseudo-tanning). the skin and fixed, while oils and fats must be oxidised (to hydroxysalts are reduced to oxides
:

by

tanning is not complete. R. Lepetit (Ann. d. Soc. chim. di Milano, 1907, p. 83) asserts that in the tanning of sole and of the fibres, but that it is upper leather it is not sufficient to effect separation and stabilisation between the fibres with phlobaphenes. necessary to produce swelling and filling of the interstices These are colloidal substances dissolved or suspended in the tannin extracts and consisting and partly of condensation products partly of internal anhydrides of soluble tannins (see p. 687)
acids), as otherwise the

of the reaction between formalin organisms. Indeed, according to Nieren stein, the products and polyphenols exhibit tanning properties, and at the present time glove leather is successfully tanned by formaldehyde (Trillat and Payne). Also Weinschcnck (1907-1908) stated that a- and 0-naphthols in presence of formaldehyde are able to tan hides, but this is denied by

of alkali carbonate), these reacting with aminic complexes in the same way as formaldehyde and the aldols react with aniline (see p. 659). Thuan (1909) found that if the hides are previously

treated with formaldehyde subsequent chrome tanning

is

hastened.

694

ORGANIC CHEMISTRY

The tanning power of the various materials used in practice may be established roughly the temperature of gelatinisation or shrivelling of the strips of tanned hide determining by when heated with water, the best tanned hides showing the highest temperature. If the gelatinising temperature of the best chrome tanned hides is taken as 100, those for other formaldehyde tanning, quinone tanning, 100 ; chamoising, 85 to 90 tanning will be 85 to 90 neradol tanning, 80 to 86 70 for vegetable tanning ; 58 to 60 for fatty acid and resin tanning, and 50 for alum tanning. Various bacteria, even injurious ones, develop on insufficiently dried or fresh hides. The ordinary antiseptics (phenols, formaldehyde, etc., which have tanning actions) cannot be employed, and the most convenient treatment is with dilute formic acid, or 0-1 per cent, sodium hydroxide, or 0-2 per cent, sodium sulphide solution at 18. The fresh hides as they come from the slaughterers are termed green hides, and in this condition an ox-hide will weigh from 30 to 40 kilos, its weight being reduced to one-half by tanning. Many hides are imported from South America in the dried and salted or smoked state. Ox-hides the uppers give the heaviest leather for boot-soles, while for lighter soles cow-hide is used
:

are

Saddles are made from horse-hide, pig-skin, and preferably from calf-skin. seal-skin, while sheep-skin is used for bookbinding leather and goat-skin for morocco leather. Deer-skin, goat-skin, etc., are tanned with oil to obtain chamois or buff leather

made

(see later).

The

hides are

first

softened

by soaking

for

two days or longer (according as they are

FIG. 448.

Fiu. 449.

-Fia-

450.

and other adherent impurities. This may green or dry) in soft water, which removes blood be accelerated, especially with large and dry hides, by adding about 3 kilos of crystallised sodium sulphide or 1 kilo of caustic soda per cu. metre of water. The hides are then placed " " on a beam (Fig. 448) and scraped on the flesh side with a curved knife (Fig. 449), which is drawn across them horizontally. They are then soaked for 24 hours, scraped again, on the beam and allowed to drain. This operation thrown few for a water in washed hours, vessel (Fig. 450) or is hastened if the softened hides are subjected to fuUing in a revolving in a vat containing cold water in which they are worked with wooden mallets.
In order to remove the hair fixed in the epidermis (not in the corium), the epidermis must be attacked and almost destroyed, this being effected in various ways (by putrefaction, out by salting the flesh side of lime, or sulphides). Putrefaction (" sweating ") is carried the hides or sprinkling them with crude acetic acid, bending the hides in two longitudinally ferwith the hair outside and stacking them ill-tanks or in a warm chamber (30 to 50) mentation soon sets in, accompanied by heating and evolution of ammonia, the hides
;

In order to avoid the possibility being then unhaired on the beam with a suitable knife. cement troughs fitted with perin sometimes hides are the of excessive heating, placed to the hides at the top, so that the forated, wooden, false bottoms, water being sprayed on 8 to 12 days the hides can be readily temperature is kept down to 10 to 12 ; after unhaired. The more delicate skins of small animals are treated with sulphides, being

smeared with ruama., which consists of a mixture of 1 part of arsenic sulphide (orpiment) with 2 to 3 parts of slaked lime ; Calcium hydrosulphide is also used and gives better In recent years, sodium sufthide has also been used for heavy hides, unhairing results. with a knife against the set of being easily carried out by scraping hid^s (after washing)

if

Jp

UNHAIRING OF HIDES
;

695

the hair, the operation being facilitated, if necessary, by sprinkling a little sand or ashes on the hide the hair serves for the manufacture of felt, but that treated with sulphide is

converted into fertiliser. In large tanneries unhairing

is

effected

by means

of machines (Fig. 451), in

which the

spread on three or four vertical plates and pressed against revolving rollers with helical knives
hides
are

nclined in two directions.

sire

The

hides

then washed in a large quantity 3f water, spread out and beaten on the beam, and the defleshing of the under side completed either with a curved knife or in the machine shown the flesh removed is in Fig. 452 mixed with lime and sold for making In many factories large hides yrlue. are rendered uniformly thick and then split into 3 to 6 sheets, sometimes only a fraction of a millimetre in thickness, by means of a moving, endless knife ; a band knife splitting
;

machine

is

shown

in Fig. 453.

The

hides

are often further de-

fatted either

by means
FIG. 451.

by pressing or, better, of a solvent such as benzine

or

trichloroethylene, the fat being recovered and used for soap-making.

for

In order to preserve the hides if they are not to be tanned immediately, or to prepare them chrome tanning, they are pickled by immersion for about an hour in a bath containing the acid is rapidly absorbed, and the salt 7-5 grins, of H 2 SO 4 and 80 grrns. of NaCl per litre prevents excessive swelling. They are then rinsed in saturated salt solution and, after draining, may be made up into bales. To eliminate the pickling prior to tanning, the hides are washed in a salt bath
;

containing borax.

Pickled hides

yield a pasty leather less tanning material.

and require

lost

hides have by this time about 12 per cent, in weight, and those which have been limed are next kept for two or three

The

days in several successive infusions of barley flour or bran

("bran drench")
fermentation
sulphurous
;

in active acid

to these are

added
acid,

or

sulphuric

lactic acid (or better,

according to Boehringer, Ger. Pat. 234,584

1909, a solution of lactic anhydride in ammonium lactate),
of

or

acetic

or

butyric acid, the

FIG. 452.

calcium soaps on the hides being thus decomposed the acids separate at the surface and the soluble calcium salts are eliminated by washing (at one time, mixtures of dog and bird dung with water were these enzymes, used, the action of these being due to enzymes and amine hydrochlorides however, act on the gelatine of the hide, this being eliminated, together with the lime, by
;

cultures

various selected bacterial washing with tepid water). The dung is now preferably replaced by and enzyme preparations. After a few days the hides swell up to double their Excessive swelling is prevented by original size and become yellowish and transparent. the addition of a little tanning material to the infusion. are required to make the material to be tanned more All these

preparatory operations

696

ORGANIC CHEMISTRY
:

permeable and more uniform in its behaviour towards the tanning agents, which are fixed to the extent of about 30 per cent, (calculated on the dry corium). The tanning can now be carried out by the following methods This process, which is used for lighter hides, consists in passing (a) Infusion tanning. the hides into tanning baths of gradually increasing strength, so that the tanning may be gradual and penetrative. The total time required is 6 to 9 weeks, and between each

bath and the succeeding one the hides are drained, pressed, and fulled in order to facilitate the absorption of the tannin. was once largely used but is now employed more particularly (b) Tanning in layers
for sole leather.

Fifty or sixty hides are placed, alternately with layers of powdered or crushed tanning material (bark, wood, etc.), in a cement or wooden vessel, the empty and the whole covered with water. The spaces being then filled with the tanning material vessel is then closed with an air-tight cover and left for about 2 months, the hides being then transferred to a second similar vessel containing rather less tanning material, where they are left for 3 to 4 months, and finally to a third vessel containing still less tanning

material (4 to 5 months).

RAPID TANNING
If the hides are

697

resistant, they are passed to a fourth and sometimes to a fifth bath or pit, the whole operation then occupying about two years and the consumption of bark being about five times the weight of the dry hides. The completion of the

very heavy and

tanning is ascertained by cutting the hide and observing that the section is uniform and without horny or fleshy layers, and that the grain does not crack when the hide is carefully
bent. 1

Rapid tanning, which gives a greater output of leather, has been attempted in many ways By immersing and compressing the hides in relatively concentrated tanning baths prepared from active, modern extracts, and containing a certain amount of acid to prevent wrinkling of the hides, the tanning liquor being circulated by means of pumps without moving the hides or the skins are placed in revolving barrels or drums, the lower
(c)

different

half dipping into tanning liquor so that the hides are pressed at intervals. The diffusion process is also applied by placing the tanning bath in bags composed of various hides sewn

together. Tanning in a vacuum has likewise been used in order to effect better penetration of the tanning material, considerable pressure being exerted automatically on the hides at

and the operation being facilitated by gentle heat, etc. By these rapid processes (see also Use of Quinone, Ger. Pat. 206,957, 1907) tanning can be completed in 6 to 8 weeks, this including the preliminary preparation of the hides. The actual
regular intervals,

tanning may, indeed, be limited to 30 hours if revolving barrels are used with hot, highly concentrated tanning baths (8 to 10 Be.). When such a rapid process is used it is, however, indispensable to eliminate all traces of lime beforehand by immersion in formic acid solution. Other very rapid methods which are largely used are chrome tanning (see above) and

formaldehyde tanning as proposed by Payne. According to Gilardini (Fr. Pat. 485,044, 1917) instantaneous tanning may be effected bypassing concentrated tanning extracts (25 to 30 Be.) under pressure through the hide rolled on a perforated drum, the outside space being evacuated. The best results are, however, obtained with the artificial tannins, neradol D and ND. Accelerated tanning is facilitated by the mechanical action of periodic compression of
the hides in rotating chests (Fig. 450) or drums (Fig. 454). When the drum rotates the hides are lifted to a certain height by means of pegs and then allowed to fall forcibly into the tanning solution and on to the hides in it.

and goat skins, (1) Mineral Tanning or tawing is frequently used for light lamb, sheep, which, after unhairing, are passed into the limes and are then, just as in ordinary tanning, swelled in an acid bath, which also removes all the lime. They are then placed in the
1 F. Carini (Ann. d. Soc. chim. di Milano, 1903, p. 23, and 1904, p. 144) proposes to use the wet hide, hydrostatic balance in order to obtain the weight of the dry hide from that of the without drying. The hides can thus be followed through all the operations, from their entry The quantity of tanning material fixed can also be determined in a more or less moist state. at any moment in this way.

VOL.

IT.

45

698

ORGANIC CHEMISTRY

tanning vat containing alum or sodium chloride solution, without impregnating them with fatty substances. For twenty hides, about 1500 grins, of alum and 500 grms. of sodium chloride are dissolved in 50 litres of tepid water. The hides are well saturated with this bath and are heaped up still wet for two or three days, after which they are pressed, washed, and allowed to dry in the air. The finishing of the tanned hides is carried out as described later. Mineral tanning is usually a rapid process, and the alum combines with the corium

and preserves
obtained.

it, but the leather is not so lasting as that prepared with tannin and can still be gelatinised by prolonged boiling with water. A highly elastic leather is, however,

Chromium
sodium
^

salts (the

alum and

chloride) are often used

nowadays

in place of

alum and

chloride.

Chrome Tanning has assumed considerable importance of recent years (since 1895), rapid and furnishes boot leather highly resistant to wejb it is often used also for Both alum and chrome tanning give a light, soft and tenacious leather, chrome girths, etc. tanned leather being far more resistant to boiling water and to tension than vegetable
(2)

as

it is

tanned

leather.

fixes only 3 to 4 per cent, of chromium oxide, the latter being hence sold by measure instead of weight. If dried the leather cannot be swollen, so that it is dyed and dressed immediately. This mode of tanning may be carried out in either a single bath or in two baths at 25 to 30. In the first case the hides are immersed

With chrome tanning the hide

in a solution of a basic

directly

chromium

salt,

whilst in the second they are first soaked in chromic acid solution or (potassium

sodium bichromate with sulphuric

or hydrochloric acid), then rinsed

and placed

in a second bath containing a reducing substance

(best sodium thiosulphate, although sodium sulphite or bisulphite, arsenious acid, hydrogen

peroxide, nitrous acid, etc., are

also used).
FIG. 455.
(a) Single

Bath.

The

basic

by

treating chrome alum with sufficient soda to give the desired basicity, corresponding, for example, with the formula, Cr 2 (OH) 2 (S0 ) , or from 4 2 potassium bichromate, an acid

chromium

salt is

obtained either

and a reducing
cut

agent.

The completion

in the thickest part of hide or placed for a few minutes in boiling water.
(b)

made

of the tanning

is determined by examining a clean by the absence of wrinkling when a piece is

and 5

Two Baths. The first bath may contain 1000 litres of water, 10 kilos of bichromate kilos of hydrochloric acid per 250 kilos of hides, less acid being used with pickled hides ; more bichromate is often used. For this bath vats with reels or the drums
be employed, the hides being treated until they are coloured yellow throughout, then drain for some hours in the dark, and then immersed in drums containing the second, reducing bath. This may contain 1000 litres of water, 25 kilos of thiosulphate and 13 kilos of hydrochloric acid per 250 kilos of hides. The treatment in this bath lasts some hours or
revolving

may

left to

hides

The sulphur which always separates is partly absorbed directly by the and partly transforms the thiosulphate into tetra- and penta-thionate. When, as is now more commonly the case, a single bath is used, this contains chromo-base, which is a basic sulphate prepared by the firm of Lepetit, Dollfuss, and Gansser the procedure is as in the preceding case. The use of chromium lactate has been recommended, since lactic acid reduces chromium salts, even in the cold.
;

at most a day.

(3) Oil

Tanning or chamoising.

clothing, etc.
[fish oil,

This is used to obtain very soft leather for gloves, Deer, stag, lamb, kid skins, etc., are smeared or rubbed with various fats

wool

fat, paraffin, egg-yolk,

alum, carbolic acid, sodium chloride,

etc.,

etc.

or,

accord-

ing to Garelli
1

and Apostolo
chromium
,

(1914) with stearic, palmitic, oleic acids,

is

or resin acids such

The
,

basic

salt

formed as follows

Cr a (S0 4 ) 8
or

S0 4 24H 2
2

'+
2

Na 2C0 3 =
2
3,

Cr t (OHf) t (S0 4 ) t

+ K SO + Na S0 4 + C0 +
2 4 2
2

23H 2 0,

K.Cr.0,

+ 3H

S0 4

+ 3Na S

5H a O = K SS0 4 +

Cr,(OH) 2 (S0 4 ) s

+ 7H a O

-h

3Na aSO 4

38.

OIL TANNING

699

as those from colophony, or, better, according to Fahrion, with unaaturated fatty acids with several double linkings], the absorption of which is effected by repeated working of the skins, followed by drying in tepid chambers ; the skins are thus rendered impermeable, while they can be washed many times without losing their tanning. The superficial fat is finally removed by washing in soda solution, the emulsion thus formed,

known
p. 478)

as

degras

(see

being used for currying ordinary hides.

Heavier hides (cow,

horse,

ox,

buffalo)

in-

tended for saddlery are mineral to subjected

tanning (without being treated with lime) and afterwards to a kind of oil
^

FIG.

45(5.

tanning which imparts ^ ne leather consider-

able resistance to tension.

hides are then subjected to finishing, which varies considerably with the nature of the hide and the kind of leather required. The tanned, moist hide is stretched on a plate moving (a) Smoothing and Stretching.

The tanned

on wheels mounted on a trolley so as to give both longitudinal and transverse movements, the machine being known as a striking- out and scouring machine (Fig. 455). A band moving over two pulleys is furnished with inclined blades of bronze, ebonite, glass, etc.,
these

impinging

more

or less strongly on the bloom side of the hide

and so squeezing out the water and smoothing out the folds. A
better machine for this purpose is shown in
Fig.

456

in this, the

hide is pressed and stretched by a bronze

cylinder having doubly inclined helical vanes.
to similar Machines those used for deflesh-

ing (Fig. 452) are also

employed. (6) In order to prevent cracking or splitting during drying, the hides are subjected to
slight oiling,
oil,
oil,

with
oil,

fish

linseed

castor

FIG. 457.

to the type of hide and to the rigidity yolk, tallow, stearine, paraffin wax, etc., according or softness required. this consisting in stretching the hide on a rubber cylinder (c) Shaving generally follows, one-half it against a second cylinder furnished with helical blades, (Fig. 457), which presses

lanoline, degras, egg-

of these sloping one

(d)

way and

the rest the other way.

Drying

than

warm

of the hides is carried out carefully in circulating air, and does not effect complete drying.

which

is

dry rather

fibres the almost dry hides less stiff and softer, adherent and hardened effected is this all directions in hides out usually and are detached by bending pulling mechanically. J
(c)

To render

45-2

700

ORGANIC CHEMISTRY
;

sole leather more compact and more resistant to wear, the hides are (/) To render excessive subjected to striking by means of a bronze piston operated by a lever (Fig. 458) striking marks the leather. A preferable method consists in rolling by means of a weighted

of an endless screw (Fig. 459). and to obtain a good, resistant lustre they should be free from If too greasy they are rubbed with 5 per cent, lactic acid or ammonia solufat and dry. tion. When dry they are rubbed with a very thin layer of a special dressing (aqueous egg albumin and milk, and other pale
roller
(g)

moved backwards and forwards by means

Many skins

are glazed,

dressings

known

as seasoning), the

rubbing being effected by a smooth

agate or glass cylinder.
(h) If

this

grooved

the

cylinder is finely leather assumes a

.rough, fine-grained surface,

may

be

rendered

which more marked

(morocco leather) either by bending the hide over on itself and rubbing the surface gently with a cork utensil (Fig. 460), or by

passing
rollers

the

hide

between
at

two
Fio. 458.

revolving

different

speeds. More pronounced impressions to give the appearance of goat, seal, crocodile skins, etc., are obtained

by means

of calenders suitably incised, the

upper roller being heated to render the impression more stable. Those hides which are required to show not graining but a smooth surface, are first surface by rubbing both sides with pumice by hand or rendered^ perfectly uniform at the more conveniently by a kind of spindle-shaped grindstone covered with emery (Fig. 461), In some cases this operation is against which the surface of the hide is gently pressed. of wood, similar to that of completed by polishing the bloom side with a concave piece cork. with lined surface a smooth but with 460, Fig. rendered unterproof by immersing them for a couple (i) Certain hides and leathers are Good of hours in baths of soap and glue and then in aqueous alum and salt solutions. results are obtained also with 2 per
cent, gelatine solution, followed by Hardened 5 per cent, formalin.

for boot soles is treated with 2 per cent, formalin for 24 to 48 hours, chrome-tanned leather being subjected also to a bath
leather

containing 8 per cent, of aluminium sulphate and 1 per cent, of sulphuric

acid.
(k)

Some

hides are dressed to

FIG

459

increase their weight with starchy substances or dextrin (brillantino,

containing

over

60 per cent, of

of maltose, and 25 per cent, of water) in dextrin, 9 per cent, of soluble starch, 5 per cent, a for are treated which with couple of hours in drums ; the increase they strong solution, used. Hides are loaded also with is greater if magnesium sulphate or barium chloride is excess of tanning agent, oils and fats, sulphite liquors from cellulose factories, glucose,

barium sulphate, magnesium sulphate, etc. of hides are carried out by the varied processes used for (I) Bleaching and dyeing For bleaching, which prepares the textile fibres, especially animal fibres (wool and silk).
hides for taking the paler tints, use is made of hydrogen peroxide, sulphurous acid, sulphites, Dyeing oxalic acid, permanganate followed by sodium bisulphite, dilute hypochlorite, etc. of vegetable or alum tanned hide is effected at 40, and that of chrome tanned ones at 60.
solutions of iron acetate
is coloured black on the flesh side by rubbing with concentrated and sulphate, treating with oil, wax, soap, lampblack, etc., and then polishing with smooth wood until a shining surface is obtained.

Leather for boot uppers

HYDROGENATED BENZENE COMPOUNDS

For
is

701

special purposes hides and leathers are coloured with basic or mordant aniline colours, the hides being first prepared by immersion for 12 hours in cold water in which is dissolved the white of an egg for each hide. The dyeing

carried out at a temperature of 30. Certain leathers are varnished with ordinary resin varnishes. In order to supply the great demand for large hides for the hoods, etc., of carriages, ox-hides and cow-hides are nowadays

divided, the

more resistant part being kept

for the hoods,

and the
cence

flesh side for the seats, etc.

Jn order to avoid the formation of the white efflorescaused by the use of hard water and due to the combination of lime with the fatty matters of the tanning materials it has been proposed to replace the fats by mineral oils, which do not give calcium salts, or to wash the hides well with dilute lactic or formic acid which form soluble calcium salts. The suggestion has also been made that the hides be dressed, not with fats, but FIQ. 461. with the anhydrides or lactones of fatty acids, as these form calcium salts more slowly (the purgatol recently placed on the market consists mainly of anhydrides or lactones).

M. NITRO-DERIVATIVES

OF BENZOIC ACIDS

o-Nitrobenzoic acid melts at 147, has a sweetish taste and at 16 dissolves in 164 parts of water. The w-Acid, m.-pt. 141, dissolves in 425 parts of water at 16 and yields a sparingly soluble barium salt. The ^-Acid, ni.-pt. 238, is very slightly soluble in water. 2 4-Dinitrobenzoic acid (see p. 652) has m.-pt. 179 the 2 5- Acid, m.-pt. 177 the 3 4- Acid, m.-pt. 165. the 2 6- Acid, m.-pt. 202 2:4: 6-Trinitrobenzoic acid melts at 210 losing C0 2 and yielding s-trinitrobenzene (see p. 649). Its use as an explosive was proposed by the Griesheim:

Elektron

Company

Numerous halogenated
N.

(Ger. Pat. 79,314, 1893). derivatives of the nitrobenzoic acids are

known.

HYDROGENATED BENZENE COMPOUNDS

Considerable interest attaches to the numerous hydrophthalic, acids studied by Baeyer in their various constitutional and stereo-isomerides (cis- and tmnsisomerides see p. 22). They behave largely like unsaturatcd aliphatic compounds (see pp. 106 108), as they no longer possess the stability of the true benzene nucleus. The position of the true double Unkings in these compounds is determined by the addition of bromine and by subsequent elimination of the latter by reduction, with or without substitution of hydrogen, according as the two bromine atoms are in para- or ortho-positions. Simple boiling with alkali often effects displacement of a double bond (as with oleic acid see p. 358), so that it is possible to pass
:

from one isomeride to another. The di-, tetra, and hexa-hydrophthalic and terephthalic acids can be many of them dehydrogenated in stages by heating with bromine at 200 form anhydrides. From the results of his investigations on the hydrophthalic acids Baeyer drew important conclusions concerning the constitution of the benzene nucleus. Many important hydrogenated benzene derivatives occur naturally, among them the naphthenes, found in abundance in Russian petroleum (see p. 71), which contain hexamethylene groupings (see Polymethylenes, p. 616). Syncalcium pimelate thetically they may be obtained, for example, from
;
:

CH2<2 PTT

'

'

L/jiQ* 1^112

PIT

^ 2 ^PTT -PH Utt ^ vy 3"r CH 2Ca==CaC -^^ pn ^-"-a ^^a Ov/2

tt

702

ORGANIC CHEMISTRY

Also, by condensing 2 mols. of ethyl succinate with sodium and then hydrolysing the product and heating at 200, p-diketohexamethylene is obtained. Hydrogenation of benzene and its homologues, by passing their vapours, mixed with hydrogen, over heated finely divided nickel, yields hexamethylene x and its

homologues, hexahydrophenol (b.-pt. 160-5), and p-diketohexamethylene (in.-pt. 78). The latter gives the corresponding alcohol, quimtol (p-dihydroxyhexamethylene), which forms various cis- and frans-isoinerides. Inositol, C 6 12 6 the hexahydric alcohol derived from hexamethylene, is isomeric with the hexoses, but with HI or PC1 5 yields true benzene derivatives. Various naphthenic adds are obtained by oxidation of the naphthenes of Russian petroleum, or more easily by acidifying the alkaline solutions used in

refining this petroleum (see pp. 79, 89), and are distinguished from open-chain acids by forming soluble magnesium and calcium salts by this means they can be detected when used in the manufacture of soaps. 2 Charitschkov (1911) showed
;

latter acid melts at a higher

that these acids are not of the hexamethylenecarboxylic acid group, since the temperature and does not give the characteristic reaction with copper or cobalt salts obtained with naphthenic acids. The latter

resemble rather Pentamethylenecarboxylic acid,

C0 2H

X CH 2 CH 2
I

CIT<^

and

Zelinsky's

Pentamethyleneacetic

acid,

C0 2H CH 2
-

CH/ X CH

cii 2 CM 2 OFT * on
|

*,

which

-CH 2

give the reactions mentioned. Naphthenic acids are optically inactive and insoluble in water, and boil unchanged. The first terms are mobile liquids of the unpleasant odour, which disappear as the molecular weight increases higher members are viscous but of lower density (0-98 to 0-95).
;

QUINIC ACID (Tetrahydroxyhexahydrobenzoic

acid),

CO 2 H C H 7 (OH) 4
ft

is

optically active, but only an inactive modification is known. It from the roots of coffee, cinchona, etc., and forms white crystals.

is

obtained

Still more interesting are the terpenes and the camphors, which are found in various plants and form the principal constituents of many ethereal oils and essences and of many resins.

TERPENES
These are regarded chemically as hydrogenated derivatives of cymene (dihydrocymene) and its homologues, and have the generic formula C 10 16 They are not soluble in water, but can be readily isolated from the natural

products owing to their volatility in steam. The chemical constitutions of the principal terpenes have been established mainly by 0. Wallach's investigations over a period of more than twenty years. By their syntheses, their halogenated additive compounds, their behaviour towards oxidising agents and their molecular refraction (see p. 27), it has been shown that they contain two double linkings and a closed ring of six carbon atoms. There is, however, a group of more complex terpenes (pinene, camphene, fenchene, etc.), which have only one double bond. In order to define the position of the double linkages (A), Baeyer numbered the fundamental carbon atoms
1 HEXAMETHYLENE (hexahydrobenzene, cyclohexane, or naphthene) is found in Caucasian petroleums and is obtained synthetically from iodohexamethylene or 1 3-dibromopropane. It is a colourless liquid smelling like petroleum, and it boils at 80 and resists the action of permanganate. By hydriodic acid at 750, or in presence of alumina at lower temperatures and preferably under pressure, it is converted into methylpentamethylene. 2 Naphthenic acids serve for the regeneration of rubber, for preserving wood in virtue of their antiseptic properties, and for making alkaline soaps of marked detergent powder; the aluminium salt is used for impregnating wood, and the manganese and lead salts as dryers for oils the corresponding glyceride is used as a lubricant, as a tanning agent, etc.
:

TERPENES
of the

703

of the following scheme, which shows the cymene constitution of five terpadienes out of fourteen possible theoretically without
ill

as

the

first figure

counting enantiomorphs.

CH 3
H,

CH 3

H
H
2

H,
H.,

C
10
8

:1

CH 3 C CH 3
-

IV

To indicate the position of the double linking in the side-chain, instead of giving only the lower number of the two carbon atoms united to the double v> II A 1>n linking, as in the case of the nucleus (e.g., Ill == A -terpadiene A M-terpadiene or 7-terpinene), the numbers terpadiene or a-phellandrene I of both the carbon atoms united to the double linking are given, the higher number being bracketed (e.g., IV A u H) -terpadiene or terpinolene A lw -terpadiene or limoncne). In the official nomenclature the name terpane is given to Hexahydrocymene, C 10 II 20 Tetrahydrocymene, C 10II ]8 being called terpene and the Dihydrocymenes, 10 16 terpadienes.
;

=
,

'

V=

As separated from plants or fruits, the terpenes are generally mixtures, and when obtained from conifers are termed oil of turpentine. Essence of lemon gives citrene thyme, thymene cumin, carvene orange, hesperidi-ne, etc. Although their boiling-points differ little (160 to 180), they form tetrabromoderivatives and dihydrochlorides with widely different melting-points, these
;

linking^, which act as in aliphatic compounds, the terpenes can combine with 4 bromine atoms or 2 mols. of HCl (the halogen being readily replaced by hydroxyl, with formation of camphor) and also react with nitrous acid or nitrosyl chloride, forming solid Nitrosites, C 10Hi 6 (N0 2 )(NO), or Nitrosochlorides, C 10 16 (NO)C1, which are also solid and sometimes blue.

compounds hence serving for their separation. PROPERTIES. Owing to the presence of double

They oxidise easily and with mild oxidising agents give benzene derivatives, whilst on energetic oxidation they resinify they polymerise readily, and by In alcoholic acids, for instance, are converted into more stable isomerides. solution they give characteristic colorations with concentrated sulphuric acid. They are usually optically active. They often accompany the natural perfumes of fruits and flowers, which, now that they have been subjected to thorough chemical study, can be obtained
;

1 purer and of increased value.

1 PERFUME INDUSTRY. A considerable number of the natural perfumes have been prepared from the very earliest times, but with the perfected methods of extraction now available they are obtained in higher yields and in a more highly refined condition. The most abundant supplies of raw material have always been, and are still, obtained from eastern countries, where whole provinces are often devoted to the cultivation of flowers. The most delicate perfumes are those obtained from flowers which contain, along with the odorous principle, other substances which refine the aroma and render it softer. The name artificial perfumes was at one time given to mixtures, in proportions carefully chosen, of the fundamental natural essences, a great variety of perfumes being thus obtained"; this, however, required a very highly developed sense of smell in the operator. The discovery of artificial perfumes did not diminish the consumption of the natural products since these became cheaper and thus appealed to a large public. The consumption of perfumes fluctuates with the fortunes of a nation. The early Eastern races and then the ancient Egyptians introduced perfumes into religious ceremonies, their secular use being often forbidden. Gradually, however, they became used for domestic purposes, together with many different pomades and, in some cases, dyes. Egyptian pomades were held in high

704
h(!

ORGANIC CHEMISTRY
arc subjected to protracted heating at 260

CINENE (A'' "-Terpadiene or Dipentene; Inactive Limonene), C 10 H 16 , is found together with eineol in Oleum cince and also in Laurm camphora and in Russian and Swedish turpentine oils. It is formed by isorneric change when eamphene, active limonene, pinene,
etc.,

to 270,

and

is

obtained, together with

esteem by Cleopatra. With the ancient (i reeks, the use of perfumes and cosmetics assumed considerable importance and often degenerated into abuse, and Socrates states that if even a slave is anointed with a good perfume he will exhale the same odour as his master. Perfumery flourished under the Romans and declined with the Empire, being re-established It then passed into France, where it became a true in Italy only at the time of the Kenaissance. national industry, fulminating at the time of the perfumed Court of Louis XV. Until about the middle of last century, France enjoyed almost a monopoly in this industry, but when science pervaded this branch of human activity, the French rulc-of-thumb manufacturers did not grasp quickly enough the benefit to be derived from a rational development of their industry, of which England and Russia and, more especially during the past quarter At (JrasHC and Cannes, in the South of France, of a century, (Jermany have taken advantage. however, the natural perfume industry is still of importance, certain factories dealing with as much as 3000 kilos of violets (40 to" 60 millions of flowers) at. a time. As has been already mentioned, the prime materials come mainly from Kastern Europe, and at the present time also from the Fsir East, but the cultivation of plants for perfumes is still largely carried on in the South of France and in Sicily. In annuals the essential oil is formed in the green organs, and the majority of it is found The extraction of perfumes from flowers and leaves is carried in the flowers before fertilisation. out in various ways (1) By distillation with direct or indirect steam or in mcuo, the distillates this method is used for lavender, rosemary, Ihynic, orange of different densities being separated blossom, and row*, which are unaltered at steam heat. (2) By infunion for 12 to 48 hours at 00 to 65" with pure fats (olive oil, etc.), the flowers being retiewed four to six times until the extracted flowers are pressed to free them from fat, and the the fat is highly perfumed perfumed fat run into ena moiled iron vessels as a concentrated pomade ; in this way are treated cassia, violet*, jonquil*, and sometimes orange blossom and roses, when mixed with other flowers.
:

(3) By absorption in the cold of the more delicate perfumes of jessamine, Itelioirope, and tuberoses : in vessels with glass walls smeared with fat or covered with cloth soaked in oil, the petals are pressed and rubbed, being renewed every day; after some days or at the end of the season the perfumed fats are shaken for a long time with alcohol, which extracts all the perfume. To obtain colourless products, I'ivcr passes a slow current of air through the flowers and then on The use of this method is spreading, as it gives highly to the fatty surface. (4) By dissolution. concentrated, very delicate perfumes. The flowers arc* immersed in petroleum ether, carbon disulphidc, etc., the perfume being extracted by a current of steam from the solvent, which is afterwards recovered, (5) By prcmiure with hand or hydraulic presses, this method being employed with orange-peel, bergamot, iris rhi/omes, etc. *Thc yields obtained per 1000 kilos 1 kilo of orange oil or of leaves or flowers arc about as follow, the prices being those of 1913 24 to 28), or 3 kilos of petit grain (from the leaves) ; 1 kilo neroli, from the flowers (value 1200 grms. of essence of cttronella (88.s. per kilo) ; 9 to of essence of basil (6 to 8 per kilo) 16 kilos of eucalyptus oil (from the leaves) ; 120 grms. of essence of jessamine (from fresh flowers) ; 6 kilos of marjoram, 1 kilo of geranium oil (from flowers and leaves) ; 10 kilos of oil of htwndcr oil; 2 kilos of mint oil ; 3 kilos of myrtle oil ; 2 to 10 kilos of rosemary oil ; and 200 to 500 grms.
: ; ,

of rose

oil.

In fiormany, although the climate docs not seem very favourable, the cultivation of certain The perfumery factories have flowers for perfumes is largely carried on in some district's. hundreds of hectares of land under flowers, not only for commercial purposes but also for analytical and research work. One hectare yields 10,000 to 16,000 kilos of rose leaves. At one time the firm of Schimmel (Leipzig) treated 'as much as 000,000 kilos of fresh rose leaves per day, 300 kilos A kilo this was repeated two or three times in a month (June). of rose oil being extracted of the oil is sometimes obtained from 2000 kilos of the leaves. Rose cultivation is, however, carried on most extensively in Turkey and Bulgaria, where of oil preference is given to the red rose (Rosa dntna*cwua), which gives on an average 1 kilo kilos of per 4000 kilos of leaves, although white roses (Rosa alba), giving 1 kilo of oil per 5000 The product from the latter variety is less fine, but it gives fresh petals, are also largely grown. an oil crystallising at 18 to 20 and is used to mask oils of lower quality the market value of the oil is judged more particularly from the freezing-point, which should be between 17 and 19 Adulteration with alcohol or spermaceti is easily discovered, but it is more for good qualities.
; ;

geranium oil or palmarosa oil. In 1887 Turkey produced 2400 kilos of pure rose oil (attar of roses), whilst in 1904 and 1906 the output reached 3600 kilos. The annual production varies very considerably, as the plants suffer greatly in dry seasons, especially if water is scarce in the month of May preceding the in 1907, indeed, the output was only 2000 kilos. harvest In Bulgaria roses arc still more largely grown, and here, too, the production varies widely. At one time two-thirds of the oil went to Franco, but oven prior to the war only one-third was sent to the French factories, one- third going to ( Germany, and the rest to Great Britain and the United States. The price of attar of roses varied before the war from 32 to 80 per kilo, and was formerly higher than this. In 1904 H. von Soden patented a process for obtaining more rfinod and delicate porfumos from flowers. He first obtained a petroleum ether extract which was then evaporated and the
difficult to detect additions of
;

PERFUME INDUSTRY
isoprene, wlien rubber going condensation.
is distilled,

705
C(CH.
4)
:

2 mols. of the isopreue,

OH 2 CK
:

OH 2

under-

It has a pleasant odour of lemons, and boils at 176. Nitrosodipentene (inactive carvoxime) melts at 93. With HC1, cinene gives two stereoisomeric dipentene dihydrochloridea (1 4-dichloroterpanes), melting at 50 and 25. The tetralromide melts at 125. CARVENE (r/-Limonene, Hesperidine, Citrene), C 10 H ]6 forms the greater part of orange:

residue taken

up in alcohol, the latter being distilled off and the residue distilled in steam. Itmust, however, be pointed out that with this process, 1 kilo of the finest rose oil would now cost 1520 and 1 kilo of oil of violets even more. From what has been already stated, it will be recognised that considerable interest attaches

to the study of the composition and constitution of these essences and to their artificial production by synthetical methods. Tn former times, various artificial perfumes have been obtained empirically, as was also the case with the first coal-tar dye, yet it. has required systematic chemical I investigation to open up new fields in this direction. Hiring the last 30 years, the consumption of perfumes has increased from 480,000 to 2,400,000, owing to the diminished prices of the natural and artificial products. The first artificial perfume was nitrobenzene or artificial myrbane oil, which was discovered by Mitschcrlich in 1834, placed 011 the market by Colles arid manufactured on a large scale by In about 1 840, Piria oxidised mlicin (a glucoside nitrating benzene from tar by Mansfield in 1847. found in willow bark) and thus obtained salicylaldehyde, which is the pleasant smelling essence of Nfjirtra itJman'a (meadow-sweet). A few years later in 1844 Cahours succeeded in isolating the active principle of yaultluna or winlcryrecn oil, consisting of methyl salicylate, which can be obtained synthetically by heating salicylic acid with methyl alcohol (wood spirit) and sulphuric acid. Many 'of the natural perfumes contain aldehydes, and in 18.53 Itartagnini showed how they could be separated pure by first combining them with bisulphite. Brnznldehydc was synthesised by Cahours in 18(>8, and coumarin, the essence of A*i*'rula odorato, by Perkiii in 1875. In 187b' Haarmann and Ticmann ascertained the constitution of mmllin, later preparing it from Fn 1888 Baur prepared artificial coniferin or, better still, from eugenol extracted from clove oil.

musk. In 1893 Ticmann and Krugcr succeeded in effecting the synthesis of violet oil, previously obtained at enormous expense from the natural llowers. They also separated imnt', the odorous Immediately afterwards they principle of iris root, and determined its chemical constitution. prepared synthetically an immieride of ironc, fononr (wr 1at< *), to which the delicate odour of in abundance in lemons, occurs the violet is due. These investigators heated citral, which with acetone, acetic anhydride, acetic acid, and sodium acetate, obtaining first pscudo-ionone, which has an unpleasant smell, and, when treated with mineral acid, yields ionone. These processes were patented by Ticmann and disposed of by him to the most important perfume manufacturers for 40,000*. The study of the chemical constitution of the components of perfumes reveals a certain relation between the aroma and the presence of definite atomic- groupings (ofimophorctt) and attempts were made to establish a perfume theory on a similar basis to the colour theory of It has not yet been aniline dyes, the characteristic groups of which are termed c/iromophorett. found possible to formulate a theory as rigorous as that for the colouring-matters, and all that has been fixed is that aldehydes, kctones, mixed ethers, etc., often enter into the constitution of perfumes, and that the introduction of certain alcoholic residues into the molecules may The tertiary butyl group produces the odour of musk in intensify or modify the aroma.
trinitrotoluene, trinitroxylcnc, etc. The action of perfumes on. the olfactory nerves is not thoroughly understood, although it is regarded by some as due to vibrations of the ether similar to those by which light and heat are transmitted, these vibrations originating from the oxidation of the substance in the air. This hypothesis seems to be supported by the fact that many odorous substances emit no smell when worked and distilled in an inert gas instead of in air. It is now, however, generally assumed that the smell is propagated by small particles or molecules, which become detached and, in the state of gas, come into contact with and excite the papillrc of the nasal mucous membrane. The fact that certain substances have little smell in the pure or concentrated state and acquire their maximum smell only when considerably diluted, is well explained by modern views oil solutions, dissociation in dilute solutions giving rise to the corresponding ions, which become detached and excite the olfactory sense. That minimal traces of these substances transmit perfume is shown by the retention of this property by garments which have been washed five series of tests, controlled by the or six times (WP Experiment described in Vol. I., p. 4). who have by no means a very delicate sense of smell in olfactonieter, showed that most men the odour of 1 part of prussic acid in 100,000 of water, with other animals

Of the women 7 per cent, of the individuals examined detecting it in a dilution of 1 in 2,000,000. tested, however, not one was able to detect prussic acid in a dilution as small as 1 in 20,000. These results support the view that male animals are very sensitive to the odour of the females, which serves to excite their sexual passions. Some individuals, termed anosmic, are quite without sense of smell. The influence exercised by the artificial perfumes on the price of perfumes in general is illustrated by the fact that before the war synthetic vanillin was sold, in large amounts, at cost 1 6s. per kilo, whereas 30 yeara earlier the natural product cost up to 140. Also heliotropin in 1881 100 per kilo in 1890 15, and in 1902 not more than 30*.

comparison

perceived

706
oil

ORGANIC CHEMISTRY
;

and also occurs abundantly in cumin oil, anethum oil, etc., lemon oil is a mixture peel of pinene and limonene. It is a liquid boiling at 175 and is optically active although It forms a dextro-rotatory tetrabromide, readily convertible into inactive dipentene. melting at 104. /-LIMONENE, C 10 H 16 the constitution of which is shown on p. 703 (V), can be obtained from d-carvone, and occurs, together with /-pinene, in pine oil. Its tetrabromide melts at 104. SYLVESTRENE, C 10 H 16 is possibly derived from ra-cymene and forms a dextro-rotatory component of turpentine. It boils at 176 and gives an intense blue coloration with concentrated sulphuric acid and acetic anhydride. TERPINOLENE (A'^-Terpadiene), C 10 H, has the constitution shown at IV on p. 703. It is obtained by the elimination of water from terpineol and melts at 185. TERPINENE, C 10 H I6 boiling at 179 to 180, is obtained in the transformation of various terpenes. Its nitrosite forms monoclinic crystals melting at 155. DIHVDROCYMENE, C 10 H 16 obtained synthetically from ethyl succinylsuccinate, boils at 170. PHELLANDRENE, C 10 H 16 is known in both thelajvo- and dextro-rotatory forms, these having the same chemical and physical properties (excepting the optical rotation) and The former (1-) is found in Australian eucalyptus oil and the latter in boiling at 172. Anethum fwniculum and in water-fennel oil (Phellandrium aquaticitm). MENTHENE, C 10 H 18 boils at 166. MENTHANE (Hexahydrocymene), C 10 H 20 boiling at 170, does not occur naturally, but is obtained by hydrogenating cymene in presence
, ,
fl ,

of nickel.

COMPLEX TERPENES
Like the preceding, these are composed of a monocyclic system, but with two rings they have only one double linking, and hence combine with two atoms of hydrogen or halogen. They can be converted readily into cymene and its derivatives. 'The following four diagrams show how a trimethylene ring or bridge is formed in Carane (not known in the free state, although the corresponding
;

saturated, synthetic ketone, Carone, is known), a tetramethylene ring in pinane and. pinene, and a pentamethylene ring in camphane
:

CH,

CH,
CH.

CH
C

CH

:}

CH.

CH
Pinane

CH
Camphane

PINENE (Terebenthene, Laurene, Menthene, etc.), C JO H 16 (constitution, see above), forms one of the principal components of oil of turpentine, occurs also in sage and juniper oil, and, mixed with sylvestrene and dipentene, forms Russian and Swedish turpentine oil.

When incisions are made at suitable seasons in certain varieties of pine, fir, and larch, a kind of balsam is exuded in the form of a juice which gradually changes to a soft resin, more or less clear according to the quality. This is known as ordinary turpentine or American, French, Venetian, according to the particular tree and to the locality of origin.
Ordinary turpentine consists mainly of resin acids (abietic and other acids and the corresponding products of acid oxidation), its saponification number being 165 to 195 and its iodine number about 150. When turpentine is distilled with steam, the liquid essence

COLOPHONY
is

707

collected separately, the residue, which is solid in the cold, or oil of turpentine (turps) 1 The direct extraction of the turpentine from resinous woods or tree being Colophony.

stumps by means of suitable solvents has been suggested. The stumps are first cleaved by and then sawn up and rasped, the fine mass being distilled with steam to recover turpentine oil and the residue extracted with benzene or trichloroethylene or hot wood tar mixed with pine oil (U.S. Pat. 852,236) ; after recovery of the solvent by distillation, a dense mass remains composed of 90 per cent, of colophony and 10 per cent, of oil of turpentine. Oil of turpentine is rectified by heating with steam in presence of 0-5 per cent, of quicklime. As the oil always resinifies to some extent when exposed to the air, it is often desirable to redistil it before use. The strong and less agreeable odour of Russian and Greek turpentine oils is removed or lessened by shaking with a solution of permanganate,
explosives

dichromate, or persulphate. Fresh oil of turpentine is clear, colourless, and highly mobile it has the sp. gr. 0-855 to 0-876 and boils at 156 to 161. It absorbs and combines with considerable quantities of ozone and oxygen part of the latter being converted into ozone and the oil at the same time resinifying. It dissolves sulphur, phosphorus, rubber, and resins, and is hence used
;

for varnishes, lacs, oil paints, etc. 2 Permanganate in acid solution transforms

it

partly into Pinonic acid,

.

C 10 H 16

3,

while

with dilute nitric acid it gives Terephthalic and Terebinic acids, C 7 H 10 O 4 It reacts violently with iodine in the hot, forming cymene. The relation between resins and aromatic compounds is established by the fact that when the former are distilled with zinc dust they form aromatic hydrocarbons, while if fused with potash they give di- and tri-hydroxybenzenes. Resin substitutes or artificial resins are now prepared by heating phenols with

formaldehyde (see Baekelite, p. 641). According to the preponderance of la?vo- or dextro-pinene, turpentine oil is laevo- rotatory (Venetian, German, and French) or dextro-rotatory (Australian). Pinene contains only one double linking, and hence unites with only 1 mol. of HOI, giving Pinene hydrochloride, C 10 H 17 C1, which melts at 125, and has the smell of camphor When treated with alcoholic potash, this hydrochloride is converted (artificial camphor).
1 and its (rotthi) is hard and brittle, its sp. gr. being 1-050 to 1-085 at 15 fracture shining and conchoidal. According to the quality, its colour varies from yellow to brown, but it gives a whitish powder. At 70 it becomes soft, and it forms a kind of emulsion with hot water. It always melts below 135 and it is readily soluble in alcohol (1 in. 10), ether, It burns with a smoky iiame and, when benzene, petroleum ether, and carbon disulphide. subjected to dry distillation out of contact with the air, yields resin oil It contains ahietic. From acid, G 19 H 28 O 2 , which has two double linkings, melts at 165, and is soluble in hot alcohol. galliot rosin (Finns niaritima) pimaric add, C 20 30 O 2 , m.-pt. 148, has been obtained. 09and the acid number 145 to 185. has the 6, rotatory power Colophony One cu. metre of iir contains about 10 kilos of turpentine, which yields as much as 7 kilos of colophony, while 1 cu. metre of pine gives 22 kilos of turpentine, this leaving 16-6 kilos of colophony ; the larch gives an intermediate yield. Colophony is used in large quantities for mixing with soaps (see Resin Soaps, p. 518), for In the United States 35 per cent, of the total sizing paper, for making varnishes, mastics, etc. output is used in soap -making. Large quantities of it are incorporated with artificial wax (cerasin), which is thus cheapened ; to deodorize the resin, it is finely ground, macerated with dilute sulphuric acid for 5 or 6 days and then suspended in hot water and subjected to a jet of steam for some time. After this treatment it melts and mixes well with the cerasin. Colophony is also used for making sealing-wax by mixing with shellac, turpentine, and a larger or smaller number of mineral substances (chalk, burnt gypsum, magnesia, zinc oxide, baryta, kaolin, etc.), according to the quality required ; the fused mass is coloured with cinnabar or red ochre. The best qualities contain only ((for the finer red qualities), minium, ferric oxide, 40 per cent, of mineral matter and are mainly shellac, while the inferior kinds contain as much as 70 per cent, of mineral matter, the residue being principally colophony. Sealing-wax is coloured black by lampblack or boncblack, green by Prussian blue, yellow by chrome yellow, or blue by ultramarine ; when fused, colophony may be coloured also with algol or indanthrene dyes (q.v.). Substitutes for sealing-wax are now prepared from artificial resins (see p. 041). Copal resin has already been described (p. 495). Dammar, a similar resin, gives fine, pale varnishes ; Australian dammar or copal is known also as kauri gum. 2 Oil of Turpentine consists almost entirely of J-pinenc (lenient hene) and d-pinene The most common commercial varieties are French, English, Russian, German (australene).

COLOPHONY

and American. The smell of European turpentine

oil has been improved by treatment with oxidising agents, such as permanganate, persulphates, or chromic acid, or, better still, with hydrogen peroxide,

Boftium peroxide, barium peroxide, or oxides of nitrogen. By suitable application of Halphen's reagent (p. 637) or mercuric acetate, C. Grimaldi (1910) was able to detect adulteration with pine oil or resin oil.

708
into

ORGANIC CHEMISTRY
FENCHENE
;

CAMPHEKE, C 10 H 16 , m.-pt. 50, which is known in three optical modifications and is transformed by oxidising agents into camphor and by ozone into the ozonide (Harries,
1910), these reactions establishing its constitution.
is

similar to

camphene

but

is

an optically inactive
,

liquid, boiling at 158

to 160

it resists

the action of nitric

but not that of permanganate. forms white volatile crystals melting at 154 and boiling at 160, and is obtained by reducing d- or Z-bornyl iodide. It is optically inactive, and is the saturated hydrocarbon of the camphor nucleus. HOMOLOGUES OF TERPENES. The most interesting lower homologue is Hemiacid,

CAMPHANE, C 10 H 18

terpene or Isoprene, C5 8 (see p. 109), which gives various terpenic polymerisation products, such as (C5 8 ) 3 (Clovene, Cedrene, Caryophyllene, etc.), C 20 32 (Colophene), C 10 16

(Rubber), etc.

RUBBER
are

made

(caoutchouc) is obtained from the milky juice (latex) exuding when incisions in the stems of certain plants growing in the tropical regions of South America

(especially Brazil),

Java,

etc. ).

liensis of

East and West Africa, Asia and Polynesia (Ceylon, Malacca, Sumatra, The plant families giving rubber arc EuyihorbiacecR (the genus Hevea brasiBrazil and Ceylon gives the best Para rubber Manihot, also of Brazil, etc. ) Mwacece (especially the Ficus elastica of the East Indies and the
:

South America); Apocynece (especially the genus Lawlotyhia, growing in Africa), etc. In some districts the trees were formerly cut down to obtain the rubber, but nowadays V-shaped or spiral or herring-bone incisions are skilfully made in the bark (Fig. 463), the latex being collected each day. When the growing use of the automobile involved a great increase in the demand for rubber, plantations were laid out with selected seeds and plants, which are carefully
Castilloa of

cultivated.
tion.

Coagulation of the Rubber is an important and delicate operaAccording to Henri (1906-1908), the faintly alkaline latex

contains the rubber, ready formed, in

emulsified drops (50 millions per
c.c.),

movement, and

of

which

this

the form of minute which are in continual author was able to obtain a

cinematographic representation ; a coagulum is produced by acids, by salts of divalent metals (Ca, Mg, Ba, etc.), and less rapidly by salts of trivalent metals, etc., but not by alkalis. The conditions of coagulation, which are not identical with different FIG. 403. varieties of latex, are in general related to the quality of the rubber The best quality (Para rubber) is obtained by drying superposed thin layers of yielded. fresh latex in a mould by means of hot gases until about a hundred layers, each about 0-5 mm. in thickness, are obtained. The commoner qualities are set by the heat of the sun, with addition of acid and water ; the electrolytic separation of rubber has also been suggested (Ger. Pat. 218,927, 1908), but better results appear to be obtained with HF or C0 2 (Pahl, Ger. Pat. 237,789, 1910) or with formalin or a trace of mercuric chloride. Various
plant juices, salt solutions, soap solution, etc., are also used. The ideal coagulant should leave the proteins unchanged and should form harmless Such substances as acetic acid do not answer these salts with the mineral constituents. requirements. The coagulating action of smoke, used by the natives, is due to the carbon dioxide present, this being, unlike other coagulants, harmless in excess. Frank and Marckwald (1912) obtain good results with tannin. Coagulation by heating in churns or by centrifugation is spreading nowadays. To preserve the latex and prevent oxidation, the
addition of 4 grms. of hydrosulphite per
litre

has been suggested.

:

The coagulated rubber is marketed in different forms * and is distinguished as American (Brazil, Mexico), African (tropical, iSast and West Africa), and Asiatic (Malay States, Polynesia, etc. ). All these forms are brown or almost black outside but pale brown or almost
white
inside.

odour. It is highly gr. 0-91 to 0-97 and is of more or less unpleasant ordinary temperatures but only slightly so at 0. When pasted for some time at 60 it becomes plastic and loses its elasticity, which is regained at ordinary temperatures.
elastic at
1 Eubber is sold as crfpe, balls (10 to 50 kilos) and marbles (3 to 5 kilos), sheets, laces, flats, buttons, cakes or biscuits, scraps or niggers, stripe, twists, clusters, thimbles, flakes and lumps.

Raw Rubber has sp.

VULCANISATION OF RUBBER
At 100
it

700

becomes

soft,

and at 140

viscous,

and at 180

it

melts, the original properties

being regained only slowly at ordinary temperature. It is a good electrical insulator, is insoluble in cold water, and swells in hot water or alcohol ; it swells even more and dissolves slightly in carbon bisulphide, benzine, ether or oil of turpentine, and completely in rubber oil obtained by the dry distillation of rubber. It resists the action of alkalies and
dilute acids, but in the air oxidises slowly at the surface, undergoing resinification becoming friable. When heated it dissolves considerable amounts of sulphur, assuming

and

new

for many purposes (see later, Vulcanisation). properties which render possible its application Treatment of Rubber. The raw product is softened in hot water and then repeatedly subjected to great pressure between iron rollers revolving at different rates, impurities

being washed away by means of a water spray. The loss attending this treatment amounts to 10 to 40 per cent. The product is then masticated to give a homogeneous mass free from pores. Strips are placed in a stationary, horizontal drum inside which a second drum, furnished with teeth or veins, and heated internally, revolves eccentrically. During this treatment and
the succeeding passage of the rubber between two tepid cylinders rotating at different 50 per cent.) the rates, the various mineral filling materials for colouring or weighting (10 to rubber may be introduced, together with the necessary amount of sulphur (4 to 15 per use is made of antimony or mercury cent.) for the subsequent vulcanisation. For colouring zinc white, lithopone, gypsum, talc, or barium ferric oxide, ochre, cinnabar, sulphate, 1 Other additions are also made for chalk, kaolin, magnesia, etc., being employed an fillers.
obtaining the various qualities of rubber required for making different articles. Rubber thus prepared is then vulcanised, the strength and elasticity being thus enhanced, and the rubber rendered more stable towards changes of temperature and to oxidation. Vulcanised rubber is not soluble at ordinary temperatures in the usual solvents of raw rubber, is not tacky in the cold, is almost impervious to water, and more resistant towards - 20" and -f 120. acids, alkalies and the air, and maintains its elasticity between

Dichloroethylene (dieline, see p. 122) forms a good solvent for it. Vulcanisation with sulphur was suggested in 1839 by (Joodyear and by Hancock, the rubber being mixed with sulphur and heated at 120 to 140. Addition of various substances (oxides of lead, zinc, magnesium, calcium, etc.) in small amounts as accelerators of vulcanisation has been proposed, and nowadays the time required is considerably shortened by means of organic accelerators, e.y. piperidine, aldehyde-ammonias, ;>-phenylenediamine,
t

the nitroso-derivatives of dimethylaniline, diphenylamine, methylaniline, etc., or, better, the dithio-derivativcs of imino-bascs, e.g., dimcthylammonium dinielhyldithiooarbamate

and piperidine piperidyldithiocarbamate (Bayer,

1915).

A system of rapid vulcanisation,

so-called
1

long

known and widespread

at the present time,

is

the

coM

rulcanisatiou.'

combined during vulcanisation and also increases the tenacity and resistance to torsion, further addition being without effect. Magnesia behaves almost like zinc oxide, but talc is indifferent
or harmful.
2

Addition of 0-5 per cent, of zinc oxide to rubber increases by 0-20 per cent, the sulphur

in a solution of sulphur chloride in carbon disulphide. Henriques (1893) showed that the sulphur Later, chloride combines with the rubber, this result being confirmed by Weber (1894). 1 mol. of the Hinrichsen, Kindscher and Bernstein found that 2 mols. of rubber unite with the addition taking place chloride, giving the compound (C 10 1() ) 2 , 8,01, (15 per cent, of S), Since, however, a rubber in the same way as that of sulphur chloride to ethylene, amylene, etc. hard and brittle, the chemical containing 5 per cent, of sulphur is over- vulcanised, that is,

Rapid cold vulcanisation, proposed by Parkcs

in 184(>, consists in

immersing the rubber

interpretation of the phenomenon is insufficient. E. Stern (1909) holds that the quantity of sulphur fixed is variable, while Ostwald (1910) of the colloidal rubber, and assumes that explains vulcanisation as an adsorption phenomenon be the sulphur forms a series of reaction products, the first and last members of which cannot Other explanations have been advanced by isolated, and that the process is partly reversible. etc. Spence and Young (1912), Skcllon (1913), Bisow, Bruni and Amadori (1919), In practice, use is made of 2 to 4 per cent, solutions of sulphur chloride in carbon disulphide The rubber articles arc immersed in the solution for a few seconds or benzine, which is safer. or minutes, according to the thickness of the material and the degree of vulcanisation required. Small and thin objects may be readily vulcanised in the vapour of sulphur chloride, rendered more volatile with a little carbon tetrachloride. Peachey (Kng. Pat, 129,82(5, 1919) obtains nascent sulphur within the rubber vulcanisation in the cold and

rapid

by

(1920),

alternate treatments with hydrogen sulphide and sulphur dioxide. In general, the sulphur chloride process gives a too superficial vulcanisation. Bruni's process which appears more satisfactory, consists in forming in- the rubber thiocarbamlides or

complete

by producing

710

ORGANIC CHEMISTRY

With age, rubber (tubing, etc.) becomes hard and brittle, and cracks. According to Wo. Ostwald(Ger. Pat. 221,310 of 1908), it lasts longer if quinoline, aniline, dimethylaniline, etc., is used in its preparation. Introduction of excess of sulphur during vulcanisation causes rubber to deteriorate more easily in the air; in some cases the excess of sulphur is eliminated by treatment with hot soda solution. Small articles keep well in closed vessels containing petroleum. In the regeneration of rubber from old vulcanised articles, the material is freed as far as possible from vegetable and mineral impurities and from any portions containing textile fabric. The necessary removal of the sulphur cannot be effected by solvents, which dissolve only the free sulphur. The sulphur compound of rubber consists of a more or less highly condensed product of C 10 H 16 with G 10 16 S 2 (or S 2C12 ), and many processes have been devised for the removal of the sulphur from this complex. Rubber rich in combined sulphur, i.e., hard rubber (ebonite) is not readily devulcanised and is usually powdered and used in making fresh ebonite. If not too hard, rubber free from fabric is disintegrated and impregnated while hot with fatty or mineral oils, paraffin wax, etc., the resulting product being mixed and passed between hot rollers so as to obtain elastic sheets.

Waste containing fabric (goloshes, tyres, etc.) is occasionally treated mechanically, being powdered and then winnowed to eliminate the particles of fabric. Such separation is, however, imperfect and it is preferable to dissolve out the rubber rather than the fibres by means of solvents. The Mitchell process consists in dissolving the fibre in hot 65 to 70 per cent, sulphuric acid, the mass being washed with water and dilute caustic soda and then rendered plastic by steam and hot rollers ; this procedure does not, however, remove mineral constituents (chalk, zinc oxide, etc.). The alkaline process suggested by Marks (1899) gives better results, and consists in heating the waste rubber with 10 per cent, caustic soda under pressure, the hydrocellulose being removed and the residual rubber Well washed and rolled hot ; the caustic soda dissolves also fatty oils (i.e., of factis). In the processes of the other class, the rubber is dissolved in hot benzene or its homologucs or certain chloro-compounds (dicline), the extraction being carried out in ordinary extractors
or in autoclaves.

According to Hinrichsen and Kindscher (1912) cold vulcanised rubber may be completely desulphurised by heating it for several days in a reflux apparatus with alcoholic caustic soda and scrap copper, and hot vulcanised rubber by heating, in a copper-lined
suggested.

Various other methods have also been autoclave, with benzene, caustic soda and zinc. Sachs (Ger. Pat. 275,061, 1913) utilises old powdered rubber by mixing it with 20 per cent, of colza oil and 50 per cent, of magnesium sulphite and heating at a pressure

20 to 30 hours. Regenerated rubber contains at most 80 per cent, of true rubber and sometimes only 25 to 30 per cent., but is little inferior to virgin rubber. The coefficient of vulcaniantwn, that is, the amount of combined sulphur per 100 parts of rubber, does not exceed 4 to 5 in
of 5 to 7 atmos. for

recovered rubber.

USES OF RUBBER.

Rubber

is

used in enormous quantities in making tyres, water-

proof fabrics, horse shoes, gloves, hosepipes, floor coverings, artificial leather and sponges, l toys, etc. Mixed with guttapercha and sawdust it is used to make kamptulicon, and large amounts are utilised in the manufacture of ebonite. 2
( S(NH other disubstituted aromatic thioureas, e.g., 2C 6 6 -NH 2 2S <\ H 5 ) 2 , the OS, action being accelerated by sulphur or zinc oxide. Romani (1920) finds that tetra-alkylthiouram disiilphidcs, c .</., (OH 3 ) 2 CS 8 8 08 N(CH 3 ) 2 , form ultra-auto-accelerators, as they vulcanise in 15 minutes at 145 in presence of zinc oxide, addition of free sulphur being unnecessary. Scott and Bedford (1920), who obtained the same results as Bruni (see cdiove) by using formation of zinc piperidine in place of aniline, attribute the accelerating action to the

=H

piperidyldithiocarbamate. 1 GUTTAPERCHA resembles rubber, but is more resinous and is obtained from the latex of various plants of the Sapotaceae family growing in Singapore, Malacca, Borneo, Sumatra, Java, Banca, etc. It occurs to the extent of 10 to 12 per cent, also in the trunk, branches and leaves and may be extracted by means of solvents such as toluene, petroleum ether, carbon Between 45 and 60 Its specific gravity is about 0-97 or, when rolled, up to 1-02. disulphide. It melts it is highly plastic and may be drawn into thin threads and welds readily with itself. at about 120 and at higher temperatures decomposes, giving a repulsive odour. It is a bad conductor of heat and electricity, and becomes electrified when rubbed. It dissolves in benzene, chloroform, oil of turpentine, etc., and to a slight extent in alcohol, ether and petroleum ether, but is insoluble in water. It resists the action of dilute acids. 15 per Guttapercha contains 76 to 84 per cent, of gutta (a solid hydrocarbon, m.-pt. 53), 14 to

For

this

note see next page.

SYNTHETIC RUBBER
SYNTHETIC
or

711

ARTIFICIAL RUBBER must not be confused with rubber substitutes. 1 During the European War large plant was erected at the works of Fr. Bayor at Leverkusen for the production of 2000 tons of synthetic msthyl rubber per annum. When the war ceased the manufacture was abandoned owing to the enormous increase in the production of natural rubber and to the low prices prevailing.
The chemical constitution of the hydrocarbon of rubber, C 10 H was determined by 18 Harries (1905) by means of its ozonide, C 10 H 16 O 6 which decomposes into levulinic aldehyde, so that the hydrocarbon must be regarded as derived from an 8 -carbon atom ring (a
,

CH 3 C CH 2 CH 2 CH
-

ring never yet

found in natural products);

results of later

||

||

CH-CH 2 -CH 2 -C-CH 3

The
yields,

(dimethylcyclo-

work (1907-1914) led Harries to abandon this formula, octadiene). since decomposition of the ozonide of a-iso-rubber (obtained by heating the hydrochloride of rubber with pyridine under pressure) besides levulinio also marked
aldehyde,
quantities of diacctylpropane, undecatrione, pentadecatetrone, formic, levulinic and hydrochelidonic acids, etc. These products, CO [CH 2 ] 3 especially the pentadecatetrone, 3 CO [CH 2 ] 3 CO [CH 2 1 3 CO 3 exclude the view that the nucleus of rubber is formed from an 8-carbon atom ring, rings of 12 or 16 atoms being ruled out for other reasons.

CH

CH

Most probably rubber contains a ring

isomerides
:

of

20 carbon atoms, which

may

yield

numerous

CH 3
-

CH 3
-CH 2 C
:
-

CH CH CHv /CHa-C^CH \CH C CH2 CH2 CH C CH, CH 2 CH/ CH 3 CH 3

2
: :

'

The molecular weight

acid, formerly used) is 535,

rubber would be a pcntamethylcycloeicosanediene. Butadiene rubber will not contain the five methyl groups, whereas dimethylbutadieno rubber will contain ten methyl groups, numerous isomerides being possible in both cases. In 1909 Harries and Hoffmann obtained an artificial rubber by polymerising isoprene in presence of glacial acetic acid in scaled tubes at 100 but the (2C H H (C 10 16 )
:
fi

of the corresponding penta-ozonide in benzene (in place of acetic approximating to the formula C 25 40 O 16 so that isoprene

')

process
1

is

too expensive to be used industrially.

The firm

of

Bayer (Elberfeld)

also obtained

SUBSTITUTES. Many of these have been prepared, but the only one of much practical importanee is the so-called faclis, of which two types are on the market white and brown or black. The latter is made by boiling rape oil or linseed oil in an open vessel for two hours, cooling, and passing a current of air through it for 36 hours. It is then vulcanised by adding 2 per cent, of flowers of sulphur, heating for two hours at 140, adding a further 1 per cent of sulphur, and raising the temperature to 150, when it White factis is obtained begins to rise. by treating the oil with 20 to 25 per cent, of sulphur chloride (free from dichloride) ; the energy of the reaction may be modilied the chloride dissolved in carbon disulphide. by adding sulphur The mass is obtained in sheets or blocks by pouring it immediately on to cold metal plates or moulds. These substitutes are almost as elastic as rubber and are used to adulterate rubber ; they are insoluble in water or acid, but dissolve slightly in dilute alkali. They are distinguished from rubber by being saponifiable with alcoholic potash.
:

RUBBER

cent, of albanan (white, crystalline substance, m.-pt. 195, soluble in hot alcohol, ir and 6 to 4 per cent, of fluavil (yellowish resin, m.-pt. 110, soluble in cold alcohol). It is used as an electrical insulator, for making tubing and vessels resistant to alkalis and dilute acids, for making mastics and varnishes, and also in electroplating, as it takes the finest It yields vulcanised products like rubber and hard materials like ebonite. impressions. It costs rather less than rubber.

BALATA, similar to guttapercha, is obtained from the latex of Mimuaops balata (Sapotacca?), a large tree of Venezuela, Brazil and, especially, British and Dutch Guiana. It is used as an insulating material and for making waterproof shoes and power transmission belts. Its price is about one-half that of rubber. 2 is EBONITE obtained by mixing rubber with 30 to 40 per cent, of sulphur and with various mineral substances (zinc sulphide, chalk, lead carbonate, heavy spar, magnesia, pigments, etc.), compressing the material in moulds, coating the objects with tinfoil and vulcanising at 130 to 150
for

some days.

hard brown or black material, which is a poor electrical conductor, expands considerably heated, and is resistant towards alkalis and dilute acids. Under pressure the various solvents dissolve first the sulphur and then the rubber, the mineral matter It may remaining. be turned in the lathe and polishes well, and becomes plastic when warmed. It is used for making many varied articles (boxes, combs, buttons, accumulator boxes, gramophone discs, knife handles, mixed with emery it is used for artificial grindstones). batons, etc.
It is a

when

712
artificial

ORGANIC CHEMISTRY
H
;

and 235,686

rubber from isoprene and from erythrene G4 6 (see p. 109 also Ger. Pat. 235,423 of 1909 and Fr. Pat. 425,582 of 1911), by prolonged heating in presence of benzene, etc., but this product is also very expensive. The Badische Anilin- und Soda-Fabrik ( Ludwigshafen) obtained rubber by heating

isoprene and dimethylbutadiene (Fr. Pats. 417,170 and 417,768 and Eng. Pat. 14,281 of 1910) in presence of alkali, which has a polymerising action. Contrary to Weber's statement, Hinrichsen (1909) showed that the latex of rubber trees does not contain diterpenes,

which polymerise to form rubber, but that the latter exists ready formed in the latex. Synthetic rubber obtained from the isoprene formed on decomposition of turpentine, cannot be vulcanised (unless a little natural rubber is added), whereas that obtained from
the isoprene of rubber is vulcanised with less difficulty. The polymerising action of sodium on isoprene which yields rubber even in the cold, was discovered by Matthews in 1910 and by Harries shortly afterwards. 1
>

STATISTICS

AND

PRICES.

tons, but after 1860, when methods of vulcanisation began to increase enormously.

In 1840 the world's consumption of rubber was only 400 had been studied, the consumption

The World's output was as follows

:

of rubber (in tons)

from the old

forests

and the new plantations

1 ISOPRENE is obtained in 25 per cent, yield by heating oil of turpentine, as proposed by Tilden. By working under reduced pressure and first preparing dipentene, Stand inger and (iottlob raised the yield to (}5 per cent., but even then the supply of oil of turpentine is inadequate and its price too high. On this account the firm of Fr. Bayer prepared isoprene by treating acetone and its hornologues with formaldehyde and dimethylamine so as to obtain methylamino oxides which, by the further action of methyl halides and subsequent decomposition of the resulting ammonium compounds, lead to isoprene. The Badische Anilin- und Soda-Fabrik obtained isoprene by converting amyl alcohol into

trimethylethylene, chlorinating in a vacuum, and removing 2HC1 catalytically ; this process depends on a supply of amyl alcohol, which is formed in small amount during alcoholic fermentation. Trimethylethylene was then obtained quantitatively from the pentane, isopentane and

tetramethylmethane occurring in petroleum. Polymerisation of isoprene, by either heat or sodium, yields an abnormal rubber which vulcanises incompletely and has, as fundamental constituent, a hydrocarbon different from that of natural rubber, and is partially soluble in benzene. The Badische Company obtained from isoprene normal rubber, which is insoluble in or only slightly swollen by benzene and exhibits great tenacity, by two different methods: (1) by treating isoprene with the ozonide of terpenes or other unsaturated compounds, a good yield of so-called ozone rubber is obtained (2) by condensing with sodium in presence of (<().,, carbon tliojrMc rubber being thus formed. The differences between the various artificial rubbers probably depend on differences in the degree of polymerisation. Of interest also are the methods of obtaining isoprene by pyrogenio decomposition of crude petroleum and its residues, although all the petroleum in the world would not yield more than 10 per cent, of the rubber derived from plantations.
;

The preparation of ^-dimethyl butadiene, ( 2 C(CH 3 ) ( '(OH.,) CH 2 by converting acetylene successively into ac*et aldehyde, acetic acid and acetone, this by reduction (with aluminium and acetic acid) giving pinacone and the latter, by dehydration, dimethylbutadiene polymerisation The same is the case of which yields methyl rubbfr, is not economically practicable nowadays. with the preparation of isoprene from isopentane (2-methylbutane) by the following stages > trimethylethylene (amylenc or pental), C((JH 3 ) 2 CH CH 3 (by chloroisopentane (with Cl) > dichloroisopentane (with 01), which, if passed as vapour over alumina at 400, red-hot lime) gives isoprene or isomerides which yield isoprene when heated with catalysts. The practical difficulties encountered in the Bayer works at Leverkusen were very groat, and only at the beginning of 1918 was a methyl rubber (polymerised in the cold) obtained which yielded a good ebonite and a methyl rubber VV (polymerised hot), which resembled natural rubber somewhat also in its behaviour towards solvents, and served for making tyres and rubbered fabrics. The polymerisation occupied, however, as much as three months the vulcanisation was completed by means of various accelerators (see, above), such as piperidine or, better,
1

p-phenylenediamine, //-aminoazobenzene, toluidine, etc., which also protect the rubber against atmospheric oxidation. Substances capable of increasing the elasticity of these synthetic; rubbers may also be added.

OXYTERPENES
The consumption
;
;
:

713

United States, in tons in different countries in 1920 (1919) was Great Britain, 25,000 (33,000) France, 14,000 (22,000) ; Italy, 6000 Canada, 11,000 (9500) ; Australia and Japan, 9000 (10,000) (14,000) Germany, Russia and Austria, 9000 (5500) Scandinavia, 6000 (3500) Belgium, 2000 (2000) ; various other countries, 1000 (3500). Experts calculate that the total output of rubber will be about 420,000 tons in 1922, 470,000 in 1923, 520,000 in 1924, and almost 600,000 tons in 1925, in spite of restrictions
220,000 (230,000)
; ; ; ;

of the principal producers. price of rubber has fallen greatly in recent years, owing to increased output diminished demand, and in 1921 was less than la. and in March, 1922, Sd. per Ib.

imposed by an association

The

and

OXYTERPENES
Other hydrocarbons related to the terpenes are
the formula,
principle of
:

ionenn

and

irene,

two isomerides
i.e.,

of

C 13 H 18

the ketones of which,

C 13 H

2(I

O, are irone and ionone,

the aromatic

having a marked violet smell. essence of violets) was prepared synthetically by Tiemann and Krtiger in 1883 by shaking equal proportions of citral and acetone with barium hydroxide solution, extracting with ether arid expelling the latter by evaporation. The fraction of the residue boiling at 138 to 155 is pseudoionone, which is transformed into the isomoric ionone by the action of dilute acid (Ger. Pat. 75,120). According to Ger. Pat. 113,672, the condensation may be effected by water in an autoclave at 170, while in presence of sodamidc it takes place at the ordinary temperature (Ger. Pat. 147,839). Ree
iris

root,

IONONE

(Artificial

aho Ger. Pat, 138,939. The constitution of synthetic ionone

is

represented by the annexed formula

CH, OH,

CX

^CH CH CH CO CH,
:

CH.

CH
Ionone (100 per cent.) cost before the war 152 per kilo, cent, solutions were sold at one-fifth of these prices.
is

and

fi-ionone,

60

the 20 per

MUSCONE, C 15 H 2H O or C 16 H 30 0, is the odoriferous component of natural musk, which obtained from a pouch situated behind the navel of the male musk-deer (Mosckus moschiCochin China, ferus), living in the mountains of Central Asia (Thibet, Tartary, Siberia, Tonkin, China). The entire pouches are placed on the market and weigh 20 to 40 grins., 60 per cent, consisting of musk. Of the latter, 60 to 70 per cent, dissolves in water (and effervesces with acids), 10 to 12 per cent, in alcohol, and very little in ether, chloroform or
the moisture amounts to 15 per cent, and the ash to 8 per cent. Musk contains ammonium carbonate and 0-5 to 2 per cent, of a volatile oil which distils in steam and forms mmcom (density 0-9268, rotation -f 10, b.-pt. 330), which is a ketoiie and has a very intense, pure odour of musk. Before the war, Tonkin musk in the pouch

benzene

fats,

albuminoids,

was

sold at about

terated.

The

price

fell

140 per kilo and Siberian at less than 80. Musk is often largely adul1 a* a result of the manufacture of artificial mu?k.

1 has not the composition of muacone, but has the same marked ARTIFICIAL odour, although a little less delicate. It was prepared by Baur in 1888, and manufactured by the .Fabriques de Produits Chimiqucs de Thanu et de Mulhouao, by introducing into *-trimtro-

MUSK

toluene

the

tert. -butyl

group, the constitution being:

N0 2 CH 3 /

_ C(CH

3) a
.

^>N0 2

Of the many

N02
chemically analogous products very few have the musk odour, among these being xylol musk, obtained by condensing m-xylcno with tert. isobutyl chloride in presence of aluminium chloride and nitrating the pseudobutyl-wi-xylol thus formed. The purified product has m.-pt. 113 and, diluted with nine times its weight of acetanilide to attenuate the excessively powerful perfume, was at first sold at 100 per kilo, natural musk then costing 200 per kilo. Various similar products have been made. 46 VOL. IT.

714

ORGANIC CHEMISTRY
CAMPHORS

While the terpenes are liquids, the camphors are generally solid. They contain alcoholic or ketonic oxygen and the principal ones with a single ring are Methone, C 10 18 0, and Terpinol with the same formula, while Menthol and Carvomenthol are C10 20 0, and Terpin C 10 20 2 Among the camphors with complex rings are true Camphor, Fenchone, and Carone, C O, and
:

Borneol,

C 10H 18 0.

10

H1G

The camphors poorer in hydrogen and oxygen contain double linkings, form additive products, and are readily oxidised, while the others behave like saturated compounds. When reduced with sodium, the ketonic camphors yield the alcoholic camphors, which are converted into the former on oxidation. It is possible to pass from the camphors to the tei penes by way of the chlorides, and reduction of the alcoholic camphors often gives the terpene hydrocarbons. Thus, Terpane (liemhydrocymcne) can be obtained by reducing the Terpanol (menthol, C 30 20 0), which contains a hydroxyl or secondary alcoholic group, this being transformed

by oxidation into the ketonic group with formation of Terpanone (twnthone)? so that the hydroxy] should be in the ortho-position with respect to the CH 3 and C 3 7 groups, as is shown below in the constitutional formulae. On the other

hand, since Carvacrol, C 6 H 3 (OH)(CII 3 )(C 3 7 ) (isomeric with carvone or carvol) of known constitution, gives on reduction a terpanol (carvomenthol, with the hydroxyl in the position 2) different from that of menthol, the hydroxyl of the latter must be in position 3
:

21

CIT,

II

CH,

II

H
\II(OH)

CII,

H, II(OH)

H
o

H/
H,

H, C 3H 7

H
which
it

C 3H 7
Menthol

3 7 Mer.tboue

Carvomenthol
Ci
ll 20

(terpanol),

C 10 lI 2 oO

(terpanone),

Carvomerithone, Ci 18

peppermint, from can be obtained crystalline by cooling. It melts at 42, boils at 213, and has the strong odour of peppermint. The position of the OH is established by the fact that, with bromine in chloroform solution, menthone (which is the corresponding ketone, boiling at 207, and also having a strong smell of peppermint) gives dibromomenthone, and elimination
oil of

MENTHOL

(3-Terpanol), C 10

H 19 OH,

occurs in abundance in

of

2HBr from the

latter gives

thymol having the known constitution, C 3 H 7<^

OH'
the

CH 3 and OH
of

are here undoubtedly in the meta-position, since elimination of the

C 3H 7

by means
cymerie.

P 2 O5

Four

When heated with copper sulphate, menthol yields yields ra-cresol. isomerides of menthol are possible theoretically. It is used as an anaesthetic
Its alcoholic solution is laevo-rotatory.

and as a

disinfectant.

(3-Terpanone or 3-Menthanone), C 10 H 18 O, is formed by oxidation of menthol with bichromate and sulphuric acid and yields menthol again when reduced with sodium. It is also found in peppermint oil and is a liquid, b.-pt. 207, with a delicate peppermint odour. It may be converted into thymol.

MENTHONE

PULEGONE
It

(A
is

pulegium).

is

-Terpen-3-one), C 10 H 16 0, predominates in oil of pennyroyal (Mentha a ketone boiling at J22, and on reduction gives menthol, so that the
4(8)
:

carbonyl group

in position 3.

CARVONE (Carvol or Terpadien-2-one), C 10 H 14 O, is a ketone giving Carvoxime, C 10 H 14 NOH, which exists in optical isomerides and is identical with nitrosolimonene. It forms
1

menthone
(p. 252).

Ciamician and Silber (1910) showed that, in alcoholic solution and under the action of light, is hydrolysed with formation of decoic acid, and an aldehyde isomeric with citr ndlal

TERPIN
the principal component of cumin oil, boils at 228, and C 10 13 OH, when heated with potash or phosphoric acid
is

715
converted into Carvacrol,

/\ CH CO II CH, CH
CH
I

/\ CH C
>
I

OH

CH CH

CH 3 - CH - CH 3
Carvacrol

TERPENOL (A -Terpen-l-ol), C 10 H 1K 0, melts at 70, and, like tetramethylethylene, forms a solid blue nitrosochloridc, the double linking being in the 4(8) -posit ion, between two tertiary carbon atoms. TERPINEOL (A^Terpen-S-ol), C 10 H 18 6, melts at 35, boils at 218, and is known in the form of various optically active isomerides. It has a pleasing odour of lily of the valley, lilac and cyclamen, and occurs in ethereal oils. With sulphuric acid it forms terpin hydrate,
4H)

which

is

also converted
(1
:

back into terpineol by sulphuric

acid.

Terpin hydrate, C 10 20 O 2 ,H 2 0, is slowly 8-Terpandiol), C 10 18 (OH) 2 formed from oil of turpentine, C 10 16 , in contact with dilute nitric acid and alcohol. This of 2 O, anhydrous terpin distilling crystalline hydrate melts at 117 and then loses 1 mol. over at 258. This is optically inactive and is not obtainable in active modifications, so that the presence of asymmetric carbon atoms is excluded. The hydrate is obtainable also from geraniol by the prolonged action of 5 per cent, sulphuric acid, 2H 2 O being added at

TERPIN

the double linkings

CH,

V
g

CH 3

CH 3

CH 3 CH 3 C OH
I

CH 3 C OH

CH
CH 2 CH 2 OH

CH 2
i

CH
-

II

"

"

ftvr vti

^ii
2

/ CH CH

OH
^

/\ CH CH
w n
2
i
I

V
CH 3
(Joraniol

V
CH,

OH

CH 3 OH
Terpin
:

Terpin hydrate

Nitric acid oxidises terpin, giving Terebic Acid,

which has the known constitution

C0 2 H
(CH 3
)2 :

C CH CH 2
-

be so that the position 8 must be occupied by a hydroxyl ; the other hydroxyl can only obtained. be would atom carbon an otherwise since asymmetric 1, from the CINEOL, C 10 18 O, has the constitution of terpiii less 2 O, which is eliminated 8. two hydroxyls, an atom of oxygen thus remaining united to the two carbon atoms 1 and oil of in and oil in in abundance occurs and 176 eucalyptus Cineol melts at 1, boils at
in position

wormseed.

FENCHONE, C 10 H 16 O. The
It is a ketone similar to

dextro-form occurs in fennel

oil

and the

laevo in thuja oil.

camphor and can be converted

into Fenchene.

462

716

ORGANIC CHEMISTRY

CAMPHOR (ordinary camphor, laurel camphor, or Japan Camphor), C 10H 16O, the constituent which separates in the solid form from the essential oil of Laurus camphora, a tree which is cultivated in China, Japan, and Formosa,
is

and grows well in Southern Europe (Italy). The wood (thirty to forty years old) is chopped up and boiled with water until the camphor floats at the surface on cooling, the crude camphor sets to a solid mass, which can readily be separated. In some cases the camphor is distilled The yield is about directly from the wood in a current of steam. 1 kilo per quintal of wood. The crude product is refined by mixing with quicklime and charcoal and subliming at a gentle heat. It is obtained thus as a white, crystalline, and not very hard mass, which has a characteristic odour, and partially sublimes at the ordinary temperature. It melts at 178, boils at 207, and has the sp. gr. 0-922-0-995 (the finer Borneo camphor has sp. gr. 1 -10). In alcoholic solution it is more or less dextro-rotatory, according to its origin, but malricaria, camphor (from the leaves of feverfew,
;

Malricaria 'parthenium) is Isevo-rotatory. With iodine in the hot it forms carvacrol

nitric acid gives

Camphoric Acid, C 8 H 14 (C0 2 H 2 ), which exists in two active and two inactive forms. Further oxidation yields Camphoronic Acid, Ci,H 14 O 6 which gives trimethylsuccinic acid on dry distillation. When distilled with P 2 5 camphor loses H 2 and forms cyinene. On reduction with nascent hydrogen, ordinary camphor gives Borneol (Borneo camphor), C 10II 17 -OH, which melts at 208, boils at 212, and when oxidised gives ordinary camphor, which it strongly resembles., Between I860 and 1893 various constitutional formula) for camphor were proposed by Kekule, Armstrong, Bredt (1884), and (4. Oddo (1891), the last of whom gave a formula which explained well all the reactions and properties observed up to that time. More and more acceptable constitutions were given by Widmann (1891), Collie (1892), Bouveault (1892), etc., and finally by Bredt (1893). The conslituiion of camphor now seems to be definitely established as the result of various syntheses, especially that from ethyl oxalate and ethyl /?/?-dimethylglutarate, two compounds which are obtainable synthetically from
,

(see above),

while oxidation with

their elements. The various stages in this synthesis are as follow, the alkyl group
:

R indicating
C0 2R

COOR

H CH C0 R
-

CO

CH C0 2R

CO

CII

CH 3 C CH 3
COOR
Kthyl oxalate

CH 3 -C-CII 3
CO
ISthyl

CH 3 C CH 3
JO - C( CO-C(CH 3 -C0 2 R
)

II
Ethyl

CII

C0 2R
CH,
CH.J

CH C0 2R
dikctoapo-

glutarate

camphorate

Ethyl dikctocamphoratc

CH
C Ho

CH
C
-

C0 2R

CH
C

CH
CH.j

CII 2

CH

CII 2

ON

CH

CH 3 CH 2

CH 3
C(CH 3 -C0 2H
)

CH 2

C(CHj)

C0 2R CH 2

C(CH 3 ) C
Campholidu

Ethyl camphorato

Honiocamphorio

nitrite

CH 2

CH CH 2 C0 2H

CH

CH-

-CH 2

CH u C C H 3 CH 2
3) 2 llomocamphoric acid

CH 3 C CH 3
C0

C(CH

CH 8

C(CH 3 )
Camphor

CH
a

CELLULOID
still

717

This constitutional formula proposed for a-camphor by Bredt, although contested, is the one generally accepted by chemists, since it corresponds best with most of the reactions of camphor. In 1911, Bredt and Hilbing prepared ^-camphor, containing the CO group .in the /J-position, from bomylenecarboxylic acid ; it melts at 182 and boils at 2134. Camphor forms strongly rotating energetic sulphonic acids, e.g.,
-

S0 3H

which are able to resolve many racemic compounds into

their active components.

Owing to the continually increasing demand for camphor, especially for 1 making celluloid, and since many terpenes give camphor when oxidised, many
,

attempts have been made to prepare artificial camphor from oil of turpentine. The latter contains pinene, C 10H 1R which is readily convertible into borneol, C 10 H17 OH, or isoborneol, this giving the inactive racemic compound corresponding with natural camphor on oxidation.
According to Ger. Pat. 134,553, when anhydrous turpentine is heated for a long time at 120 to 130 with dry oxalic acid, a mixture of camphor with pinyl formate and oxalato is obtained ; after washing with water, the latter are hydrolysed with alkali and the resultant borneol converted into camphor by oxidation with diehromate and sulphuric
acid.

At MonviJIe, near Rouen, a factory was erected in 1906 to manufacture artificial camphor by the process described in FT. Pat. 349,896 (of Behal, Magnier, and Tissier, and similar to U.S. Pat. 779,377) A mixture of oil of turpentine and salicylic acid is heated and,
:

after elimination of the excess of the reagents, the isoborneol ether is hydrolysed to a mixture of borneol and- isoborneol. Another factory, near Calais, utilises Sobering' s method
(Fr. Pat. 341,513), already in use on a large scale in Berlin, and also applied in a factory established in 1909 in Finland.

According to Fr. Pat. 349,852, pinene hydrochloride is first prepared and then heated under pressure with lead acetate in acetic acid solution, thus giving camphene, which with permanganate forms camphor or treatment of the pinene hydrochloride with a formate gives the formic ester of borneol, which can be readily hydrolysed. The final oxidation to obtain camphor is carried out in various ways by oxidising the borneol, in benzene or petroleum ether solution, with aqueous alkaline permanganate (Uer. Pat. 157,590), or by means of ozone, air, or chlorine water (see Kng. Pat. 28,036 of 1907 and C<er. Pats. 166,722
; :

CELLULOID

is

obtained by mixing nitrocellulose and camphor in the following manner

well-stabilised, powdered, and partially dried collodion-cotton (with 10 to 11 per cent. N; see p. 29 !) is soaked in alcohol in a covered centrifuge, then gelatinised with alcohol and one-third or one-fourth of its weight of camphor, coloured, if necessary, homogenised between rolls and

then tormcd into dense,. compact blocks by pressing while hot. It is then ready to be cut, sawn, compressed, polished, etc., its marked plasticity when hot being utilised in working it. It is a homogeneous, transparent, colourless, or yellowish substance without taste and of sp. gr. 1-37. If sufficiently dry it is odourless, but, when rubbed or heated, it develops a slight smell of camphor. It is a very bad conductor of heat and electricity, and its elasticity is about equal to that of
ivory. Celluloid
is used for making toys, halls, combs, walking-stick handles, tortoiseshell objects It has the disadvantage of burning (substitutes for tortoiseshell, amber, ebonite, etc.), films, etc. rapidly and energetically (without exploding) when brought into contact with an ignited or If the collodion-cotton used is well stabilised, celluloid will withstand incandescent body. a temperature of* 125 or even higher. It can be charged with mineral substances to render it less inflammable and heavier. ARTIFICIAL LEATHERS. Celluloid is used to some extent in making artificial leather, the commonest types of these being: (1) Pegnwrid. This is obtained by spreading on cotton so as to form a soft, fabrics a solution of celluloid in ethyl or methyl alcohol mixed with castor oil elastic paste, which may be coloured by aniline dyes or pigments. By means of incised rollers substitute for pegamoid may bo made imitations of different leathers may be obtained. by spreading on the fabric a dense glue solution and then treating the surface with formaldehyde consistent and insoluble the surface may afterwards be made which renders the ; solution, glue shiny with a thin layer of celluloid or ccllite (we p. 599). (2) Artificial leather* made by pressing between rollers several layers of fabric impregnated with glue or, better, rubber solution. ArtiHcial leather is also made by reducing scrap leather to fibre, incorporating it, either alone or mixed with other animal or vegetible fibre, with a little boiled linseed oil, and compressing

it

into sheets, which

may

finally

be varnished.

718
and

ORGANIC CHEMISTRY

154,107), or by oxidising isoborneol in aqueous acid solution with permanganate (Ger. Pat. 197,161 of 1906). Camphor was obtained by A. Hesso by means of the Grignard reaction, and it is also 1 formed by fusing borneol with finely divided nickel (191 1).

it

camphor may be distinguished from the. artificial product by mixing the former gives a syrupy intimately with an equal weight of chloral hydrate
Nat.ural
:

with vanillin sulphate or hydromass, but the latter does not liquefy. chloride the two give different colour reactions. About 13 per cent, of the total output of camphor is used for pharmaceutical purposes, 15 per cent, for fireworks, and about 2 per cent, for nightlights, etc., 70 per cent, for making celluloid,
rendering explosives insensitive to shock.
0.
1.

AW

CONDENSED BENZENE NUCLEI

DIPHENYL AND
,

ITS

DERIVATIVES
is

DIPHENYL, C 6H 5 C 6H 5
ethereal solution of

or

/~~~\

/'

formccl

treating an

bromobenzene with sodium ]Fittig), by the transformation of hyclrazobenzene, or by diazotising benzidine and decomposing the resultant a red-hot product. It can also be obtained by passing benzene vapour through
tube. It forms colourless crystals melting at 71 and boiling at 254, and is soluble in alcohol and in ether. On oxidation with chromic acid, it gives benzoic acid, its constitution being thus confirmed. Of monosubstituted products of diphenyl, three isomerides are possible, the carbon joined corresponding with the o-, m-, and ^-positions with respect-to to the second nucleus. Disubstituted derivatives exist in numerous isomeric in general, forms, as the substitution may occur in only one nucleus or in both
;

however, the substituents enter preferably the para-positions.

:

pure, but readily in hot water, ether subliming. It dissolves slightly in cold water, a and base a diacid is It or alcohol. 2 SO 4 sulphate, C 12 H 8 (NH 2 ) 2 gives almost insoluble in water. It is largely used in making substantive dyestuffs (such as flongo red and first diazotised and then chrysamine, which dye cotton without mordants), being combined with naphthylamine or naphthalenesulphonic acids. Crude benzidine cost before the war less than 2s. 6d. per kilo and the pure cost 2s. per kilo and the product 40.s. The crude sulphate in paste (63 per cent.)
,

C6 4 C6 4 BENZIDINE (p jp-Diaminodiphenyl), 2 2 of diphenyl yields p p-dinitrodipheny], which, when reduced with zinc dust in alkaline solution, gives benzidine. The latter may also be obtained by elecalso Ger. Pat. 122,046, according to which trolysis of nitrobenzene; see azobenzene is electrolysed in hydrochloric acid solution in presence of stannous chloride. benzidine forms colourless scales melting at 122 and then When
.

NH

NH

Nitration

pure 28s.

higher homologue of benzidine

is

o-Tolidine,

C 12H 6 (CH 3 ) 2 (NH 2 ) 2 which

,

was noticed that a difficulty ARTIFICIAL CAMPHOR. Before the might bo placed in the way of the further development of the artificial camphor industry by the excessive price of oil of turpentine, this having risen from 5b'x. per quintal in 1000 to 9(5*. Further, these conditions might easily be aggravated by the formation of a trust. in 1906
1

European War

it

diminish in the future, since substitutes are continually being in celluloid, which up to the present has consumed about two-thirds The fact that natural camphor almost entirely monopolised of the total camphor produced. constitutes a menace by the Japanese (Government can be sold, without loss, at 144*. per quintal to the future of artificial camphor, which could never be sold at that price and depends on a raw
the
for camphor' found capable of replacing

demand

may
it

material the price of which cannot be regulated. Since the war, however, conditions have radically changed, and if the high price of camphor does not return to a more normal figure, the production of both natural and artificial camphor may be stimulated.

DIPHENYL METHANE
,

719

melts at 128, and the diazo-compound of which combines with naphthionic acid to form a red substantive dyestufE, benzopurp urine 4B. The dimethoxycompound, (0 CII 3 ) 2 of tolidine is dianisidine, which with a-naphthol-usulphonic acid forms benzoazurine G (substantive blue).

CARBAZOLE,
synthetically

/>NH,

is

found

in

coal-tar,

and can be obtained

..
o-aminodiphenyl over red-hot lime or by gently heating diphenylamine vapour. The unions of the nitrogen with the two phenyl groups are in the diortho-

by

distilling

positions,

Nil,

so that carbazole may be regarded as a pyrrole derivative colourless scales melting at 238 and readily subliming, concentrated sulphuric acid, giving a yellow coloration.

(.see later).

It

forms

and

it

dissolves in

four isomeric dihydroxydiphenyls, diphenyl can be derived: the diphenylsulphonic acids hexadiphenyl oxide, (C 6 4 ) 2 and hydroxydiphenyl, C 12 8 (OH) 6 (the mother-siibstancc of cserulignonc) the diphenylcarboxylic acids (the di-p-acid is a white powder, insoluble in water, alcohol or ether the di-o-acid is diphenic acid, C0 2 C6 C 4 G0

From

Ci 2 lf 8 (OH) 2

H4

m.-pt.

229) which give diphenyl when heated with

2.

lime.

DIPHENYLMETHANE AND

ITS

DERIVATIVES

These compounds may be obtained by condensing either 2 mols. of benzene (or its homologues) with one of methylene chloride, or 1 mol. of benzyl chloride (or benzoyl chloride) with one of benzene (or its homologues or derivatives) in presence of aluminium chloride
:

2C 6 H 6

G GH 6

+ CH C1 - 2HC1 + C H CH C + C n CH Cl - HC1 + C H CH
-

6 II 5
-

fl

C.R 5

an aromatic alcohol with

similarly)
:

Condensation of 2 mols. of benzene with aldehydes (Baeyer) or 1 mol. of 1 of benzene (V. Meyer) under the influence of concentrated sulphuric acid (ketones, phenols, tertiary anilines, etc., also act

2C g H 8 C 6H 6 +

+ CII 3 OHO - H + CH CH(C H H CH OH = H + C H OH C,H

-

5) 2

forms white crystals melting at 26 and boiling at 262, has a smell of oranges and is soluble in alcohol or in ether. It is obtained synthetically (see above). With water at 150, its bromois converted into benzhydrol (diphenylcarbinol), derivative, CHBr(C 5) 2 (C 6 5 ) 2 CH OH, which is also obtained on reducing benzophenone.
<}

DIPHENYLMETHANE, C 6 H 5 CH 2 C H 5

fi

and tetramethyldiaminop-Diaminodiphenylmethane, CH 2 (C 6 4 2) 2 OH the latter obtained benzhydrol, CII[C 6 4 N(CH 3 ) 2 ] 2 by reducing Michler's ketone (f>ee below) in alkaline solution, are used in the preparation of dyestufEs.

H NH

TETRAMETHYLDIAMINODIPHENYLMETHANE

or

tetramethyl

base,

used in making dyestufts and serves also as an excellent reagent for detecting small amounts of lead, manganese, ozone, gold, etc., with
f)

CH 2[G H4K(CH 3
which
it

) 2] 2,

is

gives characteristic colorations.

BENZOPHENONE (Diphenylketone), C,.H 5 00 C 6 H5 or TETRAMETHYLDIAMINOBENZOPHENONE

CO[0 6H 4N(CH 3 ) 2 ] 2
,

(we p. 675
Michler's

).

ketone,

is

prepared

by treating dimethylaniline with carbon

720

ORGANIC CHEMISTRY

oxychloride, heating the resulting dimethyl-p-arainobenzoyi chloride in an autoclave with water, removing residual dimethylaniline by steam distillation, dissolving in dilute hydrochloric acid and precipitating the ketone from the filtered solution by means of sodium hydroxide. The crude ketone, after purification, melts at 174. It may be obtained also by heating together dim ethyl When treated aminobenzanilide, dimethylaniline and phosphorus chloride. with phosphoryl chloride, it yields the corresponding chloride. With ammonia with diethvlaniline, ethyl violet Michler's ketone gives auramine with and with /3-naphthol, wod green S, etc. benzylmethylaniline, acid violet jBN
;

o-DIHYDROXYBENZOPHENONE,
of water

[C

fl

H 4 (OH)] 2 CO,

by the elimination of a molecule

from the two hydroxyls, gives xanthone, C 6 H 4

is

< CO >C H
'

4.

^-Dihydroxybenzo-

obtained from anisaldehyde, so that the hydroxyl groups must be in the paraphenone Trihydroxybenzophenone is formed by the condensation of benzole acid with positions. pyrogallol in presence of zinc chloride. It is used in dyeing under the name alizarin
yellow
(J (see

Dyestuffs).
:

Other higher derivatives of diphenylmethaue are as follow as-DIPHENYLETHANE (see later symm.dibenzyl) is liquid and is formed from paraldehyde and benzene (see abore). Benzilic acid (diphenylglycnllic acid), (0 H 5 ) 2 C(OH) (X) 2 H,
is

a solid and

is

obtained by the action of

KOH on benzil
CH 3
,
.

by reduction with

H[

it

gives

diphenylacetic acid, (0 6 H 5 ) 2

Tolylphenylmethane,
Tolyl phenyl

CH CO H. C H 5 CH C 6 H
-

exists in several isomcric forms.

:{

ketones,

H CO
-

C G H4 CH

The

stereoisomcric oximes of these

(see

ketones were employed by Hantzsch in developing the stereochemistry of nitrogen

pp. 22, 253).

when heated

Benzoylbenzoic Acids, at 180 with

C 6 H 5 CO CeHj CO 2 H P2 O5 CG^V
.

the ortho-acid gives antliraquinone

FLUORENE

(Diphenylenemethane),

C.H/
on heating diplicnylinethane vapour. showing a violet fluorescence.
3.

/CH.>,

is

found in

coal-tar,

and

is

formed
scales

It melts at

113,

boils at

295, and forms

TRIPHENYLMETHANE AND

ITS

DERIVATIVES

These are prepared synthetically by processes analogous to those used for to lead to the condensation of diphenylmethane, but under such conditions as three benzene nuclei in the methane molecule. The action of chloroform on benzene in presence of AIC1 3 gives TRIPHENYLMETHANE (m.-pt. 93 b.-pt.
;

350)

CHC1 8

+ 3C H = 3HC1 + CH(C H
6

5) 3.

The condensation of benzaldehyde and dimethylaniline yields tetramethylCH[C 6 H 4 N(CH 3 ) 2 ] 2 which is a leuco-base diaminotriphenylmethane, C 5 When of malachite phenols, etc., condense similarly. green (see Dyestuffs) this colourless leuco-base is oxidised with Pb0 2 and HC1, it gives tetramethylis also a colourdiaminotriphenylcarbinol, C 6 5 C(OH)[C .H 4N(CH 3 ) 2 ] 2 which less base and forms colourless salts. When, however, these salts are heated in solution, they lose water and form an intense green colouring-matter, the double salt of this with zinc chloride or oxalate being known as malachite green :
(i

H4

N(CH 3

2 ,HC1

/C 6 H4

N(CH 3

,HC1

OH
or

'

C6 H 6

/CtH, N(CH 3
-C<^

2)

HCI
)

OI

C G H4

N01(CH 3

on reduction, the colouring-matter (+ 2H) gives the leuco-base

again.

ROSANILINE
:

721

PARAROSANILINE is obtained by oxidising 1 grm.-mol. of /Ktoluidine and 2 grm.-rnols. of aniline with arsenic acid or nitrobenzene. The methyl of the toluidine furnishes the carbon atom for the methane nucleus
CII 3
-

C GH 4

H4 -NH NH + 2C 6 H5 NH 2 + 30 = 2H 2 + OH oA) H 4 NII 2 (base). NJ H4 NH

/C
(5

fi

With
alkali.

HC(C 6 H

a red colouring-matter which is precipitated by When reduced with zinc and hydrochloric acid it yields paraleucaniliue, NH 2 ) 3 in colourless crystals which give the coloured base again on 4
acids, this base gives
,

oxidation.

Elimination of the amino-groups by diazotisation leads to tri phenylnwtJiane, while nitration of the latter, followed by reduction, gives par aleucani line, which yields Iriammolriphenylcarbinol on oxidation. When treated with acids the latter loses 2 0, giving the colouring-matter

X OH -OC
ROSANILINE
of the

(C 6

H4 -NH
-

2) 2

XG TI NH 6 4 2 ,HC1
is

y = H + CClf X
2

(C 6II 4

-NH 2
-

)2

C GH4

NH 2
^-toluidine
:

formed by oxidising a mixture of o- and ^-toluidines and aniline with arsenious anhydride, mercuric nitrate, or nitrobenzene, the carbon

methane nucleus being furnished

(p)

in this case also

by
2

the.

+ C 6H4<
NII 2
l

(o)

+ Oe II NH
6

-f

30

2ILO

Rosaniline hydrochloride (with 1 HOI) or fuchsine forms crystals with a green metallic lustre, while the aqueous solution is red owing to the presence of the monovalent cation, C^H^N.,, the salt being almost completely ionised. All fuchsine salts, at the same dilution, give the same absorption spectrum, as they contain the same cation. If 3 HOI are combined, the salts become yellow (yellow trivalent eation ) indeed, with excess of HOI fuchsine is almost decolorised, although in dilute 1 solution the red cation is again formed by dissociation. the atoms of of the amino-groups by alkyl groups hydrogen Replacement gives various colouring-matters, the intensity of the violet colour increasing with the number of methyl groups. Pentamethylpararosaniline is the melhyl riolet of commerce. ROSOLIC ACID and AURIN are the phenolic compounds corresponding with rosaniline and pararosaniline, from the diazo-compounds of which they are obtained by boiling with water
;
:

C^-06 H4
1

/CeH^OH) CH 3
-

OH

\C 6H4 :0
k:

Of \J6H4 :0
Aurin

y(C 6

H4

OH) 2

acid

that in the hydrochloride the chlorine is joined to the ainino-group and not to the carbon of tho methane, since, as Tortelli showed (1895), all the chlorine is It cannot, however, the compound is hence a salt and not an ether. precipitable by silver nitrate be denied that there are compounds, such as triphenylmethyl chloride, (C H 5 )j (' H, which behave
It is

commonly thought
;

fl

silver nitrate. Then, similarly, being hydrolysable by water and then completely precipitable by in 43 hours, whilst too, methyl iodide is hydrolysed by water alone to the extent of 0-6 per cent, It in tho presence of silver nitrate 90 per cent, of the iodide is hydrolysed in the same time. like salts. is hence more accurate to state that, after hydrolysis, these ethereal compounds behave

Rosenstiehl maintains that every double decomposition between salts (especially organic) he preceded by hydrolysis, and those salts and ethereal compounds which hydrolyse slowly calls bradolyt&t, and those which hydrolyse rapidly, stenolytes.
is

722

ORGANIC CHEMISTRY

They arc colouring-matters of an acid character and of but little importance, and they form dark red prisms with a greenish, metallic reflection.

PHTHALOPHENONE, C( C 6H 5

x: 6 H 4

may

be regarded as a derivative of

co

phthalic acid (see p. 684) or of triphenylmethane. It is the anhydride of triphenylcarbinol-o-carboxylic acid, C(OH)(C 6 5 ) 2 (C 6 4 C0 2 H), and is obtained by heating phthalyl chloride with benzene in presence of aluminium chloride. It forms scales melting at 115 and dissolves in alkali giving a salt of the acid, the latter not being obtainable in the free state. Its phenolic derivatives are the phthaleins (see p. 685).

(C 6 H 5 ) 3C C(C 6 H 5 ) 3 is of some interest theoretimolecule was at first regarded as C(C 6 5 ) 3 (Triphenylmethyl) and was looked upon as the first example of an organic compound containing trivalent carbon, but cryoscopic examination shows that it has the doubled molecular It was weight, and hence indicates the constitution (C 6 5 ) 3 C C(C 6 H 5 ) 3 prepared by Gomberg by the action of zinc on triphenylchloromethane, and is a solid, stable substance which, in solution, has a yellow colour and becomes unstable owing to its great power of reacting with the oxygen of the air it forms a peroxide, (C 6 6 ) 3 C On account of the facility C(C 6II 5 ) 3 with which it forms additive products, hexaphenylethane is regarded by some as having in solution the constitution

HEXAPHENYLETHANE,

cally, as its

HH

H
!

H H
An
analogous compound
is

Pentaphenylethane, (C 6 IT5 ) 3 C

CH(C 6 H"5

2,

stable

at the ordinary temperature but not in the hot.

4. DIBENZYL AND ITS DERIVATIVES The constitution of these compounds is shown by their methods and by the fact that they all yield benzoic acid on oxidation. DIBENZYL (symm. Diphenylethane), C 6 H 5 CH 2 CH 2 C 6 H 5 from benzyl chloride and sodium
,
:

of synthesis
is

obtained

20 6H5
it

CH 2

01

+ Na = 2NaCl + C H CH CH
-

H5

melts at 52.
: ,

STILBENE (symm. Diphenylethylene), C 6 H 5 CH CH C 6 H 5 melts at 125, and is obtained from benzal chloride (benzylidene chloride) and sodium. Owing to its double linking, it can unite with two atoms of Br, which can be eliminated as HBr by treatment with alcoholic potash, the resulting product being TOLANE (diphenylacetylene), C 6 H 5 C J
C 6 H 5 melting at 60, and behaving like an acetylene derivative. NH 2 C 6 H 4 CH CH C 6 H4 NH 2 is used, especially in the form of the corresponding sulphonic acids, for the preparation of various substantive C
,

^-DIAMINOSTILBENE,

dyestuffs.

BENZOIN, C 6 H 5 CH(OH) CO C 6 H 5 is formed by oxidising HYDROBENZOIN, H 6 CH(OH) CH(OH) C 6 H 6 which is obtained by treating benzaldehyde with sodium
, ,

amalgam.

It reduces Fehling's solution even in the cold (giving benzil) since it contains, like the sugars, the group CH(OH).

Benzoin exists in two stereoisomeric modifications, melting at 138 and 119. and forms a phenylosazone,

CO

NAPHTHALENE
BENZIL, C e H 5
pp. 22, 253).

728
(see

CO CO C 6 H 5

is

a yellow diketone and forms three benzildioximes

C.H.

C 6 H5

C 6 H 5 0-

N-OHN-OH
Amphi-benzildioxima

OH-N

N OH

N-OHOH-N
Syn-benzildioxime

Anti-benzUdioxime

When

heated with alcoholic potash, benzil combines with

2 0,

giving benzylic acid

CO CO C 6 H 5
C6H5

+ H OH =
,

CH 2 CO C 6 H5 is obtained from phenylacetyl chloride, benzene in presence of aluminium chloride, and also from benzoin and benzil. It melts at 55 and gives dibenzil when reduced with hydriodic acid. HEXABENZYLETHANE, (C 6 H 5 CH 2 ) 3C C(CH 2 C 6 H 5 )3 waa prepared by Schmerda (1909) by heating tribenzylcarbinol with hydriodic acid in a sealed tube at 200, the product being shaken with bisulphite, extracted with ether and the latter distilled off. It forms a it yellowish crystalline mass which is recrystallised from acetone and glacial acetic acid melts at 80 to 81. From the mother-liquor dibenzyl is obtained.
DESOXYBENZOIN, CH 2 CO Cl, and
-

NAPHTHALENE AND NAPHTHALENE, C 10 H discovered in tar in

5.
8,

ITS

DERIVATIVES

abundance in crude illuminating gas and pp. 625 et seq.), the naphthalene is obtained from the portions distilling between 170 and 230 and by rein
distilling
oils

in coal-tar.

1819 and 1821 by Garden and Kitt, occurs When the latter is distilled (see

the residues of the

from which the carbolic acid has been extracted with

care being caustic soda, taken to surround the condenser coils with hot water
to prevent stoppages.

The first separation of the naphthalene from the crude oils yielded at various
stages of is effected

JTTG>

4(54.

the

distillation

The

Attempts steamed in the centrifuge, the residual product is always very impure and unsuitable for distillation or sublimation. In consequence of this, use has been made of hydraulic presses with horizontal rods and vertical plates heated by steam, but these give insufficient pressure and too much waste, and require too much time and attention. The best results are to the presses described on given by presses with vertical colums and ring plates (similar o! 102 kilos per square a pp. 484, 485), which work continuously and readily attain pressure centimetre with a diminished consumption of steam. Nowadays hydraulic presses with to those used for oily seeds and in 10 hours each perforated steel bells are used similar of these can effect 30 compressions of 100 kilos ; when several presses are worked, hydraulic
If well pressed, naphthalene has (see p. 484) are used. of it distils between 216-5 and 218-5. cent, 95-5 and 78-6 per point made to purify naphthalene with a solution of resin soap, but such a sive (a centrifuged naphthalene containing 7 per cent, of oil gives, colophony and the corresponding quantity of caustic alkali solution,

by cooling in large tanks, crystallised naphthalene separating out. are removed in a hydraulic press with heated plates. oily impurities of the crystals have been made to centrifuge the crude naphthalene, but even when this is

accumulators

the

mean

solidifying

Attempts have been

method is too expen-

with 5 per cent, of 85 per cent, of pure is purified naphthalene with the solidifying point 78-8). The compressed naphthalene further in metal vessels with conical bases and fitted with stirrers (sometimes with airIn these the molten naphthalene is agitated for 15 minutes with 5 per cent, of suljets).

phuric acid of 50

Be",

(already used once) to dry the mass

somewhat and

free it

from

724

ORGANIC CHEMISTRY

pyridine compounds ; after removal of this acid, the mass is shaken successively with 5 to 6 per cent, of sulphuric acid of 60 Be. for 30 minutes, 4 per cent, of hot water, 4 per cent, of caustic soda solution of 19 Be. (already used once), and finally, 2 per cent, of hot water. After settling and removal of the water as far as is possible by decantation, the naphthalene is distilled in large stills holding 100 to 150 quintals and furnished with a rectifying column 2 to 3 metres high. Water distils over first and then pure naphthalene,

which

is

collected in metal boxes, allowed to crystallise in

moulds and granulated by means of a crusher the solidify;

ing point is then 70-7, while 97 '5 per cent, distils between

216-6

and 218.
in the

A purer product,
of distillation) in

form

of large, shining scales, can bo

obtained by ffublimatian (instead an open vessel, a (Fig. 464), having an area of 2 to 3 sq. metres and covered with an inclined wooden plane loading to a large wooden chamber, 20 to 25 cu. metres in

The naphthalene is heated by a pressure steam-coil and sublimes .and condenses in the large chamber, forming on the walls a thick layer of shining, white scales of pure naphthalene. In order to avoid loss and to PIG. 465. obtain continuous working, the naphthalene is introduced into long cylindrical boilers, bricked in liko steam boilers and connected with a largo wooden chamber (350 cu. metres, Fig. 465), which has a base fitted with conical outlets loading to sacks for catching the naphthalene as it becomes detached from the walls (these arc knocked from timo to time). In this way 70 kilos of pure naphthalene are obtained per 12 hours for each 100 cu. metres of capacity. Pure naphthalene forms shining scales melting at 79-6 and boiling at 218. It is insoluble in water, but dissolves readily in boiling alcohol or in other it volatilises even at the ordinary temperature and distils readily in steam. The calorific value of naphthalene is 6940 cals., and its vapour pressure at different
capacity.
;

temperatures as follows (mm. of mercury)

20
0-022

50
0-81

80
7-4

100
18-5

120
40-2

141

159

165

0-080

90-4

169

207

Its sp. gr. is 1-152 at 15 and 0-977 at its melting-point. If pure it does not colour concentrated sulphuric acid at 80. Constitution of Naphthalene. The following structural formula is attributed to

naphthalene

H
C

H
H

C C

\
C

H
H

\C /\C /
I

H
in derivatives

and to indicate the positions occupied by groups replacing the hydrogens the carbon atoms are numbered or lettered with Greek letters., thus
;

CONSTITUTION OF NAPHTHALENE
8
4
tt

725

*/\/\

That the two nuclei are united by means of two carbon atoms in the ortho-position is shown by the fact that oxidation of naphthalene in such a way as to destroy one of the nuclei results in the formation of phthalic acid, which is known to contain two carboxyl
groups in adjacent positions.
Further, since when phenylisocrotonic acid is heated a naphthalene derivative, namely, tt-naphthol, results, it is clear that the second nucleus is formed by the elimination of a molecule of water with closure of the chain of the four carbon atoms of the side-chain of

the original acid and two ortho-carbon atoms in the benzene nucleus

CH C CH

,CH

H
H
OH
CO OH
-

+
HC

CH CH
^

OH

That there arjtwo condensed benzene nuclei is also deduced from the fact that oxidation of tt-nitronaphthaJene gives iiitrophthalic acid, the benzene nucleus containing the nitrogroup being preserved and the other destroyed. If, however, the nitro-group is first reduced to an amino-group, oxidation results in the destruction of the nucleus containing the ammo-group and in the preservation of the other, phthalic acid, which undoubtedly contains a benzene nucleus, being formed. That the linkings between carbon and carbon are different in the two nuclei is shown by the addition of four hydrogen atoms to one of
the nuclei, which probably has true double linkings, while the other nucleus would seem to have a true benzenic character with centric linkings (Bamborger) ; further, the addition of

ozone proves with certainty the presence of

olefinic

double linkings (E. Molinari, 1907)

CH
HC
TTC,

CH

CH CH
USES.
Naphthalene
(eosin, indigo,
is used in large quantities in the preparation of various dyestuffs Martins yellow, tropwolin, Biebrich scarlet, croceine scarlet, etc.), phthalic

antiseptic acid, lampblack, varnishes, and cart-grease, and is employed also mixed with camphor in order prevcntative of moth in clothes. For some time it has been to render celluloid less inflammable and less explosive. Crude naphthalene cost before the war 11s. to 12s. per quintal, while the pure white scales were spld at 16s., pure in tapers at 1 7s. 6r?., and chemically pure at 80s. per quintal. The isomerides of the substitution products of naphthalene are more numerous than in the case of benzene. Thus, there are two isomcric mono-substituted derivatives, the with the substituent in tho 1-, 4-, 5-, or 8-position, and the ^-compound with

as

an

and as a

a-compound

the substituent in the

two

The isomeric disubstituted compounds with 2-, 3-, 6-, or 7-position. similar substituciits are ten in number, while with two different substituting groups

fourteen isomerides are possible, and, in some cases, all known. Compounds with substituents in the 1- and 8- or the 4- and 5-positions are

known

as

)OH
tt-

or 2>m'-compounds,

e.g. 9

Perinaphthalenedicarboxylic acid,

which

'OH

an anhydride owing to the proximity of the hydroxyls. The number of isomerides being so large, it is sometimes difficult to determine the constitution of a derivative. To this end the oxidation products are often studied, the formareadily forms

726

ORGANIC CHEMISTRY
H

tion of phthalic acid indicating that all the suhstituents are in the one benzene nucleus destroyed by the oxidation, while the formation of a substituted phthalic acid indicates the opposite to be the case.

tt-CHLORONAPHTHALENE, C 10 7 C1. Treatment of naphthalene with chlorine yields preferably additive products with two or four chlorine atoms in the same benzene nucleus. On the other hand, the action of chlorine on a cold solution of naphthalene in carbon tetrachloride in presence of a catalyst (e.g., ferric chloride) yields substituted products
:

a-monochloro-, then
thalenes.

4-

and

5-

and small proportions

of

2-

and

7-dichloronaph-

Also with boiling naphthalene chlorine forms directly a-chloronaphthalene, but this is obtained in a purer form by diazotising a-naphthylamine and then decomposing with copper chloride (Sandmeyer's reaction, p. 670). It is a liquid of sp. gr. 1-1938, b.-pt. 263, and forms a yellow, crystalline picrato, ni.-pt. 137. When nitrated it forms mainly It serves for l-chloro-4-nitroiiaphthalene, together with a little 1 5- and 1 8-com pounds. making various chlorosulphonie acids and also naphthalene green V, and has been suggested as a lubricant. Of importance in the explosives industry are various nitro-derivatives of naphthalene, and in the dyestuffs industry, besides nitro-derivatives, also the amiiiooompounds, and especially the numerous sulphonic derivatives. a-NITRONAPHTHALENE, C 10 H 7 NO 2 Of the a- and ^-nitronaphthalenes, only tho former is of industrial importance, being used for making dinitronaphthalene and
:
:
-

particularly a-naphthylamine. The industrial preparation

is carried out in a nitrating vessel (see p. 649), 100 kilos of pure ground naphthalene being added rapidly, with stirring, to 300 kilos of 55 per cent, sulphuric acid (45 Be.), the temperature being raised to 50 ; 200 kilos of a mixture containing 26 per cent, of HNO 3 60 per cent, of H 2 SO 4 and 14 per cent, of water is then added slowly, the temperature being raised gradually to 60 and mixing continued for a couple of hours. The residual acid, containing about 63 per cent, of 2 SO. and 0*5 per cent, of HNO 3 i then decanted off, and, after dilution to 55 per cent., used for treating a fresh batch of naphthalene. "The fused nitrouaphthalene is run into a vessel of hot water furnished with a stirrer, and is washed twice with almost boiling water and once with a very dilute sodium carbonate solution, the molten compound being poured into cold water, kept stirred and thus granulated, and then ccntrifuged and used moist for reduction to a-naphthylamine. It is used also for making l-nitronaphthalene-5-sulphonic acid, and when fused with sulphur
,

and green sulphur colouring matters. a-nitronaphthalene vapour and hydrogen are passed at 340 over finely divided copper, a-naphthylamine is formed directly, but if the copper is replaced by powdered With nickel, tetrahydronaphthalene (and 3 ) is obtained as a secondary product. sulphites it gives naphthionic and naphthylamine-2 4-disulphonic acids, and with chlorine
gives blue

When

NH
it

in presence of catalysts at

40 to 60

forms l-chloro-5-nitro- and also l-chloro-8-nitro-

naphthalenes (Ullmann and Consormo, 1902). It is used for removing the fluorescence from mineral oils, being stored away from the oil to minimise damage in case of fire. It is poisonous and forms a yellow, crystalline mass, m.-pt. 61 (the commercial product has m.-pt. 58 to 59), b.-pt. 304, and when molten has sp. gr. 1-223. It is insoluble in water, but dissolves in" benzene, ether, carbon disulphide or hot alcohol. The crude product cost 64s. to 76s. per quintal before the war, and the pure crystals 96s.

DINITRONAPHTHALENES, C 10 H 8 (N0 2

)2

Nitration of a-nitronaphthalene or direct

:

nitration of naphthalene with a suitable nitric-sulphuric acid mixture yields always a mixture of various dinitronaphthalenes, consisting principally of the 1 8-* (about 60 per

5-compound (about 30 per cent.) together with other isomerides and trinitronaphthalene. The mixture may be used directly for explosives (see p. 305). The two dinitro-compounds may be separated by dissolving in hot sulphuric acid of 62 Be. which, on cooling, deposits the 1 5-compound, whilst the 1 8-derivative separates at a lower temperature or, better, on slight dilution with water. Also a hot pyridine solution deposits the 1 5-compound on cooling, removal of two -thirds of the pyridino by distillation and subsequent cooling resulting in the crystallisation of 1 8-derivative. 1 5- (or a-) Dinitronaphthalene, which is used for making naphthazarin black (see later), crystallises in yellowish needles, m.-pt. 214, and is readily sulphonatcd by fuming sulcent.)

and the

phuric acid.

When

reduced with

ammonium

sulphide

it

gives

first

l-nitro-5-aminonaph-

NAPHTHYLAMINES
thalene and then
1
:

727

ammonium
1
:

sulphite solution

8- (or ft-)
:

when boiled with sodium bisulphite or 5-naphthylenediaminedisulphonic acid. Dinitronaphthalene, m.-pt. 172, is more soluble in various solvents than
5-naphthylenediamine
it
;

yields 1

the

5-compound.

With sodium
:

acid.

It behaves like the 1

bisulphite it gives 1 8-naphthylenediaminetrisulphomc 5-isomeride with fuming sulphuric acid and is used for making
:

sulphur blacks and blue.

TRI- and TETRA-NITRONAPHTHALENES are otained by nitrating naphthalene or the mono- and di-nitro-compounds with more concentrated nitric-sulphuric acids and with rather more than the theoretical quantity of nitric acid.

a-NAPHTHYLAMINE (1-Aminonaphthalene), C 10 H 7 NH 2 The commercial product forms lustrous, square scales with a reddish-brown tint it contains a little naphthalene and water and has a slight faecal odour (/2-naphthylamine is odourless). The pure, freshly made product is pale pink, melts at 50 and boils at 300-8. It has no alkaline reaction, and is readily soluble in alcohol, ether, benzene, toluene, etc. 100 c.c. of water dissolves only 0-167 grm. With oxidising agents such as ferric chloride, ehromates, etc., its salts give a blue precipitate of naphthamine, changing to purple-red (different from /2-naphthylamine) this reaction is used by van Eck (1915) for the colorimetric estimation of ehromates. With CaCl 2 or ZnC] 2 at 280 it gives a little ammonia and a-dinaphthylamine (see later). With sodium nitrite naphthylamine salts in slightly acid solution give a brown precipitate
.

of arninoazonaphthalcne, C 10 H 7 N 2 C 10 H 6 NH 2 and in highly acid solution, u-diazonaph thalene, C 10 H 7 N 2 X. On protracted boiling with water it is converted partly into a-naphthol. The hydrochloride sublimes at 200, and the sulphate crystallises with
,

2H 2 0.
a-Naphthylaminc is used to make a-naphthol (see later), various sulphonic derivatives, numerous azo dyestuffs, and Magdala red. It serves also for many direct diazotisations on cotton fibre, to be coupled with, for instance, /2-naphthol to obtain a bluish-red colour
(Bordeaux) fast against soap, etc. It is also employed in photography, together with oxidising agents, to obtain bluish tones. Before the war it was sold at about Is. d. per
kilo.

MANUFACTURE. It is usually obtained, similarly to aniline, by reducing a-m'tronaphthalene with iron and hydrochloric acid. Electrolytic reduction (Boehringer, Ger. Pat. 116,942) and reduction with hydrogen in presence of a catalyst (e.g., copper), as suggested by Sabaticr and Seiiderens ( 1902), do not give satisfactory results in practice. It is purified by distillation in a vacuum.
and /^-naphthylamine
Nitration of naphthalene does not yield /2-nitronaphthalene, obtained by heating ^-naphthol (100 grms.) with 150 c.c. of 40 per cent, ammonium sulphite solution and 100 c.c. of 20 per cent, ammonia solution in an autoclave at 140 to 150 until all the /2-iiaphthol has reacted, the slightly cooled mass being filtered by suction, washed with dilute caustic soda, dissolved in tepid dilute hydrochloric

/2-NAPHTHYLAMINE.
is

acid solution
precipitated

and

used for making /3-naphthylaminesulphonic acid and various azo dyestuffs, and costs three times as

by

filtered from insoluble /2/3-dinaphthylainine. dilute caustic soda, has in.-pt. 112, b.-pt. 294.

The

/2-naphtliylamine,

It is

much

as its a-isomeride.

The
amine,

used in making Ictnacyl violet B and new Victoria blue B9 a basic dyestuff which dyes wool directly and cotton, after mordanting, pure sky blue. (2) Phenyl-ri-naphthylamine, from aniline and a-naphthylamine at 230 to 250 in presence

C 10H 7

following are important derivatives of the naphthylamines

NH

(1) Ethyl- a -naphthyl-

C2 H5

is

of iodine, or
jet black

from

R,

etc.

night blue.

Developer

and a-naphthol, serves to make sulphotuizurine D, C 6 4 CH 3 is used for making ^-Tolyl-a-naphthylamine, C 10 7 The corresponding /?-naphthylamine derivatives are used for making: (1) (Bordeaux) for primuline dyestuffs (2) night blue ; (3) wool black.
aniline hydrochloride
(3)

NH

lustrous, monoclinic needles, ni.-pt. 94, b.-pt. 279, and dissolves in alcohol, ether, benzene* etc., but is insoluble in water. With ferric chloride or a hypochlorite it forms a-dinaphthol in blue flocks. When fused with alkali in presence
*

a-NAPHTHOL, C 10 H 7 OH, forms

of copper oxide it gives benzoic and phthalic acids. ,It unites with zonium salts in the o- and jp-positions to the hydroxyl. It is used in

two molecules of diamaking numerous azo

dyestuffs (brown, black, orange), indophenol and, especially, various sulphonic acids as intermediates for important dyestuffs (Martius yellow, naphthol yellow S, etc.). It condenses with Michler's ketone to give indigoid dyestuffs and naphthol blue.

PREPARATION. a-Naphthol

is

obtained pure by heating a-naphthylamine and sul-

728

ORGANIC CHEMISTRY
is first

phuric acid in a lead-lined or enamelled autoclave at 200 (14 atmos.), the mother liquors yielding ammonium sulphate. The process most commonly used and possibly more economical is the following, which yields a- mixed with a little /2-naphthol. Sodium naphthalenc-

prepared by heating naphthalene with sulphuric acid and pouring the This salt is pressed hydraulically under 200 'atmos. solution. pressure so that a product with only about 15 per cent, of water is obtained, this being fused with commercial caustic soda and a little water and the mass poured into cold water, which is subsequently neutralised with sulphuric acid. The u-naphthol crystals are pressed, fused to eliminate water, and distilled under a pressure of 50 mm. at a temperature of
u-sulphonato

mass into sodium sulphate

about 165.
lustrous white crystals, m.-pt. 123, b.-pt. 285, sublimes readily It dissolves in 5000 parts of cold or 75 of boiling superheated steam. water, and is readily soluble in alcohol, ether, benzene, etc. With ferric chloride it gives a greenish coloration and afterwards white flocks of ft /?-dinaphthol. When oxidised in alkaline solution with potassium permanganate it yields o-carboxycinnamic acid, and when fused with caustic soda in presence of copper oxide, phthalic and benzole acids. It is used in making numerous dyestuffs, especially of the azo group, since it may be

/2-NAPHTHOL forms
distils well in

and

scarlets for

11, paranitraniline red, various ponceaus and dianisidine blue, greens, blacks, etc., etc.). It is used also as a disinfectant in skin diseases, and its methyl and ethyl esters f'jrm fruit essences.

coupled in

many

different

ways (orange

wool and for

silk,

Industrially it is prepared solely from sodium /2-iiaphthalenesulto that used for making the u-isomeride, special conditions a analogous process by phonate being employed to prevent formation of u-naphthol and disulphonic acids.

PREPARATION.

Betol or Naphthosalol (the salicylic ester of /2-naphthol), C 10 7 O CO C 6 4 OH, melts at 95, and is used in medicine under the name of salol. Neroline, C 10 H 7 OC 2 H 5 is the ethyl (or methyl) ether of /2-naphthol and has the
-

same odour as orange flower

oil (neroli).
,
: :

Dihydroxynaphthalenes, C 10 H 6 (OH) 2 are known in various isomerides the 1 5-compound, m.-pt. 259, obtained by the alkaline fusion of sodium naphthaleiiedisulphonate, serves for making benzidino blue dyestuffs, diamond black PV, etc. The 1:8-, 2:3- and 2 7 -isomerides are also used for making azo dyestuffs, etc. Aminonaphthols, OH C 10 H 6 NH 2 the various isomerides are used for preparing
:
:

dyestuffs.

SULPHONIC DERIVATIVES OF NAPHTHALENE, NAPHTHOLS, AND

NAPHTHYLAMINES

These form an important group comprising the principal intermediates used in making Only the more important can be referred to here. The sulphonation of naphthalene is analogous to that already given for benzene (see a large number of isomerides, p. 637) and, since naphthalene sulphonates readily and gives mixtures difficult to separate are often obtained. The a-derivatives arc formed preferably at comparatively low temperatures and the /3- derivatives at higher temperatures (100 to 200). Sodium amalgam eliminates u- more readily than /?-sulphoiiic groups. NAPHTHALENE-a-SULPHONIC ACID, C 10 H 7 SO 3 H, m.-pt. 87, gives the /3-isomeride when heated with concentrated sulphuric acid, dissolves appreciable amounts of phenol, and is used for making a-naphthol.
dyestuffs.

NAPHTHALENE-/2-SULPHONIC ACID
proteins in the cold.

serves for

making /3-naphthol and precipitates

l-AMINO-2-NAPHTHOL,

NH 2

C 10 H 6

OH,

is

ether and then reducing. The ethyl ether, m.-pt. 51, diamond green, and various bluish naphthyl blacks.

obtained by nitrating y8-naphthol ethyl is used for making diamine blue 66/,

l-NAPHTHOL-2-CARBOXYLIC ACID,
dry sodium u-naphtholate with making chrome blue.
evolution of

C0 2

in

an autoclave at 130,

obtained like salicylic acid (p. 686) by heating is used as an antiseptic and in

2-NAPHTHOL-l-CARBOXYLIC ^CID,

CO 2

It is

obtained similarly, melts at 128 to 156 with used to replace /2-naphthol in making lakes coloured directly on

the

fibre.

also as Nevile and Winther's acid or forms transparent tubular crystals, melting and generating gas at 170. It is used in making azo dyestuffs, e.g., azococcine 2R, fast red VR, cloth red G and B, diamond black
acid,

l-NAPHTHOL-4-SULPHONIC ACID, known

NW

NAPHTHAQUINONE
F, alizarine

729
BX,
benzo-

bordeaux

W,

anthracene red, diamond blue 2R, diamine blue

azurine G, etc.

-NAPHTHOLSULPHONIC AND DISULPHONIC ACIDS. Treatment of /2-naphthol with sulphuric acid yields various products according to the concentration of the acid and the temperature. Owing to the difficulty of obtaining a single sulphonation product, mixtures of two acids are' usually made and then resolved into the components.
2-NAPHTHOL-6-SULPHONIC ACID, or Sehaffer's acid, melts at 125, gives dihydroxynaphthalene, m.-pt. 213, when fused with alkali, and is used for making azo dyestuffs brilliant orange O, fast red BT, bordeaux G, diamiiiogeii blue BB, alizarin acid black SN ; the iron salt of the iiitroso-derivative forms naphthol green 8. l-NAPHTHOL-5-SULPHONIC ACID, or Cleve's acid, m.-pt. 110 to 120, obtained by boiling the diazo-dcrivative of l-naphthylaminc-5-sulphonic acid with water, is used for making cochineal scarlet 4R, diamond black F, benzo azurine 3G, etc.
:

finely divided /2-naphthol gradually to acid is used for making sulphuric acid (rnonohydrate), the mixture being kept cold. The The potassium salts are used for making orange III, alizarin acid red B, Congo y-acid.

2-NAPHTHOL-3 6-DISULPHONIC ACID (R PHONIC ACID (G acid) are obtained by adding

:

acid)

and 2-NAPHTHOL-6 8-DISUL:

blue 2B, naphthol black, diamine scarlet B, etc. l-NAPHTHOL-3 6 8-TRISULPHONIC ACID
:

is

used in large quantities for making

is

naphthol yellow

>S.

NAPHTHIONIC ACID

or

l-NAPHTHYLAMINE-4-SULPHONIC ACID
:

obtained like

sulphanilic acid (p. 637) by heating naphthylamine acid sulphate at 180 to 200 and is used in making many azo dyestuffs naphthylamine brown, azorubine, crocein scarlet,

cochineal red, benzo orange, benzo-purpurines

salt is
:

4B and

10B, dianil black,

etc.

The sodium

used in making colloidal gold solutions. CLEVE'S ACID is the 1 7-isomeride, used for Biebrich black. DAHL'S ACID is 2-naphthylamme-5-sulphonic acid mixed with the 2 and is used for making ponceau for silk G.

8-compound

DAHL'S ACID

II,

l-naphthylamiiie-4
:

acid Til (2:6:8), for

making various naphthol

6-disulphonic acid, blue-blacks.

is

used,

mixed with Dahl's

AMINO R
etc.

ACID G (2:6:8),

ACID, 2-naphUiylamine-3 6-disulphonic acid, and the isomeric AMINO serve for making brilliant crocein, amine blue 6G, naphthol black B,
salt of

Eikonogen is the sodium a photographic developer.

a 1 -amino-yS 1 -naphthol-yS 2 -sulphonic acid and

is

used as

y-ACID or 2-amino-8-naphthol-6-sulphonic acid, prepared together with more or less J-ACID (2:5: 7), gives two seriea of azo dyestuffs by coupling with diazo compounds in acid and alkaline solutions and also directly oil cotton fibre. It is used for making diamine violet N, diamine blacks, diaminogen blue, dianil black PR, etc., all these for dyeing cotton
without mordants.

H-ACID or 1 -amino-8-naphthol-3 6-disulphonic acid is the most important of the naphthalene sulphonic derivatives and is used in making numerous azo dyestuffs for dyeing various diamine blues, naphthylamine black cotton without mordants or wool and silk 10B, diamine bronze G, diamine green B, fast acid magenta, lanacyl dyestuffs, etc. Before
:
:

the war

it

cost

4,s.

per

kilo,

and during the war

or
1
:

as

much

as

4.
:

8-dihydroxy naphthalene- 3 6-disulphonic acid, obtained by fusing iiaphthylaminetrisulphonic acid with alkali in an autoclave, is used for making chromotrope blue and black, Victoria violet 4B8, dianil blue, etc. ; its sodium salt forms

CHROMOTROPE ACID

chromogene

1.

O
a-NAPHTHAQUINONE,
,

is

obtained in yellow crystals melting at 125

O
From its in boiling acetic acid solution. constitution those of other substitution products of naphthalene can be deduced, since, when the substituent groups are in the para-position, oxidation always leads ultimately to
by oxidising naphthalene with chromic acid
a-naphthaquinone.
VOL.
ii.

It is volatile in steam.

47

730

ORGANIC CHEMISTRY
2

^-NAPHTHAQUINONE, C 10 H 6

or

is

formed by the oxidation of 1:2-

/O

O
aminonaphthol, and crystallises in reddish yellow leaflets blackening at 115 to 120. 2 6-NAPHTHAQUINONE forms odourless, reddish yellow crystals turning grey at 135, and is a more energetic oxidising agent than the preceding isomerides. HYDROXYNAPHTHAQUINONE (0 O OH 1 4 2) is known, and its 1:4: 5isomeride is juglone, found in the green outer shell of the walnut and readily oxidising to a
:

blackish- brown

The

following
;

Zarin llack)

compound. compounds are also known Oxy- and Dioxy-naphthaquinones (naphthaa- and /2-Methylnaphthalenes, C 10 H 7 CH 3 Naphthoic acids, C 10 H 7 CO 2 H
:

Hydroxynaphthoic Acids,

C 10 H 6 (OH)(C0 2 H)

Naphthalic Acid,
in

C 10 H 6 (CO 2 H),,

Dinaphthyl,

C 10 H 7 C 10 H 7
are in the

Acenaphthene, G lo H 6 c

rI 2
,

X CH

which the unions with the ethylenc group

cij- and appositions (found in tar, colourless, melting at giving naphthalic acid on oxidation).

85,

boiling at

277, and

ADDITIVE PRODUCTS OF NAPHTHALENE

Naphthalene gives additive products more readily than benzene does, those containing four atoms of chlorine or hydrogen being well known. It has been shown that this addition occurs in only one of the nuclei, and similar behaviour is shown on oxidation. Chlorine reacts with naphthalene at the ordinary temperature and forms naphthalene tetrachloride,

HC1

HCl
,

which forms colourless crystals melting at 181

and gives phthalic

J.

HCl

HCl
,

and dichloronaphthalene, C 1U H 6 C1 2 when treated with alcoholic potash. /3-naphthylamine is reduced (Na -{- amyl alcohol), four hydrogen atoms are added to the nucleus containing the ammo-group, giving tetrahydronaphthylamine,
acid en oxidation,

When

H'

^
H

\H(NH 2

)
,

which behaves exactly

like

an aliphatic amine and docs not form

H2
;

diazo-compounds

it is

/CH 2
C 6 Hj/

CH 2 CO a H

oxidised by permanganate, giving o-carboxyhydrocinnamic acid,

.

V:o H
2

a-Naphthylamine also gives a tetrahydro-derivative, which

;

behaves, however, as an aromatic amine and can be diaxotised

on oxidation

it

gives adipic

CH 2

CH 2 COOH
acid,
|

CH 2 COOH

which shows that the four hydrogen atoms are added to the benzene

\/ CH
a

nucleus which does not contain the amino-group

/'H

H 2 NH
HYDRONAPHTHALENES.
Dihydro-

occur in tar, especially in that obtained from coal by direct extraction with solvents (e.g., liquid 80 2 ) or from vacuum tar (see Vol. L, p. 442). Bamberger and Kitschelt (1890) hydrogenated

and tetrahydro -naphthalenes

ANTHRA CENE

731

naphthalene with sodium and amyl alcohol and Sabatier and Senderens (1004-1910) with hydrogen in presence of finely divided nickel. Hchroeter (1915) obtained tetrahydronaphthalene by heating pure fused naphthalene in presence of finely divided nickel with hydrogen under pressure (Ger. Pat. 324,861 and 324,862, 1915) and from naphthalene vapour and hydrogen at the ordinary pressure with the aid of various catalysts (Ger. Pat. 301,275, 1917) ; the naphthalene is completely purified beforehand by treating it with a readily fusible metal or with kieselguhr or animal charcoal. The tetrahydronaphthalene obtained from the crude product by distillation in a vacuum forms an oil stable in the air, - 20. up. gr. about 0-974, b.-pt. 206, in.-pt. below Its commercial name is tetraline, and since 1917 it has been used in various industries, e.g., as a solvent for rubber, celluloid and cellon, which renders it possible to prepare softer photo-

graphic films and to obtain substitutes for baekelite, gallalith, and liquid and coloured lacs (Ditmar, 1921). In 1917 Schroeter and almost simultaneously Kantorowicz found that viscous, oily substances are formed when tetraline is heated with a little aluminium chloride. Schroetcr and van Hulle (1918-1920) showed that these oils consist of
threne (otianthrene),

U H 1H

principally

octiihudrophencm-

or

Ho

H 2 'N/N/'
Ha
and

^H \/V/ H H
2

of octn/tydrorudhmcehL' (octhracene),

C 14 H 18

or

H H., '\/ \ H,,

H2
These are accompanied by a
little

H,

benzene, /?/?-ditetralyl, etc. Like those obtained similarly from petroleum hydrocarbons, such viscous products appear to have practical applications as lubricating oils, as oils for internal combustion engines, ete., and disclose new methods for utilising the large amounts of naphthalene

produced.

INDENE, C 9 H 8 may be regarded

,

as formed

by the condensation

of

a benzene group

CH
HC
with a pentamethylene group
:
ll

ti-

CH
It is a yellow oil boiling at 180",

and

CH

CH CH.
found in coal-tar and in crude pseudocumene ; it has an odour of naphthalene and gives phthalic acid on oxidation and Indrene, ( 9 II 10 on reduction.
is
1

6-

ANTHRACENE GROUP

f,

CM
is

ANTHRACENE, C 14 H JO

or

found

in

coal-tar to the extent of 0-25

to'045 per cent.

The crude anthracene

oil

which

472

732

ORGANIC CHEMISTRY

passes over at a high temperature (above 270) in the distillation of tar is subjected to a further rectification which yields a 50 per cent, anthracene. This is purified by distillation from iron retorts with potassium carbonate,

which holds back the large amount

of Carbazole,

/NH, as the non- volatile

potassium compound,

y>NK.

The

distillate

then contains only anthracene

latter being removed by dissolving it in carbon disulsolvent with concentrated sulphuric acid ((Jer. Pat. this a mixture or of phide 164,508 and Fr. Pat. 349,337). The residual anthracene is purified by crystallisation from crude benzene (see Treatment of Tar described on pp. 630 et seq.), and

and phenanthrene, the

by sublimation with superheated steam. The proposal has also been made to purify crude anthracene (containing, say, 46 per cent, of anthracene and 13 per cent, of carbazole) with hot naphtha
acid, which convert all the basic substances into salts and dissolve the anthracene them, being afterwards separated by decantation. Evaporation of the naphtha gives anthracene of about 84 per cent, strength, and this gives a product of 95 per cent, purity on crystallisation from benzene. In place of sulphuric acid use may be made of aqueous caustic potash solution, the distillathe residual tion being carried out at 145 until water no longer passes over naphtha solution is decanted from the carbazole salt and cooled to deposit the pure anthracene (Kinzelberger, Eng. Pat. 144,648, 1920). It forms shining, colourless scales with a blue fluorescence, and melts at it dissolves slightly in ether or alcohol, but is readily 216-5 and boils at 351 soluble in hot benzene. Its calorific power is 9541 cals. At 100 it begins to

and sulphuric

sublime,

its

vapour pressure
100 0-04

in

mm.

of

mercury being
245
88-5

150
1-07

192
18-2

265
145-7

Sunlight gradually converts it into the polymeric ^wra-Anthracene (C ]4 10 ) 2 With picric acid it forms a molecular condensation product, C U 10 C6 2 (N0 2 ) 3 OH, melting at 138. By reducing agents, anthracene is transformed

H H

into Hydroanthracene,

C 6II4

<^ >C H
2
6

4,

which melts at 107

and

is

readily

soluble in alcohol.
Its constitution is deduced from its various syntheses. tetrabromoethane and benzene in presence of A1C13
:

Anschtitz obtained

it

from

CHBr2
2C 6 H 6
It
is

xCH.\

4HBr

+ O.H/
is

CHBr2
formed also when
o-tolyl

XJH/

>C 6 H 4

phenyl kctonc

heated with zinc dust

C6H

/C 6 H 5

- H

\C H
6

this synthesis establishes the ortho-position of the connections between the two nuclei and also the presence of the group. Confirmatory evidence is obtained from the

CH CH

following synthesis

CH 2
4Na
-=

4NaBr

\/ CH
0-Bromobcnzyl bromide

Dihydroanthracene
*

which, on oxidation, loses

2H and

gives anthracene.

ANTHRAQUINONE
,

733

Phihalic anhydride, when heated with benzene and A1C1 3 gives o-benzoylbenzoic acid, from which PC1 5 eliminates water with formation of anthraquinone, the latter giving

anthracene when reduced with zinc dust in the hot

H6 +

H< >0 = \CO/

4

/COv

/CO C 6 H 5

C6

H/

-> H

-|-

\COOH

/CO, C 6 H4 / >C 6 H 4 -> anthracene.

XXK

Centric linkings do not seem to be present in the nuclei of anthracene, which readily combines with ozone (E. Molinari, 1907), this property being characteristic of olcfinc double
linkings (see p. 107). It is used in the manufacture of anthraquinone and alizarin. Crude anthracene oil (green oil) was sold before the war at Us. to 12s. 6d. per quintal, crude 20 per cent, anthracene at Is. 6<7. per kilo, and the purified product at 6s. to 85.

per

kilo.

OCTAHYDROANTHRACENE,

C 14 H 18

(see p. 731).

SUBSTITUTION PRODUCTS OF ANTHRACENE

possible isomerides are here very numerous, but only few of them have been yet prepared. Three monosubstituted isomerides are possible, as is seen from the constitutional formula (see above). The constitution of the isomerides is ascertained from a study of the oxidation products and of the methods of

The

synthesis.

When
1

the substituents are in the y l or y 2 position, oxidation gives

anthraquinone.

CO
l\

ANTHRAQUINONE, C 14H 8O 2

or

is

obtained

very easily

\l/\/\l/
CO
by oxidising anthracene with dichromate and dilute sulphuric acid in the hot, or, better, with nitric acid, which does not give nitro-derivatives. It can also be obtained from phthalic anhydride and benzene in presence of A1C1 3
acid in presence (see above) or by electrolysing anthracene in 20 per cent, sulphuric of cerium, chromium, or manganese salts (Ger. Pat. 152,063, and Perkin, 1904).

many Derivatives of Anthracene, the following may be mentioned : anthiacencacids (a, /3, and y) ; chhrobromoanlhraccnes, which contain the halogens in the nitro- and dinitro-anthrncencs (7) ; 7-positions, as they form anthraquinone on oxidation ; and ft), anthrols obtained from 0-anthrol and C 14 3 ; B-anthraHiinc, 2
1

Of the

carbojcylic

H -NH

NH

xCBk

y-anthranol,

CH <
4

/CH 1X OH; anthrone,VAii' /^V^-i X CO / CH v

^
I

and

its

tautomeride
2
,

(s?e

pp.

18, 394);

>C

fi

y-hydroanthranol,

C 6 H 4<

\C(OH)/
quinones,
siilphonic

>C 6 H 4 \CH(OH)/
rufol,

-CH

the anthrahydro-

\C H 4 0^4/1 \ fi/f\\j /
6

(three isomerides:
;

chryttazol,

and
;

flavol)

anthracene-

\j\\J ri

and
;

C 14 H 7 O 2 OH; qmnizarin (^ a 2 -dihydroxyanthraqumone) -pur }Mroxan thin (^ j8 2 -dihydroxyC 6 H 4 (CO 2 C H(OH) (a /8 i) is par pur in (the isomeric flawpurptirin, anthraquinone) C 6 H 3 OH (anttraflavinic and atlirajmrpurin, anthragallol, etc., are also kno\vn) OH C 6 H 3 CO 2
:

disulpfwnic

acids

anthraquinonesulphonic
;
: :
:j

acids

hydro xyantJiracini none s,

:

'i

whi

'

'" J

'

rysom
iccnes

alkylanthrahydrides,

C 6 H 4 <^

,CH 2 v
)>C 6

H4

phenylanthrarwl (phthalidine ;,

C 6 H 4/

/ "^v^e^s/v

phenylhydroxyanthranol (phlhalideine),

C 6 H 4 <^

/0(C 6 H 5 )(OH) X
)>C 6

J</ ^ TTV -C(OH) j>^c

H 4;

anthracenecarboxylic acid

(a,

)8,

7),

C 14H 2 -CO 3 H;

alkylhydroanthranoU,

C 6H 4

<^

^>C

4,

etc.

734
It

ORGANIC CHEMISTRY

dissolve

can be purified by crystallisation from nitrobenzene or aniline, which it in the hot but not in the cold. Kinzelberger (Eng. Pat. 143,885, 1920) purifies it by heating and shaking it with chlorobenzene or solvent naphtha in presence of aqueous alkali (or with concentrated sulphuric acid), the anthraquinone solution being decanted off and the solvent removed by distillation. It. gives two isomeric monosubstituted derivatives. It forms yellowish needles melting at 274 and boiling above 360, and it dissolves in concentrated sulphuric acid, but is precipitated unchanged on dilution. It is very stable, is not easily oxidised and has the character of a rather than of a quinone. It is not readily reduced, is diketpne only slightly volatile and has no pungent odour. That the two lateral benzene nuclei have centric linkings and not olefinic double bonds is shown by the fact that, unlike anthracene (see above), anthraquinone does not fix ozone. When fused with potash, it gives benzoic acid and, when heated with

zinc dust

and NaOH, Hydroxyanthranol, C6H4

< CII^Q^>C H
6

4,

which has

a blood-red colour in alkaline solution and is oxidised to anthraquinone in the air. Reduction of anthraquinone with Sn and HOI gives Anthranol, C(OII) ^VA\ /Q rJH/i, which is a weak phenol.
I

\C(OH)/
cene.

More energetic reduction, such as The Schmidt reaction permits

distillation over zinc dust, yields anthraof the introduction of sulphonic or nitro-

groups into the non-substituted or the substituted nucleus of aiithraquinono

derivatives, according as the reaction occurs in presence or in absence of boric acid, a- or /?-Nitroderivatives can also be obtained, at will, by means of the same reaction (Or. Pat. 163,042 of 1905), which is facilitated by the presence of mercury salts.

Commercial anthraquinone cost before the war about sublimed chemically pure product 28,s.

6,v.

per
1
:

kilo,

and the

The most important compound or alizarin.

derivative of anthraquinone

is

the

2-dihydroxy-

CO
C 14H 8O 4
,

OH

ALIZARIN

(Dihydroxyanthraquinone),

or

was at

oo
one time obtained exclusively from madder roots (Rnbia linrtorum), from which Ruberythric Acid (a glucoside of the formula C 20II 28 14) is extracted this is separated into glucose and alizarin by boiling with dilute sulphuric acid. It is a very beautiful red colouring-matter and was known to tho ancients. Since 1 870, * following (iraebe and Liebermann's synthesis (1869), it has been anthracene is converted prepared only artificially in the following manner by oxidation with 2S0 4 and Na 2Cr 2 7 into crude anthraquinone.
;
:

This is then heated at 100 with concentrated sulphuric acid, which leaves the anthraquinone unaltered, while it converts the impurities into sulphonic acids soluble in water. The anthraquinone is then filtered arid washed and heated at 160 with fuming sulphuric acid (containing 50 per cent, of free S0 3 ), which converts it largely into the monosulphonic acid. The latter is dissolved in water and filtered to separate it from unaltered anthraquinono ; neutralisation of the solution with caustic soda results in the deposition of the sodium salt, which is only slightly soluble in cold water. One hundred parts of this salt are mixed with 25 parts of caustic soda and 12 to 14 parts of potassium chlorate, which facilitates the reaction ; the mixture is dissolved in the smallest possible amount of water and
1

In 1868 France produced and exported madder to the value of

respectively.

The exportation
entirely.

fell

to

800,000 in 1871 and to

then ceasing

1,720,000 and 1,240,000 160,000 in 1876, the production

PHEN^ANTHRENE
:

735

the liquid heated at 180 for two days in an autoclave fitted with a stirrer. The sulphonic group is thus replaced by hydroxyl (or ONa), and at the same time a second OH group is formed by the action of the chlorate

C.H 4

< JJJ>C.H

S0 3Na + 3NaOH

+ O = Na^ + 2H O + C.H <^>C.H ,(ONa)

2

2.

Sodium uiithraquinoncinonoHiilphonate

The fused mass

(alizarin) being

is run into water and acidified with sulphuric acid, the colouring-matter thus liberated.

According to Fr. Pat. 333,144* if fuming sulphuric acid acts on anthraquinone in presence is no partial formation of the w-sulphonic compound, the sulpho-group entering exclusively the ortho-position to the ketonic group. Alizarin may also be prepared (Ger. Pat. 186,526) without sulphonation by treating, with 30 kilos of NaClO 3 (or Na 2 O 2 Ba0 2 , say, 300 kilos of a mixture of NaOH and Pb0 2 , etc.) dissolved in 100 litres of water, 100 kilos of anthraquinone being then added and the liquid heated at 200 in an oil-bath until the oxidising agent disappears. After this, the mass is poured into water through which air is then passed ; the alizarin is precipitated with milk of lime, the precipitate being filtered off and decomposed with HC1 and the This method alizarin purified from anthraquinone residues by means of caustic soda. yields a purer product than other processes. Alizarin has been prepared recently by passing an electric current through a mixture of
of mercury, there

KOH

anthraquinone and fused potash.

Alizarin sublimes in fine, orange-red needles, melts at 289, and is almost insoluble in water and slightly soluble in alcohol ; owing to its phenolic groups When distilled with it dissolves in alkali and also forms a diacetyl-derivative.
zinc dust
it forms anthracene. metallic oxides it forms insoluble lakes of various colours, and on this With ferric oxide it gives a bluish black colour and is based its use in dyeing. the lakes of tin and aluminium are red (Turkey red). with lime a blue lake

With

The constitution of alizarin is shown anhydride and catechol at 150 in presence

also

by

its

synthesis from phthalic

:

of sulphuric acid

Derivatives of anthraquinone

and

of

amino-derivatives, form colouring-matters only are in the ortho-position to one another.

hydroxyanthraquinone, especially the when the two hydroxy-groups

PHENANTHRENE, C 14H 10
with which

<yi4 -cH
,

or
|

C 6H4 OH

||

is

an isomeride

of

anthracene,

When pure, it forms shining, colourless scales, it occurs in tar. soluble in ether, less so in alcohol (with blue fluorescence) and only slightly The separation of phenanit melts at 99 and boils at 340. soluble in water
;

threne from anthracene is described above (see Anthracene). Synthetically it is obtained by condensing 1 mol. of o-nitrobenzaldehyde (or its higher homologues) with 1 mol. of sodium phenylacetate in presence of acetic anhydride
:

C 6 HB

CH 2 C0 2Na + N0 2

C 6H4

CHO

- H + N0
2

C ,II4 Oil

C 6H5 C C0 2Na
Sodium
tt-phcnyl-o-

nitrocinnainato

Reduction and diazotisalion eliminate the

copper then
gives

N0 2

treatment with powdered

C 6 H4
j3-Phenanthrenecarboxylic Acid,
I

CH
||

C 6 H4-0 C0 2H

from

which

C0 2 is eliminated in the ordinary way with formation of phenanthrene.

786

ORGANIC

H F/M I S T R Y
C 6H4 CO C6H 4 CO
|

When oxidised with chromic acid, it gives first Phenanthraquinone,

^yellow crystals, m.-pt. 200),

and then Diphenic Acid, Ci 4H 10O4 or

,

C0 2H C0 2H

\
The constitution of phenanthrene is established by its syntheses and by oxidation products. The double linking between the two methinic carbon atoms is not shown by the ordinary reaction with permanganate (Baeyer) \see p. 107), but is made evident by the reaction with o/one (E. Molinari, 1907
its
;

see p. 107).

The

constitutional formula of phenanthrene

may

be represented

thus

CH CH ciijy ~\c CH

no/

CH CH'

\rc\

CH'CH

ycR
of three

and it may, therefore, be regarded as formed by the condensation benzene nuclei.

OCTAHYDROPHENANTHRENE, C 14 H 18
petroleum and tar
distilling

see p. 731.

OTHER CONDENSED NUCLEI OF LESS IMPORTANCE,

above 360, arc as follow
/:

found in the portions of

CH

CH

;>

C
C!

fi

CH

^C,H 3-CH
Fluoranthrene, ('isHjQ

^ CH
CH'

^
C3

10

H 6-CH

Pyre no, t'leHio

rhrysrne, CisHj]

fioHe

C 6 H 4-CH

C 10 H 6

I'iconr, (.'22^ 14

Rrtene,

Picene, Chrysene, m.-pt. 250, b.-pt. 448 b.-pt. 394 m.-pt. 364; Fluoranthrene, m.-pt. 110 and b.-pt. 250 (60 mm.); Pyrene, m.-pt. 148, b.-pt. 260 (60 mm.).

Retene has m.-pt. 98

and

BB.

HETEROCYCLIC COMPOUNDS

These are substances containing at least one nucleus, the atoms forming the ring being of more than one kind, i.e., they are not all carbon atoms as in the Jwmoeyclic compounds as yet studied, one or more of these carbon atoms
being replaced
heterocyclic

by nitrogen, oxygen, sulphur, etc. One of the simplest of these compounds is furfuran. 1. FURFURAN (Furan), C 4H 4O, is a colourless liquid which is insoluble in water, smells like chloroform, boils at 32, and is found among the first products of the distillation of pine-tar. With metallic sodium it does not give
;

nor is it in the form of hydrogen, so that the oxygen is not present as Oil carbonyl (CO), since furan does not react with phenylhydrazine or hydroxylamine. It can be converted into coorulinic aldehyde, while, under suitable conditions, succindialdehyde loses H 2 giving furan. These reactions indicate
its

constitution

CH 2 CHO
2 2 Succindialdehyde

CH CH N
:

CH

CHO

CH C
:

Furan

HIOPHEN

737
witli

A
furan.

shaving of pinewood moistened with HC1 gives a green coloration The latter reacts with HC1, forming a white mass.
,

FURFURAL (a-Furol, Furfuraldehyde), C 5 H 4 O 2 is obtained readily and abundantly by the action of sulphuric acid on pentoses, peiitosans, and woody substances (see p. 527) it is found in fusel oil and in clove oil. It is a colourless oil of aromatic odour, turning brown in the air and boiling at 162 ; it is soluble in alcohol and, to a less extent, in water.
;
fJ

~"

CHO

Its aldehydic properties justify the constitution

\
,

With

alcoholic

potash

it

OH 2 OH
gives

C0 2 H
and Pyromucic
acid,

a corresponding Furfuryl alcohol,

0;

the latter melts at 132, sublimes readily, dissolves in hot water, decolorises alkaline permanganate and combines with 4 atoms of bromine, the presence of two true olefinic double linkings being thus confirmed. If heated in a sealed tube at 275 it gives furfuran and CO 2 With aniline and HC1, or with aniline acetate paper, it gives a characteristic intense red coloration (see p. 528).
.

2.

THIOPHEN, C 4 H 4 S,

their similarity in boiling-point (84) free from thiophen, see pp. 630, 633.

occurs in tar and always accompanies benzene, on account of and other properties. For the preparation of benzene

Thiophen is produced on a large scale, but in small yield, by passing acetylene or ethylene through boiling sulphur, or by passing illuminating gas over red-hot pyrites. W. Steinkopf (1911) obtains an increased yield by passing a current of acetylene over pyrites contained in a revolving iron drum and heated to 300 in a furnace, the exhausted pyrites being continually discharged and fresh pyrites introduced. The condensed liquid product contains 40 per cent, of thiophen, which can be extracted by fractional distillation. One of the syntheses of thiophen consists in the distillation of suceinic acid in presence
of phosphorus sulphide,

hydrogen and hydrogen sulphide being evolved

:

this synthesis

confirms the constitution

C CO 2 H

ft

HC .=
-*
I

CH,
(Thiophen).

H C C0 H
2

"|

\S HC == CH/
1

ft

Thiophen is a colourless and almost odourless, refractive liquid, boiling at 84, and having the sp. gr. 1 -062 at 23. The presence of the double Imkings is confirmed by the
quantitative addition of ozone.

Pure thiophen, prepared synthetically, costs as

much
is

as

18 per kilo.

CH C(CH 3 K
:

Dimethylthiophen
enolic

(ihioxene),

\S,
:

obtained by the interaction of the

:

CH C(CH 3 )/
form of acetonylacetone and phosphorus pentasulphide, and 1 4-diketones in general yield higher homologues of thiophen, which, when oxidised, give carboxyl groups in place of the side-chains. Thiophen compounds, such as halogen and nitre-derivatives, sulphonic acids, etc., behave very similarly to those of benzene. With isatin and concentrated sulphuric acid, thiophen gives a blue coloration (indophenin,
3.

C 12 H 7 NOS). PYRROLE, C 4 H 5 N,
oil

animal

(bone

oil),

purified

pyridine bases by by converting into the potassium derivative,

is found in small quantity in tar and in larger quantity in Dippel especially in the fraction distilling at about 130, which is freed from It is saponifying with soda and washing with dilute sulphuric acid.

C 4 H 4 NK (by

the action of potassium),

ether, in which it is insoluble, and then treated with water, the pyrrole being thus liberated. After fractional distillation, it is obtained as a light, colourless oil, boiling at 131, and possessing a faint odour of chloroform. It readily turns brown and polymerises under

which

is

washed with

the action of light.

(see above).

With

isatin

and sulphuric acid

it

gives the blue indophenin reaction

738
moistened with HC1.

ORGAN 1C CHEMISTRY

A reaction characteristic of the pyrroles is the red coloration they give with a pine shaving
of the iminic group is replaceable by metals, acetyl, and alkyl groups. Pyrrole now forms the basis of a number of important compounds, which arc obtained by various syntheses investigated by Ciamician and his collaborators during the past quarter of a century. The constitutional formula of pyrrole is as follows
:

The hydrogen

this being

deduced from a number of reactions and syntheses, e.g., the- formation of pyrrole by the action of ammonia on y-diketones or on succinic aldehyde, with intermediate formation of diammonaldehyde
:

CH 2 CHO
|

CH OH.
:

+ NH 3 =2H

CH2 CHO
-

CH

>NH.
:

Oil'

This pyridino nucleus occurs frequently in nature, in combination with other groups in alkaloids (nicotine, etc.), in the colouring-matter of the blood and of chlorophyll, etc.

CH 2 CH N OH
:

When

boiled with hydroxylamine, pyrrole gives succindialdoxime,

CH 2 CH N OH
:

CH 2 CHO
which, with nitrous acid, gives succinic aldehyde,
|

CH a CHO CH 2 C(k
Pyrrole
or
zinc
is

formed by the
while

distillation of

succinimide,

CH 2 (XX
-

/NH,

with sodium

dust,

the

gxidation of pyrrole

with chromic acid gives maleimide,

CH COv
II

CH CO/
mass

>

H.

is changed by acids ; with HC1 in the hot, it polymerises and condenses to a red (pyrrole red). It has a faint basic character, but gives a hydrochloride, (C 4 5 N) 3 , HC1, only in ethereal solution.

Pyrrole

derivatives.

it gives not additive products but only, like benzene, substituted Tetraiodopyrrole (iodol) is obtained from pyrrole by the action of an alcoholic, alkaline solution of iodine ; it is an efficient antiseptic and is used instead of iodoform, being without the unpleasant odour of the latter. It melts at 190, and is colourless when

With the halogens

freshly prepared, but

it

With

nitric

and sulphuric

gradually turns brown and deposits iodine. acids, pyrrole resinifies ; the nitre-derivatives, which contain

the isowfro-group, NOOH, are prepared indirectly (e.g., with alkyl nitrate). Pyrrole is analogous in many of its properties to the substituted phenols and anilines ; thus, a methyl- or acetyl-group united to the nitrogen (N-derivatives) is displaced, on heating, to a carbon atom (C-derivatives)
:

HC CH
II
II

HC CH
II II

HC CH
P
;

HC-CH
II
II

HC CH

HC C-CH 3
~>

HC CH ->

\/ N
I

\/ NH

V
N
I

II

HC C CO CH 3

\/ NH

CH 3

CO CH 3

PYRAZ
Potassium pyrrolate, C4 H 4 NK, and
(m.-pt.

LE
acid,

739
C4 H 3 (CO 2 H)
it

102)

this loses

CO 2 give pyrrolecarboxylic CO 2 and gives pyrrole again when heated,

NH

while

loses

water and

N
forms a dimolecular anhydride, Pyrocoll,

CO
,

when

treated with acetic

CO

anhydride. Like the substituted phenols, the C-alkylpyrroles give pyrrolecarboxylic acids by simple fusion with potash. In analogy with the formation of nitrosophenols from phenols, pyrrole, with ethyl nitrite in presence of sodium alkoxide, forms which exists in
Nitrosopyrrole,

tautomeric modifications

HC
II

NOH
and

HC--CH

II

HC CH

HC C NOH.
:

II

N
and sodium alkoxide, another atom of carbon is introduced into the nucleus, a pyridine derivative being formed. Hydrogenated derivatives of pyrrole, are formed more easily than those of benzene, and,
of chloroform
like the latter,

By means

of zinc

do not show purely aromatic properties. When pyrrole is reduced by means and hot acetic or cold hydrochloric acid, it yields Dihydropyrrole (or pyrroline, m.-pt. 91), which, with HI and P, gives Tetrahydropyrrole (or pyrrolidine, b.-pt. 87),

H2

H
NH

the latter, together with N-mcthylpyrroline, are the simplest cyclic alkaloids

known and

are found in tobacco. Pyrrolidine is found in carrot seeds and a C-methylpyrroline in pepper. When proteins are decomposed by means of trypsin or hydrochloric acid, the aminoacids formed arc accompanied by la.vo -rotatory u-Pyrrolidinecarboxylic Acid. Among the
is

products formed by the degradation of egg albumin by baryta rr /i r^u U U OH

2

u'-pyrrolidone-u-carboxylic

acid,

OC

CH C0

H, which

is

also

known

as pyroglutamic acid;

it

melts at 183, has

NH
a neutral reaction and, when heated, loses CO 2 and H 2 O, forming pyrrole. PYRAZOLE, C 3 H 4 N 2 is a heterocyclic compound with two nitrogen atoms in the ortho-positions. It can, indeed, be obtained by the condensation of 1 mol. of diazomethane
,

with

mol. of acetylene

CH
HI

/N
CH/II

CH =
|

N,
(Pyrazole).

CH

\N

>NH CH - CH/

It is very stable, melts at 70, is a feeble base, and has a neutral reaction in water. The u'/S'-dihydro-compoimd is known as Pyrazoline, C 3 6 N 2 and the a'-keto-derivative

CH
of
this,
|

Nv

CH 2 -CO/
-

/NH,
,

as

Pyrazolone.

Condensation of

methylphenylhydrazine,

CH 3 NH NH C 6 H5 CH 3 C-N(CH 3 k
||

with

ethyl

acetoacetate

yields

Dimethylphenylpyrazolone.

H C

\N CO/

C 8 H 5 which
,

bears the

name

antipyrine

and

is

used medicinally

owing to its marked antipyretic action on the animal organism ; it melts at 113, dissolves in water and in alcohol, and gives a greenish blue coloration with nitrous acid and a red coloration with ferric chloride.

740

ORGANIC CHEMISTRY
is

PYRAMIDONE
xN(CH 3 C 6 H 5 N<^
)

dimethylaminoantipyrine or phenyldimethylaminopyrazolone,

\CO

O CH 3
||

and
)2

is

prepared by reducing isonitrosoantipyrine, with

C-N(CH 3

ft forms a subsequent alkylation (Meister, Lucius und Briining, Ger. Pat. 71,261, 1891). white crystalline powder, m.-pt. 108, has a somewhat bitter taste, and dissolves readily in alcohol and in 1 8 parts of cold water. It is used as an antipyretic, the dose being 0-3 grin.

N-=.-CHv

THIAZOLE, C 3 H 3 NS,

or
|

CH

= CH/
,

\S, may be regarded as thiophen with one

CH

group replaced by N. It shows analogies with the pyridiue bases. Just as benzene may be obtained from aniline, thiazole may be obtained from aminothiazolc (see below). AMINOTHIAZOLE, C 3 H 2NS NH 2 is obtained by the action of monochloracetaldehyde on pseudo-thiourea

CHo
|

Cl

H1SL

CH
HC1

CHO
and
is

>C NH 2 HS/

+H

|j

CH
N=CHx \NH,
|

a base analogous to aniline.

or Glyoxaline, C 3 H 4 N 2 or

IMINAZOLE

molting at 92,

is

a strong base

HC =. CH/
with a fishy odour, and
of
is

isomeric with pyrazole (see above]

little

glyoxal in presence of a regarded as a derivative of iminazole.

ammonia on

formaldehyde.

it is obtained by the action Alloxan (see p. 435) may be

LYSIDINE, Methyldihydroiminazole administered as a solvent for uric acid.

or

Ethenylethylenediamine,

C 3 H 3 (CH 3 )N 2 H 2

is

OXAZOLE, C 3 H 3 NO,
with furfuran
(see above).

or

HC=CH/
Its

O,

is

also

termed Furazole, owing to

its

analogy

phenyl derivatives are known, as also are those of Isooxazole,

HC-CH
HC=N,
OSOTRIAZOLE,
It melts at
|

HC=-N/
22,
boils at

J>NH,
arid

is

faintly acid

and

also

faintly basic

in

character.

204,

is

soluble in water.

N-=CHv

TRIAZOLE
in water.

(or

Pyrrodiazole),

HC

J>NH, = N/

melts at 121, and

is

extremely soluble

HC=Nv
TETRAZOLE,
at 155

N=N/
HC=N, =,

J>NH,

is

a weak acid which forms explosive salts

it

melts

and

is

soluble in water.

AZOXAZOLE,

HC=N/
4.

O, yO,

is

also

termed Furazan.

PYRIDINE AND

ITS

DERIVATIVES

Pyridine a heterocyclic nucleus containing 5 carbon atoms and 1 of nitrogen. It resembles benzene in its behaviour, but it is more stable or more indifferent towards sulphuric, nitric, and chromic acids, permanganate, etc. Oxidation of the homologues with side-chains gives pyridinecarboxylic acids, and the latter, when distilled with lime, give pyridine.
is

PYRIDINE DERIVATIVES

741

Its hydro-derivatives are readily formed in a similar manner to hydrobenzenes. Halogen derivatives are obtained more easily by the action of PC1 5 or SbCl 5 at a high temperature than by the action of the halogens themselves. Oxidising agents attack only the side-chains and not the pyridine nucleus. With sulphuric acid, a pyridinesulphonic acid is obtained, and this gives a hydroxyl-derivative of pyridine on fusion with potash, or a nitrile when treated with KCN. There is hence a marked analogy to benzene, although direct nitration of pyridine is not possible unless phenolic or aminic groups are present. Pyridine and its derivatives are decidedly basic in character (tertiary bases) and form soluble salts with hydrochloric or sulphuric acid and insoluble ones the double salts with platinum and gold chlorides are with chromic acid soluble. Like tertiary bases, they combine with methyl iodide to form
;

slightly

quaternary bases.

From the complex alkaloidal groupings, pyridine compounds are often obtained either by distillation with caustic potash or merely by energetic
oxidation.

Goal-tar and Dippel animal oil contain various pyridine compounds which are separated after conversion into salts. General Methods of Formation, (a) The oxidation of quinoline (see later) which C' 3 N(C0 2 TT) 2 5 yields first quinolinic acid (pyridinedicarboxylic acid),

/J-Methylpyridine is obtained by distilling giving pyridine. this explains the presence of pyridine products in acraldehyde-ammonia in the dry distillation of nonDippel oil, acrolcTn and ammonia being formed defatted bones. An important synthesis is the general one of Hantzsch by which ethyl

then loses

00 2

dihydrocollidinedicarboxylate, for example,

ammonia with

ethyl acetoacetate

from different aldehyde-ammonias

-

is obtained by heating aldehydeother pyridine compounds are obtained and /?-ketonic acids
;
:

CO CH 2 C0 2 C 2H 5 + CH 3 CHO 2CHo " c5N(cn 3 3 H 2 (co 2c 2 H 5 ) 2 + :m a o.

)

+ NH =
3

and CH is eliminated by the ester thus formed tho hydrogen of the of nitrous acid, and the resulting collidinedicarboxylic acid, when treated with potash and distilled with lime, loses the two carboxyls and gives collidine oxidation of the latter gives pyridinecarboxylic acid, and (trimethylpyridine) elimination of carboxyl from this in the ordinary way forms pyridine.

From

NH

means

When ethylidena* chloride Aldehydine, C 8 H n N.

-

is

heated with alcoholic ammonia,

it

yields

group,

The constitution of pyridine, corresponds with that of benzene in which one mcthinic CH, has been replaced by a nitrogen atom. Koriier in 1869 proposed the following
still

constitutional formula, which

agrees well with

all

the general properties of the pyridine

compounds

CH

en

N
of hydrogen, is reduced with alcohol and sodium, it fixes six atoms of which is shown by its synthesis constitution tho or hexahydropyridine, giving piperidine when pentamethylenediamine hydrochloride is rapidly heated

When

pyridine

CH 2 NH 2 CH -NH 2
2

H <H

= NH 3 + CH / >NH. X CH 2 -CH/

X CH 2 CH 2x

742

ORGANIC CHEMISTRY
derivable theoretically from Korner's formula. There are. indeed, (a, /?, and y), and six disubstituted isomerides : aa',

When pipcridine is heated with sulphuric acid it gives pyridine, and the latter, when strongly heated with hydriodic acid, gives normal pentane. The constitution of pyridine is confirmed by the fact that the isomeric substitution products correspond exactly in
number with those
a/3, a/3',

three monosubstituted isomerides

Py, 00' , and ay. position of a substituent group is determined by converting it into a carboxyl group with formation of the corresponding acid of known constitution (see later). Thus, picolinic acid has the carboxyl in the a-position, nicotmie acid in the /?-, and isonicotinic

The

acid in the y-position.

sp. gr.

PYRIDINE, C5 H 5N, is a colourless liquid, J -0033 at 0. It dissolves in water in

alkaline reaction (not sensitive so to methyl orange).

It has

and having the and has a slight proportions to phenolphthalein, slightly to litmus, and more
boiling at 115
all

an unpleasant odour and is hence used to denature alcohol (see p. 177). It forms a slightly soluble ferrocyanide, by means of which it can be purified. It forms pyridineammonium iodides, e.g., C5 5N,CH 3I, which with KOII in the hot gives dihydromethylpyridine, C5 II4 2 with a characteristic 3

H H NCH

pungent odour. Metallic sodium polymerises pyridine, forming dipyridine, C 10H 10 N 2 (b.-pt. 290), and y-dipyridyl, C 10H 8N 2 or NC5 H 4 C5 4N (m.-pt. 114). With sulphuric acid it gives /?-pyridinesulphonic acid, NC 5 H4 S0 3 H. Pyridine is administered hi cases of asthma and has been suggested as a

means of purifying synthetic indigo. Mixed pyridine bases for denaturing kilo and pure pyridine 8,5.
,

cost before the

war about
:

Is. 2d.

per

Of the homologues of pyridine, the following may be mentioned PICOLINE (Methylpyridine), NC 5 H 4 CH 3 exists as three isomeric liquids

similar to

pyridine and of disagreeable odour ; their boiling-points are : a, 1 29 ; ft, 142 ; y, 144. Besides by general synthetical methods (see above), yft-picoline is formed by heating strychnine with lime. u-Methylpyridine condenses with aldehydes by means of the methyl

group, giving alkines

NC 5 H 4 CH 3 + CH 3 CHO - NC 5 H 4 CH 2 OH(OH) CH 3
-

This

a-picolylalkine gives up a molecule of water yielding a pyridine derivative with an un-

saturated side-chain,

e.g.,

a-allylpyridine,

NC 5 H 4 CH OH CH 3
:

These reactions proceed in one

stage? if zinc chloride is

LUTIDINES
boiling-points
:

(Dimethylpyridines),
aa', 143
;

NC 6 H 3 (OH 3
;

)2 ;

present with the aldehyde. three isomerides are known, with the

ay, 157. COLLIDINES (Trimethylpyridines), 5 2 (Crl 3 ) 3 , are isomeric with propylpvridinp. a-Allylpyridine (see above) fixes hydrogen (alcohol and sodium), giving the alkaloid CONIINE

pp', 170

NC H

(inactive racemic), which is a-propylpiperidine ; fractional crystallisation of the tartrate separates the laevo- from the dextro-form, the latter being identical with natural coniine (the poison of hemlock), boiling at 167. The asymmetric carbon atom causing the activity is the a- one united with the propyl group.

isomerides are known, 148. They are obtained by heating the corresponding hydroxypyridinocarboxylic acids with lime. They are phenolic in character and give red or yellow colorations with ferric chloride. a-Hydroxypyridine forms two series of derivatives corresponding with the two tautomeric formulae
-

PYRIDONES

or

HYDROXYPYRIDINES, NC 5 H 4 OH. The three

,

their boiling-points being:

107;

ft,

124; and

y,

C2 H2<|

yC(OHk

\N

>C2H 2 /

and

C 2 H 2<

yjOv

\NH/

>C2H 2

the former giving, for instance, a methoxypyridine and the latter a methylpyridone. PYRIDINEMONOCARBOXYLIC ACIDS, NC 5 H 4 CO2 H. The three isomerides arc as a or picolinic acid, m.-pt. 135 ; /? or nicotinic or nicotic acid, m.-pt. 231 ; y or follow
:

isonicotinic acid, m.-pt.

309.
of pyridine derivatives with

They are formed by oxidation

a side-chain or by elimination

of one carboxyl from the pyridinedicarboxylic acids, that nearer to the nitrogen being the

P
more
easily eliminated.

PE
is

RIDINE
obtained on oxidation of
nicotine.

743

Nicotinic acid

When

boiled

with sodium amalgam in a highly alkaline solution, these acids lose nitrogen as 3 and give saturated, open-chain, dibasic hydroxy-acids. When the carboxyl is in the a-position (with the dicarboxylic acids also), an orange coloration is given with FeS0 4 As they are both acid and basic in character, they exhibit analogies with glycocoll (see
.

NH

p. 423).

The PYRIDINEDICARBOXYLIC ACIDS, NC 5 H 3 (CO 2 H) 2 have the

,

following melting-

points

aa or
a/3' or

dipicolinic acid,

226

ft/3'
;

190
acid,

isocinchomeronic acid, 236

or dinicotinic acid, 323 ay or lutidinic acid, 235

a/3 or quinolinic acid,

;

fiy or cinchomeronic

249.

Quinolinic acid is formed by the oxidation of quinoline, its constitution being thus established, and since in the hot it loses CQ3 from the a-position, giving nicotinic acid, the constitution of the latter is also fixed.
Pyridinetricarboxylic acids (obtained by oxidising cinehonine or quinine), as well as pentacarboxylic acids and hydroxypyridinecarboxylic acids, are also known. HYDROPYRIDINES. The dihydropyridines are mentioned above. The Mrahydropyridines and their derivatives are known also as piper ideines, while the Jiejcahydropyridines

and their derivatives

lupetidine,

NC6 H 9 (CH 3 2 copellidim, NC6 H K (CH 3 3 etc. PIPERIDINE, NC 6 H n is obtained by heating piperine C 12 H 9 O 3 (m.-pt. 129), which is the alkaloid contained in condensation of 1 mol. of piperic or plperinic acid, G ia H 10 O
)
; )
, ,

included in the term piperidities

embrace pipecoline,

NC5 H 10 CH 3
1

or piper ylpiperidinf^

H 10 N

(1

pepper, and , or
-

is

formed by the

CH
with

<>C H
6

CH CH CH CH CO 2 H,
:
:

For the constitution and syntheses of the latter, see p. 741. I mol. of pipcridine. is soluble in water Piporidine boils at 106, has an odour of pepper, is strongly basic, and or alcohol. With H 2 O 2 it gives aminovaleraldehyde. I an ammonium iodide derivative Piperidine, being a secondary base, forms with 2CH o which, when distilled with silver oxide, gives an unsaturated open-chain, tertiary base ; O and distillation, loses tritnethylaminc and forms in its turn the latter, with CH 3 I, Ag " 2
piperilene,

CH 2 CH CH 2 CH CH 2

To the group
little

importance

ON
:

of heterocyclic

compounds belong the

following,

which are

of

HCCH
HO

HO

CH 7
CII
CFL,

CI1 2 CI1 2

HO
l
f

CH

Y
)

CH
aliline

Y
H
;

CH 2

yrone or pyroromane (m-pt. 32')'; tlHMHOis moric a-pyrouo

coitmalin

rymzine or
(in.-pt. 47
is

ryrimMint
or w-dtozine (m.-pt. 22")

and with
piperazine,

basic gives

MorpJiolinr, a kiso, b.-pt.

129 J

From these compounds may be derived coumalinic or comanic. acid, meconic acid, OgHO C5H 3 2 C0 2H (also formed from malic acid) which can be obtained from opium and gives pyromeconic acid by Jg, chelidonic acid, C 5 H 2 2 (C0 2 H) 2 which is found in celanelimination of C0 2
;
,

dine, loses

C0 2 giving

comanic acid and pyrone.

ALKALOIDS
These are found in various plants and have medicinal and often poisonous some of them, such as caffeine, theobromine, etc., were described properties on pp. 437 et seq., and the principal ones having basic characters (vegetable bases) will be considered here. are almost all laBvo-rotatory and have an alkaline reaction and a
;

They

744
bitter taste.

ORGANIC CHEMISTRY
They

are soluble in alcohol and to a less extent in ether, and are water and in alkali ; in acids they dissolve with formation in usually insoluble of crystallisable salts. Nearly all alkaloids are precipitated from their solutions iodide, HgI 2 KI, or by tannin, phosphomolybdic acid, potassium mercury 1 From etc. nitro-derivatives aromatic acid, etc.), plants they are
,

(e.g.,

picric

extracted with acid solutions and are then liberated with alkali and either
distilled in

steam or, if they are non-volatile, filtered off. converted into salts by means of strong acids, their specific rotatory acids are almost completely dispower is not greatly influenced, since these with weak solution acids, however, the salts are only sociated in aqueous the hence and rotatory power is different, being due to very slightly dissociated,

When

"different ions.

A. Pictet (1906) regards the alkaloids not as assimilation products of the of proteins, nucleins, organism, but rather as nitrogenous decomposition products condensed with other substances present in the chlorophyll, etc., which have that alkaloids containing the pyrrole group have their plants. Jt is supposed in which such group is certainly present, while or in chlorophyll, origin protein a similar origin, the transformation of the have those with a pyridine grouping the nucleus the into being possible even in the laboratory pyridine pyrrole itself does not appear to exist in the proteins, or group quinoline pyridine
;

2 chlorophyll, etc.
1

A mixture of these is separated as follows Separation and Tests of Alkaloids. From the neutral or acid aqueous solution, other extracts: difjitalin, picroloxin, and tannin. colchicine, and from a solution of these the first and last are precipitated by confine, -nicotine, Irucine, delphinine, II. From the alkaline aqueous solution, ether extracts
:

I.

alkaloids can be distinguished by the following colorimetnc tests, arranged colours are represented shortly (as with the colouring-matters ; see later) as decolorised or colourless ; Y yellow ; O orange ; B blue ; Br brown ; follow intense ; tin =- green ; V -- violet ; -\rose ; black ; 7? *=- red ; r Gr grey ; hi r^ weak. The reagents most commonly used are : to 20 drops of a solution containing 10 drops of 3 (sp. gr. 1-lft.l) (1) KrdmainCs reagent : One cubic centimetre of .this 2SO 4 and 20 c.c. of water are added 40 c.c. of concentrated of the dry alkaloid and the changes observed after 15 to 30 liquid is poured on to 1 to 2 grms.

and pfiyeoatiymim*. narcotine, veratririe, atropin*, strychnine, aronitine, quinine, codeine, II I. From the alkaline aqueous solution, chloroform extracts : cinc/ionine, caffeine, curarine, morphine, wlaninr. and tJteolromine.

The separate by Hager. The

HNO

(2)

Frdlnh'x reagenf

0-5 grm.
:

(3) (4)
(5)
2

Mandelin's reagent
flffltt/MfVw reatjcnt
:

grm.

sodium molybdate in 100 c.c. cone. H aS() 4 ammonium vanadate in 200 grms. H 2SO 4 (monohydrate).
.

sought Galen (A.D. 131-200) studied various medicines more rationally than had been previously done by Hippocrates (400 B.C.). Numerous medicines proposed by Galen were used as sovereign remedies for some centuries, until indeed Paracelsus (1493-1541) gave a new direction to medicine by contesting the theory in of Galen and of Avicenna and by founding ialrocJi"ini8lry, which had such a large following " History the Middle Ages, and which ultimately degenerated into the most fanlastic sorcery (fee
control of the yield medicine real support, by rigorous of all the natural and artificial drugs. In the past the curative properties of various substances were discovered by pure chance ; to a patient this was the case, for instance, with antifebrin (acetanilide), which was administered in mistake for Nowadays, however, a rational procedure is followed, use being made
of Chemistry," Vol.
I., p.

: a solution of formalin in sulphuric acid. sulphuric acid solution of ammonium selenite. Even during the most remote ages human beings Synthesis of Alkaloids and Medicine. remedies for their ailments in the principles contained in various plants and animals.

Lafou'ft redf/int

14).

Modern chemistry alone could physiological and chemical actions

naphthalene.

others either of analogy in chemical constitution between the substance under consideration and on human of known action or of systematic physiological tests, first on animals and afterwards

Until the beginning of the nineteenth century, the energies of chemists were directed to the those parts of plants successfully applied in discovery of the active and essential principles of their medicine. When these were isolated in the pure state, attempts were made to establish chemical structures and, in some cases, to effect their manufacture synthetically. As early as 1805 Sortiirner discovered and isolated morphine, the active principle of opium, and in 1821 Pelletier and Caventou discovered the alkaloids of cinchona bark, which were studied in 1850 by Strecker with the object of ascertaining their chemical constitution. The synthesis have not of these alkaloids was by no means an easy task, but in cases where they themselves been obtained by laboratory reactions, simple derivatives have been prepared, and these often
.

REACTIONS OF ALKALOIDS

745

Thus synthesis has given roddnr (or methylmorphine) exhibit similar therapeutic properties. and dionine (ethylmorphine), which in many cases are excellent substitutes for morphine, as they Derivatives of cocaine, such as ucaine (a derivative of ^-mcthoxyare scarcely if at all poisonous. piperidine ; Ger. Pats. 90,235 and 97,672), and of quinine, such as euquinim (the carbcthosyclerivative of quinine, without the bitter taste of the mother-substance), have also been prepared. Chemical investigation not only gives new products but leads to improved manufacture and 40 per kilo, consequent cheapening of the old' ones. Thus, quinine, which 20 years ago cost was sold before the war in a highly pure state for 32-*. Vast works now turn out enormous quantities of synthetic drugs, although these are administered in doses of centigrams ; thus, of kilos anlipyrine, discovered by Knorr, was consumed to the extent of hundreds of thousands in the first few years during which infliienza made its appearance. Modern industrial conditions have rendered possible the development of serotherapy (see p. 138), and groat results are now promised by organotherapy or otothrrapy. This is based on the fairly are continually general phenomenon that in the different organs of a healthy individual substances
produced capable of guarding them against different affections. This principle, introduced forward vaguely and confusedly by Brown -Sequard in France in 1891, wa.s. in 1895 brought 48 VOL. II.

746

ORGANIC CHEMISTRY

The work of Pictet and of Ellingcr has shown how these groups, occurring in the alkaloids, may be derived from the transformation of the pyrrole and indole Ciamician and Kavenna (1911-1913) found that the production of groups.
with triumph by Baumann, who found that in many persons goit.ro is due to deficient secretion of iodo-products by the thyroid glands (we Vol. I., p. 162), and, having extracted the active iodine principle, ihyroidin, from the thyroid of healthy sheep, that this constitutes a rapid and effective cure for goitre. For the treatment of other diseased organs, ovarin, ccrcbrh), nnclein* etc., were prepared from the corresponding organs of healthy animals. Coal-tar derivatives have been employed for the synthesis, not only of artificial alkaloids, antipyretics, and antiseptics, but also of an important group of ancesthclic or hypnotic, substances which have been of great service to medicine and especially to surgery in rendering painless the most complicated operations. At first, substances such as 'ether and chloroform were employed which produced general anmthetiia of the organism, but the use of these, especially of chloroform, was attended by much inconvenience and often by death of the patient. Sulphuric ether was recognised as an anaesthetic by Faraday as early as 1818, but it was used for the first time by the American doctor, (A AV. Long, in 1842. The anaesthetic is carried by the blood into contact with the nerve-centres which perceive pain, producing a poisoning and a paralysis which last for some time, but at the same time thoe centres which govern the action of the* heart and of respiration are also affected, thus causing the dangers and disturbances accompanying general anaesthesia. The nervous currents start from the periphery, from the points where the surgical operation begins, and are transmitted to the brain, which transforms them into the sensation of pain, and it is precisely by the influence of the aiiH'sthetir on the cerebral centres that pain is avoided. Anaesthesia ceases to be dangerous when the paralysis is effected on the peripheral nerve-centres at the beginning of the nervous In this way the ideal of local amc*thc*ia was currents, without, however, reaching the brain. arrived at, this being much more rational and much less dangerous, since by its means only the or of the to be single organ region body operated on is rendered insensible. To chloroform, ether, etc., were added, in 1885, cocaine, which paralyses only the sensitive peripheral nerves and does not- influence the motor nerves. It can now be indicated which Hpccilic atomic groupings in the molecules of ancrsthctics or hypnotics confer on these their special
properties.

Hypnotics include those of

(chloralformamide)

(1)

the chloral hydrate group, to which belong also chloralamide

;

and

paraldehyde

(2)

the tert.amyl

alcohol

class,

f'jj

>^'<OH

B
t

characterised by the presence of a hydroxyl and of a carbon atom united to throe alkyl groups, the action of these compounds increasing with the molecular weight- ; (3) the intermediate dormiol [tert. amylchloral, CC1 3 ( H(OH)(OC 6 1 , ) j class ; (4) the urcthane derivatives, including hi'donal [methylpropylcarbinol urcthanc, CO () CH(CI1 3 )(C 3 7 )] ; (5) a group of compounds 2 containing a single carbon atom united to two ulkvl groups and to two sulphonic residues,
4

NH

r.f/.,

(0)

(^^hylsulphonal or diethylsulphoiiemcthylcthylmethane); a group studied by E. Fischer and consisting of urea derivative,*, e.g., 2 00 'NH CO
tr tonal,

CH

SO

n'^^^Sof -CMl!

NH

CH(C 2 H 5

(dicthylacetylwa) or, better, (Ui thylmalonylnrca,

barbituric acid), which bears the name of vcronal (m.-pt. 191 ; it was prepared by E. Fischer and J. Mering, patented by Messrs. Merck in 1003 and then made by Messrs. Fr. Bayer, of Elberfeld) and serves to replace chloroform, being free from the dangerous consequences of the latter (provided that it is not administered to patients with weak kidneys). Change of the alkyl groups in veronal is accompanied by change in the properties ; thus, dimethyl barbituric acid has no hypnotic properties, dipropyl barbituric acid is more effective than veronal, while dibptizy] barbituric acid is without action, possibly owing to its slight solubility. Aocording to H. Meyer and Overton, all substances capable of dissolving fats are more or less anaesthetic, and according to Nicloux (1909) the substance of the nervous system contains an abundance of Upoidx, i.e., of compounds soluble in the same solvents as fats and hence capable of fixing the anaesthetics (they may contain nitrogen and also phosphorus). Thus the quantity of anaesthetic fixed by the organism and hence effective is directly related to the quantity of It is also interesting that structural isomcrism lipoids present in the various parts of the body. produces marked change in the physiological action, tropncocaine, for instance, being an anaesthetic, while benzoyltrojrine acts as a mydriatic. Of the numerous other anaesthetics, orthoform (methyl ester of m-amino-p-hydroxybcnzoic
acid), alipine, holocaine,

may be mentioned. In order, however, that local anaesthesia may be efficacious and lasting, it is necessary to prevent the anaesthetic inoculated at a certain place from being carried away (resorbed) by the blood, and this was at first attained by causing the venous blood at that place to stagnate by preventing circulation. The same end was reached later by intense local cooling produced by

the rapid evaporation of ethyl or methyl chloride. For internal surgical operations (e.g., in the thorax, etc.), ad-rcnalinc, C 6 3 (OrI) 2 '011(011) OH 2 CH 3 , is of the greatest use, as it produces considerable contraction of the blood-vessels without driving all the blood from them, although it prevents fresh blood from arriving the anaesthetic can thus be kept as long as is desired in the inoculated region. The substitution of cocaine by stovaine (less. poisonous) leads to partial spinal an&stkwiq, or medullary anesthesia,

NH

NICOTINE
alkaloids in plants (e.g., in Datura and tobacco) may be increased cent, by inoculating the plants with pyridine tartrate, which

747

up to 30 per undergoes complete transformation into alkaloids. Salicylic alcohol injected into maize plants yields salicin and in general chemical compounds inoculated are found in the plants, not in the free state, but converted into glucosides. Thus, the plant protects itself against the poisonous action of those substances by converting them into innocuous compounds. These observations explain why the powerful alkaloids produced in certain plants as waste products of the decomposition of complex nitrogenous substances exert no harmful action on the plants, although in the free state they exercise serious effects on the animal organism, which is not able to immunise itself. Inoculation of plants with non-nitrogenous substances may also increase the formation of alkaloids, injection of glucose into tobacco increasing the amount of nicotine formed by 40 per cent.
constitution

CONIINE, C 8 H 17 N, is found in hemlock (Comum maculatum). and syntheses, see above.

,

For

its

citric acids,

is a strong diacid base which, in combination with malic and forms the poisonous alkaloid of tobacco. Lt is an oil boiling at 247 and possessing a very strong odour ; it is soluble in water, alcohol, or other, and turns brown in the air. When oxidised by permanganate it forms nicotinic acid, and as further it contains also a

NICOTINE, C 10 H n N 2

pyrrolidinc group, its constitution

is

represented as follows

OH \

CH

N(OH3

CH2
is

Synthetically it is obtained from /^-aminopyridine which acid salt, and then passes through the foUowing stages :

converted into

its

mucic

OH CH
:

_v

CH OK
-

/3-Pyridylpyrrolc

0- 1 'yiidylpyrrole

CH
.

CH
I!

>

Nicotine

N
Practically alkaline with NaOH,
it is

\N(CH3 ).CH
Nirotyrine

diluting, rendering strongly the ethereal solution, the alkaloid is extracted by shaking with dilute sulphuric acid and decanting off the acid solution. The latter is again made strongly alkaline and shaken with ether, and the ethereal solution dehydrated by means of solid NaOIL The ether is then distilled off and the remaining nicotine distilled in a stream of hydrogen.

prepared from ordinary tobacco extract, by

and extracting with

ether.

From

It is

a very powerful poison and

is

used medicinally to counteract nervous irregularity

which now permits the most

Adrenaline
or

difficult surgical

renders possible painless childbirth.

auprarcnine.

operations on the abdominal organs and even

OH

>CII(OH)

CU 2 NH -CH 3

was extracted from

OH
the suprarenal gland in 1901 by Takamine. Synthetically it may be prepared in various ways, r.{/., treatment of chloracetocatcchol (from catechol and chloracetic acid) with excess of methylamine gives methylaminoacetocat-echol (<td.rcnaloi)< ), and reduction of the latter forms racemic adrenaline, which is less active than the natural Irevo-rotatory compound; separation of the optical antipodes is effected by preparing the d-tartrate, the salt of the lievo-base being only slightly soluble in methyl alcohol. Nagai (1019) treats diacetylprotocatechualdehyde with iiitromethano (1 mol.) in presence of a weak alkali; the diacctoxyphenylnitroethanol, C,H,(O OH 3 00) 2 CH(OH) CH 2 N1I 2 formed being crystallised, washed with ether, and treated with zinc and acetic, acid in presence of formaldehyde. Simultaneous reduction and methylation. then occur, giving diacetyladrenaline. Tho zinc is removed as sulphide, and hydrolysis of the
i

diacetyl

compound

effected

by means

of hydrochloric acid.

482

748
of the heart

ORGANIC CHEMISTRY

and is employed in agriculture, as tobacco extract, to kill insects. 1 Impure The 75 per cent, nicotine cost before the war 148s. per kilo, and the pure product 184s, French and Italian Governments place at the disposal of agriculturists tobacco extract (2 to 10 per cent, of nicotine) at about 2s, 6d, per kilo (pre-war).
1 Tobacco is a herbaceous plant, originally an annual but now sometimes a biennial, of the order Solonaceae (Nicotiana tabacum), which includes about fifty species and sub-species of American origin, e.gr., th*e Virginia tobacco plant (Nicotiana tabacum, see, Fig. 466), the Maryland N. suffruticosa, etc.). These grow well in various large-leaved tobacco (N. latissima, N. rustica, countries, as is shown by the following Table, giving the mean production of raw tobacco a few years ago (the figures given are tons)
:

leaf (about 1,080,000) and exported Italy imported before the war about 2000 tons of tobacco manufactured tobacco to the value of about 200,000. The world's pre-war production of raw tobacco varied from 900,000 to 1,000,000 tons, of the value of 48,000,000 to 56,000,000. The price was about 32 to 40 per ton for the ordinary 120 to 160 for the finer qualities quality and (Manila, Havana, Sumatra). Ordinary tobacco plants are only slightly branched and have a height of about 1 metre, although some exceed 1 J metre. They are studded with sticky hairs, and the leaves are wide and oval or, sometimes, long and narrow, as with Chinese tobacco (N. chinensis).

The flowers are in clusters and resemble those of The cultivation potatoes, but are usually flesh-red. of tobacco requires a good soil rich in humus, and the climate, soil, and mode of growing exert a conThe siderable influeno3 on the quality of the tobacco. readiness with which a tobacco burns in the form of on the potash-content of the plant,
cigars

while

account

Thomas

The young plants slag and stable manure. from the forcing house are planted out in about March, and at the beginning of July the dry and dirty leaves near the soil are detached, together with the

On this hinder the combustion. with stable manure, sewage, or potassium chloride is avoided, preference being given to potassium or ammonium sulpliate mixed with a little
chlorides
fertilisation

depends

The other, useful useless branches and the flowers. leaves are then removed as they begin to yellow and are dried on strings or in steam drying-ovens, and are then sorted and tied in. bundles. In January the leaves are placed in heaps so as to induce fermentation, which renders them brown
and gives them flavour. The leaves arrive at the factory in cloth bales. They are first sorted into kinds suitable for different sand types of tobacco and are then beaten to remove and dust. They are then arranged hi layers, each of which is sprinkled with 5 to 10 per cent, salt solution renders cigars hygroscopic) to soften (it is this which to facilitate the subsequent operations and to it,
466.
this state it is someprevent putrid fermentation. In times placed in tepid apartments to initiate a second

ATROPINE
ATROPINE, C 17 H 23 O 3N,
is

749

the alkaloid of the berries of Atropa belladonna (deadly nightshade) and of the fruit of Datura stramonium (thorn-apple). In dilute solution it is used as a mydriatic (enlarging the pupil of the eye) and as an analgesic (relieving pain). It is somewhat poisonous and melts at 115-5. As the products of the decomposition of atropine in various ways comprise heptamethylene derivatives, substituted pyrrolidines

and

pionic acid,

10 O 3 or a-phenyl-/?-hydroxyproregarded as an ester, a tropate of tropine, the structure of the latter (which has also been prepared synthetically) being,

piperidizips, tropine,

NO H H 15 O,
)

and

OR CH

tropic acid [C 9

CH(C 6 H 5

CO 2 H|,

atropine

is

CH 2 CH
I

CH 2 (a)
I

N CH 3 CH OH
CH a CH-

(m.-pt. 62

b.-pt.

220).

Hyoscyamine, stcreoisomeric with atropine, melts at 109. Tropine, formed by the splitting of atropine with barium hydroxide, is a tertiary base containing a secondary alcoholic group and is therefore known also as tropanol. When oxidised with chromic acid, it forms first a ketone, tropinone, H H 1:I ON, ami then tropinic C4 6 (C0 2 H)(CH 2 CO 2 H), owing to the rupture of the piperidine ring. With acid, CH 3

in some eases this ond is attained by washing fermentation, which refines the milder qualities with dilute solutions of salts, alkali, or acid, or, more rarely, by torrefying at (J() u to 70. The best flavour and aroma are obtained, however, by curing, i.e., by immersing the leaf in an aqueous solution of saccharine substances, various drugs, nitre, colouring-matters, aromatic the drained substances, alcohol, etc. (each manufacturer has his particular method of curing) or pressed leaves are then left in heaps for a longer or shorter time until they are uniformly soaked. By suitable machines the ribs of the leaves are either cut or beaten off and the cut leaves then dried by heating in revolving metal drums ; the dried leaves arc rapidly cooled in a current The subsequent operations for the preparation of cigars- cigarettes, cut tobacco for of air, etc. pipes, or snuff are merely mechanical and need not be described here. Mention may, however, be made of recent attempts to dimmish the harmful effects of tobacco, which is now smoked in every country in the world. It seems that when the Spaniards invaded America, the use of tobacco was already known in that country, and they not only extended its use there but introduced it into Europe (by the Thevct brothers in 1517), arousing grave apprehension owing to a statement by the medical men that it was highly injurious to health. In 1013 Tsar Michael Federowitz prohibited its use in his territory under penalty of death or of the cutting off of the nose. James I. of England published in 1619 a decree forbidding the use of tobacco and describing smoking as a " habit disgusting to the sight, nauseating to the smell, dangerous to the brain, harmful to the heart, and spreading around the smoker repugnant exhalations." In 1600 the Senate of Berne punished the use of tobacco like robbery or homicide, and in 1623 Amurat IV. prohibited its use by the Turks in order that they might not become intoxicated or infertile. To human nature, however, the forbidden fruit is the most desired, and, being useless, is none the less necessary. The employment of tobacco spread rapidly everywhere, and many States, to limit its consumption, imposed enormous taxes on tobacco, and ended by making it a Government monopoly and thus deriving a vast income to the Treasury. Since then no Government has occupied itself with the health of its subjects, the only care being the enlargement of the Exchequer. In Italy, after the partnership between the Government and a private company from 1868 to 1883, the trade in tobacco became a monopoly of the State, which derived from it a net annual income of about 7,000,000 (pre-war ; in 1920 far more). The mean yearly pre-war consumption of tobacco per head was as follows North America, 3-1 kilos ; Netherlands, 2-5 Belgium, 2-8 Switzerland, 2-3 Germany, 1-5 AustriaHungary, 1-6 Sweden, 1-2 Russia, 0-9 Servia, 0-8 France, 0-8 England, 0-7 ; Italy, 0-6 ; Roumania, 0-2 Denmark, 0-1 Finland, 0-1. The harm caused by tobacco is due especially to the nicotine, to which man becomes accustomed without serious inconvenience, in the same way as to change of climate, food, drink, or other conditions. Attempts have been made in recent years to render tobacco less injurious by extraction of the nicotine with one of a number of solvents, but such treatment results in the removal of the aromatic substances of the tobacco (see aUo Gcr. Pats. 178,962, 197,159, and 212,410 of 1908). Better results are obtained by filtering the smoke through fibres or textile materials before it reaches the mouth. Thus the Thorns process (Ger. Pat. 145,727), which has proved very satisfactory, consists in arranging in the mouthpiece of the pipe a small plug of cotton-wool impregnated with ammoniacal ferric chloride or ferrous sulphate, this retaining all the burning ethereal oils, the hydrogen sulphide, a considerable proportion of the hydrocyanic acid, and almost all the nicotine and its basic derivatives in the smoke. Treating the raw tobacco with ozone has also been employed with the view of facilitating the elimination of the nicotine, increasing the combustibility, and improving the quality. The aroma of tobacco is also intensified by the addition of small quantities of methyleugenol and methylisoeugenol.
; ; :

750

ORGANIC CHEMISTRY
H

concentrated HC1, tropine forms tropidine (or tropene), C 8 H 13N, which is obtained also by elimination of CO 2 from anhydroecgonine and forms an oily base, b.-pt. 162. OTHER ALKALOIDS are : Veratrine (cevadine), C 32 29 O 9N, found in Veratrum album ; 16 25 O 6N, found in the Sparteine, C 16 26 2 , found in Sparticum scoparium ; Sinapine, seeds of white mustard and derived from choline and from sinapic acid (dimethyltrihydroxycinnamic acid), C I ^H. 12 O & ; Hydrastine, C21 21 N, obtained from the roots of Hydrastis canadensis, has similar properties to the alkaloid from Secah cornulum and

H N

gives hydrastinine,

of Papaver smuniferum when condensed forms opium, which, along with various other compounds (see leloiv), contains considerable quantities of morphine (about 10 per cent.). Morphine, melting and decomposing at 230, is slightly soluble in water and odourless, and possesses narcotic and analgesic properties, being used in medicine as hydrochloride, C 17 19 O 3N,HC1,3H 2 O. Jt is a tertiary base with phenolic characters and, when distilled in presence of zinc dust, gives pyridine,

C 11 H 11 2N,H a O, on oxidation. MORPHINE, C 17 H 19O 3N. The latex of the capsule

pyrrole, quinoline,

and phcnanthrene. extracted from opium by means of water, the evaporated aqueous extract being treated with sodium carbonate to precipitate all the alkaloids (about twenty) of the opium ; after 24 hours the precipitate is washed with water and then with alcohol, which
Morphine
is

resins and all the alkaloids excepting nearly the whole of the morphine. The crude morphine remaining is dissolved in acetic acid (which leaves behind the narcotine impurities), the solution filtered through animal charcoal, and the morphine liberated by means of ammonia, washed with cold water and dried. It is obtained in a purer form by repeatedly boiling its alcoholic solution with animal charcoal and recrystallising. The action of opium on the human organism is analogous to that of other stupefying agents, being intermediate to that of alcohol, ether, etc., and that of cocaine. The smoking of opium, either alone or together with tobacco, is a habit which has been long rooted in certain countries, especially China. The action of opium is due to the presence of a number of alkaloids, which arc divided by A. Pictet into

removes the

(1)

The Morphine Group, including

Morphia,
17
a

H 17 ON(OH) Pseudomorphine, [C 17 H 16 ON(OH).J

:

Codeine,
2

Tfwbaine,

C 17 H l7 O\(OH)(OCH a ) C 17 H 15()N(OOH 3 2
)

(2)

The Papaverine Group, comprising mainly

Papaverine, C 16 9 N(OCH 3 ) Laudanidine, C 17 H 15 N(OH)(OCH 3 ).,
1
'

isoquinoline derivatives, which have a

mild physiological action

Codfimine,
Narcotine, Protopine,

C 18H 1H ON(OH)(OCH 3 C 19H 14O 4N(OCH 3 ) 3 C 20 H 19 O 6 N

)a

Tritopine, (0 21

H 27 O N) O
3
2

Papaveramine,
Santaline,

C 21 FT 21 C 37H 36O 9 Lautopine, C23H 25 4N

O l7 H 15N(OCH 3 ) t C 19H 17 O 3N(OCH 3 ) 2 Qjcymrcotim, C 19H 14 O 5N(OCH.) 3 Narceine, C 20H 18 O 5 N(OCH 3 3 Meconidine, C 21 K 23 O 4N Gnoscopine, C 22 H 33 O 7N Hydrocotarnine, C nH 12 O 2 N(OCH 3 Berberine, C 20 H 17 O 4N
JMudanosine,
Cryplopine,
)
,

Laudamine, C 17 H 16 N(OH )(OOH 3 ) 3

Opium
further:
acids,

contains also Meconic Acid, C 7 H 4 7 in combination with various alkaloids, and wax, proteins, caoutchouc, pectic and gummy matters, lactic and sulphuric
salts, etc.

ammonium

contains 8 to 24 per cent, of water, 3-5 to 5 per cent, of ash, 45 per eent. of aqueous extract, 9 to 15 per cent, of morphine, about 5 per cent, of narcotine, 0-8 per cent, of papaverine, 0-4 per cent, of thebairie, 0-3 per cent, of codeine, and 0-2 per cent, of narceine. The pre-war price of good opium was 28a. to 32$. per kilo, pure crystalline morphine

Good opium

costing

18 per kilo. In 1905 Germany imported 68 tons of China imported 2600 tons in 1908, about 2500 in 1909, and nearly 2000 in 1910. In 1910 Great Britain imported about 220 tons of opium and in 1911 exported 22 tons. The United States imported 300 tons in 1911. COCAINE, C 17 21 4N, is obtained, together with other alkaloids (Cinnamylcocaine, Cinnamylecgonine, ci-Truxilline, Hygrine, etc.), from the leaves of a small shrub (Erytkroxylon coca) which grows abundantly in Peru, Bolivia, Colombia, Brazil, and Argentine and is now cultivated also in Ceylon and Java. Peru and Bolivia alone produce annually

24 and

its

hydrochloride
80,000.

opium

of the value of

Q
about 15,000 tons of dry coca

U;T

NINE

751

26 per cent, of various alkaloids, including 0-2 to 0-8 per cent, of cocaine. The leaves are mostly used by the natives, who chew them, and are partly treated on the spot for preparing crude cocaine containing 80 to 90 per cent, of cocaine and 10 to 12 per cent, of other alkaloids, this being marketed at Hamburg and London. Before the war the dry leaves were sold in London at about 4 per cwt.
leaves containing 0-5 to

Not only cocaine, but also the other alkaloids accompanying it in coca loaves, are derived from a single base ecgonine. Pure cocaine, m.-pt. 98, is loevo -rotatory and has an analgesic action; it is used in opthalmology and surgery to effect local anaesthesia, and is employed by drug-takers owing to its stupefying action.
decompose it into methyl alcohol, benzole acid and ecgonim, which is the a-carboxyl derivative of (Lossen, 1865), ^HisO^N tropine (see. above), and, as with methyl alcohol and benzoic acid it gives cocaine again, the latter must contain the
"~

Htroiig acids in the hot

groups

C 9 rI l3 O 2

N^Jc H

confirmation of this

is

given
is

Ly the synthesis (rather a

complicated one) of cocaine.

The

CH2 CH

constitution of cocaine

CH-C0 2CH 3
3

as follows (Willstatter, 1898)

N CH
CH 2 CH-

CH CO aCgH 5 CH
2

the characteristic group (ancrsthesiophore)

is

the benzoyl

residue, while elimination of the

methyl group united to the nitrogen atom or of the C0 2 CH 3 group scarcely affects the anesthetic properties. On the other hand, almost all the aminohydroxybeiizoic esters arc wild local anesthetics (Einhorn and Heinz, 1897), e.g., aniesthesin
or ethyl ;>aminobenzoate, C 6 B, CO 2C2 H 5 The anaesthetic characters of these sub2 stances are intensified if, in place of 2 , N(CH a ) a groups are present, preferably joined to other Tiiethyl groups. This is the case, for instance, in :
.

NH

NH

C 6H 5

(XV

yCH 3
and
3 )2

C 6 if 5 C0 2N
.

/CH, N(CH 3
-

)2

C2

H/

>(\

\CH 2 .N(CH

C2

H/ \CH
Alypine

\C<

N(CH 3

)2

Stovaine

prepared by Messrs. Bayer iii 1905. Both of these are less poisonous than cocaine, but have not its property of contracting the blood-vessels. They are therefore mixed with adrenaline, which shows this property in a marked degree and also diminishes the of certain
toxicity
alkaloids, especially of cocaine. The price of cocaine was about

and

800 per kilo prior to 1885, 140 in 1887, 22 in 1906, During and after the war the price rose enormously. Owing to the high of these a few have been successprice of cocaine, many substitutes have been prepared fully used, such as ft-eucaine (trimethyl-y-oxypiperidine o-benzoate) holocaine, obtained by condensing phenacetin with ^-phcnetidine (in spite of its lack of the benzoyl antesthe12 in 1913.
;
;

siophore group) ; acoine (di-p-aiiisyl-;p-phenetylguanidme), etc. HYGRINE, obtained from coca leaves, has the constitution

H CO CH
-

\CH
NARCOTINE, C 22 H 23
is

CH2
|

CH

2.

7 N, exists to the extent of 6 per cent, in opium, melts at 126, a slightly poisonous, weak, tertiary base containing three mcthoxyl groups. When hydrolysed, narcotine gives meconic anhydride, C 10 10 O 4 and cotarnine, C la H 13 O 3 N, which is a derivative of isoquinoline (see later), and with bromine gives dibromopyridine. STRYCHNINE, C 21 H 22 O 2 N 2 is present, with brucine, C23 H 26 4 N2 , and curarine, in the

and

seeds of Strychnos nux vomica. They arc very powerful poisons, which, even in small doses, cause death, accompanied by tetanic muscular contorsions ; curarine is used as an antidote to the other two alkaloids. Strychnine melts at 265, and is a mono-acid
tertiary

base slightly soluble in water it gives indole and quinolinc when fused with potash and /?-picoline on distillation with lime. QUININE, C 20 H 21 O 2 N 2 The bark of various species of cinchona has yielded, up to the present, twenty-four alkaloids, the most important being quinine and cinchonine,
;
.

752
C 19H 22

ORGANIC CHEMISTRY
N

The other 2 , both of these possessing in different degrees febrifugic properties. 2 alkaloids include Hydroquinine, C 20 26 O 2 2 ; Cinchonidine, C 19 22 2 ; Hydrocinchonidine,

H ON

C 19H 24 ON2

Quinidine,
is

C20H 24

2,

etc.

Quinine
bitter taste

Isevo-rotatory, slightly soluble in water

it

and odourless and has an intensely

crystallised with 3H 2 0, at 57. It is a di-acid base, containing two tertiary nitrogen atoms capable of salt-formation with two equivalents of acid, then often giving aqueous solutions showing blue fluorescence characteristic of quinine.
;

melts at 177,

or,

when

It contains a hydroxyl and a methoxyl group, and its constitutional formula, although not completely established, must consist of two cyclic systems, NO 10 16 ( OH) -NC 9 6 OCH 3 , the first being somewhat analogous to tropine (see above) and the second representing 5-methoxyquinoline, which can be obtained by fusing quinine with potash. After protracted investigation, W. Konigs (1906-1907) arrived at the following probable structures for cinchonine and quinine jq-

CH 2

~(OH)0 CH 2 CH 2

OH C
HO
I

CH 2

/\/\ C OH
II
I

H2

CH -OH:CHo

CH
CH
Cinchonino

HO

\/\/ CH N
N
CH ~
2

-(OH)C CH 2CH 2

OH OH 3
-

/\/\ OH C
!

CH 2

H,0

CH CH OH,
:

II

CH
I

HO

CH
Quinine

\/\/ OH N
Rabe
(1906-1907), however, proposed for cmchonine the formula
:

CH 2 - OH

CHCH

CH 2

CH 2
CH 2
OH)-N
which

CH 2

is in harmony with the Beckmann oxime reaction. Oxidation of quinine gives, among other products, Quinic acid, C 9 H 5N(OCH 3 ) CO 2 H. To combat fever, especially malarial fever, use is made of the normal sulphate of quinine, (C 20 24 2 N 2 ) 2 ,H 2 SO 4 ,8H 2 O (from alcohol it crystallises with 2H 2 O), or of quinine hydro-

chloride,

C20 24 2 2 ,HC1,2H2 0, which is far more readily soluble in water. Quinine bisulphate or acid sulphate contains 1 mol. of quinine per 1 mol. of sulphuric

acid.

Quinine is extracted from the finely ground bark by mixing it with lime and extracting with hot mineral oils (paraffin oil, etc.) of high boiling-point. From this solution the alkaloid is obtained by shaking with dilute sulphuric acid, neutralisation of the acid solution with sodium carbonate in the hot resulting in the crystallisation of most of the quinine as sulphate from the cold solution, the other alkaloids remaining dissolved. From the 1 sulphate the quinine is liberated by means of ammonia.
1

Since quinine and

bitter

compounds.

its true salts are very bitter, attempts have been made to prepare leas In 1896 tasteless euquinine or quinine ethyl carbonate, (C 20 a3 ON 2 )
t

QUINOLINE
The
purification of quinine is not easy and id sometimes effected solution as tartrate by addition of Rochelle salt.

753

by precipitating it from STATISTICS. Before the war quinine bisulphate cost about 28s. per kilo, the sulphate 32s., and the hydrochloride 405. The world's output of cinchona bark was 12,000
tons in 1916. 1
5. QUINOLINE AND ITS DERIVATIVES and pyridine are related in the same way as naphthalene and

Quiiioline

benzene.
CH

QUINOLINE, C 9H 7 N,

i.e.,

or
HC

is

CH
highly refractive, colourless liquid of peculiar odour and is found in bone tar and also in coal-tar, but is now prepared in the pure state by Skraup's synthesis. It is slightly soluble in water, has the sp. gr. 1-1081 "at 0, boils at 236

and functions as a tertiary base (the nitrogen not being combined with nitrogen). With acids it forms salts, e.g., the bichromate (C 9H 7N) 2H 2Cr 2 O 7 Its constitution is deduced from the following syntheses
.

(1)

By

the interaction of allylaniline and

Pb0 2

at a red heat

H CH

(2) Skraup obtained it by heating aniline with giycerol, sulphuric acid, in this way acrolei'n is formed, which then gives acrolemand nitrobenzene The nitrobenzene acts purely as an oxidising aniline, C 6H5 N CH CH CH 2 agent and may be replaced by As 2 3 Margosches (1904) suggested the replace;
:
: . .

ment
which

of the nitrobenzene
loses 1 mol. II 2

by

rare oxides of the cerium group.

(3)

o-Nitrociimamaldehyde

on reduction gives o-aminocinnamaldehyde,

is

and

yields quinoline, the fact that the latter

:

an ortho-

derivative of benzene being thus proved

CH

/H -H,0
When

=
is

quinoline

is

oxidised, the benzene nucleus

^ <0

attacked

first,

with

formation of a dibasic quinolinic acid,

which gives pyridine,

'COOH

on tho market (Zimmer, Ger. Pats. 91,370 and 118,352), and in 1902, 5 )C0 3 , was placed 2 ) 2 C0 3 (Bayer and Zimmer, Ger. aristoqninine (aristochin), or quinine carbonate, (C 20 23 It was claimed that 2 grins, of either of these products has the effect of Pat. 105,666, 1898). 1 grm. of quinine. Biginelli (1914) showed, however, that they are not salts of carbonic acid, that true quinine carbonate is very bitter, that their action on the organism is slight and slow compared with that of quinine, and that euquinine is ethyl quininecarboxylate, O CO. ('2oH 23 2 2 COOC 2 B , and aristochin, carbonylqmnine, (C 20 23 2 2 ) 2 1 At one time cinchona was cultivated extensively in Ceylon, but, owing to over-production in 1885 and consequent lowering^of prices, it was abandoned and replaced by rubber. In Southern India, however, tho industry increased, 1050 tons of the bark being exported in 1914, and nearly 900 tons in 1916. In Java the production commenced in 1879, 3000 tons of bark being exported in 1889, 9500 tons in 1910, and about 10,500 tons in 1915.
(C 2

H ON

754

ORGANIC CHEMISTRY
when
distilled

with lime.

Hence, as was suggested long ago by Korner,

It is analogous quinoline contains a benzene and also a pyridine nucleus. to naphthalene, one a-CH group being replaced by a nitrogen atom. That the linking* in quinoline are, at least in part, olefinic double bonds is shown the

behaviour of this compound to ozone. Quinoline forms many isomeric derivatives, seven monosubstituted, twentyone disubstituted, and still more trisubstituted compounds being possible. The positions of the replaceable hydrogen atoms are indicated by numbers or by the letters a, /?, and y for the pyridine nucleus and o, m, p, a (ortho-, meta-, para-, ara-) for the benzene nucleus. The constitution of quinoline derivatives can be determined by means of the general synthesis of Skraup, variously substituted anilines with the substituents in the benzene nucleus or often by oxidation, which being used usiially attacks the benzene nucleus and not the pyridine nucleus, so that it is easily ascertained whether the substituent is in the one or the other nucleus.
;

by

The

sulplio-acids (or sulphouic acids) of quinoline,

when

fused with

quinolines,

these, on being heated with KCN, form cyanoqmnolin^, which are converted by hydrolysis into the corresponding qitinoUnecarboxylic acids those containing the carboxyl in the benzene nucleus are called acids. Oxidation of

and

KOH, give hydroxy-

cinchonine gives cincttonic acid, C 9 6 CO 2 (m.-pt. 254), which is quinolim-y-carboxylic acid, and from this is derived quinic acid (see above), C 9 5 N(OOH ) CO 3 2 (p y), conWhen acridine is oxidised it yields quindinesisting of yellow prisms melting at 280.

HN

quinolinebenzocarboxylic

(i :

/3-dicarboxylic acid or acridic acid.

Carbostyril

is

2-hydroxyquinoline

and has the character

of the phenols,

dissolving in alkali and being reprecipitated

by C0 2

etc.

When

quinoline

is

reduced with nascent hydrogen, this unites with the nitrogenated

nucleus,

forming tetrahydroquinoline,

C 9 H 11 N,

or

which behaves as a

NH
secondary aromatic amine (>NH). If the reduction is pushed further, the hydrogen is added also to the benzene nucleus, forming decahydroquinoline, C 9 17 N, which behaves like an aromatic amine.

C 10 9N, is found in coal-tar and boils at 246 ; with gives a fine colouring-matter, quinoline yellow, C 10 7N(CO) 2 C 4 When quinoline is heated with metallic sodium it gives diqninolyl, C 9 6 C 9 6N, analogous to dipyridyl and diphenyl. Polymerisation of quinoline yields diquinoline, (C 9 7 N) 2 crystallising in yellow needles.
Quinaldine or tt-methylquinoline,
it

phthalic anhydride

HN

METHOXYQUINOLINE,
quinoline
;

C 9 H 6N

OCH 3

corresponding
antipyretic,

with

anisole,

resembles
,

among

its

derivatives

are the

thalline,

C 9H 10N OCH 3 and

analgen (o-ethoxy-a-benzoylaminoquinoUne).

ISOQUINOLINE, C 9 H 7 N

or

is

a colourless liquid

boiling

at

237,

melting at 21 and forming a slightly soluble sulphate.

FLAVONE
It is obtained

755
salt of

from tar and also synthetically by heating the ammonium

2 4

homo-

phthalie acid

C' 6

yCH COONH H <( 2H

4

+ NH
,

H-

C 6H 4 /

/CH2 CO
|

\COONH 4

\CO
and elimination
of

Ntt
this yields

which with POC1 3 gives C 6 H 4 <^

/CH\>

CCL,
|

Homophthnlimide

2HC1 from

\XVNH

i.e.,

dichloroisoqmnoline.

N
ci

When

oxidised

it

gives phthalic acid

and cinchomeronic

acid,

C 5 H 3 N(C0 2 H) 2

(a pyridine

derivative).

Since it does not fix ozone, it must be assumed, contrary to the former view, that it does not contain olefinic double linkings, but that centric bonds are probably present in both
nuclei (Molinari, 1907).

Other condensed nuclei, similar to quinoline, are as follow

O
CHROMONE, C 6 H
m.-pt.

/O /

CH
||

c-cir 3
,

of which

the ^-methyl-derivative,

XJO CH
71,
is

CH
CO
C6

well

known.

FLAVONE,

the phenyl-derivative of chromone,

/O H/

C C
||

5
,

melts at t)7, and

HJO CH
occurs as hydroxy- derivatives in many glucosides, to which it imparts the yellow coloration. Thus it occurs in quercetin (or flavin), which is a pentahydroxyflavene, while with isodulcitol
it

forms the glucoside quercitrin, C 21 23 O 12 , obtained from tea, hops, and the bark of Qnerciis tinctoria (morin is an isoraeride of quercetin, and is found in Madura tinctoria). found in poplar buds ; Luteolin, C ir> 10 O 6 ,2H a O, Chrysin, C 15 10 O,, is a

a tetrahydroxynavone, and forms the colouring-matter of Reseda luteola, while apigenin is a glucoside of trihydroxyflavone, and is found in parsley and celery. Of the many condensed cyclic groups, the following, which contain a benzene nucleus and also a furfuran, thiophen or pyrrole nucleus, and are obtained by various syntheses,
is

may

be mentioned

444
:

dihydroxygavone

3/\~-

-/\
1

O
C 12 H 8

NH
C 12 H 9 N
Diphenyleneiiiiine,

C 12 H 8 S
Diphenylene sulphide or Dibenzothiophen

I)i]>lirnylene oxide or

Dibenzofiirfuran

Dibcnzopyrrolc, or Carbazole

Of

all

these groups numerous halogenated, acid, alcoholic, ethereal derivatives, etc.

is

are known.

COUMARONE

liquid, b.-pt.

177,

is

obtained synthetically, and also, together with

756

ORGANIC CHEMISTRY
bromine and

various methylcoumarones, from coal-tar. Concentrated sulphuric acid polymerises it to coumarone resin, which, on dry distillation, yields coumarone and phenol with- partial At 200, alcoholic potash opens the smaller nucleus, various products being charring.
It readily unites with two halogen atoms. a-Bromocoumarone loses 3. 2 yields a-nitrocouinarone, m.-pt. 134, when treated with BENZOTHIOPHEN, m.-pt. 32, b.-pt. 221, occurs in lignite tar.

formed.

will

Of numerous dyestuffs formed by the condensation of heterocyclic groups, mention be made later in the chapter on colouring-matters, but a group of substances with

heterocyclic nuclei

and intimately connected with indigo

will

be considered here.

ISATIN, C 6 H 4

forms reddish yellow <^>CO, VxU

prisms soluble in alcohol and in hot

CO COOH. 4 2 C water, and maybe regarded as the lactam (see p. 423) of Isatinic acid, It is obtained from o-nitrobcnzoylformic acid (see later, Indole), by oxidising indigo with
-

NH

nitric acid, etc.

It dissolves in

KOH, giving
C 6 H4

first

a violet colour (C
-

< (iQ>C'Q)
C 6 H4^

while

in the hot

it

yields potassium isatinate,

<^f CQ R

Oxidation of isatin with chromic

,NH CO
|

acid gives rise to Isatic acid (anhydride of aritliranilcarboxylic acid),

\co o
-

XXX
From
Pseudoisatin,

C 6H <
4

V) OH
C 6H 4<(

(which would be a lactiw)

is

derived the

\lsK

methyl ether or Methylpseudoisatin,

XCO \ VJ OCH

(red powder).

Methyhsatm,

>CO>

is

aLso

known<
is

DIOXYINDOLE, C 6 H 4

OH ^>CO, <^JNrl

formed by reducing

isatin

with zinc and HCl

acid,

and readily gives isatin again on oxidation. It is the internal anhydride of o-aminoinandelic ]t crystallises in colourless prisms, and exhibits both basic and acid properties.

melting at 180.

OXINDOLE, C 6 H 4 <J?^ CH >CO,

2

acts both as

an acid and as a base, and hence dissolves

in alkali arid in HCl.

be It is the lactam of o-aminophenylacetic acid, and can, indeed, obtained by reducing o-nitrophenylacetic acid. It forms colourless needles, m.-pt. 120, and forms dioxyindole on oxidation.

INDOXYL, C 6 H 4<^

/ NH

\ C(OH)

,X H *

ia

isomcric with tne

P rece(nng compound, and

of

'

is

formed by fusing indigo with

indophore.

KOH

or

by the elimination
form

C0 2

from indoxylic acid or

It occurs in the urine of herbivorous animals in the

of Potassium indoxylsulphate,

C 8H 6N

S0 3K

of Pseudoindoxyl, (indican of the urine). Derivatives

< CQ >CH

2,

are also known.

SKATOLE, C 6 H 4<^
fusing the latter

/ NH

\C(CH 3 with KOH,

K,X
>

H ^
is

formed

(luring tne putrefaction of protein or

by

and

hence found in the

faeces.

It

forms white scales,

m.-pt. 95, with an intense

fsecal

odour.

INDOLE, C 6 H 4^
indigo.

NH \

\CJK

^CH

is

of importance

owing to

its

intimate connection with

By

treating o-nitrobenzoyl chloride with

:

AgCN,

the nitrite

is

obtained and this,

on hydrolysis, gives o-nitrobenzoylformiy acid CO .COC1(1) _^ "^

N0 2

PTT^ C6H4<

'

(2)

N0 2

CN "^ CH ^C C 'H4<

INDIGO
this acid,

757

on reduction, gives the amine, which

loses 1 mol.

2 O,

C 6H
Indole
is

/CO COOH /

forming Isatin
-

=H

C 6H 4 <

/COv

\N

>C

OH.

laatin

obtained by distilling oxindole with zinc dust and by various synthetical it is formed in the pancreatic processes (see later, Indigo) putrefaction of protein or on fusion of this with KOH. In the impure state it has a faecal odour, but when pure and highly diluted it smells like flowers, and is hence used in perfumery. It forms shining scales which molt at 52, are volatile in steam, and with ozone give indigo. With sodium bisulphite it forms a crystalline compound, and with nitrous acid a red precipitate ; it imparts a red colour to a pine shaving moistened with HOI. It may be regarded as formed by the condensation of 1 mol. of benzene and 1 mol. of pyrrole
;
:

It

forms numerous derivatives with

two

substituents in the benzene or pyrrole nucleus, the being termed a and ft. groups near the

CH

NH

INDAZOLE, C 6 H

is

weak base

prepared by decomposing the diazo-compound of

^-mtro-o-toluicliiie with acetic acid in the hot

and

then eliminating the

N0 2

group.

INDIGO, C 1G 10 2 N, is a very stable, natural, blue colouring-matter, which was in use in the Far East in the most remote
times,

mummies

and was bartered to the Egyptiansof the Eighteenth Dynasty (1580

years B.C.) are found with wrappings coloured with indigo then to Greece, and later to Italy. Until the middle of the nineteenth century the trade in indigo remained a monopoly of the Dutch. It is extracted from the branches and leaves (of a yellowish green colour) of Indiyofcra
tinctoria

FTO. 407.

(Fig. tropical countries extensively cultivated in India, Java, China, etc., being sown in the 1 At one time ifc spring and cut two or three times a year before flowering.

467), which grows very readily

in

and

is

1 Indigo belongs to the leguminous plants, and is hence capable of enriching the soil with nitrogenous products owing to the action of bacteria which fix atmospheric nitrogen (see Vol. T., It has therefore been proposed to plant indigo in rotation with sugar-cane, especially p. 348). in soils which have been exhausted by the latter. At every cutting 25 to 30 quintals of indigo plants are obtainable per hectare and 5 to 6 kilos of 00 per cent, indigo for every ton of plants. In India indigo is sown in February or March in well- tilled land at the rate of about 14 kilos of seed per hectare. After three months the flowering stage is reached, the plants, which then contain the maximum of colouring-matter, being cut off close to the ground, tied in bundles, and despatched immediately to the factory to be extracted. A second cutting in September gives a smaller quantity of indigo. The cultivation of indigo reached its greatest extent in 1806-1897 with a total area of 040,000 hectares, one-third in Bengal, one-fourth in the North- West Provinces, one-fourth in Madras, and one-twelfth in the Punjab. In 1880 India contained 2800 indigo factories and 6000 works employing primitive methods of extraction, the total number of persons employed, exclusive of agricultural labourers, being 360,000. After the appearance of artificial indigo, the area under indigo steadily diminished, being only 180,000 hectares in 1906 1907. There is a tendency in India to extend the cultivation only on the most suitable soils, and co abandon the old varieties of plant in favour of Natal indigo, which gives a greater yield of leaves containing a higher proportion of colouring matter. Rational methods of extraction are also being introduced.

758
was extracted

ORGANIC CHEMISTRY
also in

etc.) from wood- (I satis occurs only in the leaves and in smaller quantity. There are several varieties of Indigofera (tinctoria, disperma, anil, argent ea, and others of less importance). They are herbaceous shrubs 50 to 100 cm. in height, covered with silky hairs, with pinnate leaves and many

Europe (Hungary, Thuringia,

it

tinctoria, Fig. 468),

where, however,

.small leaves.

made at Calcutta it would seem that Indigofera cultivated in Java but indigenous to Natal, is better in every leptostacliya, respect than Indigofera tincloria, while it lasts four to five years. Still better results seem to be given by Indigofera erecta.
the results of tests
In order that the indigo may be extracted from the cut plants, it is necessary that the glucoside they contain (indican) consisting of a compound of glucose with indoxyl be decomposed by fermentation in large vessels with water. After 10 to 14 hours the glucose
is

From

tion.

fermented, while the indigo, owing to the presence of ammonia, forms a yellowish soluThe liquid is transferred to deep vats, where it is subjected to " beating " for two to three hours with Avooden paddles or wheels, or to " " blowing by means of a current of air. The oxidation thus effected causes the separation of the indigo in flocks, which are removed by decantation after three to four hours
:

C.H/

/C(OH

NH
IndiRoliu

NH

20 6 H,
-

NH

luiioxvl

CC

yCO

<

XNH/
fmligo blue

cent, indigo paste separated by decantapassed through sieves to remove fragments of the plants and is then boiled by means of steam for p rr 15 minutes in order to sterilise ths mass which would otherwise undergo change and to eliminate part of the brown matter and to effect better separation of the particles of indigo. These then deposit more easily and are collected on a large cloth filter, the first liquid passing through being returned to the the 8 to 12 per cent, paste thus obtained is filter until it comes through faint red pressed in primitive presses. The large cakes thus formed contain about 80 per cent, of water and are cut into small cubes, which are arranged on grids, dried in the air for two or three months and placed on the market in boxe* holding 50 to 140 kilos under the name of cakes. During the drying, thess cakes evolve ammonia and become covered with mould, which is finally removed with brushes. The yield of indigo is about 0-2 per cent, on the weight of the green plant or 2 per cent, on that of the dry plant. To combat the competition of artificial indigo, various improvements have been introtioii is
;

The 5 per

duced during recent years into the methods of cultivation, manuring, and extraction may be directed to the rational fermentation with suitable enzymes (oxydases) proposed by Calmette and others (Fr. Pats. 300,826 and 302,169). The indigo-content of the cakes varies considerably, some of those on th? market containing only 20 per cent, and others as much as 90 per cent. It hence becomes necessary to determine the value of any sample on the basis of the proportion of pure indigo ascertained by exact analysis. 1 According to Fr. Pat. 323,036 an increased yield and an improved
;

attention

1 Analysis of Commercial Indigo. Commercial indigo from Bengal contains, on an that of Madras, 30 to 50 per cent. ; that of Java, 72 to ^2 average, 60 per cent, of indigotin per cent. ; that of Guatemala, about 40 per cent. ; that of Martinique, 60 to 70 per cent. ; ana that of Cambay, China, and Tonkin, 8 to 15 per cent. Indigotin may be estimated as follows : 1 grm. of well-dried indigo is mixed (in a bottle
;

PROPERTIES OF INDIGO
The cakes
reflection.

759

product are obtained by macerating the fresh plants in presence of tannin materials which leave only the indigo undissolved.
of indigo are blackish blue in colour and give a fracture showing a bronzy Natural indigo always contains, besides indigotin, other substances and colouring-matters (such as indigo gum, indigo brown and red, etc.) which affect the tint, sometimes favourably.

A good Bengal indigo gave, on analysis, 62 per cent, of indigo blue, 7-3 per cent, of indigo red, 4-7 per cent, of indigo brown, 1*5 per cent, of indigo gum, 6 per cent, of water and 19 per cent, of mineral matter. Pure or refined indigo is obtained in various ways, e.g., the crude indigo is treated with
a mixture of concentrated acetic and sulphuric acids, the indigo alone passing into solution as sulphate, which is decomposed after filtration by excess of water, this precipitating pure indigo or indigotin. In order to avoid dilution with water and loss of acid, it has been proposed to separate the sulphuric acid directly by addition of calcined sodium sulphate

which transforms it into bisulphate the acetic acid is then distilled off and the bisulphatc removed together with a little water. According to Ger. Pat. 134,139 pure indigo is extracted from the crude product by means of hot, crude pyridine. To purify artificial indigo, it is heated, according to Ger. Pat. 179,351, at 200 to 270, at which temperature it docs not sublime or decompose, while the indigo red and other impurities are destroyed, leaving an
;

indigo highly valued for

its tine

bronzing.

Of some

interest is colloidal indigo,

which behaves

like dissolved indigo,

and has been

recently prepared by Mohlau by heating, out of contact with the air, a suspension of indigo in an aqueous solution of alkali and sodium hydrosulphite, the liquid being treated, after cooling, with protalbinic acid (obtained by Mohlau by the alkaline hydrolysis of protein

and subsequent dialysis ; this acid has the power of precipitating various metals in a colloidal state from their salts). Addition of hydrogen peroxide to the filtered liquid gives indigo blue in the colloidal condition, which is retained even after evaporation.
1

PROPERTIES. Pure indigo forms a dark blue powder which, when rubbed, It sublimes at about 300, giving red gives a metallic, coppery reflection. vapour and forming copper-red, shining prisms. It is insoluble in water, alcohol, ether, alkali, or acid, and dissolves only slightly, even in the hot, in
alcohol, chloroform, phenol, carbon disulphide, pure acetic acid, nitrobenzene, aniline or melted paraffin wax. It has neither odour nor taste and is indeed an almost completely indifferent substance this explains why, although materials have been dyed from time immemorial in the Far East, in Europe no process for dyeing textile fibres was discovered for so many centuries -until the sixteenth. The portion soluble in hot aniline colours this blue but colours fused paraffin

amyl

with a ground stopper) with 10 grins, of garnets or glass beads and 20 c.e. of sulphuric acid mixture (composed of 3 parts of concentrated sulphuric acid and 1 part of oleum containing 20 per cent, of free SO 3 ). The mass is thoroughly mixed and is afterwards shaken occasionally over a period of 12 hours or so, until solution is complete, the whole being then poured carefully The aqueous solution is boiled for into cold water and the bottle thoroughly rinsed out. 10 minutes and filtered, the filter being washed with hot water until the washings become colourless and the filtrate then made up to a litre. Fifty cubic; centimetres of this solution is mixed with IKK) c.c. of distilled water, and the liquid titrated with 0-05 per cent, potassium permanganate In order to solution until the blue colour becomes golden yellow without green reflection. accustom the eye to this end-point, which is not sharp, it is advisable to make a comparative test with pure indigo of known strength 1 c.c. of the permanganate solution corresponds with about 0-00125 grin, of indigotin. In order to prepare pure 100 per cent, indigo for purposes of comparison, 10 grms. of pure, powdered artificial indigo (98 per cent., marked B. A.S.I or M.L.B.) is treated in a beaker with 120 grms. of caustic soda solution (sp. gr. 1-21), 330 grms. of concentrated sodium hydrosulphite solution and 100 grms. of water (or, if 50 grms. of 20 per cent, indigo paste is taken, only 60 grms. of water are added), the mixture being heated on a water-bath at 40 to 50 with occasional shaking and the air being gradually expelled from the beaker by means of a current of coal-gas. When solution is complete, the liquid is rapidly The precipitated indigo filtered and a current of air passed into the yellow or greenish filtrate. is collected on a hardened filter and washed first with hot water, then with hot dilute hydrochloric ftcid (30 c.c. of the concentrated acid diluted to a litre), next with water again, and repeatedly with alcohol and with alcohol and ether. When dried at 101 to 110 until of constant weight, the product represents pure 100 per cent, indigo,
;

760

ORGANIC CHEMISTRY
;

from these solutions, rhombic crystals showing marked purple-red dichroism separate on cooling. From hot oil of turpentine indigo crystallises in blue plates. Concentrated sulphuric acid converts it in the hot into a monosulphonic With fuming derivative, soluble in water but insoluble in salt solutions. sulphuric acid it forms the disulphonic compound, which gives more soluble salts, the sodium salt being sold as a paste under the name of indigo-carmine,
dyeing wool like an acid aniline dye. dry distilled, indigo gives aniline and other aromatic compounds. Energetic oxidising agents (nitric or chromic acid or permanganate) decolorise it more or less rapidly, converting it into isatin. Chlorine, bromine, and iodine give halogenated derivatives of isatin. Indigolin white, which is the leuco-base of indigo blue, is obtained from the latter in a soluble form, by the action of alkaline reducing agents (sodium
this

wax

When

"

amalgam, ferrous sulphate, hypophosphorous or hydrosulphurous

acid, glucose,

heated with acid, the greenish yellow alkagallic acid, etc.) or enzymes. line solution deposits indigotin white, which is readily converted into the blue

When

form by the oxygen

of the air. be regarded as a substantive dye which colours both animal Indigo may and vegetable fibres without a mordant. It is first reduced in the vats by means

in presence of sugar, urine, zinc, arsenic, or reducing salts (sulphites, hydrosulphitcs), thus becoming decolorised, soluble in alkali and capable of impregnating textile fibres, on which it becomes firmly fixed when rendered
of

enzymes

by the action of atmospheric oxygen. In 1890 the German Government permitted alizarin blue to be used for dyeing part of the cloth for military uniforms, these having been previously coloured exclusively with indigo.
insoluble
to ascertain the chemical nature of indigo were those of Erdmann and (in 1840) obtained isaiiii hy oxidising indigo with nitric acid. In 1848 Fritzsche obtained aniline by distilling indigo with caustic potash ; Baeyer and Knop, in 1865, reduced indigo to dioxyindole, oxiiidole, and indole, the last of these
first efforts

The

of Laurent,

who simultaneously

being prepared synthetically by Baeyer and Emmerling in 1869 from o-nitro-cinnamic acid. In 1870 Engler and Emmerling effected the first complete synthesis of indigo by heating o-nitroacetophenone with lime and zinc dust, and in 1874 Ncncki prepared indigo by
oxidising indole and ozone. Jn an interesting series of studies extending from 1870 to 1878 Baeyer and his pupils established the constitution of, and synthesised, oxindole, transforming it into isatin, and

the latter, in various ways, into indigo. The new complete synthesis effected by Baeyer in 1880-1882 firmly established the structure of the indigo molecule. Of the new syntheses of indigo following that of Baeyer which, in spite of costly attempts, could not be rendered capable of industrial application the most important
fs

from a practical point of view is that of Heumann (1890), in which fusion -car boxylic acid with alkali is succeeded by oxidation.
I.

of phenylgly chie-

The

starting-point
:

and the various intermediate products

of Baeyer' s 1880 synthesis

of indigo are as follow

o-Nitrophcnylacetic acid

Oxindole

lautoxime

Amino-oxindolo
Isatin

e4
Isatin chloride

Indigo

und Soda-Fabrik

Baeyer's other synthesis, which was tried on an industrial scale by the Badische Anilinof Ludwigshafen in 1882, and gave a yield of 60 per cent., started from

SYNTH ESIS OF INDIGO

761

benzaldehyde, the product of the interaction of benzylidene chloride and sodium acetate being nitrated (and subsequently esterified) and a mixture of 70 per cent, of o-nitrocinnamic acid and 30 per cent, of p-nitrocinnamic acid thus obtained. After removal of the latter, the former is converted into the dibromide, which, with alcoholic potash, loses 2HBr and forms o-nitrophcnylpropiolic acid, this giving indigo when heated with alkali and glucose

o-flit-rorinimmic arid

o-Nitrophenylpropiolir acid

Indigo

to the high price of o-riitrophenylpropiolic acid, this artificial indigo is used only for printing textiles. 1J. In 1882, by moans of a new and theoretically elegant synthesis, Baeyer and Drewson succeeded in raising the yield to 70 per cent. ; and acetone were

Owing

o-nitrobenzaldehyde
:

condensed in presence of caustic soda, indigo being formed as follows

CH a CO OH, 2
-

.*

o-Nitrolx'iizuldchyde

Acetone
3

2H 2
111

+ 2CH

-C02H

C 6H4

<
Tridtao

printing, the synthesis takes place directly on the fabric, the acetone being rendered soluble by conversion into the bisulphite compound (Kalltfs salt). The industrial preparation of o-nitrobenzaldehyde presented, however, a serious disadvantage, the direct nitration <;f bonssaldohyde yielding a considerable proportion of the unusable w-iiitrobenzaldehyde whilst, starting from benzil, the ^-nitro-coinpouud is obtained. A happy solution of this
:

40 per sulphuric acid then giving a good yield of o-nitrobenzaldehyde. To the general application of this process were opposed a number of difficulties. In order that the artificial indigo might displace the natural product, the annual consumption of which was about 5,000,000 to 6,000,000 of

difficulty w.as found in the preparation of o-nitrotoluene directly from toluene (only font, of ji-nitrotolutknc is formed), oxidation with dioxide and

manganese

per cent.), it was necessary that there should be on the market a sufficient quanraw material (toluene) at a reasonable price. It was found that, even although the use of modern metallurgical coke furnaces (see Vol. I., p. 451, and this Vol., p. 632) increased the quantity of crude benzene (in 1900 the total output in Europe amounted to 30,000 tons), yet, since the latter contains only one-sixth of its weight of toluene and since 4 kilos of toluene arc required to furnish 1 kilo of artificial indigo, the use of all the toluene oxtractablo from the benzene on the market would give only 1,000,000 kilos of indigo, i.e.,
kilos (100

tity of

one-fifth or one-sixth of the whole consumption. Increase of the production of crude benzene for the purpose of obtaining more toluene would lead to over-production of unusable benzene, and hence to increase in the price of toluene and in that of artificial indigo, which would bo unable to compete with the natural product.
III. After much further investigation and many unsuccessful trials, the industrial preparation of artificial indigo has, however, become an accomplished fact. Having acquired Baeycr's patents for a sum approaching 20,000 without deriving any practical benefit from them, the Badische Anilin- und Soda-Fabrik of Ludwigshafen did not hesitate to

purchase later the patents of K. Heumann, who was the first to discover, in 1890, that is obtained on fusion of phenylglycocoll with caustic potash, but that a better yield is obtained if the phenylglycocoll is replaced by phenylglycine-o-carboxylic acid, C 6 K4 (CO 2H)(NH CH 2 C0 2H). The economical preparation of this acid necessitated investigations and trials extending over more than seven years, and the synthesis became of industrial value only when it was found possible to employ naphthalene as the initial suhstanco. Quite 50,000 tons of naphthalene are produced annually in the distillation of tjr, and up to that tim3 only about 15,000 tons of this had been utilised, the rest being left in the heavy tar-oils or used for making lamp-black (p. 624). The complete synthesis takes place in the following stages
indigo
:

o
Naphthalene
ti.

vx/-

00
Phthalimide

Phthalic anhydride

49

762
-C0 2 H

ORGANIC CHEMISTRY
CH 2C1-C0 2 H =
HC1
,

-NH 2
Anthranilic acid

NH CH C0 H
2
2

Phenylglycinc-o-carboxylic arid

V \C- COoH
NH
indoxylic acid

Indoxyl

Tndigo

of naphthalene to phthalic anhydride by means of chromic acid is too expensive, but the same end was attained by the use of fuming sulphuric acid rich in sulphur trioxide, after it had become possible to prepare this cheaply by the catalytic method

The oxidation

The action of the acid was moderated with mercury bisulphate, while the was recovered by the catalytic process (in 1901 the Badische Company dioxide sulphur recovered in this way, for the manufacture of phthalic anhydride alone, about 40,000 tons
(see Vol. I.).

of s.ilphur dioxide).

Phthalimide is then easily obtained by the action of ammonia, while the monochlorocan be prepared cheaply and in large quantity by using the liquid chlorine (1,000,000 kilos in 1900) resulting from the electrolytic manufacture of caustic soda or potash, and glacial acetic acid (about 20,000 quintals) obtained from the distillation of wood (about 100,000 cu. metres per annum). The reaction between anthranilic acid and monochloroacetic acid proceeds readily, but the formation of indoxylic acid was found to be much more difficult, the conditions required for the fusion of the phenylglycmecarboxylic acid being inconvenient ; this obstacle was, however, finally overcome. The ultimate oxidation of the indoxyl is effected by means of a current of air. The indigo separates in small crystals, and in order to obtain it in a finely divided state, it is converted into sulphate and this decomposed with water. After being washed, the paste thus formed is identical with natural indigo and is, indeed, of greater value owing to its higher purity and to its
acetic acid

constancy of composition. IV. Process of the Farlwerke vormals Meister, Lucius mid Bruning of HdcJist (1900). This consists in the action of sodamide (obtained by treating gaseous ammonia with sodium) on phenylglycocoll, subsequently heating in an autoclave at 250
:

NH Na
2

|-

fi

H NH CH CO Na = NH + Na O +
-

6
:

(indoxyl),

2 mols. of the indoxyl then condensing in presence of oxygen

2

2H 2

+
A

C 6H 4

This process was originally patented by the Deutsche Gold- und Silber-Scheide Anstalt Frankfort), from whom it was purchased. yield as high as 65 per cent, has been obtained, but sodium at 28rf. per kilo is too expensive to make the process practicable.
(

V. Sandmeyer' s synthesis (patented by Messrs. Geigy of Basle ; Eng. Pat. 15,497 of Aniline is treated with carbon disulphide in presence of alcoholic potash, diphenylKHS CS(NH C 5 ) 2 -f 2 O. thiourea being obtained CS 2 -f -}- 2C e H 5 2 The action of lead cyanide on diphenylthiourea gives Hydrocyanocarbodiphenyl1

899).

KOH

NH =

fl

C eH6
imide,

CN, which

with

ammonium

sulphide

yields

the Thioamide,

C 6H6

H NH N
8
5
,

and

this

with sulphuric acid forms a-Isatinanilide,

C 6 H5

NH
N
C

NH

C 6H 6

\/\co/
reduction of the latter by means of ammonium sulphide then giving indigo. All the materials used in this syi thesis are cheap, but the indigo produced was not able to compete for long

INDIGO STATISTICS
acid.

763

improved Heumann processes starting from phenylglycocoll and phenylglycinecarboxylic

years, between the producers of natural connected with the various industrial undertakings has now ended in uncontested victory for the latter. The figures already given showing the areas under indigo at different times (see p. 759) justify the conviction that in a few years' time Indigofera tinctoria will be of interest only historically, just as is the case with madder, now

with that of the Badische Company and of Messrs. Meister, Lucius und Briining, who continually lowered the price in order to suppress natural indigo and made use of the two

The

struggle, lasting for

more than twenty

indigo and the scientific

men

supplanted by artificial alizarin. With its lower price, its more ready applicability in dyeing, and the considerable use now made of its halogenated derivatives, the consumption of indigo will certainly increase. In 1908, owing to the slight difficulty of reducing indigo, even when finely powdered, several firms placed on the market the leuco-product itself (indigo white), this being obtained by reduction with iron and alkali, or, better, with hydrosulphite
(Grandmoiigin),
etc.

of

The following figures will give a clearer idea of the commercial and industrial importance indigo, both natural and artificial. STATISTICS. The production in India was 50,000 quintals in 1892 and 75,000 quintals

(containing 56 to 70 per cent, of indigotin), of the value of 3,200,000, in 1896. Of Indian indigo 60 per cent, is sold at Calcutta, which supplies Europe and America, 30 per cent, at Madras to Egypt and the East, and 10 per cent, at and Karachi. 1

Bombay

of indigo (with 56 to 70 per cent, of indigotin) tion in India were as follows :

The output

and the surface under

cultiva-

1892

1896

1909
12,000 150,000

1912
23,850 86,000

1913
18,800 80,000

1917
48,000 170,000

Quintals 50,000 75,000 Hectares 640,000

1918-19 1919-20 1920-21 22,000 19,000 24,000 .120,000 95,000 73,000

:

In 1895 the consumption of indigo in different countries was as follows England, United States, 11,500; Germany, 10,000; France, 7100; Belgium, 1500 Austria-Hungary, 5500. In 1913 the world's consumption of indigo (calculated for 100 per cent.) was estimated to be 100,000 quintals, the price being lowered by the competition of new vat dyestuffs (indanthrcne, etc.) which compare favourably with indigo
13,000 quintals;
;

as regards fastness and price. The price of indigo (100 per cent.) was 16s. per kilo between 1895 and 1900, 125. in 1902 and 65. Gd. in 1904, the fall being duo partly to competition between the two great firms, the Badische Aniliii- und Soda-Fabrik, and Messrs. Meister, Lucius und Briiiiing, who later came to an agreement, the price then rising to Ss. per kilo. In 1917 the price was more than quintupled, and in 1921 it fell to about double the pre-war value. In 1907 the total output of artificial indigo was estimated at about 4320 tons (100 per 2 cent.), i.e., about four-fifths of the world's consumption.
1 In 1882 tho Indian Government abolished the export duty on indigo. Until 1865 almost the indigo was sent to London, which was the centre of the European trade. In 1905-1906 exportation from India had fallen to 15,000 quintals (400,000), the cultivation of indigo being replaced by that of rubber (28,000 quintals), turmeric (25,000 quintals), hemp, cotton, 'tanning plants, etc. During recent years the cultivation of natural indigo has increased in the districts more suitable to it and diminished in those less fitted. In 1866 the Philippines exported 251,574 kilos of indigo paste (96,950) and 959,206 kilos of liquid indigo (tintarron) (28,180). The industry was still flourishing in 1875-1881, when the producers began to adulterate with sand and other substances ; prices were thus ruined and fell from 12 per quintal to 4, the cultivation being to some extent abandoned. With careful cultivation, as much as 4 quintals of good indigo can be obtained per hectare. By 1905 the exportation had diminished to a total of 250,000 kilos of pasty and liquid indigo. The output in Java amounted to 500,000 kilos in 1905, but in 1909 the exports were only 100,000 kilos. The increasing competition of artificial indigo led to the formation, in 1920, of the Indigo Planters' Co-operative Association, supported by about one-half of the countries producing indigo, with the objects of centralising the treatment, placing on the market a uniform grade of and free the from methods of since adulteration, much land used cultivation, indigo improving It has been found that suitable artificial fertilisafor growing indigo had become almost sterile. The fermentation tion, especially with superphosphates, raises the yield to 45 kilos per hectare. of indigo was formerly carried out in cement tanks and was retarded by the lime liberated by hydrolysis of the cement. j.t appears that natural indigo, properly prepared, gives results about 10 cent, better than per those yielded by the artificial product having the same indigotin content. 2 The first artificial indigo plant of the Badische Anilin- und Soda-Fabrik in 1897 cost

all

492

764

ORGANIC CHEMISTRY
CO.

COLOURING-MATTERS

Only a certain proportion of the innumerable coloured substances are capable of being fixed on vegetable or animal fibres, imparting to them a more or less stable coloration, and only those able to fulfil this function, directly or indirectly, belong to the true Colouring-Matters. Coloured substances are those which absorb constituents of white light of certain definite wave-lengths, emitting the rest. Generally speaking, only the luminous waves visible to the eye have yet been closely studied, and it is probable that new laws, possibly more important than those already known, will be discovered when the infra-red and ultraviolet rays absorbed or reflected by coloured substances are considered. Hartley has indeed shown that the apparently colourless substance, benzene, is, strictly speaking, coloured, as it absorbs certain ultra-violet rays invisible to the eye, and that in the benzene series the luminous vibrations are gradually rendered slower and so made visible as the molecular weight is increased by
substituent groups. Dichroic Substances allow certain rays to traverse them and reflect certain others, so that they appear to be of one colour by transmitted, and of another

such are, for example, fluorescent substances. Certain by reflected, light alkaline fluorides, such as those of the alkali metals, allow infra-red and ultraviolet radiations to pass through them, while various nitrates, nitric acid,
;

the hydrocarbons, the aldehydes, etc., although they do not retain any of the constituents of white light and hence appear colourless, yet do absorb waves of many wave-lengths. Light itself is to the human organism only a sensation due to absorption of a portion of the radiations by the crystalline lens of the eye. Between coloured and non-coloured substances there is often complete or nearly complete identity in chemical composition, so that the colour depends, not on the composition, but only on the constitution or atomic structure of the molecule. It is now universally admitted that tho colour of substances is closely dependent on the presence in the molecule of certain well-defined atomic

groupings or nuclei. As early as 1867 Graebe and Liebermann arrived at the conclusion that the colouring-matters capable of fixing hydrogen with decoloration and formation of the so-called leuco-bases (see p. 721) are transformed into colouring substances on oxidation. In 1876 N. 0. Witt defined the nature of these simple groups, termed
chromophores

= 0:0,

(e.g.,

N:N

- N0 - N N -, - CO, = NH, =s C
2,
:

NO,

= C = S,

etc.),

which by union with more complex groups (even

N N C 6H5 is a chromogen conand is coloured red, but does not dye textile fibres, although it is the mother substance of dyestuffs. Repetition of one and the same chromophore in a chromogen may alter the colour, e.g., from yellow to green, blue, etc. (such chromophores are called hypsochromic),or from
not colouring. Thus, azobenzene, taining the chromophore,

colourless ones like the aromatic hydrocarbons, benzene, naphthalene, etc.) form the so-called chromogcns, these being usually more or less coloured, but

N N
:

C 6H 5
,

yellow to orange, red, etc. (bathochromic). 480,000, and in 1900 two competitors, namely, Messrs. Meister, Lucius und Briining and Messrs. Geigy, made their appearance, the considerable fall in price thus produced resulting in Messrs. Geigy's abandonment of the manufacture and of the fusion of the indigo interests of the two remaining firms with a capital of 1,200,000. In 1910 the manufacture of artificial indigo was started by the Kahtjen Company of Hamburg which is a company with a capital of 280,000 and makes use of Rahtjen's improved Sandmeyer process and by the firm of Heyden (Radebeuf ) which employs the phenylglycine method. The Society of Chemical Industry in Basle a-No began making artificial indigo in 1911-1912. During the war the manufacture was commenced in England, the United States, and France.

CHROMOGENS
N N
:

765
-

Coloured chromogens usually become colourless by fixation of hydrogen ; C 6 5 (azobenzene, orange) CH 5 thus, C 6H 5 C6 6 2 C 6 4 2 (benzoquinone, yellow) C H (hydrazobenzene, colourless) 2 6 6 2 (quinol, colourless). The original coloured compound is obtained on oxidation of the colourless compound, which is known as a leuco-derivative. Dibi-

+ H = H NH NH +H =

phenylenethene,

yC

= C<^

a red hydrocarbon, gives the colourless

rl 4 ^ 6TT
"I

dibiphenylenethanc,

CH<
numerous and

on reduction. 1

36

H4

CHROMOGENS
1

are

of very varied composition. 2

Some of these leuco-products regenerate the original colouring- matter simply by oxidation, while others do not. For instance, reduction of nitro-groups gives, as final products, aminoThe complete reduction of derivatives, which yield nitro-groups again on oxidation. azo-compounds yields amino-groups, but there may also be intermediate, less highly reduced products (hydra/o-compouiids), which are themselves new kuco-der lattices. In some cases reduction leads to more highly coloured substances. For instance, the greenishyellow arithraquinoneazine gives deep blue indanthrenc on reduction
:

N
'

||

N
I

O
O
>

Nil
|

N1E
'

\/ \

the two imino-groups formed being intense auxochromes, especially if they occur in a closed ring. Similarly indigo with the auxochrome, -CO f -^ (.! CO , should bo yellow, but is blue owing to the presence of two auxochromes forming closed rings.
J

Examples

of

chmnwycn* are

Indamiue

ludophenol

llosuniliue

0=\_" V-0-(C
Kosolic acid

H 4 -OH) i;

Aiithnuiuinouc

NF
Thlodiphenylamino

ra
Phcnoxazme

766
by a deepening

ORGANIC CHEMISTRY
:

Introduction of amino groups into the chromogen azobenzene is accompanied of the colour from yellow to orange to brown, these chromo-

Aminoazobenzene, C12 9N 2 NH 2 is pale yellow. Diaminoazobenzene, G 12H 8N 2 (NH 2 ) 2 is orange. Triaminoazobenzene, C 32II 7N 2 (NH 2 ) 3 is brown. Chromogens are mostly neutral substances and if groups termed auxochromes capable of imparting a baric or acid character are introduced, colouring matters capable of dyeing textile fibres are obtained. The auxochromes are, more especially, hydroxyl and amino groups and their alkyl or phenyl derivatives OH, OCHj, NHCH 8 N(CH 3 ) 2 NHC 6H 5 N(C 6H 5 ) 2 Hydroxyl2 amine and hydrazine residues, NH OH and Nil NH 2 may also behave as auxochromes, but the auxoehromic character diminishes or disappears on entry of an acid tmbstituent, as in COCH 3 Nil COCIT 3 N(OH 3) NO, etc. Sometimes the auxochrome group is formed during the dyeing, as when the CO becomes OH. 1 group Further, what are usually the more energetic chromophores cease to be so when they occur in molecules which are small or poor in carbon. To this is due the very small number of colouring-matters in the aliphatic series.
,
,

phores being -bathychromic

NH

Thirteen chromophores of well-defined constitution are now known, while concerning others there is still doubt owing to the pseudoisoinerism (tautomerism)
2 they exhibit.

UN

NH

\/\/\/\/
N
Thionine

OK

\/\/\/\/
Jlesorufln

seen the analogy between the chromophores in the different molecules, characterised by divalent or polyvalent atoms or atomic groups ( N -, NH, O, S, >CO) united to the ring in a closed chain, the whole forming the true chromophorc,
is
,

In these chromogens

which, joined to the rest of the molecule, gives the chrornogen. The passage from simple to more complex chromophores is often accompanied by change from a yellow colour to a more intense yellow or to red or blue. 1 With fuchsines (rosanilines and yj-rosamlines) the colour becomes more intense and more violet with increase in the alkyl groups replacing the aminic hydrogen. The faintly acid, phenolic colouring-matters which, are fixed by mordants give highly resistant colours if they contain and COOH, in the ortho-Haitian, and better still if these are also at least two groups, or In the colouring-matters of the nitrophenol in ortho -positions with respect to the chromophores. group, the colour passes from greenish yellow to orange-yellow as the distance between the OH and NO 2 groups increases. Fast colours on mordants are given especially by those colouringmatters containing hydroxyl-groups in the ortho -position with respect to one another and to the chromophore (alizarin, etc.). Of the triphenylmethane colouring -matters, those which have a sulphonic group (S0 3 H) in the ortho -position with respect to the central carbon atom are stable to alkali and to soap (Suais

OH

OH

and Sandmeyer).
2

all the true nitro-hydrocarbons of the aromatic or aliphatic also all polynitro -compounds are colourless when quite pure, so that the 2 group a never by chromophore. Only certain nitrophenols are coloured when their phenolic is free and hence mobile tautomeric (forming hydrogen compounds), and for the same reason all salts of nitrophenols are coloured. By the discovery of the quinonic (aci-) ethers of nitrophenols besides the true ethers, it was shown that many colourless or almost colourless hydrogenated compounds capable of forming highly hydrogenated salts, are pseudo-acida, so that the coloured salts are derived from a hydrogenated compound differing from the original ; if it were possible to obtain these free, they also would be coloured.

According to Hantzsch (1906)

series

and

NO

itself is

Nitrophenols are certainly true tautomeric hydrogenated compounds which give two of structurally isomeric ethers, such as are given also by nitrous, sulphurous, hydrocyanic, and cyanic acids. The true nitrophenolic ethers are colourless, while the aei-ethers (tautomeric) are coloured an intense red ; the former correspond with the general formula,
series

C 6H f<f

/0-CnH^-H
a

\NO

(derived from the colourless true nitrophenol,

C 6 H 4<f

/OH

\NO

),

and the

latter

SALT-FORMING GROUPS
H N N
:

767

Certain acid groups (C0 3 H, C0 2H, etc.), i.e., salt-forming groups, influence the colour but, even more than the chromophores, reinforce the influence of the auxochromes. C 5 although a coloured Thus, azobenzene, C6 5

with C-H.jx

OC nH 2 n
tell,

[derivatives of aci-nitrophenol (quinonic),

f

....

C 6 H 4 f^

\NO OH

].

It

is

hence possible to
belongs.

of the two groups a given nitre-compound (even in the solid state) are slightly coloured, it is assumed that is minimum quantity of the aci-nitrophenol dissolved in a large quantity of true nitrophenol Also, the fact that the colour of the substance is sometimes not intensified (solid solution). by increase in the number of iiitro-groups is explainable, not on the old view of the theory of chromophores, but only by the new theory of transposition (tautomerism)

from the mere colour, to which

When true nitrqphonols

/OH C H
6

4<

\N0

fl4
2

\NO-OH

tautornerie transposition may, indeed, be increased or diminished by the Thus, in solutions of nitrophenols and their salts, the coloration is not due to ionisation, as it would bo according to the modern theory of indicators (sea Vol. 1., p. 100) but rather to the formation of coloured tautomeric compounds (aci-iiitrophenolic ethers) in agreement with the old chemical theory of indicators. It is thus proved that the formation of coloured salts and coloured ions derived from colourless hydrogenated compounds is of a purely chemical nature. It is caused first of all by intramolecular transposition, from which, by the action of a positive metal (salt), there results a negative quinonic atomic grouping (chroinophore), the appearance of coloured ions being a secondary reaction. Hence the actions of chromophore arid of auxochrome cannot be held to be distinct but are exerted together, both of them (nitro- and phenol-group) causing the appearance of colour at the expense of their mutual transformation, which generates a quinonic grouping containing neither nitro-

entry of

The tendency to new groups.

nor phenolic -group. Those views may be extended to other groups of organic substances since, in general, colourless acids unchangaable in constitution (>., not giving tautomcric forms) give only colourless ions and yield colourless salts with colourless metallic oxides, and colourless ethers and esters with If coloured ions and salts are derived from a colourcolourless organic radicals (alkyl and acyl). less alkyl compound, it may be stated with certainty that intramolecular change occurs. According to K. Fischer and O. Fischer (1900) many colouring-matters derive their properties from the presence in the molecule of quinonoid groups, although A. v. Baoyer (1902-1905) and Hantzsch (1905) showed that the true quinone group docs not always cause coloration (I.G., is not the chromophore), and Kostanecki and Hallcr pointed out that, in addition to the two carbonyl

CO
HC
groups of the quinonc, two cthylene double linkings must be present,
:n
;

in fact,

HC
CO CO

CH

H
diketohexamethylene,

C/\CH
CO

2
,

which has not these double bonds,

is

completely colourless.

H 2C
As a metaquinone with two

'C1I 2

f thylene double linkings cannot exist, such meta- com pounds are incapable of producing colouring-matters. Further, according to vVills tatter's results (1908), conversion of the benzenoid to the quinonoid form is not sufficient to produce intense coloration, since then the complete quinonoid derivatives (holoquinonoid^ should bo highly coloured, whereas the benzoquinones, like the qumoiiirnines C 6 4 NH, are only slightly coloured. On the other hand, O:C C 4 :NH and quinhyd rones, formed by the condensation of quinol and quinone old the partial valency, are highly coloured compounds

NH

OH
I

O ..... OH

\/
OH
Quinol
(colourless)

\/
II

\/
II

\/
I

O
Quinone
(yellow)

O ..... OH
Quinhyd rone
(highly coloured)

768

ORGANIC CHEMISTRY
N N
:

chromogen (containing the chromophore

),

does not colour textile

fibres since it is neutral, whilst its sulphonic derivative is a feeble colouringmatter. Also the direct introduction of sulphonic groups into true colouring

matters usually produces, not an intensification, but a distinct attenuation. However, these groups, which are feeble auxochromes, give to the colouring matter an acid character which influences its behaviour towards various textile fibres and thus, besides rendering certain insoluble colouring matters soluble
in water,

makes them

dyeing wool and

acid dyestuffs.
its

silk directly in

suitable (either as they are or after salt-formation) for an acid bath that is, they form the group of
;

The auxochromic function

of the sulphonic

group increases with

proximity to the chromophore group. The basic auxochromes usually consist of amino groups more or less substituted by alkyl or phenyl residues, etc., and are transformed under certain conditions into chromogens, giving rise to basic dyestuffs which dye wool and silk

and dye cotton only after this has been directly in a neutral or .slightly acid bath mordanted with tannin. When similar auxochromes and chromophores are both able to form salts, the salt-formation of the chromophore is the more important, as is shown by the
behaviour of the rosanilines. 1

NH,

NH

Nil.

\/
N(CH 3
)2

N(CH 3

2,

HC1
Cl

N(CH 3

)2

N(CH 3
Wnwtpr's

)3

l)impthyl--phenyleiiPdianiino
(colourless)

iiJMmethyhiui-

ml

10 iionedi-inimo

(highly coloured)
j

(yellow)

These partially quinonoid compounds arc termed mt riqninom>M. The intense colour of magenta may be explained by the simultaneous presence of a quinoiioid nucleus probably united by partial valencies to the beiizenoid group or groups and, moreover, to the methane carbon atom. With certain groups of substances intensification of the colour is due more especially to a and crystal phenomenon of wit formation, e.g., with the rosanilines, the base of malachite green Colourless phenolphthalein gives a red sodium salt, and yellow alizarin becomes intense violet. thus In certain cases only salt formation annuls the coloration violet in alkaline solution. the three nitroanilines are yellow, but become colourless when salified by an acid, the latter amino group. paralysing the auxochrome action of the Oil salt formation aminoazobenzene gives an orange-yellow colour for the azoid form, ( N N C 6 H 4 NH 8 ,HC1, and a violet colour for the quinonoid from, C 6 H 5 NH N C 6 H 4 N 8H
;
-

1 1 ,

HCl

CH CH
/
1

Rosaniline,

HN

--

C\
>IH

\ /

,/C s H a

r<TT
' '

xrVr

3
2
(

8ec

forrespfmding

bane,

p.

721),

CH

XH.-NH,
CH
r-.

CUV

which

is

coloured, contains as chromophore the group

NH

C<^

\CH -

CtK

/C<,

and as

auxochromes two amino-groups. When the salt with a single molecule of HC1 i- obtained and the substance is dyed red, proof is given that the salt is formed with the imin i-group of the chromophore, since a red coloration is formed on the fibres. On the other hand, sajts of rosauiline with 2 or 3 molecules of HCl, which form salts also with the auxochrome ami m-groups, are yellow but do not dye textile fibres yellow. It can hence be affirmed that the auxochromes do not unite with the fibres and hence have no action as salt-forming groups but ,nly contribute
to increase the basic character of the colouring-matter or even to increase the intensity of the In colour ; this is clearly shown with safranine (see later and aUo above, Aminoazobenzene). general, the union of an acid chromophore with a basic auxochrome gives colouring-matters *of more intense slight intensity ; for instance, the nitroanilines are feeble and the nitrophcrols colouring-matters. The replacement of the hydrogen of the auxochrome by a metal increases the power of the auxQcnrome, while an alkyl or aromatic radical lowers it and an acid ramcal often annuls it.

OH

COLOUR
If

FN

HYDROCARBONS
is
*

769

the auxochrornc of a colouring-matter

weak and the chromophore

strong, or vice versa, the colouring-matter is generally feeble. Kaufmann (1921) considers that carboxyl and sulphoxyl, S0 2 OH, act as auxochromes, not when they are united directly to the chromophore, but only when separated from it by either a benzene nucleus or a corresponding group. a weak acid auxochrome, increases the fastness of the The

carboxyl group,

and often imparts the ability to form lakes with metallic mordants. The nitro group acts as a chromophore and, when added to other chromoA similar it towards the blue. phores, renders the colour faster and displaces to its cost used is little iodine but the action is shown by owing halogens, also vat for and eosins is used for the which colour, dyestuflk bromine, deepens
colour
;

but render Alkyl groups, as part of the chroniogcn, exert little influence, the colour more blue and more brilliant if they occur in the auxochromes as either alkylaminic groups, as in Hofmann's violet, or alkyloxy groups. Similar behaviour is shown by arylaminic groups, NHAr, as in aniline blue and alkali
blues.

Colour in an organic compound was formerly regarded as being connected with the presence in the molecule of nitrogen, oxygen or sulphur, and the colour of a few hydrocarbons was considered exceptional or due to traces of impurities. Various coloured hydrocarbons are, however, now known. Diphenylbutadiene and the two tetraphenylbutadienes, C 6 5 OH Oil C(C 6 6 ) C(C 6 5 ) 2 and C C(C 6 H5 ) 2 are colourless, but diphenylhexatriene and tetraC(C a r )o CH CH CH C(C 6 5 ) C(C 6 H6 ) 2 are yellow. phenylhexatriene, C 6 H 5 CH

Perylcne,

also, is coloured.

Of more interest are the following hydrocarbons derived from fulvene

CH-CH
CH CH

CH

CH

CH CH CH CH

CH-CH
CII

CH CH

V C

V
Plionylnicthylfulvene, red

OH

H
Many

CJL OIL, C CH 3 OH, C C 6H5 C 6 H 5

i

O bII5

II

()

H5 H

C OJT5

J'henylfulveno, Diineth>lfulvene, red orange -yellow

Diphcnylfulvc.no, rod

PhrnylbeiiHofulveno, yellow

IMienyldibcnzofiil\(Mic, colourless

coloured fulvene derivatives were prepared by Courtot (1915)

by means
or,

of

the Urignard reagent. These and other similar compounds contain tlieftdrenic chromophore C~C C C double linkings, generally, at least three conjugated
(Thiele,

more

C=C

1899).

Of the two tetraphenylbutadienes

(see abore),

however, the

radicals raises the colouring power, Substitution of the hydrogen of the auxochrome 2 by alkyl while two aromatic radicals sometimes lower it considerably, exceptions to this being shown by to assume an acid character. which cause the 2 group sulphoiiyl and picryl, C 6 2 (NO 3 ) 2 The hydrazinic and hydroxylaminic groups also behave as auxorhromcs ; thus phenylhydrazine is more highly coloured is slightly yellow while aniline is colourless, and mtrophenylhydrazine than nitroaniline. Anthraquinone (faintly acid chromogen) gives an intensely coloured derivative but with hydrazine groups. The hydroxylamine derivatives are few in number and have been H. Kaufmann (1911)' has shown that two auxochromes reinforce one another little studied. when they are in the para-position and to a less extent or not at all when they are in the orthoThis rule is confirmed, not only by the greater intensity of the colour, but also or m^ta-position. substances when they are exposed by the increased luminescence or fluorescence assumed by these in solution, only compounds of the para- series give to ultra-violet rays (see Vol. I, p. 125) and sometimes direct fluorescence. By the law of distribution it is proved that the maximum and the only effect of auxochromes in the para-position is exerted when the chromophore in the same benzene nucleus,

NH

NH

770
first

ORGANIC CHEMISTRY
;

contains only two conjugated double linkings and the second the linking C C C the coloured diC, both of these compounds being colourless and tetra-phenylhexatrienes contain three conjugated double linkings. Perylene contains six such linkings and is coloured, whereas tetraphenylethylene is colourless, as the conjugated linkings are not accumulated in a restricted nucleus as in

= = =

a red colour.

perylene. It is sufficient, however, to establish a conjugation between two double linkings of two phenylic nuclei to obtain a yellow colour, as in diphenyldibenzofulvene (I), two such conjugations, as in diphenylenedibenzofulvene (IL) giving

/"
C

=n
(1)

N
,

'

>C

= C<
()

fact that phenyldibenzofulvene is colourless, whilst phenylbeiizoulvene, with the same number of conjugated double linkings, is coloured is explained by the presence in the latter of fewer benzene nuclei and hence of a greater accumulation of double linkings (Kaufmann, 1904). As regards the constitution of dyestuffs benzenic double linkings must be distinguished from ethylene linkings, the latter being less saturated than the former and combining more readily with bromine and hydrogen owing to the

The

residual partial valencies (see p. 620).

For dyeing purposes the colouring-matters are placed on the market in a state soluble in water, the auxochrome groups being converted where possible into salts (e.g., SO 3Na, etc.). When wool (which is both basic and acid in character) is dyed with acid colours, since the basic properties of the wool are usually not sufficiently strong to displace the metal (Na) of the acid colour, an energetic acid (acetic or sulphuric) is added to the hot aqiieous dyeing bath, this liberating the acid residue of the colouring-matter, which can then combine with the basic group of the wool to form a coloured stable insoluble salt in the fibre itself. Thus wool is dyed directly both by acid and by basic colours (with the latter it is not necessary to render the bath acid). Cotton, on the other hand, is not usually dyed by acid dyes but only by basic ones, and then only when the fibres are previously mordanted with tannin materials and metallic salts. During the past twenty years, however, numerous neutral or substantive dyestuffs have been discovered, capable of dyeing cotton directly in a neutral or faintly alkaline, but not acid, bath, previous mordanting being unnecessary. Many of these colouring-matters have a common benzidine group (see p. 718), others contain a basic group (primulin) and others again a phenolic group (curcumin). Colouring-matters sometimes acquire this property by mere accumulation of chromophores in a single molecule (Rupe, 1901). The nature of the metal present in these colouring-matters alters to some extent the properties and the affinity towards cotton, but this is always related to the capillary constant of the aqueous solution. The precipitation of the unaltered colouringmatter on the fibres is facilitated by increasing the osmotic pressure of the bath

by the addition of considerable quantities of salts (NaCl or Na 2S04 ). As a rule phenolic compounds form weak colouring-matters, but they have
the property of giving intensely coloured lakes with metals (phenoxides), the metallic atom united to the phenolic oxygen functioning as an energetic auxochrome. These colouring-matters having no affinity for textile fibres, the latter are previously charged with metallic oxides (mordants). Lakes of different colours are formed with different metals (Hummel hence called such colouringmatters polygenetic), but for practical purposes it is indispensable that they

DYES IN RELATION TO FIBRES

771

2 S0 4 acid colouring-twtters (Simpson and Nicholson, 1862) are often obtained. In the form of soluble salts of the alkali metals, these can be fixed directly, in an acid bath, on animal fibres with the same colour as the colouring-matter, the animal fibre forming a kind of new salt indeed the fibre assumes the colour of the original salt of the colouring-matter and never that of its free coloured acid liberated in the bath by means of acetic or sulphuric acid (see above, Process of Dyeing). These acid colours are fixed also by cotton, provided the latter is first rendered basic either by nitrating and then reducing, or by oxidising (oxy cellulose), or by hydrating (with NaOII mercerisation), or by treating with 3 under pressure in presence of ZnCl 2 (Vignon). Basic colouring-matters which owe their basicity to the chromophore and more especially to the auxochrome 2 form salts with acids and are used in practice in the form of hydrochlorides, sulphates, etc., from hot acidified aqueous solutions of which wool and silk fix the coloured base. These basic dyes also form insoluble salts with tannin, etc., so that they are capable of dyeing cotton which has no affinity for basic dyes if this' is previously mordanted by prolonged immersion in cold solutions of tannin extracts (sumac, etc.), followed by fixation of the tannin in another bath containing an antimony, aluminium, or iron salt, or gelatine. In tho subsequent dyeing-bath, the dye is fixed rapidly, even in the cold (the fixation is more regular, i.e., slower, in presence of a little alurn). The full (intense), bright colours thus obtained on cotton resist the different reagents well but are destroyed during washing by the rubbing. In 1901 C. Favre suggested the use of resorcinol and formaldehyde as mordants in place of tannin. 3
, ;
:

should be resistant to atmospheric agents and to ordinary physico-chemical treatment. 1 The best among these substances are those containing in the ortho-position either two phenolic groups (OH) or one OH and one COOH, and of such those are best in which these groups are in the ortho-position with respect to the chromophore (Liebermann and Kostanecki, 1887-1893) and in which the auxochrome is formed from iron, aluminium, or chromium. Not all colouringmatters which give insoluble lakes can be fixed on fibres mordanted with metallic oxides, and this perhaps depends on the fact that only certain coloured lakes are capable of combining with the fibre, the constitution of the colouring-matter 2 (see Alizarin) being here also of considerable importance. When basic or neutral colouring-matters are sulphonated with concentrated

NH

NH

In addition to what has been already stated with reference to the application of lakes, bo said that they are derived from acid or basic; colouring-matters, coloured pigments, or colouring-matters of tho anthraquinone group. The soluble acid colouring-matters arc precipitated by salts of calcium, barium, strontium, aluminium (chlorides), magnesium (sulphate , etc. Solutions of basic dyes are precipitated by tannin, Turkey red oil, resin, or, more commonly, sodium phosphate or sodium arsenate. Anthraquinono dyes (alizarin, ccerulein, etc.) form lakes with greater difficulty, and it is necessary to observe rigorously the proper temperature conditions. In preparing lakes, great importance attaches also to the substance on which tho precipitated lake is deposited or with which it is mixed (aluminium hydroxide, barytes, zinc or lead white, ferric oxide, fresh aluminium silicate, etc.), and of these, the ones more easily decomposable Lake -formation is hence not a simple absorption by dilute acids retain the colour best. phenomenon but also a chemical phenomenon. 2 There are certain substances which are fixed on mordants even if they contain no hydioxyl 1:4:5: 8-tetra-alphylaminoanthraquinones (R an aliphatic croup), groups, such as
it

may

NHR

NHR

The corresponding tetrahydroxyanthraquinones show

affinity

only

for

WR

NHR
:

beryllium mordants, with which they give a deep blue lake, whereas 1 4-dihydroxyanthraquinone dyes well with various mordants. Werner showed that even colourless substances may colour certain mordants ; thus, dimethylglyoxime yields a deep blue coloration with nickel mordants owing to the formation of complex metallic salts (see Vol. I., p. 848). 8 Behaviour of Colouring-Matters towards different Fibres and Mordants according

772

ORGANIC CHEMISTRY

PHYSIOLOGICAL ACTION OF DYESTUFFS. Certain dyestuffs, even in dilute solution, are very readily fixed by cellular protoplasm and may cause death ; thus methylcne'blue is used for staining bacteria and other microscopic
If a skein of wool, silk, or cotton is immersed for some hours in a solution to Noelting. of a basic ferric salt, the fibres assume a brown colour, having fixed a certain amount The same holds generally for all salts of oxides corresponding with of ferric oxide or basic salt. The salts of protoxides (RO), e.g., those of copper, iron, manganese, nickel, the formula 2 () a cobalt, etc., especially the tartrates or in presence of tartar, are fixed by wool or silk, but not at

or but slightly by vegetable fibres. Not only metallic salts, but also certain organic substances (tannin materials) and salts of be fixed by fibres. hydroxyoleic and hydroxystearic (sulpho-oleates) acids, can A largo number of colouring-matters are fixed directly on animal fibres in a neutral or acid bath, more rarely in an alkaline bath. To this group belong the mtro-derivatives of the phenols and amines the azo, basic, and acid dyes ; basic, acid, or sulphonated derivatives of triphenylmethane ; certain phthaleins (fluorescein and eosin) ; the aminophenazines, safratlines, thioindamines, phenoxazine derivatives (gallocyanino and Meldola's blue), phenylacridine complexes (phosphine), quinoline complexes (cyanine, quinoline red, quinophthalone), hydrazides, osazones (tartrazine), ketonimides (auramine) and, among the natural colours, indigo-carmine, Almost all of these dyes are fixed in minimal berberine, safilower, saffron, archil, and catechu. Those which are fixed by the latter arc less numerous fibres. or not at all 011
all
:

a first group of substances which arc fixed only with difficulty (better with tannin), Victoria blue, e.g., certain aminoazo-compounds, phenylene brown, chrysoidine, mclhylene blue, a second group fixed stably and directly and consisting of numerous azo-derivatives safranine of benzidine, tolidine, diarninostilbene, p-phenyienedianime, naphthylenediaminc, diaminoazobenzene, diaminoazoxy benzene and its homologues, diaininodiphcnylamine, canarino (oxidaa third group tion product of thiocyanates), and the sulphur dyes of Croissant and Bretonnicre which do not dye wool, cotton, or silk directly but give bright fast colours if these fibres (especially such are mordanted with salts of iron, aluminium, or chromium are with
: ; ;

quantity and include

vegetable

wool)

previously

and methylene blue magenta forming an orange, malachite green forming a yellowish-green, to which Noelting forming a blue colour. AH the benzidine colours have the same property, Direct also to all dyeing with mordants. gives the name secondary dyeing, a term applicable dyeing would then be primary dyeing. for instance, the violet lake of In some cases a third colouring-matter can be superposed The red lake of alizarin and iron combines with methyl violet giving a brilliant triple lake. rather opaque, is rendered brilliant and alizarin, alumina, and lime, which is not very bright and more fast by the fixation of a sulpholeate, which forms a quadruple lake finally, this can still fix tin from a soapy solution of tin salt, a new lake with five components being formed. If a fabric removed from a solution of a basic iron salt, instead of being washed immediately with alkali or soap (or with a solution (in which case it becomes yellowish), is treated directly of a salt the acid residue of which forms an insoluble compound with oxido of iron), it becomes much more intensely coloured and the quantity of iron fixed by the fibres is considerably increased. Oxide of iron can be accumulated on the fibre, not only, as just mentioned, from an alkaline bath, but also by impregnating the fibre itself with ferrous salts of volatile acids, e.g., the acetate, and then exposing it in tho moist state to the air. The ferrous salt is thus converted into basic an insoluble, ferric salt, this in warm, moist air losing part of its acid and undergoing change into fibre even by repeated washing. highly basic salt, which is not removed from the In order to help the action of the air and render a larger quantity of basic, salt insoluble, the arsenate. fibre may be passed into a bath of cow-dung or lime and potassium silicate, phosphate, or The basic Aluminium salts are similarly rendered insoluble by formation of a basic salt. chromium salt is fixed by a subsequent bath of sodium carbonate or, better still, by impregnating the tissue with a solution of chromium sesquioxide in caustic; soda and exposing it to the air, the caustic alkali being thus converted into carbonate, which precipitates the sesquioxide of chromium instead of exposure to the air, the action of steam may be employed. Chrpmous oxide is precipitated by simple washing of the impregnated tissue with a tin salt. Sulphoricinate emetic or ferric or is fixed by solutions of aluminium salts, and tannin by solutions of tartar aluminium salts. The action of a chromate bath on catechu is twofold first, the catechu undergoes oxidation with considerable darkening, and then combination takes place between the oxidation product and the chromium sesouioxide resulting from the reduction of the chromate.
;
;

certain phthaleins (gallein), derivatives of anthraquinone (alizarin, purpiirin, alizarin orange, and almost all the anthragallol), anthraquinoline (alizarin blue), phenoxyanthranol (crerulein), Noelting natural colouring-matters (logwood, cochineal, quercitron, cudbear, sandalwood, etc.). and vegetable fibres directly and that gave the name substantive dyes to those which dye animal of adjective dyes to those which dye the fibres only after mordanting. Certain dyestuffs are fixed directly by wool and silk and only indirectly by cotton, i.e., when the latter has been mordanted. Such are gallocyanine and various earboxylic acids of azoaniline salt and also tho compounds. In dyeing with aniline black, tho fibre fixes both the formation of an insoluble aniline oxidising agent, the latter oxidising the aniline on the fibre with with tannin black. Dyes which arc not iixed directly by cotton, dye it only after mordanting or sulpholeic acids if they are basic in character, or after mordanting with metallic oxides, with or without sulpholeates, if they are acid. Further, various substantive colouring-matters have the property of fixing others on them ; and canarine, which are yellow, fix basic; colouring- matters, such as for instance,

chrysamine

OSTWALD'S COLOUR THEORY

773

preparations. Formerly, when prepared wih arsenious acid, triphenylmethane dyes were poisonous. More or less poisonous are Victoria orange, aurin, metanil
yellow, safranine, orange II, fast yellow, Martins yellow, methyl orange, magenta, acridine red. Methyl violet and auramine are used in ophthalmology and surgery as a bactericide, and methyl ene blue (base) is employed as an internal analgesic in cases of malaria, carcinoma, etc.
'

The use of the potassium derivative of dinitro-o-cresol (antinonnin) has been suggested to combat the growth of fungi in moist situations and on beams. If fluorescein is injected into the living body it turns yellowish-green in a few minutes, whilst if the body is dead, no change occurs. The use of zinc, copper, barium, etc., salts for salt-formation gives poisonous dyestuffs.

'

OSTWALD'S
DEFINITION

NEW THEORY OF COLOURS AND THEIR NUMERICAL

(1916-1920). The perception of colour is a psychic phenomenon. Absolute coloim are those apparent in a dark field, as in emission spectra (see Vol. I., p. 57), that is, pure colours uninfluenced by the white light of the surthe latter darkens the colour, what is observed being the relative roundings colour resulting by reflections from the luminous surfaces present in relation to then: intensity and extent. Thus, if a bright orange-yellow disc is projected on to a dark screen the colour appears in all its purity and brightness, but if white light is projected all round the disc, the latter appears chestnut-colour, that is, is darkened. In practice these relative colours are the more important. Distinction must also be drawn between non-chromatic colours, i.e., greys comprised between white and black, and chromatic colours, comprising the rest White is the colour which gives a complete diffusion (reds, blues, yellows, etc.). of the incident light (typical is precipitated barium sulphate). The ideal black is that observed on looking into the orifice of a dark wooden box, lined with black silk velvet, but the most intense black practically obtainable in painting 1 still reflects 2 grey formed ot 51 per cent, of ideal white per cent, of the light. and 49 per cent, of ideal black appears very light, whilst that appearing to the eye to be the true mean between black and white reflects only 14 per cent, of the light this is explained by Vechner's law, according to which the excitation on the organ of sight should increase in arithmetic ratio, because the sensation increases in this way. The fact that the practical mean grey is formed of 14 parts of white and 80 of black being established, it is possible to make up the whole
;

by fixing types judged by the eye. Similarly, with the chromatic colours, we can form a graduated colour scale by arranging the fundamental colours (yellow, red, blue) at equal distances on the circumference of a circle and interpolating intermediate colours between is obtained a chromatic circle, in which the differences are these. In this
scale of greys

100. b o, whilst for a grey, p is zero or w In practice no pure colour, giving a single coloured line in the spectrum, exists, the range of wave-lengths being moderately wide, and Ostwald states

two colours diametrically opposite, these being known as complementary colours, since an optical mixture of them yields a neutral grey. If two moderately near colours a and b on the chromatic circle are chosen, it is always possible to find experimentally a colour c which, when mixed in an the distance on the circle between c and 6 equals equal amount of a, gives b that between b and a. Hence any colour can be analysed or defined by this and system, but to make such mixtures it is necessary to be able to determine define the pure colour which lends itself to such mixture. To this end Ostwald supposes that every practical chromatic tint is composed of a mixture of white 100. For a pure colour, b p (w), black (b), and pure colour (p), so that w
greatest for
;

way

+ =
b

+ + = + =

1 To the question, Is black a colour ? Ostwald replies that in the region of absolute colours black does not exist, but in that of relative colours black is a colour, since it does not represent total absence of luminous emanation ; this emission may be very slight (even only 0-5 per cent.),
nv+, is

perfectly deterininable.

774
tha.t

ORGANIC CHEMISTRY
waves corresponding with the half

any pure colour practically consists of of its chromatic circle. The

practical procedure for the qualitative and quantitative definition and analysis of a colour is as follows. A continuous
flee/

part

Violet

Orange

spectrum is projected on to the coloration; the on which radiations of the same colour impinge should appear white, but actually appear* a greyish white which can be analysed by comparing it with the linear scale of greys, corresponding with known percentages of white and black. It can then be affirmed that, in the
is

colour analysed, there

is

as

much

black as there

in this grey.

The percentage

of white in the

FIG. 469.

being easy to define as accurately, very dark grey. The percentage of white in this dark grey and hence the amount in the original colour are then ascertained by "comThe percentages of black (b) and parison with the linear scale of greys. white (w) being thus determined, that of the pure colour is p 100 For this analysis, the spectrum used may be replaced by a transparent chromatic screen, through which the colour to be analysed is observed. Ostwald has collected the principal laws of the new theory in a colour primer and has added an atlas of about 3000 colours, so that the analysis of any colour may be made by simple comparison. lie has prepared also a centesimal chromatic circle containing 100 gently graded
:

original coloration is determined by illuminating the latter with that part of the spectrum which corresponds with its complementary colour, this it makes the coloration appear black or, more

wb.

colours,

any
I

two

complementary

polar positions. The positions of the 100 colours on the circle are indicated by the numbers, 00, 01, 02, to 99. To render the characterisation
of

colours

occupying

any

tint

more

easy,

Ostwald has prepared, for each of the

100 colours, an equilateral triangle, the vertices being occupied by pure colour (P), pure white ( W) and pure black (B)
respectively (see Fig. 470). To synthesise any given coloration, that point in one of the triangles is ascertained which agrees exactly with the coloration.
straight line joining this point with the apex p is continued to meet the opposite side, wb, at a point indicating
colour, p,

20

The

M)

60

Equi black scale

the grey which, together with the pure gives the coloration under
investigation.

equi-colour

equi white
equi black

Ostwald has attempted to determine

1

FIG. 470.

Rosenstiehl's Old Colour System is less perfect, but far simpler, than that of Ostwald. based on Young's theory, according to which any coloration is produced in the eye by superposition of three fundamental colour sensations. At the vertices of Maxwell's trianguLar diagram are placed the three fundamental or primary colours, red, yellow and blue (Fig. 469) colours exactly intermediate to any two of these are the secondary colours (orange, green, violet). Mixture of the colour (material) of any apex with that represented by the mid -point of the opposite side gives black, whilst mixture of the corresponding luminous waves forms white. Rosenstiehl constructed a diagram of 24 colours, representing 12 pairs of complementary colours, the angle between two adjacent colours being 15. In 1864 Chevreul prepared a chromatic scale comprising 14,421 colours, and from this Valett<* and Klinksiec constructed a code of 720 colours.
It is
;

OSTWALD'S COLOUR THEORY

; ;

775

twenty-four components obtained being defined quantitatively by the following divisions of the centesimal chromatic circle
:

violet, orange, turquoise, sky-blue, green, and yellowish green), and each of these eight zones thus may be subdivided into three components, the

laws concerning the so-called harmony of colours. He points out that every pure colour may vary its tone x in three ways in the intensity or value of the pure in becoming lighter owing to the colour, thus forming the equi-colour scale presence of more or less white, thus forming the equi-white scale (Weissgleiche Reihen) and in becoming darker owing to the presence of more or less black, the equiblack scale (Schwarzgleiche Reihen) boing formed. For the quantitative definition of the equi-colour scale the chromatic circle may be divided into eight principal zones of colour, starting from yellow (yellow, red,
;

Yellow

Orange

Red
Violet

Turquoise

Sky blue
Green

Yellowish green

...... ..... ...... ...... ..... ..... ...... ....

Components
1

of each zone.

00
13 25 38 50 63 75 88

04
17

08
21

29 42 54
67 79 92

33 46 58
71 83

96

In this manner each tint is standardised, and to indicate the white and the black entering into any colour to be synthesised the rules indicated to establish harmony in the non-chromatic colours, i.e., the greys (sec preceding note), may be followed. For instance the tint with the colour index, 111, g, is that occurring in the orange zone in the second component and contains as much white as there is in the grey I, and as much black as in the grey g. The content in white may range from c to p, and that iu black from a to n, and as the second letter should always be less than the first, for every tint there are 28 derivatives differing in their contents of white and black. Hence for the 24 fundamental colorations of the 672 chrojmlic standards, which are preceding table there will be 24 X 28

suificient to satisfy all practical demands. For each colour there exists an isochromic triangle, the chromatic indices for the triangle having the same number whilst the letters exhibit all possible

The colours may, however, be disposed so that the letter remains constant whilst the numbers vary, the resulting equivalent circle having equal contents of white and black. The principal rules of harmony in colours are : (1) Any colour may be replaced wholly or partially by those of its equi-colour scale, and (2) Any colour may be replaced completely by the colours immediately adjacent to it in the chromatic circle. In general, harmony in colours depends, firstly, on the contents of white and black and, secondly, on the pure colour itself.
variations.

During recent years various attempts have been made, without practical to utilise the colouring matters produced by certain chromogenic bacteria, e.g., B. prodigiosus.
success,
rules for establishing harmony in the. non-chromatic colours (white, grey, If the linear scale of the greys (see above) is divided into, say, 20 equal parts distinguished the letters by a, 6, c, etc., a will represent white and 6 a very light grey, while beyond I the grey becomes almost black and t represents the most intense black realisable in painting. For practical these purposes gradations are too close, and the alternate ones, a, c, e, etc., suffice. Such gradations, still equidistant, dominate the whole region of the greys. Arbitrary superposition of three different greys may produce an effect of incoherence or discord, but harmony is obtained if three equidistant e such as or are chosen. c, t g a, g, n, gradations,
1

More simple are the

black).

776

ORGANIC CHEMISTRY

MANUFACTURE OF COLOURING-MATTERS .Since 1856-1860, when Perkin in England made mauveine and Renard and Frank in France made fuchsine (magenta) on an industrial scale, scientific
progress in colouring-matters has advanced pari passu with the industrial

development.
In the history of the
of the scientific
artificial

colouring-matters, side

by

side with the

names

men, such as Perkin, Williams, A. W. Hofmann, Graebe,

etc., who laid the first stones in this marvellous chemical edifice, are those, not less worthy, of the brilliant and daring industrial workers who, and the by

Liebermann, Baeyer, Witt, Nietzki, Noelting, Caro,

uninterrupted energy

application of ingenious processes, carried these theoretical discoveries into the larger field of industry and commerce. The dye industry, although not born on German soil, has there reached its greatest development and borne its richest fruit, far in excess of the dreams of its founders. This result has been reached in Germany as a result of various fortunate circumstances. l
1 At first France was at the head of tho aniline dye industry, with numerous pioneers, such as Verguin, Keiiard Brothers, Frank, Poirrier, Guinon Mamas and Bonnet, Coupler, Girard and de Laire, Baubigny, Persoz, Bardy, Lauth, Kopp, Itosenstiel, Koussin, etc., hut of all these very few have been able to withstand the wonderful organisation of the large German manufacturers. Even England, the cradle of the industry, is now in a position greatly inferior to that of

Germany. The six English factories working in 1913 employed altogether 35 chemists, whilst the six largest German firms employ 600, besides 350 engineers and technical directors. From 1886 to 11)00, the firms took out 86 patents, while the six more important German ones took out 1)48. ^English The principal English firms producing dyes were Brooke, Simpson, and Spiller, London The Clayton Aniline Company, Manchester Read, Holliday, and Sons, Limited, Huddersfield; arid I. Levinstein and Company, Limited, Manchester. The German firms which enjoyed almost a monopoly of the world's trade in aniline colours were: (I) Badische Anilin- und Soda-Fabrik, Ludwigshafen (2) Farbenfabriken vormals Fr. Bayer und Co., Elberfeld (3) Farbwerke vormals Meister, Lucius und Briining, Hochst Casella and (4) Leopold Co., Frankfort (5) Actien-Gesellschaft fur Amlin-Fabrikation, Berlin of less importance are the firms of Oehler in Offenbach, Leonhardt (6) Kalle and Co., Biebrich of Mulheim, etc. Firms (1), (2), and (5) work together to regulate the output and trade, and the same is the case with (3), (4), and ((>). Jn 1916 these two federations, together with other
:

companies, united to form a syndicate, termed the Jnteressengemeinschaft, with a capital of 1,000,000,000 marks. In connection with this syndicate another company was formed, with a capital of 500,000,000 marks, for the manufacture of synthetic ammonia. The dividend paid by this vast organisation was 12 per cent, in 1918, 18 per cent, in 1919 and 20 per cent, in 1920. Of the German factories, the Badische Anilin- und Soda-Fabrik alone, with a capital of over 1,400,000, employed in 1908 about 8000 workmen (in 1896 less than 5000 and in 1865, the first year of working, 30), and more than 160 chemists and 75 engineers ; for more than 20 years before the war the dividends paid by this company had been about 25 per cent. The Bayer Company of Elberfeld employed, in its various works, 170 chemists, 35 engineers, and about 6000 workmen. Its principal works were originally at Elberfeld, but the most important of their manufactures colouring-matters, pharmaceutical and photographic materials were transferred several years ago to a new factory at Lovcrkusen, near Cologne, which occupies an area of 529 hectares and in 1912 found employment for 4000 workpeople. The company, starting from the idea that the employer owes to the employee more than his wayes, has created a number of institutions which in 1912 represented a total capital of 600,000. Among these was a library of 12,000 volumes used by 44 per cent, of the workpeople, the books demanded in 1907 consisting of popular works on scientific subjects to the extent of 52 per cent, and of miscellaneous literature to the extent of 48 per cent. the library committee consists of chemists, Five hundred baths were built, 150,000 baths being taken annually. engineers, and workmen. There were dormitories with beds at 2%d. per night, refectories which supply the three meals of the day to men for a shilling and to boys and girls for 9rf. There were also free technical schools and schools of art and music. A lying-in hospital (also for wives of workmen not employed in the factory) cost 7200, the annual expenses being 1600. A hall for theatrical performances and conferences, another for lectures, concerts, etc., and a third for conferences of workmen, cost 18,000. There were sickness funds, savings banks, and a life insurance scheme, supported to the extent of two-thirds by the funds of the company also old-age pensions, and accident funds in addition to the State fund, the company paying for the first three days after the accident (not paid by the insurance companies) and supplementing the legal payment by 50 per cent. The sale of alcoholic drinks beer included is forbidden in the refectories, but coffee, tea, On all these institutions the Bayer Company spent milk, etc., are obtainable at very low prices. more than 80,000 annually and was yet able to pay its shareholders a dividend of 25 to 30 per cent, on a capital of 1,200,000. The scientific and technical work of the company is indicated in the 4000 patents filed up to the year 1907.
;
;

DYESTUFF STATISTICS
wwWs
%

777
;

To the output of dyestirffs Germany contributed in 1913, 75 per cent. Great Britain, 6 per cent. France, 5 per cent. Switzerland, 7-5 per cent. United States, 3-5 per cent. Austria, 1-6 per cent. "Russia, 1-1 per cent. ; and Belgium, -6 per cent. In 1912 the total amounts of the principal dyestuffs made were
;
;

tons

Indigo (100 per cent.) Sulphur, black Various sulphur dyes. Azo dyes.
. . .
.

8000 at
15,000 at
tf 000

at

Triphenylmethane dyes,
Anfc racene dyes, etc.

etc.
.

60,000 at 10,000 at
6,000 at 6,000 at

Various dyes

400 per ton 80 80 80 240 240 120

Total
.
.

3,200,000 1,200,000 400,000

4,800,000 2,400,000 1,440,000 720,000

14,160,000

Total

110,000

Great Britain, 19,000; Of these, the United States consumed 26,000 tons Germany, 15,000 France, 9500 Kussia, 10,000 Italy, 8000 other countries,
;

22,500.

The prime materials for dyes besides sulphuric, nitric and hydrochloric are the various acids, sodium carbonate and hydroxide, ammonia, lime, etc. aromatic hydrocarbons obtained from tar, which may, however, be first transformed into substances more active chemically (phenols, amines, etc.), i.e., the
so-called intermediates.

very Thus, nitrobenzene and its homologues yield aniline, toluidine, etc., by simple reduction with iron turnings and hydrochloric acid, and aniline then gives diphenylamine, dimethyl aniline, sulphanilic acid, etc. Oxidation of aniline, toluidine, etc., gives fuchsine (magenta), safranine, methyl violet, etc. The nitroanilines serve for the preparation of azo-dyes, while the action of sulphur on amines leads to primuline and the new class of sulphurmatters.
dyestuffs.
*.

reactions to which the distillation products (benzenes, in general, of phenols, naphthalene, pyridine, etc.) of tar arc subjected consist, nitration, reduction, dwzotisation, sulphonaiion, fusion with caustic soda, cMormalion, and oxidation. near to the true colouringThese reactions lead to intermediate products

The fundamental

With another reducing agent (Zn

etc.),

+ KOH),

nitrobenzene gives other

classes of colouring-matters

products (hydrazobenzenes,
originate.

from which other

further important reaction consists in the introduction of sulphuric acid residues (sulphonic group, SO 3 H) into benzene (or naphthalene) nuclei in place of hydrogen or other groups by treatment of benzene derivatives with concentrated sulphuric acid. The resulting sulphonic acids are of great importance and often decide whether a dyestuff is add in character and hence able to dye wool and silk directly in an acid bath, or neutral (or almost so) and capable of mordanted with colouring cotton directly, or still basic and able to dye cotton tannin or wool and silk directly in a neutral or faintly alkaline bath.
of the Russian and French factories were branches of German ones. In point of magnitude, the German firms are immediately followed by those of German Co. ; Geigy ; Switzerland (Basic): Gesellschaft fur chernisehe Industrie; Durand, Huguenin Kern and Sandoz, etc. in France, made During the European War, when Germany was isolated, attempts were Great Britain, America and Italy to develop the manufacture of dyestuffs, assistance being accorded by the respective States. In the United States such attempts met with considerable, if not complete, success. In Great Britain various projects were supported to the extent of some millions of pounds sterling without, however, achieving all the results desired, and this country is far from being emancipated from German importations. 50 VOL. n.

Many

778

ORGANIC CHEMISTRY
OH

group may Bohn-Schinidt reaction, which consists in treating various substances in the hot with sulphur trioxide dissolved in concentrated sulphuric acid. Oxidation is likewise of great value and was first used for preparing magenta, It has been found that naphthalene can be oxidised with safranine, etc.

The sulphonic group, in its turn, may be replaced by hydroxyl by fusion of the sulphonic acid with caustic soda, this being a very important reaction, as it allows of the ready preparation of resorcinol and of alizarin. The also be introduced into the molecule directly by means of the

and anthranilic acids at sulphuric acid in presence of mercury, giving phthalic of artificial the admit to of a cost so low as Indigo with the natural competition
product

The methods of dyeing textile fibres are becoming continually more simple and more certain and capable of giving the most varied colours. Nowadays stable dyes can be produced directly on the cotton fibre in a single operation,
starting with simple chemical reagents.

(see p. 760).

CLASSIFICATION OF COLOURING-MATTERS
Nietzki divides the artificial organic colouring-matters into the following to their chemical composition general groups, with reference especially 111. Derivatives II. Azo- colouring-matters. I. Nitro- colouring matters. 7 and JV. and of h} drazones Hydroxyquinones pyrazolones. quiiipneoximes. VI. Derivatives of and V. colouring-matters.
:

triphenyl-methane Diphenyland acridine derivatives. quinonimide. VII. Aniline black. VIII. Quinoliuo flavones, and X. xanthones, Thiazolc IX. Oxyketones, colouring-matters. XI. Indigo and similar and other natural colouring-matters. coumarins.

XII. Sulphur colouring-matters. For practical dyeing, however, more importance is attached to the division into the following "five groups on the basis of the behaviour of the colouringmatters towards different textile fibres, since in practice it is more important to know if a colouring-matter is basic or acid, or if it dyes with or without mordant,
than to know if it is a nitro- compound, quinone, hydrazone, etc. 1. Basic colouring-wallers, which in a neutral bath dye animal and vegetable the latter should, however, be previously mordanted with tannin. fibres 2. Acid colouring-mutters, which dye animal fibres in an acid bath. 3. Adjective or mordant colouring-matters, which dye fibres mordanted with metallic oxides (of iron, chromium, aluminium, etc.). 4. Almost neutral or substantive colouring-mailer* which, as alkali salts, dye vegetable textile fibres directly, without mordanting. 5. Insoluble colouring-miller,^ or pigments are formed directly on the fibie, or are developed on the fibre. i.e., are used for vat- dyeing
;

All the nitre-derivatives of the amines and of the those are phenols especially being markedly acid colourenergetic dyestuils, phenols the acid character of the group. 2 reinforces ing-matters, since the chroinophare It is partiEven the basic substances may become acid if many 2 groups are present. arc coloured ; ^-nitrophenol, for example, is cularly the salts of these compounds which colourless whilst its salts are yellow. The coloration of the nitrophenols disappears if the phenolic groups are etherified by

/I.

NITRO-COLOURING-MATTERS.

NO

OH

NO

Of the nitrophenols the ortho-products (OH NO 2 = 1 2) are the more important and the more highly coloured. Examples are Picric acid (trinitrophenol), G 6 H 2 (NO 2 ) 3 OH sodium salt of dinitronfiphthols^dphofnic acid', C 1U H 4 (NO 2 )(NO 2 )(OH) Naphthol yellow S = dinitrocresol C 6 rI 2 (OH) (SO 3H) (2:4:1:7); Victoria yellow (or Victoria orange)
:

alkyl groups.

(CH 3 )(N02
/

)2

II.

AZO-COLOURING-MATTERS.

The

azo-colouring-matters, unlike other groups,

have retained their original importance, not only owing to the number that can be procan be modified duced, but especially because the gradations of colour and the stability

AZO-CO LOURING MATTERS

at wilt.

779

Thus, the azo-group includes substantive dyestuffs, mordant, woo] colouring-matters fast to milling and to sulphuring, and stable adjective dyes such as alizarin. and the chromogen, R N = N R', R and N == N Their basic chromophore is R' being aromatic radicals. These compounds form the largest and perhaps the most important group of artificial in the case of the more simple colouring- matters. They are not of themselves (especially on the introduction ones, such as azobenzene) intense dyestuffs, but they become such into the benzene nuclei of acid (OH) or basic (NH a ) auxochromes, and with increase of the number of these the intensity increases, passing from yellow to red, to blue or to brown.
Blues are obtained with several chromophores (di- and tetra-azocompounds), while naphthalene groups give reds. The higher the molecular weight the more intense becomes the colour. In certain cases it must be assumed that these auxochromes are united in some way

which dye cotton without a

Liebermann attributed to

with the chromophore, and, since /2-naphthazobenzeiie no longer exhibits phenolic character, NH N O 10 H e instead of the ordinary it the structure C 6 H B
, <

O
(\ H 6 OH. Certain azo-compounds show behaviour recalling that of quinones and ketones, e.g., the formula is represented thus they combine with sodium bisulphite. In such case,
constitutional formula
:

C 6 H5

N N

<(

<VVNH-N:C H 10 O.
6

a characazo-compounds dissolve in concentrated sulphuric acid, giving teristic coloration, which, in general, serves for their recognition and distinction from other colouring-matters (see Table given later). Substituted azo-cornpourids arc always obtained by coupling a diazo-compound with a phenol or with an amine, and, in the latter case, diazoamino-compoimds arc formed as

Almost

all

intermediate products. The first azo-dyestuff of industrial importance (triaminoazobenzene) was prepared in and Roussin 18fi7 by Caro and Griess, and it was only with the dyes discovered by Witt of a assumed this importance. that 1876 to practical position group subsequently After 1 880 azo-eolouring-matters again came to the front owing to the preparation of cotton fibre, direct dyes for cotton, and later these" dyes were produced directly on the new dyeing methods being thus created. or its sulphonic acid They are prepared industrially by first diazotising the amine, tho mass being sodium nitrite, and acid of means diluted with water, by hydrochloric coobd with ice and tested with starch-potassium iodide paper so as to avoid any large excess of nitrite. After diazotisation, the coupling is carried out by pouring the whole the mass being kept alkaline. The colouringslowly into an alkaline solution of the phenol, matter thus formed is separated in an insoluble state on addition of salt and is then filterTho reaction between the amines and tho diazo-eompounds is more complex pressed.
:

R NH

2 ,HC1(

1N 2

8)

-> R

NCI

N(+ R' OH,

phenol)

-> HC1
2,

-j-

R N N
-

R'

OH.

The diazo-group

enters in the para-position to H,

OH,

or

NH

or

if

this

is

occupied, in

the ort ho -position.

in constitution and behaviour Azo-colouring-matters are so numerous and so varied that they may be divided into several sub-groups. The MONOAZO-COMPOUNDS may be sulphonated (aminoazo-dmvatives give basic acid colouringcolouring-matters and the hydroxyazo-derivatives without carboxyl, basic and acid colouringnot or give aminoazo-compounds (the matters) sulphonated matters and the hydroxyazo-compounds basic and adjective colouring-matters). p OLYAZO-COMPOUNDS yield substantive and adjective dyostuffs (i.e., without bonzidine and mordant Finally there is the then form

nuclei,

and

acid, basic,

colouring-matters).

on the cotton fibre. sub-group, the members of which are generated directly in the usual way, in the cold and in obtained are These Aminoazo-derivatives. (a) alkaline solution, from diazo- com pounds (amino- or not) and amines.

Among these axvjast yellow, acid yellow, tropreolin, chrt/soidin [C 6 R 5 N N--<

:

NH ,HC1],
2

acid), orange

the oranges, Indian yellow (nitro -derivative of phenylaminoazobenzenesulphonic C6 4 IV or tropoeolin OO (sodium salt of the non-nitrated product, 8O3

502

780

ORGANIC CHEMISTRY
C 6H 4

N N
:

NH

C 6 H 5 ) and

vesuvine or Bismarck broim, which

:
.

is

diazotised safranine with /3-naphthol. On textiles they are not very fast to light, the less fast being those which do not contain the sulphonic group. In printing textiles these colours arc corroded by the stannous

triaminoazobenzene, 4 2 C6 Indoin is a basic blue obtained

NH

H N N

C 6 H 3 (NH 2 ) 2 mixed with C 6H4 [

,

the hydrochloride of

N N
:

C 6 H 3(NH 2

) 2] 2 .

by coupling

chloride.
(b)

Hydroxyazo-derivatives

(or

C 6H 5

N N
:

C 6H4

azoxy -compounds),

OH.

Tropatolin

is

e.g., hydroxyazobenzeno. a dihydroxyazobenzenesulphonic acid.

N:NOf greatest importance are the derivatives

of
a-

and /2-naphthols,

N:N

\/ OH
(/3),

/\/\OH
and
;

the compounds with the auxochrome in the ortho

/2-position with

N ) being colouring-matters of greater fastness to acid respect to the chromophore ( and alkali than the ortho a-compounds. If, however, another azo group be introduced
:

OH
N:N<
into the latter,
it will

occupy the ^-ortho-position,

the fast brown

N:Ndyestuffs being obtained. Those most used are the sulphonic derivatives, obtained from various naphtholmlphonic
acids.

Of the numerous colouring-matters of this group, the most important are: orange II 1 tropceolin OOO N. II or JV. /, croceine orange, orange G, etc., Ponceau (various), Bordeaux iS
y

,N-<J 10 H. S0 3 H
amaranth,
rocelline, croceine,

(4)

azorubin

\\

VN-C 10 H 6 <so H (V
3
(

QJ^

(I))'

^ Ct

Azo-Colouring-Matters derived from Ca r boxylic acids are obtained from carboxylic diazo-compounds and phenols or amines. These compounds (especially the o-hydroxy car boxy lie acids, such as salicylic acid)
(c)

have an affinity for metallic mordants, particularly and carboxyl groups are in the ortho-positions.

for

chromium

oxide.

The hydroxyl

Among the nitrobenzeneazosulphonic acids are alizarin yellow, the diamond yellows, etc., which, on cotton and wool, give colours vory resistant to light and to fulling. The hydroxyazo-acids include various tropseolins (V, R, O, OOO, etc.), chrysoin, cochineal scarlet,
ponceau, palatine scarlet, etc. Several of these com(d) Azo-Colouring-Matters derived from Dihydroxynaphthalenes. pounds are fixed by mordants when they have two hydroxyl groups in the ortho (1:2)

OH OH
or peri (1:8) position, as in anthraquinone (see Alizarin)

and

but these com-

S0 3H
1

Orange II, prepared from diazotised sulphanilic acid and j3-naphthol, has the constitution

N N
:
I

("

X S0 3Na. /
'

^ /\OH
\/\/

POLYAZO-COLOURING MATTERS

781

pounds are used practically, not on mordants, but for the dyeing of wool, as they give very regular results (such are the azofuchsines), while the peridihydroxynaphthalenes are used

on mordants and form the so-called chromotrope colouring-matters, which dye uninordanted wool in an acid bath, giving a fine red turned violet by addition of alumina mordants or blue-black with chrome mordants. POLYAZO-COLOURING-MATTERS (di- and tetra-azo) contain the chromophore N N several times and vary according as the chromophores are in the same benzene nucleus or in different nuclei and as the auxochromes are or are not in the same nuclei as
:

the chromophores. Here are found benzidine derivatives in which the two chromophores are in two different
nuclei, joined

by a

single linking.

the sulphomc derivatives are, for example, Biebrich scarlet, and the croceines, while among the polyazo-compoumls are also naphthol black, naphthylamine black

Among

diamond black (which

is

obtained from aminosalicylic acid and

is

fixed

by mordants),
treated

etc.

BENZIDINE,

NH/
first

/~\

/ NH

see

P-

718 )>

when

with

nitrous acid, gives a tetrazo- derivative which yields yellow, red, blue, or violet colours on combination with amines or phenols. With naphthionic acid, tctrazodiphcnyl gives Congo
red,

which was the 1882:

substantive dyestuff obtained and was patented by C. Bottiger in

the free sulphonic acid is blue while the salts are red and are fixed directly on cotton, but have the disadvantage of becoming blue or black in contact with even weak acids. The Benzopurpurines (see p. 719) are obtained in a similar manner. These benzidine derivatives cease to form substantive colouring-matters if the metapositions (with respect to the 2 ) are occupied. Substantive or direct colours, when fixed on cotton, function as weak mordants for basic

NH

dyestuffs. The different firms

making colouring-matters place on the market a large number of substantive dyes under various names. For instance, Messrs. Cassella have a long and important series of diamine colours (dianiine yellow, green, red, black, blue, etc.), while
Meister, Lucius

und

Briining call their substantive colouring- matters dianil colours.

The

Bayer Company have the most numerous and important series of substantive dyes, which they term benzidine or benzo dyestuffs (e.g., bcnzo azurines, benzo browns, benzo reds,
etc.).

The

Actieii-Gesellschaft fur Aniliii-Fabrikation, Berlin, call these dyes Columbia,

Zambesi,

etc.

The

Derivatives

(e.g.,

sulphonic)

of azoxystilbene,

C 6 H 4/

/-\
H
I

\C= C/
H
I

yC 6 H4

have the

special property of dyeing cotton directly in

an acid

bath.

of Meister, Lucius und Briining, in 1896, placed on the market a class of strongly basic colouring-matters (Janos dyes), which colour cotton directly without previous mordanting in an acid bath and also dye with the same colour the wool and cotton
of a mixed fabric when the latter is boiled in a bath acidified with sulphuric acid. These dyes change their tint temporarily if brought into contact with hot objects (hot iron). Of very great , importance is the group of azo-dyes produced directly on the fibre by processes of diazotisation and combination, these bearing the name of Ingrain Colours. Cotton fabrics or yarns are impregnated in the cold with a base (aniline, p-nitraniline, aminoazobenzene, benzidine, safranine, etc.), or they may be first dyed with one of the substantive tetrazo-dyes containing free auxochrome amino-groups (e.g., diamine black, primuline yellow, benzo brown, blue, or black, etc.). They are then transferred for 15 minutes to a wooden vessel containing a cold diazotising solution, this consisting, per 100

The firm

782
kilos of cotton, of

ORGANIC CHEMISTRY
2000
litres of
;

hydrochloric acid at 20 Be.

this diazotisation

water, 2 to 4 kilos of sodium nitrite, and 6 to 10 kilos of is carried out in dimly lighted rooms, since

the cotton

sunlight readily decomposes the diazo-compounds formed. After removal from this bath, is allowed to drain for a short time and is then placed in a developing bath (coupling
bath) containing

2000 litres of water, 0-5 kilo of sodium carbonate and 0-5 to 1 kilo of /?-naphthol previously dissolved in 415 to 430 grms. of caustic soda solution at 40 Be. The cotton is manipulated rapidly and in a few minutes intense development of the colour takes place. When substantive dyestuffs are thus further diazotised on the fibre, they exhibit increased fastness to scouring, and this is still more the case if the fabric is subsequently treated with a bath of potassium or sodium bichromate at 90 to 95 for 20 minutes a final copper sulphate bath at 50 for 25 minutes gives greater fastness to light, but both copper and chromium compounds diminish the brightness of the colour to some extent, and on this account the firm of Geigy suggests the use of a final bath of formalin. Instead
;

of /2-naphthol, a-naphthol, resorcinol, phenylenediamine, beuzonilroie (diazotised ^-nitram1 line), etc., may be used. By this method of diazotising and developing on the fibre the is intensified, certain yellows become orange or scarlet of the basic substance tint original
(p-nitraniline gives with /3-naphthol a fine scarlet similar to Turkey red, while with a-naphthol it yields a violet-red), certain reds become brown or even blue, the blues become intense

Different developers give different colours or shades. of a phenol with a diazo-compound is prevented by the presence of a reducer which destroys the latter ; as reducing agent stannous chloride was at one time used, but use is now made of sodiiim or zinc hydrosulphite, which permits of the printing
blacks, etc.

The coupling

of textiles in white designs

III.

on a coloured ground.

HYDRAZONE AND PYRAZOLONE COLOURING-MATTERS.

on compounds conobtained by the action of phenylhydrazine, C 6 2 Thus, for example, the condensation of phenyltaining ketonic groups (see p. 252).
fi

H NH NH

Hydrazones are

CO
hydrazine

with a-naphthaquinone,

gives a hydrazone of the constitution

CO
C 6H5

NH N

C 10 H 6

and diazobenzene, so

The same compound is obtained by the interaction of a-naphthol that its constitution might be that indicated by the equation
:

O.

C6 H5

N2

Cl

C 10 H 7

OH =

HOI

C6H 5

N N
:

10 H

OH,

one hydrogen atom being mobile and oscillating between nitrogen and oxygen. The hydrazones may hence be regarded as azo-conipounds and can be prepared from diazoderivatives and phenols. This is true for aromatic compounds (which can be diazotised), but not for those of the aliphatic series, which are only exceptionally diazotised ; in the latter case, the hydrazones must be obtained by means of phenylhydrazine. The colouring-matters of the hydrazone group have not as yet been practically applied, It was formerly thought that tartrazine was a hydrazone, but as they are too weak. Anschiitz showed it to be a pyrazolone. In general the Tartrazines are obtained by condensing, in hot acid solution, the aromatic hydrazines (sulphonated) with dihydroxytartaric acid, CO 2 C(OH) 2 C(OH) 2 CO 2 H, which probably reacts with phenylhydrazine

CO 2 H G N
-

NH

C 8 H4

8O 3 H

as

true di-ketone,
is

CO 2 H CO
then
lost

CO CO 2 H,

giving

C0 2H C N NH C 6 H 4 SO 3 H
:

a molecule of water

from a carboxyl- and an imino-group,

N/

,N(C 6

-S0 3 H)-CO
|

\_ C(C0 H)
2

N NH C 6 H 4 S0

H.

The sodium salt is*used as a fast yellow for wool, in an acid bath. Some tartrazine In an acid bath tartrazine dyes wool a bright and nitrates are fixed also by mordants.
fairly fast yellow.
1 O. N. Witt (1913) avoids diazotisation on the fibre (with saving in ice) by using p-nitrobenzenediazonium in the form of the crystallised double salt obtained by condensation with sodium naphthalenesulphonate, NO 2 C 6 H 7 N N S0 3 C 10 H 7 -f SO 3 Na C 10H 7 + H 2 0. Such salts are non-explosive and highly stable, even at 60 to 70, and dissolve in water.
:

QUINONE DYE STUFFS

IV.

783

COLOURING-MATTERS DERIVED FROM QUINONES AND QUINONOXIMES.

All thews colouring-matters give very fast tints on fibres mordanted with metallic oxides, with which they form lakes. If the hydroxyl groups present are not in the ortho-position with respect to one another and to the chromophore C0<, the lakes formed have no
1 affinity for the fibros.

The most important

colours of this group are formed by

;

phorea, naphthalene groups

e.g.,

Naphthazarin, which

is

irit cxliicing into the chromoa dihydroxjnaphthaqiiinone,

9 OH

OH

The quinonoximes contain tin group: N OH in place of the ketonic oxygen; they have proportion similar to the hydroxyquinone ?, and here too the affinity for metallic mordants is most marked in the derivatives of the orthoquinones. A few colouringmatters derived from the oxime
notion, naphthol
2 green, etc.

O-

^>

NOH,

are known,

e.g.,

fast green for

Among these
(see p.

quinone derivatives are almost

all

the alizarin

731) colouring-matters, purpurin, blacks, greens, etc.

colours,

etc., in all gratia 'ions

(see. p. 734 and anthracene from yellows to reds, blues,

For hundreds of years alizarin was the sole epresentative of a group of excellent and was only obtained naturally mixe 1 with purpurin, from which it was separated
difficulty. Nowadays, not only is alizarin prepared artificially, but there are quite other colouring-matters of this group, fast to light and chemical and atmospheric

with
fifty

reagents.
(as these are

While nature yields colours such as madder and indigo in an impure condition secondary products of vegetable life) and not directly applicable for dyeing,

the artificial products are highly pure,

as dyes. Alizarin

much

brighter in colour

and more

easily utilisable

and anthracene dyes, which are the prototypes of mordant colouring-matters, are used in large quantities for the fast dyeing of wool for clothing and military uniforms. As a rule the wool is mordanted first, by boiling for an hour with an aqueous solution
containing 2 to 3 per cent, of potassium dichroniate and 1 per cent, of sulphuric acid and amounting to 15 to 20 times the weight of the wool. After mordanting, the wool is rinsed

and dyed in a solution of the dyestuff faintly acidified with acetic acid this heated very gradually to boiling, the latter being maintained for 1 to 2 hours to obtain the maximum intensity and fastness. If fresh addition of the olouring- matter is necessary in order to obtain the desired shade, it is best first to lower the temperature of the bath to 40 to 50 with cold water in order to prevent non-uniformity of tint.
well in water
;

bath

is

<.

V.

DIPHENYL6 6

CH.><^' U
1

!! ri 5

and

AND TRIPHENYL - METHANE C 6 H 5 OH < ^!! 5 It has been shown

O 6 tL 5
.

COLOURING-MATTERS,
on
p.

764 that in these colouring-

and (or CO and position in the anthraquinone series intense

:

Mordant colour ing- matters are generally obtained with the following groups in tho orthoNO OH NOH), 2NO1I, 2OH. Also, according to Noelting (1909), mordant dyes are obtained also with Oil and NH 2 HI ^he ortho-position (less important and less intense are those with OH and N11 2 in the para-position).

CO
Alizarin,
,

dyes red either cotton mordanted with alumina or wool.

OH OH /\_CO~-/ \OH
N

mordanted with chromium. Anthracene Brown, or alizarin brown or anthragallol

(tri-

to hexa-hydroxy-anthraquinone),

OH

CO

lOH.

784

ORGANIC CHEMISTRY
B ~ 0^
/=--- \

matters the chromi*phore consists of the benzene group with two double Unkings in the
para-position,

The mode of formation and the general properties of diphenyl- and triphenyl-methane derivatives were described on pp. 719, 720. 1 In this group are found Auramine (basic) and Pyronine (also basic) which dye wool in with tannin. mordanted cotton and an acid bath

The

methane,

groups, sulphonic acid fuchsine, etc. There are also azo-derivatives of triphenylmethane, such as Rosamine, which dyes silk
"violet -red

rosaniline group embraces all the basic colouring-matters derived from triphenylwhile with e.g., malachite green, methyl violet, formyl violet, fmhsine, etc., acid dyes are obtained, such as patent blue (carmine blue), and other

with a yellow fluorescence, and has

8
"

the.

formula
'"

CoH-o/'
|

No.
C H 3 [N(OH 3 2Oir
fl

The

Rosolic Acid group,

\-

^^H^OH
H aSO
,

'

rraed

by

fU8i

matters,

4 phenol with oxalic acid in presence of concentrated violet. e.g., aurine, coralline, pittacal, chrome Benzo azurine is formed from 1 mol. of phenylcliloroform with 2 mols. of phenol

also furnishes numerous colouring

<^

N
C
fl

1
:

C^pVr
/CO,

these colouring-matters, which have no practical applicaof phenols

tion, are obtained

by the condensation

with phthalic anhydride

H/

No +

2C 6 H 5

OH = H 2 + C 6 H/

X 0(C 6 H4

\CCK

OHU )O. / CO
-

J'henolphthalein

Phthaleins (see p. 685) with the hydroxyls in the para-positions are of some importance if resorcinol, C 6 H 4 (OH) 2 , is used in place of phenol, Fluorescein (the sodium salt of
:

which

is

uranine)

is

obtained

O
)H

C 6 H t CO O
chloride is if dimethylaminophenol is taken instead of resorcinol, or if fluorescein which are heated with a secondary amine, 2 , fine red colouring-matt. rs, Rhodamines,

/\
O

while

NHR

basic in character, result

H.>

NCI -

'NR,
COOH
V

\
[f

previously brominated phthalic anhydride

6

is

used, the Eosins are obtained

/C HBr2 (ONa).

CO-0
Auramine has the formula

\c 6 HBr2 (ONa

>N(CHJ t

QUINONIMIDE GROUP
these give beautiful fluorescent red colours on silk but are not
(see p. 685).

785
very fast to light

VI.

COLOURING-MATTERS OF THE QUINONIMIDE GROUP.

and indamine.

To

this belong the

derivatives of indophenol

Of the hypothetical quinonimides,

HN=<^

\=0

and

NH=

various derivatives and condensation products are known,

e.g.,

Indamine,

Indophenol,

OR

>

N=<

-NH, O=

"N-N-

>NH 2

The Thiazones,

e.g.,

thiodiphenylcunine,

with

indamines

form

Thiazimes

(e.g.,

LaidVs

violet or thionine,

methylene blue,

methylene green,

etc.,

which are

basic dyes).

The Oxamines and Osazones have an oxygen atom

in place of the sulphur of thiazones,

and undergo various condensations

Capri Hue, naphthol

blue,

Nik

H
blue, etc.,

which are also

basic.
;

The Cyanamines arc

related to Nile blue

Resorufin

is

an osazone, namely, hydroxy-

diphenosazone,

Gallocyanine,

C 16 H 12

2,

is

obtained by heating

N'
nitrosodimethylanilinc with gallic acid in alcoholic solution. They dye chrome-mordanted wool a very fast violet, and are used in printing linen, which is treated with sodium
bisulphite

and chromium acetate and subsequently steamed. The Azines were formerly called Safranines the simplest type
;

is

Phenazine,

C 6H 4/

/N\
|

\K/

")C 6

H4

The

eurodines are used for dyeing cotton mordanted with tannin.

The

Safranines contain four nitrogen atoms

and three aromatic nuclei

HN
2

NH

and are strongly

basic

and give red colours on cotton mordanted with tannin.

/ SCI =*'
1

N(CH 3

,ZnCJ 2
is

Methylene

blue,

-N

a basic

dye which

colours cotton, mordanted with tannin

786

ORGANIC CHEMISTRY
The
:

Indulines are obtained by heating aniline hydrochlorido with aminoazobenzene. following constitution has recently been established for one of the indulines

N-C H
6
II-

C.H.

HNN-O.H.

/\/N\C_H
The Quinoxalines contain the nucleus
1

LH

the Fluorindines can be

represented by the formula

\/\N/\/\ N
H
VII.

ANILINE BLACK. The

oxidation in various ways of aniline salts in acid solution

gives aniline black, which is of considerable importance in the dyeing of cotton. Among the different oxidising agents, a special place is occupied by vanadium salts

by Witz in 1877), which bring about the oxidation of large quantities of aniline 1 part of vanadium, in presence of a sufficiency (transferring oxygen by catalytic action) In of potassium chlorate, oxidises as much as 270,000 parts of aniline hydrochloride.
(suggested
;

point of efficiency, vanadium

lead, the action of iron being

is

followed by ctwimn, uranium, copper, manganese and

less.

much

Aniline black has a feebly acid character and is insoluble in almost all solvents. It dissolves with difficulty in aniline and forms with it a violet and then a brown colour ;

phenol dissolves it more easily, giving a green coloration. With fuming HgSO.,, it yields Acetic anhydride gives a faintly coloured acetylsoluble, coloured sulpho-compounds. When treated with perderivative, and potassium dichromate a violet-black product. manganate and then with oxalic acid, aniline black is partially decolorised. Energetic
reducing agents (Sn
1

completely. The chemical constitution of antline black has been the subject of much discussion. Assuming that the first intermediate product of the oxidation of aniline is aniline black (Nictzki), it cannot be true, as is often thought, that the transformation of aniline into quinoiie by oxidation takes and p-aminophenol, since these place through the intermediate stages of phenylliydroxylamine do not yield aniline black on oxidation, phenylhydroxylamme giving a nitrosobenzene and not nor can amiiiodiphenylamine (Nover, 1907) be formed, since this, on oxidation, a quinone It has now been found gives cweraldine, a compound never obtained in the oxidation of aniline. convert aniline black to the extent of 95 per cent, into quinono by oxidising with possible to lead peroxide (chromic acid giving less than 80 per cent.), so that the indaminic formula (proposed by Bucherer, 1907) can no longer be attributed to aniline black, since, according to this, it would and S. Dorogi (1909) to suggest give only 50 per cent, of quinone. This result led H. Willstatter fact for aniline black the formula (C H 4 N C 6 4 NH) 4 i.e., H which is confirmed by the 4a H 36 that the oxidation requires 1 J atom of oxygen per molecule of aniline with a yield of 97 per cent. Further, the determination of the molecular weight by hydrolysis of aniline black with dilute acid at 200 indicates clearly the separation of one-eighth of the nitrogen as ammonia
-f;
:

HC1) decompose

it

sulphuric

H 4N CH
:

NH + H
~\

C 6H 4 O
:

+ NH
'^

All these results point to the trebly quinouoid formula of aniline black as the

"

"

"^~'

most probable

N:

:N-

NH / ~~\ NH
N:
:NH.

'

X
:

~"

:N-

This aniline black is obtained by oxidising aniline in the cold with rather less than the Further oxidation with 2 O 2 for theoretical quantity of dichromate, chlorate, or persulphate. formation of a quadruply quinonoid aniline example, results in the elimination of 2H and the It salts are dark green. black, C 48 H 34 8 , the base of which is very dark blue-black while the

QUINOLINE DYE STUFFS,

Paraf, etc.

ETC,

787

In practice aniline black is produced directly on the fibre, and the use of this very stable colouring-matter is due especially to the studies and initiative of Prud'homme, C. Koecklin,
After

many improvements,

the production of aniline black (termed also oxidation

black) directly on cotton fibre is now carried out as follows (the quantities given are for 50 kilos of cotton). The throo following solutions are prepared separately : I. 5-5 kilos of aniline oil (see p. 659) -{- 4-25 kilos of commercial HC1 -|- 50 litres of water
;

Hack or fine

II. 3-5 kilos of

sodium
;

sometimes added)

(or potassium) chlorate f 50 litres of water (1-5 kilo of starch is 111. 3 kilos of potassium ferrocyanide in 20 litres of water. When

mixed (1 grm. of vanadium chloride is sometimes introduced) and the yarn or fabric immersed until it is well soaked. It is then gently pressed and passed slowly over rollers through the oxidation chamber (see illustration given later) so that at least an hour elapses before it emerges at the opposite end. The temperature of tbe chamber should not exceed 50 and the humidity 25. The fabric assumes a coarse greenish colour
cool, the solutions are

which is changed to a fine black when it is transferred to a Jigger (see later) containing 2 kilos of potassium dichromate, 250 grms. of sulphuric acid and 100 to 120 litres of water at the temperature 50". The black thus obtained, when thoroughly washed, is turned green only to a slight extent in the light.
VIII.

QUINOLINE AND ACRIDINE COLOURING-MATTERS.

,CK - OH

Among

the quinoline
;

dyest-uffs are quinoline yellow (water- or alcohol-soluble), quinoline red, cyanine, etc.

all of

them contain one

or

more

of the chrornophores,

OgH^ \

N = CM
chromophore

or

its

homologues.

Acridine

derivatives

possibly contain

a quinonoid

of

the

formula

/J RC/

:J

(:NH)
-/

>NH.

X-.c^H,

They are obtained by condensing w-diammes with formaldehyde, heating the resulting tetraminodiphenylmethanc with acid to remove ammonia, and finally oxidising with ferric chloride. To this group belong acridine orange and yellow, pJiosphine, benzaflavine, etc.

=
IX.

N.
|

THIAZOLE COLOURS.

These

contain

the

group

-C-S/

^C

with

the

and are formed by heating ^-toluidinc with sulphur, the resulting Primuline being probably of the constitution
chromophoro

it

may be easily sulphonated, dyes cotton directly and may be diazotised and developed on the fibre (see p. 781). The methyl derivative is Thioflavine. These colouring-matters are not very fast against light. X. COLOURING-MATTERS OF THE OXYKETONES, XANTHONE, FLAVONE, COUMARIN. This group embraces many valuable mordant colouring-matters alizarin
:

yellow, anthracene yellow, alizarin black (see Alizarin Colouring-Matters, p. 783), flavopurpurin, alizarin green, alizarin blue, alizarin cyanine, anthracene blue, etc. The characteristic

2H01 whilst the trebly quinonoid black absorbs 4HC1 all of the latter are displaced in the former case, leaves IHf-l (4-5 per cent, of Cl in the nucleus). In practice the quadruply quinonoid black is obtained with excess of a slow oxidising agent On acting in the cold, PJJ., with chlorate and copper sulphate or with chlorate and vanadium. hydrolysis, the quadruply quinonoid black also loses one-eighth of its nitrogen as ammonia, the H of more which is S() Oxidation ON not turned forming 2 complete black, 48 33 7 green by the corresponding product of hydrolysis of the trebly quinonoid black gives the same quadruply The practical preparation of aniline black in a single bath leads quinonoid black, 4? H 33 ON 7 to the quadruply quinonoid black that turns green, and further oxidation of this in the hot yields the black which does not turn green, the terminal imino-group being hydrolysed. This latter black is obtained also by the two- (or more) bath process or by steaming. Oxidation of aminodiphenylamine instead of aniline gives first the reddish-blue inline (C 24 ....), emeraldine, which then polymerises, forming the black (trebly quinonoid).
absorbs only
;

by ammonia, which, however,

788

ORGANIC CHEMISTRY
o

\
group of the xanthones
is

\
and that
of the flavones

CO CR

CH
Indian yellow
is a hydroxy- derivative of xanthone. XI. INDIGO, INDIGOIDS, AND OTHER NATURAL COLOURING-MATTERS. In addition to what has been stated with reference to indigo (see p. 757 et seq.), it may he said that there are a number of derivatives of artificial indigo which are reduced with hydro-

sulphite

and alkali and give very fast colours which are superior to indigo and resist even concentrated solutions of chloride of lime. 1

1 Bohn has given the name vat dyestuffs to those insoluble pigments the molecule of which contains at least one ketonic group capable of being reduced (e.g., by hydrosulphites), taking up hydrogen and thus becoming soluble in an alkaline liquid and lixable by animal and vegetable fibres. These vat dyestuffs may be divided into two classes inditjoids and indanthrene
:

derivatives.

The

(iiidirubin, etc.),

comprises two series symmetrical (indigo, etc.) and unsymmclrical and each series contains various families of the following types, to all of which
lirst class
:

the chromogen,
(1)

CO

C=C

CO,

is

common.

With nitrogenous chromogen.

Indigo and

-CO

_NH c

CO

NH

hulogonated and other substitution chloro-, brorno-, alkyl-, and napht hoi-indigo. The substitution takes place in the benzene nucleus ; many porybromo-derivatives are formed. The colours range from reddish blue
its
:

derivatives

CO

'

\/
(2)

NH

NH

to greenish blue. The antique purple recently studied by Friedlandcr is 6'-dibromoindigo. 5-Brotnoindigo (pure indigo It), 5 S'-dibromoindigo (pure indigo 2B), 5:7: 5'-tribromomdigo (Ciba blue tt) t 5:7:5': 7'-tetrabromoindigo (Ciba blue 2B or indigo -4J5) have been prepared.
:
:

Naphthhuligo CO.
Besides the chromophore

NH/

of indigo, these

CO

NHx ; s Mixed symmetrical with nitrogen and

l

have

also the

chromophore
:

Belonging

rulphur chromogens
(3)

CO
Symmetrical with sulphur chromogen
(4)

to this family are Ciba grey G (monobromoderivatives), Ciba violet 7?, B, %R (these are polybromo-derivatives of Ciba violet A). The iirst term is .FriedJander's thioindigo (or thioindigo red It) ; Ciba bordeaux (5 : 5'-dibromothioindigo) and numerous derivatives in which the 5- and S'-positioris are occupied by alkoxy- and thioalkyl- groups have been prepared, among these being red and brown colours and the various colours of the helindone series of Meister Lucius

und

Briiniiig.

-NH
C

C'

-TO/
Indirubin with asymmetric nitrogen

Indirubin is not a colouring-matter, since on reduction it forms indigo, but use is made of tetrabromoindirubin (Ciba heliotrope B)
:

C 6 H 2 Br
chromogen
(6)

CO

Nil

^,8

,CO.

dibromo-derivative forms thioindigo scarlet

S
Thioindigo scarlet
(6)

CO

K
known by
scarlet G).

< \C H

NH
B 2

CO

C
I

-=

<

\s

is

the

name

of thioindigo scarlet

2G

(Ciba

\/\/

INDANTHRENE CLASS

789

The Indanthrene Colours, which were at first very expensive, are now obtainable at more reasonable prices and give medium and dark shades. They are so resistant to various
reagents that they are used as pigments in place of ultramarine, etc. ; they are used also for blueing sugar and other foodstuffs, as they are fast to light and non-poisonous. Materials dyed with indanthrene dyestuffs do not stand heating in an autoclave with alkali, the colours being reduced and rendered soluble. The Badische Anilin- und JSodaThis

(7)

'

,Ar

is

a new family which has given the

first

yellow

\
CO
The second
(1)

colours of tho indigoid group (Ciba indigo yellow 3(7 and Ciba yrttnw G, which is a dibromoderivative of the preceding). The group Ar is tho benzoyl residue, but it is not known whether V is or Oil, or whether it represents a double linking to the nitrogen atom.

class

is

that of the anthracene derivatives, with the following families

/Indanthrene

/\

formed by condensing 2 mols. of ammoanthraquinone by means of fused alkali and is a dianthraqinnonedihydroazine. With reducing agents, partial reduction of the ketonic group occurs, dihydroindanthrene becoming soluble in alkali and dyeing cotton directly. The halogenated derivatives are of a more greenish-blue, resistant to oxidising agents and to chlorine. Use
is is

made

3 RC and of algol blue and algol green. The GCD blue is obtained by boiling indanthrene with aqua regia. Anthraflavone (yellow) is similar to indanthrene, but without the groups.

of itidanthren?. blue flC, (*CD, 3(>,

and

NH

Judanthrene
(2)

blue,.

Flavanthrene (or indanthrene yellow G and JR) is obtained by oxidising 2-aminoanthraquinone with antimony pentachloride in boiling nitrobenzene solution. An analogous compound which has an orange-yellow colour, and in which the two nitrogen atoms are replaced by CH, is pyranthrene (or indanthrene golden orange (_}), the halogen derivatives of which tend to rod of these, dibromopyranlhrene (or indanlhrene searlel (!) is
;

used.
()

Flavanthrenr

BfnzanlhruHc

is

quinone or

its

obtained by condensing anthraderivatives with glycerol in presence

of concentrated

H 2 8O 4

Benzanthrone and

its

halogen derivatives are not colouring-matters, but by various condensations they lead to excellent colouring-matters, such as riolatilhrene, the dibrotno-derivativo of which is indtinthrene green ; iftouiolatilhrfiie (which has a similar constitution to its and dichloro-derivative (indanpyranthrene)
threnc riofct

Be tizant krone

RR

extra).

A nthniqittnonutu'dc

derivative*

Indanthrene bordeaux B and indanthrene, red G and R are formed from 3 mols. of arithraquinone joined in various ways by two imino-groups. Algol red, which was the first red val dyestuff of the anthraquinone series, consists of 2 inols. of anthraquinone united by an NTT group, one of them being condensed with a pyridone ring.
(Characteristic of these is the

(5)

Aciaminoanthraquinone derivatives

complex of several

NH

NH-CO-NH-

O
Helindone yellow

groups united once or more times to (X) groups. Helindone yellow Mi represents two arithraVarious cjuiiiono groups condensed with urea. other condensations of aminoanthraquinones with benzoyl, succinic, tartarie, phthalu;, etc., groups
give algol r?d
G,

R and
9

5</, etc.

3GN

790
reduction.

ORGANIC CHEMISTRY

Fabrik recommend the addition of an oxidising agent to the autoclave bath to prevent the
XII. SULPHUR COLOURING-MATTERS. These colouring-matters, which have been discovered since 1893, are very fast on cotton, which they dye directly without a mordant, but in alkaline and reducing solution (sodium sulphide and sometimes a little glucose) which prevents any unevenness which might be produced in the colouring owing to contact with the air. The sulphur colouring- matters do not dye wool or silk in presence of sodium silicate (or of blood or diastofor), so that two colours can be obtained on wool and cotton fabrics, the wool being dyed first with an acid dyestuff and the cotton subsequently with

a sulphur colouring-matter in a bath of sodium sulphide and silicate (or blood or diastofor). They are obtained by melting together sulphur or sodium sulphide and various other colouring-matters or other organic; compounds. Cachou de Lawd has been known since 1873 but has boon used but little. It was obtained by Croissant and Bretonniere by fusing sawdust, bran, or th? like with sodium sulphide. In 1893 the discovery of Vidnl black directed the attention of manufacturers to this interesting group of colouring-matters, which now include almost all tints except reel, and are obtained by fusing with sulphur or sodium These sulphide, derivatives of benzene, naphthalene, diphenylamine, anthraquinone, etc colouring-matters are placed on the market by various firms under different names, although their compositions are practically the same the firm of Cassella calls them immedial colours ; the Bayer Company, katicjenic colours ; the Badische Company, kriogenic colours ; the Berlin Aktien-Gesellschaft, sulphur colouring-matters, etc. The constitution of these colours has not been firmly established, but during recent years a little light has been thrown on th:m. According to Sandmeyer (1901) they are derivatives of Piazthiol
1

the

compound

soluble in

sodium

sulphide

having

the

constitution

I/V-NX
I

\/

LX;
/
Nft
i

but.

nowadays other interpretations have been

given.

When diphenylamine-derivatives ar<* fused with Na2 S, black colouring-matters are and the corresponding preferably formed, with aminohydroxydiphenylamine derivatives colours are, obtained, while in presence of stable metaJN-alkyl and N-aryl compounds blue substitut^d compounds, brown or yellow colouring-matters are formed.
These colouring-matters are obtained by fusing aminoanthraqui nones with sulphur or alkaline sulphides (rujnnthrcne browns, greys, olives), '.<,., indanthrmc brown, cibanone brown, cibanone yellow ; the first cibanone black was obtained from methyl benzanthrcnc, and the leucol colours A of the firm of Bayer are also of this group. mixed indigoid-anthracciie group has also been obtained. Thus, the action of isatin chloride, etc., on a-naphthol (or its ortho-derivatives) gives the
Various types Rufanthrene, leucol, cibanones, hydronw, indigoliynoidit
:

indigoid colouring-matter and an isomeride of analogous properties, e.g., indonapkthalene or itidoliynone (Friedlander and Bezdzich, 1909) both the indigoid and the indolignone are decomposed by alkali into anthranilu; acid and the corresponding hydroxynaphthaldehyde. A group of sulphur vat dyestuffs is that of the indrone blue* (Cassella), derived from carbazole, which with 2?-nitrosophenol gives a base,
;

,NH
and
this,

NH

forms
alkali,

when fused with sulphur or sulphides reducible colouring-matters soluble in

LOGWOOD
N
condensation products,
e.g.,

791

In general the reaction takes place with preliminary formation of aromatic mereaptans or to (3), which give further or polymercaptans (in the ortho-position with respect to
black derivatives of thiodiphenylamine (of thiazine),

and yellow or brown colouring-matters derived from thiazole

(see above),

They form insoluble condensed products (rlisulphides) with the oxygen of the air, these being rendered soluble again by alkaline reducing agents (sodium sulphide, hydrosulphites, The fixation and development of the colour in the cotton fibres consist simply in the etc.). oxidation of the rnercaptan to disulphide. The black or blue sulphur colouring matters are are now used in quinonimino-derivatives of the thiazine group. These colouring-matters the production of sulphur black alone in 1909 being estimated at nearly
large quantities,
Tt has been proposed (1909) to render them faster to washing by treatment with formaldehyde or by immersion in a nickel sulphate bath. The principal natural mordant colouring- matters are logwood, brazilein, archil, and the natural substantive dyes for cotton and wool cochineal, catechu, sandalwood, etc.

5,000,000 kilos.

bixin, curcumin, carthamin, etc. These dyewoods are placed on the market in small trunks or in chips ; for economy in transport and convenience in use. dense aqueous or concentrated dry extracts arc often
:

are

prepared.
is obtained from the harked trunk of a tree (Hanwloxt/lon 471 shows twig, leaves, flowers, and seeds) which grows in Central America arid in the Antilles, the best qualities being those of Honduras, San Domingo, and Jamaica. Just as the consumption of indigo has not diminished in spite of the comof the numerous artificial aniline arid alizarin colours, so also the use of logwood

LOGWOOD

or Campeachy
Fig.

catnpechianum

in dyeing tends to increase, although not in similar proportion to the artificial dyes. The wood arrives in Europe in logs weighing 150 to 200 kilos, which aiv sawn into short pieces, are ground. chopped and reduced to chips or raspings ; more rarely they was studied by Ohcvreul in 1810, by Rrdmann in matter of The

petition

colouring-

logwood

and by Hess and Keirn in 1871. It consists of a glucoside which occurs in the fresh wood and which, perhaps by simple fermentation or by the action of water and air, separates under the the base of the colouring-matter, i.e., Haematoxylin, 16 H 9 O(OH) 5 and this,
1842,
,

atmospheric oxygen (best in presence of kfpmatein, (which dyes with metallic oxides), C3 16 H, a O
influence- of
fl

alkali), gives the

,

colouring-matter

2H

being thus

lost.

Htematein

is

or glacial acetic acid, and insoluble in chloromoderately soluble in water, alcohol, ether, form or benzene. In amnioniacal solution it assumes a purple-red colour, which becomes brown in the air. (H 2 S, SO 2 Zn -f HOI, etc.) haematein is decolorised

By reducing agents without, however, giving hsematoxylin. Hiematoxylin is probably 3 4 3' 4'-Tetrahydroxyrufenol
, :
:
:

OH O

,0-OH CH CH 2 C 6 H 3 (OH 2 )(3

4),

and hflcmatein would have a quinonoid formation in place of the hydroxyl of the first of the second nucleus. nucleus, H being lost together with another H from the para-CH In dyeing, logwood is used in chips or as an extract. The chips are first matured and stirring every two or three days (? fermented) by moistening with water, heaping up for one or two weeks, care being taken to prevent heating of the mass, which would destroy the colouring-matter. The wood changes from a yellowish to a brownish red colour and 2-5 to 3 per cent, of its weight. The it is extracted with gives up boiling water, to which

792
solution,

ORGANIC CHEMISTRY

which is rich in hrematein, is used as it is in the dye- vat, whereas logwood extracts are prepared in the way used to obtain tanning extracts (p. 691) ; these extracts are very Solid hcemtitein, a pure, granular product, free from tannins, is rich in haematoxylin. obtained by direct extraction of the ground logwood with ether. Hsematein is a mordant colouring-matter, i.e., is fixed and gives intense and fast colours on mordanted fibres, and is generally used for black or blue-black shades with various
only shot
effects,

according to the nature of the mordant

with aluminium salts

it

gives a

with chromium salts blue-black, with iron salts grey-black, with jgreyish violet-black, violet-black. copper salts greenish blue-black, and with tin salts obtained by mordanting, e.g., wool, for 2 hours in a boiling fine black is

usually

bath containing 2 to 3 per cent, of potassium dichromatc, 3 to 4 per cent, of tartar (or 2 per cent, sulphuric acid, 3 per cent, lactic acid, etc.) and 0-5 to 1 per cent, of copper sulphate The mordanted fabric is well washed and dyed in (all calculated on the weight of fabric). a boiling aqueous bath, to which is added the dilute logwood extract or 5 to 8 per cent. of the concentrated extract or the matured chips in bags. To obtain black-black (coal-black without
blue reflection), 0-2 to 0-5 to 1 per cent, of Cuba wood extract is added. Dyeing is followed by thorough washing in cold water. Cotton is first mordanted in the usual way in

yellow

into

a tannin bath (2 to 3 Be. overnight), then passed an iron nitrate bath (see Dyeing of Silk, and note on p. 771), rinsed and dyed in the hot aqueous bath with logwood and yellow wood. After dyeing the bronze-red appearance is removed by a soap
bath.

For dyeing

Logwood

silk black, see later. extracts are often adulterated with

chestnut-bark extract, molasses, dextrin, sumac, etc., and as a rule the best test consists in dyeing equal weights of mordanted fabric, with equal

weights of the suspected and a pure extract. Sugar (molasses) or dextrin may be detected by precipi-

and tating with a slight excess of lead acetate examining the filtrate by means of either Fehling's solution or the polarimeter. Chestnut-bark extract is detected by treating of the extract, dried at 100, with ether 1
grin,

and weighing the portion dissolved by the

FIG. 471.

ether.

The residue is then extracted with absolute alcohol and the amount dissolved determined. A good,
dried extract contains 86 to 88 per cent, of matter while, if chestnut-bark extract is

soluble in ether
present, less

and 12 to 14 per cent, soluble in alcohol, dissolves in ether and more in alcohol.

is extracted from Roccella tinctoria (2 to 12 per cent.) or from other lichens coast or on bare rocks in mountainous districts. The red colouring-matter is on the growing formed after fermentation in presence of a little ammonia, and after the action of atmoPrior to fermentation, the colourless compounds contain roccellic acid spheric oxygen. the after the decomposition, orcin (see p. 645) is present (p. 365) and erythric acid, while, which forms violet-red latter, when oxidised in presence of NH 3 gives orceine (see p. 645), lakes. Archil is placed on the market as extract or solid preparation. Cudbear (or perseo) is obtained from Lecanora tartar ea and dyes wool and silk very uniformly in presence of alum, tin salt, and tartaric acid. Litmus (or tournesol) is formed from orcin by the action of ammonia or soda, and is obtained from various lichens (Eoccella tinctoria). The extract is mixed with gypsum or chalk and made into tablets, which contain various colouring-matters (azolitmin, erythrokin, It is very sensitive to acids, which redden it, and to alkalis, erythrolitmin, spaniolitmin). which turn it blue, and hence serves as an excellent indicator. COCHINEAL has been long used as a colouring-matter and is the female of the insect Coccus cacti, which lives on the cactus of the Canary Islands, Algeria, Java, Guatemala, etc.

ARCHIL

DYE WOODS
=
.

793

When the insect is three months old (weight 0-0065 grm.) it is killed with hot water (black grain) or in an oven (silver grain). The colouring-matter is Carminic Acid, C l7 H 16 Oj The dry insects are powdered and extracted several times with boiling water, the dye-bath being prepared with hot water, 3 per cent, of oxalic acid and 0-5 per cent, of tin salt ; the wool is immersed in this for at least 30 minutes at a boiling temperature. The wool may be first mordanted separately with oxalic acid and tin salt and then dyed in the
aqueous cochineal.
tinctoria or of

obtained from the trunks of Morus and Mexico, the best kinds being, however, those of Cuba, Tampico, Porto Kico, and Jamaica. The colour may be extracted from the wood by means of steam, and the concentrated extract contains a tanning material (nuiclurin), since a brighter yellow is obtained on dyeing if a little gelatine is added if this is not done, prolonged boiling gives dark or to precipitate this tanning substance brownish shades. Although Cuba yellow dyes pure fibres directly, really fast colours are hence Cuba yellow is used together with obtained only by chrome mordanting, etc. logwood or even alizarin or anthracene colouring -matters. QUERCITRON is sold in small chips or, better, as a coarse powder obtained by grinding the bark freed from epidermis of Querctut tinctoria and Q. nigra, which grow in Pennor

YELLOW WOOD

Cuba

Wood

(Old fustic)

is

Madura

tinctoria of the

West

Indies, Brazil,

sylvania, Carolina, Scotland, France, and the South of Germany. The dilute aqueous extract does not keep, and must hence be used immediately. Chev2H 2 O, which when reul separator! from the bark the compound Quercitrin, C 21 22 O 11

boiled with acid takes

up

mol.

O, giving Quercetin,

C 15 H 10 O 7 and Isodulcitol, C 6 H U O 6
,

Quorcetin

is

1:3:3':

4'-Tetrahydroxyflavanol

OH CO

HO
6
it

>OH;

OH
It is sulphonated

dissolves in alkali, giving

an o ange-yollow coloration, and

alkali.

protocatechuic acid
acid,

when fused with

yields phloroglucinol and by concentrated sulphuric

fibres (wool) either previously mordanted or with an alum or chrome mordant added to the dye-bath. Similar behaviour is shown by Jlavin, which is a more concentrated preparation of quercitron ami contains quercetrin and

It dyes

forming a direct dye for wool. more especially animal

quercetin.

Natural INDIAN YELLOW is still extracted in Bengal from the evaporated residue of the urine of cows fed on mango leaves. It contains a hydroxyl derivative of xanthone,

namely, Euxanthone, as glycuronic ester (euxanthinic.

acid,

C l9 H 1H Oj), which
CO-

is

decomposed

HO
by hot hydrochloric acid
into

Euxan thine, C 13 H 8 O 4

or

(obtained

Osynthetically

OH

by condensing hydroquinoiiecarboxylic acid with /3-resorcylic acid). Natural Indian yellow functions as a mordant dyestuff, but is now scarcely used for textiles, as it is not very stable to light. BRAZIL WOOD or Red Wood is obtained from the trunk of Coesalpitm brasiliensis and other varieties. The colourless glucoside it contains gives, on fermentation or when treated with acids, glucose and Brazilin, C 16 H 14 5 or C 6 H 3 (OH) 2 C 4 H 4 O C 6 H 5 2 , which
it gives intensely is coloured carmine by alkali and decolorised by acids or reducing agents coloured lakes and oxidises in the air, forming Brazilein, C 16 12 O 5 while with concentrated It is a red nitric acid it gives trinitroresorcinol and, when fused with alkali, resorcinol. mordant (alum or chrome) colouring-matter, but is only slightly fast to light. Brazilin seems to have a constitution analogous to that of ha>matoxylin (see p. 791) with a loss in the first benzene nucleus, brazilein being apparently the
;

hydroxyl group ccrresponding quinonoid derivative similar to haematein (see above). SANDALWOOD is the wood of Pterocarpus sardalinus, which grows in Madagascar, the colouringtropical Asia, and Ceylon. Santalin or Santalic Acid, C 17 10 O , which forms

fl

VOL. IL

61

794

ORGANIC CHEMISTRY

matter of this wood, occurs in abundance in other plants (in barwood or Baphia nitida of Sierra Leone and in camwood or lamlewood from West Africa). Santalin gives resorcinol, acetic acid, etc., when fused with alkali, but its constitution is not yet established. It is a mordant colouring-matter, like logwood, and was once used with alizarin to dye cotton red. CATECHU (or Cutch) and GAMBIER are extracted from various plants of India, Bengal, Malay, etc. (palm, mimosa, Rubiaceae, Acacia catechu, Areca catechu, Uncaria gambier, etc.). They contain tannin and colourless catechol, partly combined to a brown colouring-matter. When fused with alkali, they give phloroglucinol, pyrocatechol, and protocatcchuic acid. With various mordants they give stable browns or olives, which do not, however, withstand chlorine or acid. On cotton they give reddish or yellowish brown colours which become fast to light after treatment with alkali dichromate at 60 to 70 (khaH used for uniforms in the British, German, and Italian armies). Nowadays a much faster khaki is obtained by impregnating the white fabric in a cold concentrated bath of pyrolignite of iron, chromium acetate, and a very small proportion of manganese chloride, drying it thoroughly, immersing it in a boiling bath of caustic soda (11 Be.) and a little sulphoricinate, and oxidising in a hot-air chamber or by means of dichromate solution. With a less concentrated soda bath or one not boiling, the metallic oxides would be precipitated superficially on the fibre, and the dry fabric would be dusty and would wear out sewing needles. This khaki is very fast against light, scouring, and chlorine, but does not resist perspiration (test with a mixture at 1 Be. of hydrochloric, formic, and acetic acids for 5 hours). Fastness to perspiration is given by boiling the dyed fabric for 2 hours in a silicate bath
at 6 to 7

Be.

occurs in

is not a colouring-matter for textiles but is the green pigment which plants (those which assimilate CO) and brings about the transformation of the carbon dioxide into starch in the leaves under the action of sunlight especially of certain rays of the spectrum and apparently also with the help of an enzyme (Willstatter

CHLOROPHYLL
many

as Chlorophyllase. With starch, wax, etc., it forms the characteristic chlorophyll granules of green leaves (see p. 52.5). It is soluble in oil, alcohol, ether, or chloroform, its solutions showing blood-red fluorescence and readily undergoing change. Its constitution is still uncertain, and it dons not appear to contain combined iron, as was formerly thought. Following the indications of

and iStoll, 191 1 ) known

th* botanists Borodin (1882) and Moiitevcrde (1893), Willstatter and Benz (1908) obtained u pure chlorophyll x (2 grms. from 1 kilo of dried leaves) in dark, bluish black crystals with a metallic lustre, which are insoluble in petroleum ether but soluble in alcohol or ether, giving a bluish fluorescence. The green solution of this product, which exhibits the same spectrum as the chlorophyll of fresh leaves, is turned brown by alkali, but again becomes green. Its formula is probably C 55 73 O 6 4Mg, and the magnesium present (3 per cent.) is perhaps the cause of the catalytic action effecting the transformation of CO 2 into starch ; it does not contain phosphorus, as many, including Stoklasa, have thought. Acids remove all the magnesium, the residue being Phoeophytin, which is similar to chlorophyll, is ethereal in character, and forms various products (e.g., methyl alcohol, phytol, phytochlorin, and phytorodin, which has the formula, <' 34 34 O 7 4 is acid in character and contains four pyrrole groups) and three carboxyl groups when hydrolysed with alkali. Phytol forms one-third by weight of the chlorophyll of plants and is a primary, unsa-

turated, monohydric alcohol, C 20 H 40 O, capable of combining with Br2 Plants produce also an amorphous chlorophyll which, unlike the other, gives phytol on hydrolysis. It is thought
.

analogous in chemical composition to the colouring-matter of the blood (see later), when distilled with zinc dust. Willstatter and Islcr (1911) showed that chlorophyll contains two colouring-matters (a) bluish green and (6) greyish black (one-fourth as much as of the first), having the formula, C 56 rI 70 6 N4Mg, thus confirming the hypotheses of .Stokes (1867 and 1873) and of Tswett (1906) ; the two colours are separated
it is

that

since both yield pyrrole

As chlorophyll readily undergoes change, it is extracted in the cold with methyl alcohol from the carefully dried, powdered leaves (Willstatter), previously washed with petroleum ether. In order to separate it from other colouring impurities, its alcoholic extract is suitably diluted and extracted with ether (benzene or carbon disulphide), many of the impurities remaining dissolved in the alcohol or the alcoholic extract may be shaken with a large amount of water, which dissolves the chlorophyll in the colloidal state, the decanted aqueous solution being treated with salt and extracted with petroleum ether containing a little alcohol. From this solution the chlorophyll is deposited pure if the whole of the alcohol is eliminated by washing.
;

TESTING OF DYESTUFFS
by more or
less dilute alcohol.
;

795

preserved vegetables, etc. product, 806-. per kilo.

Chlorophyll before the war it

is

used in practice to colour oils, soaps, fats, cost 8s. per kilo or, for the highly purified

TESTING OF COLOURING-MATTERS
Out
of the thousands of colouring-matters sold

by

different firms

under most varied and

fanciful names, the majority represent, not chemical individuals, but intimate mixtures of several colours which give directly the tints desired.

The colouring- matters obtained at the end of the manufacture by precipitation or separation from their solutions by means of salt (just as with soap) arc not sold in the pure state, but are diluted with 50 per cent, or 75 per cent, of finely ground sodium chloride or

A mixture may be distinguished from a chemical individual by the following a few milligrams are blown in a cloud from a watch-glass and are caught simple test on a moist filter-paper spread on a sheet of glass at a short distance from the watch-glass. If the filter-paper were not too moist, it shows on drying isolated, swollen points of colour, the uniformity or non-uniformity of which is readily seen. A variation of this test consists in sprinkling a little of the powder on to the surface of concentrated sulphuric acid contained
sulphate.
:

in a flat porcelain capsule. The use of the spectroscope has been suggested for differentiating between various groups of colouring-matters, the positions of the absorption bands being observed when white
light is passed

through an aqueous or alcoholic solution of the colouring-matter of definite concentration contained in a glass vessel with parallel glass walls. The spectroscope is now, howeve-, scarcely ever used, owing to the uncertainty of the results obtained, but it is useful in detecting the colouring-matter of the blood (see later Haemoglobin). The qualitative analysis of colouring-matters for the detection of the principal groups may be carried out according to the method of A. G. Roto I or to those of Weingartner and Green. The latter, which are largely used, are briefly as follow
:

I.
1

COLOURING-MATTERS SOLUBLE
:

IN

WATER.

(A) If the aqueous solution gives

Rota's method, extended by Buzzi (1911), for analysing colouring-matters consists of four

series of tests

A. This is based on the usually quinoiioid character of these matters and henee on their behaviour towards add reducing agents, preferably stannous ehloride the alkaline reducing agents do not serve well, as with all colouring-matters they give leu co-derivatives which are not very characteristic. The behaviour with 8nCl 2 -f- HC1 permits of the division of all colouring-matters into the following four groups I. Those which are decomposed may contain the following chromogens (p. 704)
; :

()

= N-OH

>NH

=O
,

etc.

II.

Those which are reduced to colourless leuco-compounds, which can be reoxidwed, contain
:

the chromogens

/\/\/\
;
I

'

H.N

(or O) Colouring-matters which are neither reduced nor decomposed, but have a basic character arid are partly decolorised or precipitated by caustic soda, contain the chromogens Cl (or O) 2
111.
:

512

796

ORGANIC CHEMISTRY
:

a precipitate with a solution containing 10 per cent, of tannin and 10 per cent, of sodium acetate, the presence of basic colouring-matters is denoted (1) If the solution of the colouring-matter is reduced with zinc dust and dilute hydrochloric acid, a few drops of the decolorised solution are placed on a piece of filterpaper
:

(la)

The reappearance

of the original colour of the substance

when the paper

is

waved

acid)

IV. Those which are neither reduced nor decomposed, and have a phenolic character (feebly and are increased in colour and solubility by caustic soda, contain the chromogens
:

OH
i
\

O
n

X)H

OH
CJroups III

OH
to these belong the acridines,

and IV always contain the chromophore\C/ and

tho thiazoles, the auramines, the rosanilines, the pyronines, the rosamines, the phthaleins, the rhodamines, the hydroxyacetones, tho hydroxyanthraquinoiieH, the coumarins, flavone,
flavonal, etc. B. To distinguish between the different reactions are used, for instance :

chromogens

of the separate groups, other special

The

acridities,

with concentrated sulphuric acid, give a fluorescence resembling that of

petroleum.
azo-dycstuffs, with concentrated nitric acid, regenerate the respective diazo-salts. hydroxyacelonic, Jiydroxyquinonic, etc., colouring-matters are precipitated as lakes stannoua chloride and subsequent treatment with sodium acetate. The transformation of azo- colouring-matters and their derivatives into thiazole

The The

by

acid, phenolic, substantive, or a basic, substantive phenolic.

dyeing vary auxochromes and salt-forming groups (see p. 766), imparting to the colouring-matter a basic, mixed character, such as basic phenolic, acid phenolic, substantive

The conversion, by special reagents, of one colouring-matter into another, e.g., gallein into c<erulein. C. After the restriction of the colouring-matter to one of the four groups and after the various tests for defining more exactly the character of the chromophore have been carried out, the tests which with the process of identification is continued by means of systematic

(polychromin).

The group with azo-chromophores

S0 3 H
(see p.

contains, for example, Bismarck brown, which

is

basic

K62)

mrtaull yellow,

''

N=N
\
'

__
/
/OH,
t'0 2 H
:

^ NH
-

-/
phenolic;

which

is

acid

alizarin yellow R,

NO 2 N
X

'

\~N^-N

which

is

Congo red

(see

SO,H

p. 781),

which

is

substantive;

cJiromutropp *2R,

NH N

'

O, which

ia

\OH
SOYH

_ >-NH N-<
acid phenolic;
carbazole
ye!lotr,

O
,

NH

which

is

substantivc-

CO 2 Na phenolic in character. In the group with hydroxyazine chromophores are, for instance, Meldolas blue,

N
]

which
9

V" s/\
is

y\

C() 2

basic; guHocya-nine

(see,

p. 688),

(CH 3 ) 2N
which
basic-phenolic in character. So, also, the thiazirie group (see p. 785) contains methylcne blue, which is acid.
is

/\x\/\/x O OH o

which is basic, and ihiocarmine,

and acid baths, in each of which four samples are mmersed, namely, cotton, cotton mordanted with tannin, wool, and wool mordanted with
tests are

The dyeing

made

in hot neutral

DYEING TESTS
in the air indicates azines, oxazines, thiazines,

797

acridines, i.e., according to the colour, pyronine, safranine, rosinduline, phosphine, benzoflavine, induline, etc. (16) If the original colour appears but weakly or not at all, but is formed

and

on moistening with a drop

immediately

to the rhodamines or to the triphenylmethane group ; (Ic) The non-appearance of the original colour under any conditions indicates auramine, thioflavine, chrysoidine, Janos colours, Bismarck brown. B. Non-precipitation of the solution by tannin, etc. (see af)ove), denotes the presence of acid colouring-matters :
is reduced as in (1) or with Zn -f3 and a drop placed paper (2a) The reappearance of the original colour on shaking the paper in the air indicates sulphonic or mordant dyes of the groups of azines, oxazines, thiazines, soluble induline,

of 1 per cent, chromic acid solution, the colouring-matter belongs

(2)

The

solution of the colour

:

NH

on a

strip of

nigrosines or azocarmine, thiocarmine, indigo-carmine, gallocyanine. Mikado orango. (26) If the coloration reappears only after treatment with chromic acid or ammonia vapour, the original aqueous solution is acidified with sulphuric acid and shaken with

ether ; coloration of the other and complete or almost complete decolorisation of the solution indicates phthaleins or auramines, while nori-coloration of the ether shows triphenyl-

methane dyes.
(2c)

vapour points to

Non-coloration of the paper even when heated in a flame or treated with ammonia azo-, nitro-, nitroso-, or hydrazine-colours, which, when burnt in

powder

dichrom.ite (for the mordanting, see p. 771 and later, Dyeing Tests). The more or less intense colours assumed by the samples give indications concerning the character of the colouring-matter (see p. 772), and confirmation of this is obtained by various tests on the dyed fabric is The colour substantive when the if, (a) dyed sample of natural wool is heated in faintly alkaline water, the colour passes to the white cotton placed in the same bath in The colour acid if the indicated in (a) is not observed, and if, when the bath is (b) change acidified, the wool takes up the colour it gave, to the alkaline bath ; (c) The colour iff btwic if in bath (a) the colour passes from the wool to a sample of white cotton mordanted with tannin (d) The colour is phenolic if the tint on mordanted wool varies with the nature of the mordant. Tests may also be made on the solution of the colouring-matter thus, if it is precipitated by tannin or picric acid, the colour is ba#ic ; if ether extracts the colouring-matter in an acid medium, the colour is phenolic, whereas if ether extracts the coloured base in an alkaline medium, the colour iff basic. If it is established that the colouring-matter, containing a given chromophore, is basic in nature, all acid, substantive, phenolic, etc., colouring-matters with the same chromophore are excluded. D. For the further individualisation of the colouring-matter, useful information is given by the following reactions characteristic of the substituent radicals. The N H 2 group is recognised by diazotising and then coupling (sec p. 782), by which means a new azo-colouring- matter is formed, or by boiling the diazotisecl product with water, the formation of the group being shown by the increased solubility in NaOH compared with that of the original colour. The more or less basic groups are indicated by the greater or less sensitiveness of the solution to mineral acids : The N(CII 3 ) 2 group is sensitive as seen in methyl violet and methyl orange ; The 2 group is less sensitive, as in fuchsine and acid yellow
: ; ; ;

OH

NH

The group

NH

'
,

is less

sensitive

still,

as in aniline blue and metanil yellow.

Different colorations with different concentrations of acid indicate several salt-forming groups. To complete the characterisation of a colouring- matter, the latter must be tested for

halogens and nitro-groups.

yellow G,

CO 2 H/

\N /

--

(see abore) from diamond Thus^jto distinguish alizarin yellow the nitro-group is tested for by reduction and ^OH, '

N/ N

C0 2 H

Other colouring-matters are differentiated diazotisation, its presence indicating alizarin yellow. by testing for chlorine and bromine. The azo-dyestuffs are characterised also by the formation of the corresponding diazonium nitrates when treated with concentrated nitric acid :

~\

N-N /
\

\OH
\

_> /
S(),H

N-N-N0 + N0
3

;
<^~~

/OH
\

80 a ff'

-"~

then, by testing for diazo -com pound with j8-naphthol and ascertaining the solubility of the nitro-derivative, the position of the sulphonic group in the molecule may be determined. The Tables given on pp. 708-802 afford considerable help in the rapid characterisation of colouring-matters.

798

ORGANIC CHEMISTRY

WOOL DYES
II

799

ft

Si

PH

x
ii

o
,

"rfi
PH*
II

!,

||

ti

^ A

OK
JH

3^.1^.^ a

rt

^r

{x
I

H
6/0

O X

.
1

1101;

IS
|

110
PH
II

11
O
I

d d ^ 3

'

a*
II

8
U

ft

!ft
II

6?

s^<

Vr^S^S :l^^ 11^

,,

H"

1,^70;

r8-^

'

|.P llgffl

i!l!sl

PH

PM

800

ORGANIC CHEMISTRY

COTTON DYES
.

801

ft

>
>

,/Tappqflftft
'

II

fi

s'!^
as*

8a+

Ii

i!

PH
I

al d

MPQ
II
I'

pqpq
.

jp
.2
M

^^k
n
ii

00

*^
'
II

rtP^ HHC'._ + +'^PQC"

^O
J

II

II

ii

II II

I**

-.
1

PVi^ -^ *
ww k
ii ii

+as+2
nS IS T* PQ
ispq
PH
n
I,

hH^CH Sgfi
'

PQ

PQ
5

'wg-f
II

rfl

^tifn

^fil
,?PH

+"
fc

PQ
j^"

pI!

^PH

11^

'

ir

PH
43

^
-43
'1

S
S.

I
'g

f
'oS^ca

s
PQ

.t,5S5S

|
I

802

ORGANIC CHEMISTRY

FQ

"*

il
d o

I:
"fe

fc?

-,,,

rt

1.S

^
3 3

d
s

c
--Kfp4

^
,+

t;

M;

".

3l

ii

fr
? ^

S
C ^ o jj
-

1
cS

"S^

.2^
-

gci5

*l
lfi

& ^1

| ll!li3lrf w l

*!o

.a. s -s

l*

S a ol

^l

fillli

DYESTUFFS ON FIBRES
directly on a platinum
foil,

803

give coloured vapours

(e.g.,

naphthol yellow S, picric acid, Victoria

yellow).
(2d) If on reduction the solution is not decolorised but becomes reddish brown and in the air regains its original colour more or less, alizarin S, alizarin blue S, and the like are

indicated,

HC1 to decolorise the 3 or Zn (2e) Complete or almost complete failure of Zn -f solution shows thiazolo yellow, mimosa, quinolino yellow S, primuline, thioflavine S,
chloramine yellow, etc. II. If the colouring-matter, in a little water and HC1, is precipitated and gives an evolution of SH 2 (detectable with lead acetate paper), and is redissolved in 10 per cent, sodium sulphide solution, the presence of a sulphur dyestuff is certain. III. If the colouring-matter is insoluble in water, it is moistened and treated with a couple of drops of 5 per cent. NaOH solution : A. If it dissolves it is reduced with zinc dust and ammonia and a paper streaked with it: (1) the rapid reappearance of the original colour in the air shows coerulein, gallocyanine, of the colour gallein, galloflavin, alizarin blue, black, or green ; (2) the non-appearance
in the air indicates alizarin derivatives, alizarin
itself,

NH

nitrosonaphthol, nitrosoresorcinol,
:

dissolve in NaOH but is soluble in 70 per cent, alcohol with 33 per cent. NaOH solution either disappears which shows solution the fluorescence, (a) (6) the solution (Magdala red) or docs not disappear (alcohol-soluble eosin, cyanosine) is not fluorescent and is coloured reddish brown by 33 per cent. NaOH (alcohol- soluble (c) the solution remains induline, alcohol-soluble nigrosine, alcohol-soluble anilino blue)
; ;

Soudan brown, etc. B. The colouring matter does not

fluorescent (indophenol). nor 70 per cent, alcohol [indigo C. The colouring-matter dissolves in neither alizarin black, sulphur colours (soluble in sodium sulphide) ].

NaOH

Green (1905) has shown that the different groups of colouring-matters may be characterised by their behaviour toAvards the compound of sodium hydrosulphite with
formaldehyde.

RECOGNITION OF THE PRINCIPAL COLOURING-MATTERS ON DYED FIBRES.

first (see later)

the nature of a colouring-matter is to be studied, a dyeing test should always be and the tests described below carried out in the cold on the dry, dyed 1 to 2 c.c. of fabric, a small piece (about 1 sq. cm.) being treated in a porcelain dish with the reagent, and any change observed, [n testing with nitric acid, one or two drops of the latter are placed on the fabric and the colour of the drop and that of its edges noted. The hydrochloric acid solution of stannous chloride is prepared by dissolving 100 grms.

When
made

of the

of the latter in 100 grms. of the concentrated acid and 50 grins, of water. Abbreviations names of the colours and of the changes produced are used, and when a compound

colour

is

formed,

it is

indicated

by the two fundamental colours composing

it

thus com-

bination of red (R) and yellow (Y) gives scarlet (RY), green (On) and brown (Br) give olive (Or Br), etc. (nee Note at foot of Table, pp. 798 et seq.). To ascertain if an indigo dye on wool contains also logwood or sandalwood, a piece of the fabric is heated with dilute nitric acid (1:6); indigo alone gives a straw-yellow, while in presence of either of the other colouring-matters, a more or less brownish colour is textile is heated for an hour with fused phenol on the obtained. Or the shredded

dyed

water-bath, the phenol being decanted off, the operation repeated with fresh phenol, and the material washed two or three times with strong alcohol and pressed. If the wool were dyed with pure indigo it will be quite white, but if there wcro threads dyed with other colours anthracene blue, sandalwood, etc.) these are seen under the microscope to
(e.g.,

be

still

coloured.

determined quantiAccording to E. Knecht (1909) the indigo on a cotton fabric may be 4 grms. of the fabric, cut into pieces, is dissolved at 40 in 25 c.c. of 80 per cent, sulphuric acid the volume is then made up to 1 20 c.c. with water, the indion a Oooch filter, gotin of the soluble sulphate being thus precipitated. This is collected dried at 110 to 115 and weighed. It may be redissolved in a little sulphuric acid by acid in the diluted heating on the water-bath for an hour, the indigotinsulphonic The presence of basic or sulphur colours solution being titrated with permanganate. does not interfere with the estimation, since these either remain dissolved or are must first be dissolved decomposed. If the fabric has a coating of manganese dioxide, it
tatively as follows
:

in bisulphite.

804

ORGANIC CHEMISTRY

p-Nitraniline red may be distinguished from other reds (Turkey-red, bcnzo purpurine, primuline, etc.) on cotton by heating the fabric at one point over a small flame ; a clear spot is formed and part of the colour sublimes on to a piece of paper placed above the fabric. The spot docs not resume its original colour either on cooling or on moistening

(Knecht, 1905).

TEXTILE FIBRES
Before a description is given of the processes and plant used in dyeing textile fibres, the physico-chemical properties of those may be outlined. WOOL. Only sheep and certain goats furnish true wool used in the great textile industries. The wool fibre is readily distinguished from the hairs of other animals by its softness and fineness and by its waviness and curling, which can be seen with the naked eye. Also under the microscope a

marked

difference

from

all

other hairs

is

easily dis-

cernible (Figs. 472

and

s?ems to be composed which arc more or less large according to the quality
of the wool. of these scales
It
is

The whole filament 473). of closely superposed scales,

the saw-like or serrated structure

which explains why wool readily forms a felt when rubbed, the filaments becoming more or 1 less firmly attached one to the other. The quality of a wool is closely dependent on the breed of sheep producing it and only partially on the climate, food, and age. The yield of wool is greatest from the second to the sixth year. The finer wools,
furnished generally
slender,
soft,
8 by the Merino breed, are long, and very wavy, and form the so-

Fro. 472.

called combing wool for the best woollens. Shorter wools cannot be combed but only carded (Sik*wn, flaxon), although nowadays nearly all could be combed with the improved machinery available, and a large part of the carded
1
II
III

IV

Fid. 473.

The whole of the wool covering the sheep forms tine, fleece, which is kept entire even after shearing (this is done in May) owing to the scaly structure of the filaments. Wool obtained by shearing twice a year is called bifttfutc, while that from slaughtered sheep is termed sJein wool and frequently contains dead hairs, which have little affinity for colouring-matters and arc often impure owing to the use of lime, arsenic, etc., as preservatives. If the sheep is washed in the tank before shearing, the wool is known as washed, the other being called in grease or unwashed. The fleece (weighing 2*6 to 3 kilos) contains different parts of different qualities, and these the sorters separate by cutting. In one and the same fleeco the finest wool is that of the shoulders, then comes that of the neck, stomach, flanks, and back, the poorest qualities being those of the head and legs. Certain African sheep (Morocco), and, to some extent, the Lincoln, Leicester, and Wellington breeds, give long, coarse, and only slightly curved fibres, which are used for special fabrics and for mattresses. 2 Merinos are indigenous to the plains of Estremadura and Andalusia (Spain), where they were jealously guarded for some centuries, exportation being prevented. In the nineteenth century the Spaniards themselves introduced them into the Argentine, where three principal Rambouillet, Negrette, and Lincoln, and a similar result followed the types were developed
1
:

WOOL
natural
in
size).
fi

805

wool is obtained from xhoddy. 1 The lengths of wool fibres vary from 4 cm. to 30 cm. and the diameter from 0'014 mm. to 0-06 mm. The finer wools (merinos, Fig. 472) have as many as 13 waves per centimetre, while the more ordinary ones have only 3 (Fig. 472 B 9

The world' output of wool was about 1,300,000 tons in 1903,- 1,450,000 in 1907, 1,530,000 1913, and 1,400,000 in 1920, the consumption in 1920 being 875,000 tons. The great market for wool in Europe is at Antwerp, and the price is fixed by auction,

account being taken of the yields of the various wools (Conditioning, see later) after washing, some of them losing 40 to 70 per cent, of their weight owing to the removal of dirt, grease, the normal or natural moisture, after washing and drying, is taken as 18-25 per cent. etc. The price of raw wool varies somewhat from year to year and even in the same season from about Is. 2d. to 2s. per kilo (pre-war). Australian wool is worth more than that from the Argentine. Unwashed wool (Australian weighs about 160 kilos per bale), after sorting, is washed with soap and soda at 45 to 50 in vessels (Leviathans) provided with loose forks for mixing and, when rinsed, is dried in revolving drums by means of hot air. The washed (or salted, such as Italian or Cape wool, weighing about 110 kilos per bale) wool is then carded and
;

concessions made to France and Sweden. The English introduced them, with great success, The Electoral breed originated in merinos which were imported into Australia and ('ape Colony. in 1700 into the Electorate of Hesse, and spread into Silesia, Saxon\, Wurtemberg, Hanover, Moravia, and Hungary ; it now furnishes a large proportion of the raw material of German and

Austrian wool factories. In England the C Jteeiol breed has assumed considerable importance and yields a long, yellowish Crowbrecds, obtained by crossing Argentines with Cheviots, are also wool, not so fine as merino. largely bred in England. The Russian breech are derived from pure and Saxon merinos. The commonest varieties are the Jitiuyxkt aidtirtik, rencetiovenk, and ronuiHowk (this is used for furs). Tn France the wool of the Burgundy and of the Berry is highly valued. 'Italian wool*, which were once famous, are now of little importance, and only Apulia, the Tuscan marshes, and the Roman province furnish a small pan of the wool consumed in Italy. Good wool is also obtained from certain breeds of goats, such as those of Caithmir, which flourish in the Himalayas, nearly 5000 metres above sea-level. They furnish a very fine wool, The it is exported to France and Russia. mixed, however, with much white or grey hair Thibetan yoal, acclimatised also in France and in Bengal, likewise yields a valuable wool. The Angora goat of Asia Minor gives milk and a long wool (mohair) va ued for its lustre, even after
;

dyeing.

The vicuna of the Peruvian, Chilian, and Mexican mountains gives a fine wool, used in certain cloths, which arc now made partly from rabbit fur (the name vicuna or vigogne yarn, is also applied to fabrics of wool and cotton which are quite distinct from vicuna wool). Alpaca is greyish, and is furnished by a kind of tall, long-necked sheep (llama) indigenous to Peru. Camel-hair, which is worked like wool, has coarse fibres, and in its natural colour is woven into certain very strong textiles, used, for instance, for the seats and curtains of railway carriages.
flhoddy is obtained by disintegrating woollen rags (previously sorted with respect to colour and separated from those mixed with cotton) by means of an opener or devil, formed of a drum furnished with a number of steel points and rotating rapidly inside a second, fixed drum also from this the rags issue in short, floceulent fibres, which are carded and provided with points then spun. This industry, started in England in 1845 and since then extended to other countries, allows of the utilisation of all woollen waste (fabrics and yarn) England alone imports from all parts of the world about 15,000 tons of woollen rags per annum. The coloured rags may often be partially decolorised by boiling them with 2 to 3 per cent, potassium dichromate and a little so-called sulphuric acid. Admixed cotton (sewing and other) may be eliminated from the rags by carbonisation, which consists in immersing the rags in sulphuric acid (4 to 5 Be.), eentrifuging and heating them in ovens, the temperature of which is raised to 120 to 140. In the course of an hour the cellulose of the cotton is transformed into brittle hydrocellulosc and partly carbonised, so that it can be easily removed by subsequent rubbing or by washing with water, In this also carrying away the acid from the wool, which is not affected by such treatment. some cases, hydrochloric acid vapour or aluminium chloride solution is used instead of sulphuric The carbonised wool shows increased affinity for acid colouring-matters. acid. Also woollen fabrics which contain bits or fibres of cotton in such quantity that it is or aluminium chloride impracticable to pick them out by hand are carbonised with sulphuric acid before dyeing and are thoroughly washed after removal from the oven. Decolorised shoddy mixed with new wool can be recognised under the microscope owing to its different colour, which often recalls the original tint. 2 The greatest sheep- breeding countries are as follows, the numbers of thousands of sheep
1
; ;

in 1916 being given in brackets Spain (16,052), France (10,845), Great Britain (25,007), Italy United States (48,483), Argen(11,824), European and Asiatic Russia (77,000), Turkey (27,095), tine (81,485), Uruguay (11,482), British India (23,016), Union of South Africa (35,711), Australia (69,245), and New Zealand (25,000).
:

!06

UKUAJNlUCHUMlfcTltY
In some
districts the

ombed.
he grease
t

washing

is

preceded by treatment with benzene to remove

(see pp. 486, 488) .

The great European market for combed wool, not yet spun but wound into balls of to 5 kilos (tops), is in France, at Roubaix (and also at Tourcoing and Lille), where prices ixe fixed at auction, although there is a considerable trade in combed wool at Bradford
ind to a less extent at Leipzig. These wools are classified, according to then- fineness, as A, B, ... F, the first being or AAA. ,he finest and the last the commoner sorts very fine wools are marked
;

AA

subjected to the operation of blending, i.e., the various qualities of wool (fine, ordinary, long, short, waste, shoddy, etc.) being mixed so ts to obtain yarn of the desired count and fabric corresponding with the price and quality.

Before being spun the washecl wool

is

To

facilitate spinning

and avoid
oiled

felting,

the wool
olive

is slightly

commercial oleine, soap emulsion, etc., but not with non-saponifiable substances, such as mineral oils or resins, which would be difficult to remove from the fabric by washing, and would lead to irregular dyeing). In passing through
(with
oil,

the combs or cards, the various fibres are perfectly mixed and The coarse rendered parallel.
strands (tops) are gradually converted into finer but not twisted strands, which are wound on

bobbins (prepared) and are then,

by

means

of

ingenious,
of

self-

acting

machines

enormous

capacity, spun to the desired fineness to give, when twisted, 1 yarn of the required count.

During spinning, the air of the room must be kept moistened with water vapour (see Vol. I.,
p. 337)

to prevent the parallel

Satisfac-

fibres

from diverging and giving

weaving
also

a non-uniform yarn.
tory

FIG. 474.

requires a certain degree of moisture. Chemical Properties of Wool.

Pure wool consists

of C,

H, 0, N,

and

and being partly removed by repeated 8, the last varying somewhat in amount consists of a single chemical washing in boiling water. It is hence improbable that wool to be keratin, containing 4 to 5 per cent. S, but there one time at was thought (it compound to be other substances also). In 1888 Richard showed that the compounds forming
appear wool contain
1

NH

and

NH groups.

In a solution of alkali or a

salt,

wool

fixes

chemically

of Yarn, either cotton or wool, is given by the number of kilometres weighing the count represents count) or half a kilo (French count). In Great Britain, hence English 0-914 metre) per 1 Ib. (453 grms.) the number of hanks of 840 yards (1 yard count No. 1 is equal to French count No. 0-847 and to international count No. 1-694. Division the French of the international count by 1-66 gives the English count, multiplication of ^count count by 1-18 gives the French by 2 gives the international count, while division of the English

The Count

I kilo (international

A thread spun from two yarns of count 60 has the count 30, its weight per unit length being doubled. Fine wools are spun so as to give a count of 60 to 80 or even of 120, while the commoner qualities give counts of 30 or even less. For silk, the International Congress at Paris in 1900 accepted the Italian count, which 0-05 grm.) of a length of 450 metres, the finer yarns expresses the weight in denari (1 denaro thus having the lower counts. Silk is often spun to a count of 12 to 20 denari, and artificial silk to 60 to 120 denari.

COTTON
part of the alkali or salt.

807

most important exhibits the same behaviour towards colouring-matters as does wool. It is probable, therefore, that wool contains
one carboxyl group.

Concentrated alkali dissolves wool, forming amino-acids, the being lanugic acid, which was isolated by Knecht and Appleyard and
at least

The

affinity of

wool for acid

colouring-matters (often sulphonic acids) is explained by the presence of amino-groups and that for basic dyes by the presence of the carboxyl group. Certain

highly basic colouring-matters (such as methyl green) do not, however, colour wool, the acid character of which is too weak, while they colour silk, which is more markedly acid. The fixation of metallic oxides (of Cr, Fe, Cu, Al, etc.) in the mordanting of wool is due to the formation of salts with the carboxyl group.

The salt-forming property of wool can be easily demonstrated by immersing it in a hot colourless solution of rosaniline (base), which colours it red just as though it were dyed with red rosaniline hydrochloride. Knecht, Witt, and Nilsen have shown that the action of chlorine on wool is to intensify its acid character, so that it at the same time it lixes basic dyes the more readily
;

loses partially its capacity to felt.

Bolley found that wool decomposes potassium bitartrate in boiling solution, generating the neutral tartrate and fixing tartaric acid. In 1898 Kertesz utilised indus-

475.

the simultaneous production of two colours this shows of fixing acid colouring-matters more intensely at points where it has been carefully treated with caustic soda, the latter neutralising the carboxyl group and thus rendering the basic character
trially, for

on wool, the property

(Magnified 300 timew)

more pronounced.

Wool
when

loses

much

of
it

its

affinity

for

acid colours

treated with phosphotungstic acid, but recovers of ammonium bicarbonate (Scrida, 1909).

when

subjected to the action

is the behaviour of wool (or cotton) waste containing ordinary or fats (not wool-fat), as it readily ignites owing to energetic oxidation and causes fires (see Pyrophoric Substances, Vol. L, p. 189). An aqueous extract of pure wool gives a precipitate with either tannin or basic lead acetate, while true glue or gelatine yields no precipitate with the

Of practical importance

oils

latter reagent.

Pure wool contains 14 per cent, of nitrogen. the white down surrounding the black cotton-seed and is contained in capsules (each weighing about 30 grms., 10 grms. being cotton) which, to the number of 300 to 400, form the fruit of Oossypium a shrub 2 to 4 metres in height (see Fig. 474). When the fruit is ripe (in America in August), the capsule opens and

COTTON

is

throws out a white tuft of cotton, which is fixed to the seeds. After harvesting, the cotton is frted from seeds by means of cotton-gins and compressed hydraulically into bales holding 500 Ibs. (227 kilos). Cotton is produced most abundantly in North America and, to a less extent, in South America (Brazil, Peru, Colombia, etc.), and the
Antilles (Haiti, Cuba, etc.).
Its cultivation is also of

Fia. 476.

importance in (Magnified 200 times. the East Indies, Syria, Macedonia, etc. Egyptian cotton (mako) is valued on account of its lustre and length of fibre. Cotton is also grown in Australia. Attempts have recently been made to cultivate it in the Italian colony of Eritrea, but
without great success.

The
10 to 14

best qualities have fibres 30 to 40 mm. The fibres are 0-015 to 0-020

mm. in length and the lower qualities (Indian) mm. in thickness and under the microscope have

the appearance of flattened ribbons with a twist here and there (Fig. 475, the upper part When treated with ammoniacal copper oxide of which shows the transverse sections). concotton swells solution, very considerably, forming superposed capsules separated by

808
strictioiis (Fig. 476).

ORGANIC CHEMISTRY

By cold concentrated caustic soda solution (30 to 35 Be.) the flat converted into a cylindrical one almost circular in section (Fig. 475 / ; see Mercerisation) with a thin central channel. If immersion in the soda is prolonged for two or three minutes, during which the skein or fabric is kept stretched, and the soda is subsequently washed away while the tension is maintained, the skein will not contract and the fibres present a lustrous appearance (mercerised cotton) and are stronger and heavier than in their
fibre is

original state (soda-cellulose

and then hydrocellulose are formed). 1

1 In 1844 J. Mercer, chemist in a History and Properties of Mercerised Cotton. Lancashire calico-printing works, having filtered a concentrated caustic soda solution through a cotton filter, noticed that the cloth had contracted somewhat and had become thicker and 1-265. transparent. Before filtration the liquid had the sp. gr. 1-300, but after filtration only On studying the phenomenon more closely, Mercer found he could reproduce it at will with yarn immersed in caustic soda solution of 20 to 30 Be., while he established with certainty that, under such treatment, the cotton tibre shortens by 20 to 25 per cent., thickens and becomes stronger (by about 50 per cent.) and of increased affinity for colouring-matters. He showed, too, that the phenomenon is more rapid and more intense at Jow temperatures, while at the Similar changes are produced by treating cotton with boiling-point no contraction occurs. sulphuric acid of 50 to 55 Be. or with zinc chloride solution. In October, 1850, Mercer was granted an English patent (13,296) for increasing, by this treatment, the strength and compactness of cotton and its affinity for dyes. In 1884 P. and C. Depoully patented a process for the partial mercerisatioii of fabrics by which these parts contracted parts of the fabric were brought into contact with an alkali solution and caused the other parts to curl, beautiful crape effects being thus obtained. In 1896 the textile world was astounded to see on the market samples of fine cotton of the most brilliant colours and the lustre and feel of silk. This product was prepared by the great of Crefeld, according to their Cerman Patent, No. 85,564 of dyeing firm Thomas and Prevost kk March 24, 1895, which reads: improvement in the mercerisatioii of vegetable fibres with alkaline or acid solutions, by subjecting the tightly stretched yarn or fabric to the action of alkali (caustic soda of 15 to 32" Bo.), or of acid (sulphuric acid of 49-5 to 55-5 Be.), the and is relieved spontaneously stretching being maintained until washing is complete \vhen it the shortening of the yarn or fabric thus prevented." The specification does not refer to the lustre assumed by the yarn, but this is mentioned in a later addition. These Thonws and Prevost patents were, however, annulled a couple of years later in all countries, since various competitors found that an identical process had been patented (No. 4452) in England in 1890 by It. A. Lowe but had not been renewed within a year because Lowe could not find an English manufacturer disposed to make practical use of it. Large quantities of mercerised cotton are now freely produced in all countries. The shortening of the fibre and its increased strength produced by concentrated alkali solution may be understood if the changes occurring in the fibre itself are followed under the microscope. While the fibre of ordinary cotton is seen to be a flattened empty tube with an occasional twist, that treated with caustic soda without stretching is shortened and swollen and forms an oval, outside it shows almost round tube with thickened walls, but still with an internal channel creases and a rough surface. By mercerisatioii under tension, however, the iibre becomes like a straight, round tube, smooth and without visible creases outside and almost entirely filled fibre up inside. These changes explain the silky lustre and also the increased strength, the Buntrock's experiments showed that mercerisatioii occurs very becoming more compact. with caustic soda of 30 Be. the shortening of the fibre after one minute is 23 per cent, rapidly and after 33 minutes 29 per cent., which is the maximum attainable. W. Vieweg (1908) determines the degree of mercerimtion by a method based on the fact that, in 13 to 24 per cent. NaOH solution, cotton fixes an amount of NaOH corresponding with this amount, (C H 10 5 ) 2 2NaOH. (C 6 H 10 5 ) 2 NaOH, while in a 40 per cent, solution it fixes double This soda-cellulose loses its soda when washed, and the recovered cellulose has the property of taking up more or less caustic soda in a 2 per cent. NaOH solution, non-mercerised cotton NaOH according to the degree of previous fixing 1 per cent., and mercerised 1 to 3 per cent, of 3 grms. of In practice this degree of mercerisatioii is ascertained as follows mercerisation. the dry mercerised cotton is shaken for an hour with 200 c.c. of exactly 2 per cent. NaOH solution titrated with semi-normal acid and the i n a separating funnel, 50 c.c. of the solution being then amount of NaOH absorbed by the cotton calculated. A qualitative test for detecting mercerised cotton mixed with ordinary cotton and oxycellulose was given on p. 602. To ascertain if a fabric is then is mercerised H. David (1907) places a drop of concentrated soda on the fabric, which washed and Uyed with a substantive dye a more intense colouring on the place touched by the soda indicates that the original fabric was not mercerised. To distinguish between mercerised and ordinary cotton, Kiieeht proposed the following A mixture of the two cottons is dyed test, which, however, sometimes gives uncertain results in 5 c.c. of hot benzo purpurine 4B solution (0-1 grrn. in 100 c.c. of water), about 2 c.c. of concentrated hydrochloric acid being added to the hot bath lion- mercerised cotton then becomes If oxycellulose (formed by the action of calcium bluish-black, whilst mercerised remains red. is dyed in Congo red and acid then added ordinary cotton hypoehlorite) is present, the cotton after prolonged and oxycellulose turn bluish-black, whilst mercerised cotton remains red black and the mercerised washing, the pure cotton then becomes red, the oxycellulose remaining cotton red. solution and then drops Lange (1903) soaks a piece of the fabric in saturated zinc chloride
;
.
.

COTTON STATISTICS
'later.

800

The chemical characters of cotton are those of cellulose described on p. 599> purified cotton being pure cellulose. For its behaviour towards different dyes, see p. 772, and also The world's production and 0,228,000 (27,703,000
Britain,

was about 3,500,000 tons in 1904, 5,000,000 in 1908-9, 1913-14. Tho world's consumption was 17,500,000 in bales) bales in 1919-20, including 3,800,000 bales in the continent of Europe, 3,200,000 in Great
of cotton

and 6,500,000 in the- United States. 1 The conversion of cotton from flock to yarn is effected by carding or combing in a similar manner to shoddy (see above). Very fine counts (150) arc spun in some countries, but in Italy, where at one time 30 was the finest, 60 and 90 are the usual ones, although 130 is

sometimes obtained.

The immense importance

of the cotton industry

is

shown by the following Table

1 The total quantity of cottonseed produced annually throughout the world (11,000,000 tons) should yield almont 2,000,000 tons of oil, but in the United States more than one-half of the oil and cake are wasted.

on to different parts of it 10 to 12 drops of a solution containing 20 grins, of KI and 1 grin, of in 100 c.c. of water. The fabric is manipulated and pressed for a minute and then gently squeezed between the fingers under a gentle water jet until the brownish red colour at iirst seen just under this treatment mercerised cotton remains deep blue, whereas non- mercerised disappears cotton becomes white. Similar results are obtained by Htibner (1908), who immerses the 52 VOL. u.
I
:

810

ORGANIC CHEMISTRY

In one of the cotton mills of the United States 134 workpeople are sufficient to overlook 2000 Northrop looms, a clever workman attending as many as 20 looms, while with the less expert the number never falls below 12 ; these looms make 165 strokes per minute with good warp and weft. KAPOK is a cotton-like fibre from the fruit or capsules of the tree, Eriodendrum
anfractuosum, growing particularly in the. East Indies (Java), and is separated from

the oily seeds

cotton.
largely

(see p.

499), just as with

As

its fibre is

not very long,

it is

used

for

cushions, etc.

The

stuffing mattresses, fibre is pale yellowish-

grey and lustrous, is difficult to wet and readily floats, being used also to make From 8000 to 10,000 tons of life-belts.

kapok

fibre is exported annually, from Java, mainly to Holland. FLAX (Linum usitatissimum) is a

annual, growing usually in temperate regions, and reaching a height It bears of 60 to 80 cm. (Fig. 477). clusters of blue flowers which give cap-

herbaceous

sules

(Fig.

478, 2) containing flattened

lenticular seeds (Fig. 478, 1). It was cultivated first in Egypt, then in Greece, and
later in Italy

and various other parts of Europe (Belgium, Holland, Russia, etc.)

;

in Italy the cultivation has diminished

very considerably,

although

it

is

still

FIG. 477.

followed in some parts and is carried on in the south of Sicily for obtaining the seeds. There are two ordinary varieties which are has a coarse fibre mnd is sown grown for both fibre and seed : autumn or winter flax, which in October and harvested at the end of spring, the ground being left free for another crop ; and that sown in March, which is pulled in the summer when the

brown but are not quite ripe. Flax plants are pulled by hand and arranged in sheaves to dry and to mature the seeds. After removal of the latter by threshing, the plants are made into
seeds begin to

which are left for 15 to 20 days in stagnant water, where the action of micro-organisms (Amylobacter, butyric bacteria) results in the dissolution of those parts of the tissues which unite fibres to the cortex and to the pith. The bundles are then the
large bundles,

long

moistened and squeezed cotton for a few seconds in a solution of 20 grms. of iodine in 100 c.c. of saturated potassium iodide solution. When cotton is mercerised with tension its strength increases by 35 per cent., and when mercerised without tension by as much as 68 per cent. The elasticity is greater in cotton mercerised without tension (27 per cent.), while with cotton mercerised under tension it The lustre of mercerised cotton is not is unchanged (20 per cent.).
FIG. 479. (Magnified 200 times.)
altered

by washing or dyeing. In order to obtain satisfactory results and a good lustre

by

fibre mercerising, it is best to use long-fibred cotton ; the shorter the the greater must be the tension. It is also necessary to boil the cotton thoroughly and wash less it completely before placing it in the caustic soda bath, as otherwise, besides obtaining lustre, there is great danger of irregular dyeing. The dyeing is carried out in the usual way with basic dyes, being preceded by mordanting, oil or soap, the temperaor, better, with substantive dyes in baths containing a little Turkey-red Old caustic soda baths, which become ture being kept low at the start to avoid non-uniformity. diminish in activity, can be used for soap-making. largely converted into sodium carbonate and so To impart a silky feel to mercerised cotton, the latter is well washed, immersed for a few minutes in a calcium acetate bath at 0-5 Be., pressed, introduced into a, bath of Marseilles soap an acetic or tartaric acid bath (10 grms. per litre) (1 grm. per litre), again pressed, placed in and finally pressed and dried without washing.

FLAX
bpened and dried
in the
field.

811

Instead of being retted in this way, flax is in some countries heated in large autoclaves for half an hour at 125 with water from a preceding operation and then for an hour with steam at a pressure of 5 atmos. The dried flax is freed from the

Fia. 480.

FIG.

4.81.

friable cortex by bruising between sticks, the operation being completed by blows from scutching knives (the waste forms the tow). The flax is then combed and placed on the market in large, twisted tresses of 200 to 300 grms., the price before the war being 144s. per quintal or 80s. to 965. for short fibre. In Italy, a hectare of winter flax yields about

300 kilos of fibre and 900 kilos of seed, March 200 and 700 kilos respectively in Ireland, Belgium, and Germany double as much
flax giving
;

fibre is obtained.

of spindles for spinning flax 100,000 (flax and hemp) in Italy, 1,500,000 in the British Isles (threefourths in Ireland), and 700,000 in France. The cultivation of flax is falling in all countries

The number
in

was,

1912:

except Russia. Thus, France had at one time 120,000 hectares under flax but now has only 20,000 (in spite of Government awards of 100,000 annually to encourage its growing), about 800,000 quintals being imported (fourfifths from Kussia) to supply its 700,000 spindles, 20,000 hand looms, and 22,000 power
looms.
FIG. 482.

In 1913 England produced 12,000 tons of (Magnified 200 times.) flax and imported 90,000 tons (80,000 from in 1918 almost 35,500 hecRussia). In 1914 Ireland had 22,860 hectares under flax and in 1918. tares, whilst the area in Yorkshire increased from 516 hectares in 1914 to 7545 The flax fibre has a diameter of 0-02 mm. and is readily distinguishable underfthe 2, extremity of the 1, spiral striation microscope from other vegetable fibres (Fig. 479 The fibre is spun into yarn in the same fibre and polygonal section 3, bruised places). way as with cotton, but special machines are used for the recombing and repreparing of coarse fibres, which are drawn out in the moist state to a finer thread, and, at a certain
:

522

812

ORGANIC CHEMISTRY
;

The tow from these operations is worked up by carding (see Shoddy). stage, twisted. certain qualito 200 Flax can be spun by hand to a count of 300, but by machinery only to a count of 1400, such yarn costing (preties of flax can be hand-spun, for very fine work, war) as much as 80 per kilo.

HEMP (Cannabic saliva) belongs to the order Cannabinese and bears male and female flowers on different plants (dicBcious). When growing wild it branches (Fig. 480), but when cultivated of 2 for industrial purposes it grows to a height finer a has and without more or branching metres and closer tuft in the case of the female plants
(Fig.

481).

Of the
is

different varieties

of

hemp

(Manila,

New Zealand, Bombay, and ordinary), the

the ordinary.
soil,

most important

It

is

sown very
is

gathered close in on the in August, the plants being dried in bundles The treatment is similar to that of flax,

heavy, deeply worked

and

The but with a more protracted maceration, is used (o some extent the from breaking residue the hemp, more or less combed, in paper-making flax and made up into is twisted into tresses like a diameter of 150 kilos. Hemp fibres have
;

ground.

bales

of 0-04-0-05 mm. and are easily distinguished 1, disother fibres (Fig. 482 microscopically 'from form of the tip of the fibre fibres o-d, 2, ; placed of fibres ; 4, striation : the 3, section of a bundle the crossed transverse lines are not always seen, more common). striations being parallel longitudinal stems are cut into three lengths of about The
:

then by a 70 cm. and are combed first by hand and formwaste the coarse points, machine with long, which can be subsesecond tow, and first the ing A third combing is carried out quently carded. coarse and then the finer ribbon being passed through with finer and closer teeth, the those used for cotton and wool (preparing), and machines similar to but coarser than of 7 to 10), etc. Two twine coarse yarn, for canvas yarn (count finally twisted for several strings coma string, twisted twines together give bined and twisted form a rope, and several ropes a cable. As well as for string, rope, etc., hemp is largely used
for

long

making

coarse, strong cloth for bags,

waggon

covers,

In order to render hemp fabrics more comare sometimes mercerised. pact and durable, they JUTE (Corchorus capsularis of the order Tiliaceac) has been grown on an enormous scale in India and is now replacing Bengal from time immemorial and India 1851 282,350 quintals, in Even exported indigo. and in 1858 the exports of jute sacks were valued at
sails, etc.

almost 240,000. These figures are now nearly doubled, owing to the development of the large works in Calcutta. In Europe its cultivation was commenced subsequently in South America and in the to 1830. It is grown
also^

FIG. 484.

(Magnified 200 times.)

in four
etc
is

United States. Jute requires a moist, hot climate and soil. It is sown in spring, and the plants, 15 to 20 cm. apart, mature

months and attain a height of 3 to 4 metres. The shape of the leaves, stem, seeds, shown in Fig. 483. It is treated in a similar manner to hemp, and the bales, weighing centre of the jute 180* kilos, are tightly pressed for transport. The principal European fibre is brownish yellow, and is bleached in a trade and industry is at Dundee. The jute a of lime bath (5 Be.) at 25 to 30, then rinsed, immersed ia faintly alkaline chloride washed. and 15 minutes, finally thoroughly acid bath for cent 0-5
per
sulphuric

SILK
Raw
Fig. 484
:

813

jute fibres are easily distinguished! from other fibres under the microscopa (see 2, fibre with broken lumen ; 1, irregular lumen of the fibre dotted at the top more or less 3, tip of fibres ; 4 and 5, sections of fibre with thin or thick walls) and show lustre according to their fineness. Jute competes directly with hemp since it serves for making the same articles (sacks,
;

of jute the^e do not packing cloth, carpets, tents, furniture coverings, etc.), but when nude withstand washing or continuous rubbing, although they resist the action of acid or alkaline solutions rather better than cotton. SILK. The Chinese seem to have known the silkworm as early as 2600 years B.C. Although they understood the preparation of silk materials, they did not at once trade with other races, but maintained great secrecy on the rearing of silkworms and strictly

prohibited the exportation of the eggs. According to tradition it was only in 150 B.C. that silkworms arrived in Japan, where they were Imported secretly by the daughter of a Chinese emperor, and whence they later throughout the rest of Asia. They were apparently imported into Italy in

spread the sixth century by three monks

of imported silk

who

hid them in their staves, although the manufacture

to the present Italy three centuries earlier. From that time up of Europe for the rearing of silkcountries the has maintained the first among place Italy worms and the production of silk. 1

was begun in

1 Silk is produced by one of the Lepidoptera, Bombyx mori, a larva which after birth when weighs about 0-5 mgrm.), feeds on mulberry leaves (Mortis alba) and attains the height of its development (with "a weight of 3 to 5 grms.) in five weeks, passing through four moults or It finally passes to brushwood arranged above, where it sleeps during which it casts its skin.

it

a, double thread (bava) section of double thread c, isolated, smooth bava, after cleansing. (Magnified 120-180 times.)

Fiu. 485.;

with scales, d

6,

FIG.

48(3.

constructs a cocoon with the silky exudation secreted by two long glands filled with fibroin and leading along the body beside the intestinal canal to two very fine apertures in the mouth. The two contiguous arid parallel threads thus formed are immediately stuck together by a liquid (seriein) exuded by two other channels near the first pair, the result being an apparently single thread, which is either white or some shade of yellow (the double thread is shown in Fig. 485). In three days the silkworm is transformed into a chrysalis from which the butterfly originates The butterfly emits from (in 10 to 14 days) if the temperature is sufficiently high (15 to 30 ). its mouth an alkaline liquid with which it moistens one end of the cocoon and then perforates it and issues to proceed to the coupling necessary for the preservation of the species. Immediately afterwards the female deposits numerous fertile eggs (graine), and both it and also the male die, their short life-cycle being at an end (Fig. 486). One kilo of cocoons gives 3 ounces of eggs. Part of the eggs (or of the butterflies) are selected under the microscope and are kept in a cool place until the following spring, when they are hatched by incubating for a couple of weeks in an oven, the young worms being distributed to the rearing-houses. By means of extreme cleanliness, disinfection of the brushwood and microscopic tests of the eggs, the numerous diseases which cause havoc among silkworms at all stages (cafcino, flacherie, The crossing of different varieties has also proved beneficial, etc.) have been partially overcome. and in Lombardy the use of the Chinese cross is fairly general. The silkworms from an ounce of eggs consume It has been proposed to disinfect the altogether about 12 quintals of leaves.
leaves with lysoform, tachyol (ozone
:

Molinari, 1908), etc., but without

good

results,

814

ORGANIC CHEMISTRY

In the twelfth century sericulture developed considerably in Sicily, and during the Middle Ages it flourished in Tuscany, Emilia, Venetia and Lombardy. In the thirteenth
In order that a maximum yield of good silk may he obtained, the butterfly is not allowed to issue from the cocoon, since the silk cannot subsequently be readily unwound from perforated indeed, when the cocoons are placed in water (see. later), cocoons, and much waste is produced the perforated ones become filled with water and sink, thus breaking the thread during the unwinding. The formation of the butterfly in the cocoon is prevented by stifling (i.e., killing) the chrysalis by heating in an oven, where the cocoon loses two-thirds of its weight. Such procedure also allows of the sale of the cocoons at the season of the year when the prices are most remunerative. Ten or 11 kilos of fresh cocoons yield 4 kilos of dry cocoons, and these
;

give

kilo of silk.

ounce of eggs yields 50 to 60 kilos of cocoons, which before the war were sold, freed from as waste are considered waste, at prices varying in different years from 2s. to 3*. firf. per kilo doubled cocoons (doupionx), stained or mouldy cocoons, those attacked by calcino, and also and the soft flake silk or cover which surrounds the c*ocoons and cocoons, incomplete, light, attaches them to the brushwood. The suffocated cocoons have an average weight which varies, more particularly with the The ratio between the weight of dead chrysalis and silk lies between variety, from 0-5 to 0-8 grin. 1-4 1 and 1-6:1 and the length of silk per gram is 900 to 1500 metres the thread (bava) varies in thickness from 0-018 to 0-030 mm. The cocoons are first placed, a few at a time, in basins of almost boiling water and are rubbed with a hand -brush of twigs, to which the tangled filaments covering the cocoons become attached. Among these filaments is that by which the cocoon can be completely unwound. The other filaments form the floss, which is worked up with the other waste (see above). Five (or more) of the threads are attached to a reel, which revolves rapidly and completely unwinds the cocoons. The latter float in hot water, which softens and dissolves part of the gum uniting the threads, while the remainder of the gum dries again on the reeled silk, joining the five threads to a single filament constituting raw silk. As one cocoon is finished, it is replaced immediately by another so as to form a homogeneous thread. The chrysalides remaining form about 70 per cent, of tho weight of the fresh cocoons and contain 22 to 26 per cent, of oil (fetid) they are generally defatted and sold as nitrogenous fertiliser (for hemp, etc.) at 13s. or 14s-. per quintal. Cocoons which do not unwind regularly also pass into the waste. Good cocoons give as much as 800 metres of good silk and the count of the single thread varies from 1*5 to 4 denari according to the breed of silkworm the tenacity lies between 5 and 12 grms. and the elasticity between 80 and 150 mm. White or greenish yellow cocoons give white or almost white (Chinese) silk and the yellow ones golden-yellow silk. The following types of silk are distinguished commercially European* .Japanese, Chinese, Canton, Bengal, tweak (Chinese wild silk), and Indian tussah, and of each of
; : ; ; ; :

An

these there are various qualities. In the raw silk trade the variations of the count are indicated ; thus, first-quality silk from 8 to 10 denari is marked fa first-grade tussah of 40 to 45 denari, ^p, etc.). Tho price of tussah silk (]6s. to 24x. per kilo) is less than half that of fine European silk, but the prices vary from year to year. With Asiatic silk it is always stated whether spun in Europe or on tho spot ; the latter gives much more waste in the subsequent operations. Kaw silk threads are seldom made into textiles (then called raw silk) and real silk thread is obtained by joining two or more threads of raw silk and twisting them to form the tram silk or organsine. (warp) used in weaving. To this end the raw silk is first wound on bobbins, from which it passes through felted forks-Ft is then ready for twisting, which is carried out in to free it from down to other bobbins. different ways for train silk and for warp (organsine). For the latter the best silks are used, these being at once twisted from right to left, the product being known under different names according as the number of the twists per metre arc 244 to 440, 440 to 488, or 488 to 610. Tho twisted threads are then joined in twos, threes, or fours, the combined threads being twisted from left to right (or vice verm) 380 to 450 twists per metre for taffeta, 320 to 360 for satin, 550 to 560 for velvet, and 2200 to 3000 for Chinese crape. Before cluing or bleaching, the raw organsine is wtgmnmed or stri'jypedior about 30 minutes in boiling neutral soap solution (25 to 30 Fn order to remove the gum and to obtain a maximum per cent, of soap calculated on the silk). The baited silk weighs about lustre, a second boiling soap bath is used, and finally a third. 25 per cent, less than the original organsine. When the organsinc is to be dyed a pale or delicate colour, it is subjected to special treatment with sulphur or hydrogen peroxide (see Vol. I., pp. 267, tussah organsine (brownish) is only bleached with hydrogen peroxide. 278) In preparing tram silk the raw thread's are not immediately twisted, but are first joined in fives or tens (or more) and then twisted, but only with 80 to 125 twists per metre. The cleansing with soap is carried out at 35 and the colouring-matter is readily destroyed by immersion for 15 minutes in an aq\ia regia bath (2-5 to 3 Be.) at 20 to 25, and thorough washing with water. The white tram (so-called souple) has lost in these operations only 5 per cent, of its weight ; if it is to he dyed a pale tint it is then sulphured. When a more lustrous tram is required for obtaining special effects in textile design, it is subjected to boiling like the organsine. Silk Waste, including doupiorw (cocoons formed by two larvre in the same covering these cannot be unwound in the ordinary way), pierced cocoons, the waste from twisting (2-5 per cent, in Italian and 8 per cent, in Asiatic silks), stained (mouldy) cocoons, diseased cocoons, small or incomplete cocoons (from inert worms), silk tow, etc., constitutes 25 to 35 per cent, of the tota
;
I;

DYEINGOFSILK
was started in France, being introduced by
Italian immigrants.

815

The Arabs century it introduced it into Spain in the year 740. In 1443 Florence contained 84 large silk factories and in 1580 Milan began to acquire the ascendancy, but fell back later, to advance again in the middle of the nineteenth century. In 1804 Oomo had only 920 looms, which increased to 1800 in 1858, while Lyons possessed 10,000 looms as early as 1685, 40,000 in 1834, and 65,000 in 1852 (present conditions are indicated later).

Raw

silk consists of

60 to 70 per cent, of Fibroin (the fundamental constituent

and 25 to 35 per cent, of Sericin, which is the gum surrounding the threads and holding them together, and can be easily eliminated with hot water and soap or, partially, with hot water alone. (J 15 H2 Various formula) have been attributed to fibroin 6N5 (SchiitzenFrom the chemico-tintorial point berger), C 71 H 107 025N 24 (Bourgeois, 1875). of view, silk has the character of an aniino-acid (or of the corresponding internal anhydride), but its acid nature is more marked than that of wool. The decomposition of fibroin by means of hydrochloric acid gives glycocoll, aminopropionic acid, tyrosine, Z-leucine, and other amino-acids (B. Fischer). The formula J8 H 15 8N5 is ascribed to Sericin, which closely resembles It is thought by some fibroin, but gives large proportions of diamino-acids. that the silkworm contains only fibroin, and that at the moment when the
of pure silk)
:

thread

is

produced this

is

transformed superficially into sericin under the

influence of air and moisture. The yellow colour of certain to a natural colouring-matter, Carotin (Dubois* hydrocarbon).

raw

silk is

due

Under the microscope raw

silk

has the appearance of slightly flattened,

cylindrical, transparent threads, not very smooth on the surface-, and composed of two bave joined by the sericin (which can be distinguished from the inner art or fibroin) and thinly covered with an adhesive soluble in hot water and

5ifferent'from

sericin,

which dissolves only

in

hot soap solution.

In many rases the Dyeing of silk, especially with mordant dyestuffs, is similar to that of wool. Under all circumstances, however, the silk should bo thoroughly cleaned before dyeing, and as in spinning and weaving the silk is treated with dressing (soap emulsion, vaseline oil emulsion, soluble starch, etc.) to facilitate the operations and sometimes also
to increase the weight, both yarns and fabrics (even if white) are subjY^d to rapid cleansing with hot soap solution (80" to 85) containing a little sodium carbonate, and are then well rinsed in tepid water. 1 If the wares are to remain white, they are sulphured (see Note) or

treated with hydrogen peroxide solution, the characteristic rustle (swoop or mtckle) of silk being imparted by immersion in a 1 to 2 per cent, sulphuric or acetic acid bath, centrifu-

gation and drying without rinsing. Dyeing is in general carried out in soap baths, using one-third or one-fourth of the soap solution remaining after the boiling of the raw silk, acidifying it with sulphuric acid
crop of cocoons and often goes under the name of floss (sold before the war at 4*. to &r. per kilo ; It is worked very similarly to cotton and to woollen rags by real floss cost tte. to Is. per kilo). means of special carding and rombing machines, giving first a kind of wadding and then ribbons and threads with parallel iibres. These can bo converted into yarn culled rfatppr, which is consumed in large quantities as it costs less than one-half as much as pure silk and for some The waste from the carding and combing fabrics (velvets) is a good substitute for ordinary silk. In Italy a large company with seven works enjoys a of chappo is also spun, giving bourettc*. kind of monopoly in this trado ; they work up foreign waste and part of the native waste, the Italian Government imposing a small export duty which acts detrimentally against the spinner and forms a protective duty on foreign waste yarn. 1 It is generally necessary to ascertain, before dyeing, what will be the loss in weight of the White Italian silk loses on an average 21-5 per cent. ; silk during ungumming or stripping. .Japanese, 20 per cent. ; Canton and Chinese, 24 per cent. ; raw yellow Italian, 24 per cent. ; and chappe, 4 per cent. The loss, which includes also any weighting of tho yarn with vaseline, is manipulated in a solution soap, oils, glycerine, oto., is determined as follows 50 grins, of the silk of 15 grms. of seasoned Marseilles soap of good quality in a litre of hot water, which is allowed to boil gently for half an hour, and is then removed, pressed or centrifuged, boiled for a further period of 30 minutes in a soap bath similar to the first, and washed thoroughly with water until the Intter remains clear ; after being centrifuged, the silk is dried in an oven until of constant Tho loss of weight on stripping is referred to 100 grms. of dry silk, so that allowance freight. should be made for tho normal humidity (11 per cent.) of silk.
:

816
boiling

ORGANIC CHEMISTRY

and agitating. The silk is immersed in this emulsion for a time and then removed, the bath being diluted with water and the colouring-matter (aeid or basic) ; the dyeing is begun at 35 to 40, the temperature being gradually raised almost to the boiling-point. Acid colouring-matters are fixed by silk also from a hot acidified aqueous solution, but the tints are not so lasting. The dyed silk is rinsed in water and transferred to the acid bath to obtain the crackle, which becomes more pronounced as the acidity and temperature of the bath are raised, hut the acid remaining in the dry fibre slowly attacks it, with injury to its tenacity and elasticity. Nowadays silk is usually weighted, i.e., impregnated with various substances (organic and inorganic), in order to increase its weight (by 30 to 40 per cent, and sometimes, with black silk, even by 300 per cent, or more). Silk possesses, indeed, the property of absorbing
from solution large quantities of tannin tannin can then be absorbed, and so on.
(tin salts,
silk,
;

this can

be fixed by means of

salts,

and

fresh

Successive amounts of insoluble metallic salts

phosphates, silicates, etc.) nmy also be precipitated on silk. To weight white the boiled silk is soaked for an hour in a stannic chloride bath of 25 to 30 Be. (at one time pink salt, Sn01 ,2NH 4 Cl (see. Vol. I., p. 781) was largely used, but at the present time, crystallised tin salt, SnCl 4 ,.5H 2 O, is mostly employed), manipulated for 30 to 40 n minutes in a hot disodium phosphate bath (4 to 5 Be.) washed slightly with water, introduced into a sodium silicate bath (3 to 4" Be.) and again washed. Treatment with this series of baths (stannic chloride, phosphate, and silicate) is repeated several times, according to the degree of weighting desired ; five such repetitions give a weighting of 100 1 to 120 per cent, (the weight being doubled). Weighted silk can be dyed, and in the pret
1

insoluble in acid and in subscqiient stannic chloride baths. Boiling or treatment, with a soap bath of washed silk containing Sn() 2 ,2H 2 <) results in the separalion, in a firmly fixed condition, of the hydrate Sn 4 () 2 ,H 2 (), i.e., Sn 4 O(()H) 2 , which has, however, but little affinity for phosphates and silicates ((Tianoli, 1907). Weighting with stannic chloride gives a regular increase of 10 to 12 per cent, in the weight for each separate operation on the same silk. Jn Aveighting with tin phosphate (after the chloride bath, the silk is passed into a hot disodium phosphate bath and then washed thoroughly with water, the operation being repeated if necessary), the first operation gives an increase of about 20 per cent., but subsequent operations produce larger increases ; the third may give as much as 35 per cent. Silk alone has no afiinity for salts of polybasic acids (phosphoric, tungstic, etc.), but if it is first passed > into a tin salt bath jt fixes them, for example, as Sn() 2 ,Na 2 W<) 4 or Nii() 8 , Na 8 llL () 4 (sodium phosphostannate, insoluble in water but solubje in concentrated sodium phospliate solution) ; only phosphates containing hydroxyl groups are fixed by tin, so that trisodium phosphate and sodium pyrophosphate are not fixed. If the sodium carbonate bath follows the chloride bath, Treatment of the silk in the- acid bath results in less sodium phosphate is subsequently fixed. the removal of the nthnle or a good part of the sodium. When the silk has been treated in the first sodium phosphostannate bath, it is washed and introduced a second time into the stannic chloride bath, the double decomposition thus produced resulting in the formation of insoluble phosphate of tin, which is fixed on the fibre, and of sodium chloride, which passes into the bath while at the same time the silk becomes impregnated anew with Sn('l 4 this fixing tin hydroxide on the fibre when the latter is w ashed. This tin hydroxide gives fresh sodium phosphostannato when introduced into a second disodium phosphate bath, while the bath, which becomes impoverished in soda, continually increases in acidity and the weighting of the silk increases during successive operations. silk i& introduced into one /Still higher weighting is obtained if the sodium
I

The weightings which have given the best results in practice (2) tin phosphate (3) tin hydroxide (used as early as 1809 in a Lyons dyeworks) Sislcy (181)0) showed, and Fraiickel (4) tin and aluminium silicophosphates. silicophosphate and Fasal (1897) and Severini (1000) confirmed, that weighting is due purely to a physical and not to a chemical phenomenon, since the weighting bath undergoes no chemical change and no alteration in concentration. Further, when silk soaked in stannic, chloride is washed with water, the precipitated stannic hydro\ide which is formed in abundance as a result of hydrolysis is not fixed by the silk and is derived from the chloride on the surface of the thread, that absorbed inside the fibre remaining as a kind of colloidal solution of stannic hydroxide in hydrochloricacid the acid diffuses into the fibre, which retains it, whilst the stannic hydroxide is fixed as a gel and does not influence the feel and lustre of the silk. The absorption of stannic chloride In 12 hours silk which has absorbed is avoided if the silk is previously treated with tannin. 11 per cent, of tannin fixes from a stannic chloride bath of 30" Be., only 1-25 per cent, of Sn() 2 these different while silk without tannin fixes about 12 per cent, of Sn<) 2 from the same bath AVhcii washed, the stannic hydroxide silks also take up varying quantities of colouring-matters. formed on the fibre is Sn(OH) t or Sn() 2 ,2H 2 (), retaining small amounts of H(1; the washed silk is therefore introduced into a bath of sodium carbonate, which forms a labile compound of Na a CO and SnO 2 ,2H 2 O, this being decomposed by acid with formation of a, tin hydroxide ?
and dyeing- and are not dyed.
are
:

of irrightiny is explained, according to Sisley (1011), by regarding silk 100), which absorbs hydrogcls (e.g., stannie^of various wilts of polybasie acids, but many substances which give precipitates and insoluble salts do not serve for \\eighiing, since they are iiot firmly retained by the silk iibrc and are therefore eliminated during washing

The phenomenon

as a colloid

(w Vol. L, p.

(1) tin

phosphostannate

WEIGHTING OF SILK
paration of black silk, the weighting

817

may be increased considerably by passing the weighted white silk (washed with a little soda) into a cold bath of ferrugine (a slightly acid solution of basic ferric sulphate prepared by heating a solution of ferrous sulphate with sulphuric and nitric acids), slightly washing the silk thus coated with oxide of iron and immersing it in a bath of potassium ferrocyanide (acidified with HC1) which colours it blue. It is then placed in an almost boiling tannin bath (e.g., chestnut extract), next in a tin bath to fix the tannin, and finally in a hot bath of logwood extract to obtain an intense blark tint ; the dyed silk is rinsed in soap solution or an acidified oily emulsion, livened in a sulphuric acid bath, centrifuged and dried. By repeating the tannin and metallic baths ten or fifteen times, weighting of 300 to 400 per cent, may be obtained. Black silk weighted to the extent of 400 per cent, and partly attacked shows under the microscope a heavy incrustation round the fibre (Fig. 487) ; much of its strength has been destroyed, and under the aetioti of sunlight it undergoes rapid corrosion (umbrellas of heavily weighted black (). Meister at silk split even without using). Zurich (1002) and independently (*. (lianoli at Milan (1904 Or. Pat. 103,622) found that Fra 487 this inconvenience can be largely avoided by means of a thiocyanate bath, hi 1006 the Societa della stagionatura della seta di Milano (as a result of investigations of Sisley at Lyons and of (Jianoli and Colombo) filed a patent in America for the preservation of weighted silk by introducing it in a bath of thiourea faintly acidified with citric acid; U.S. Pat. 873,002, was granted in February, 1008, and 1 O. Meister ( 1 010) suggests the use of formaldeappears to give excellent results in practice*.
;

or several more or loss concentrated and more or less hot sodium silicate baths. By this means pirt of the phosphate residue united to the tin oxide is replaced by silica, the compound 3Si() 2 ,Na 2 (),Sn() 2 being formed; the silicate bath becomes acid and contains trisodium In the acid bath, this silk readily loses sodium, being formed of insoluble tin phosphate. trisihcMte. This weighting was patented by Neuhaus in 1803, but had been previously used in France.
,

The highest weighting of silk is obtained by following repeated phosphate baths with a bath an alum salt, as was proposed by Puller (('.'refeld) (Fr. Pat. 254,(>59 of 1006). In this way the aluminium is fixed as phosphate and a little sodium passes into solution. After washing this silk is passed into a sodium silicate bath and has the property of fixing much more silica than in the case described by Ncuhaus further, the silk loses practically nothing in the acid bath, since the sodium of the tin silicophosphate has been replaced by aluminium. Nicollo and Sisley (1011) found that various other salts may be used in place of those of aluminium, but that only those of zinc gave good results in practice. This general theory of Sisley on the phenomenon of weighting of silk is not universally P. Heermaim (1904r- 101 1) holds that \\ Idle the silk is immersed in the stannic chloride accepted. bath the latter diminishes in concentration, and part of the tin remains fixed even when the silk is washed with water he also regards the formula1 of the salts fixed on the silk as different from
of
; ;

those given by Sisley. J In determining the iwigliling of N ilk 2 grms. is boiled for two hours in a soap bath (30 grrns. soap per litre) and then for at least an hour (to expel the ammonia) in a sodium carbonate bath at 1-5 lie., the water evaporated being gradually replaced. It is then rinsed well with water and dried and the nitrogen in 0-H to 0-8 grm. determined (as was suggested by St. Claire Deville in 1878) by Kjeldahl's method (we p. 1 1) from this the quantity of true fibroin can be determined, knowing that 5-455 parts of fibroin correspond with 1 part of nitrogen. With black silk containing cyanide (Prussian blue), the latter must be previously eliminated. In order that the fibroin may 2 grms. of the fabric be acted on as little as possible, P. Sisley (1007) separates it as follows is boiled for 10 minutes in 25 per cent, acetic acid, cashed, heated for 10 minutes at 50 in a 3 per cent, sodium phosphate (Na 3 PO 4 ,12H 2 O) solution, washed again, and boiled for 20 minutes in a bath containing 3 per cent, of soap and 0-2 per cent, of soda ; this procedure is repeated, the tissue being washed and dried and its nitrogen -content determined. Tho percentage - c )/r, where g weighting p (the increase in weight of the original silk) is given by /> == 100(r/ indicates the weight of the dyed silk while r represents that of the raw silk (i.e., fibroin -j- sericiii -f11 per cent, moisture) or fibroin normal loss on stripping (21-5 or 24 per cent. ; see preceding Note). A silk is said to be weighted 50 per cent, when 1000 grms. of raw silk give 1500 grms.
; :
-

of

dyed

silk.

During recent years, another simple method has been used for determining the ordinary tin silicophosphate* weighting : 2 grms. of weighted silk of known moisture content (e.g., 10 per cent.) is treated for an hour in a platinum dish with 100 c.c. of a cold aqueous 2 per cent, hydrofluoric acid solution ; the latter is poured away and another 100 c.c. of the acid added and left in contact with the silk for an hour. The silk is washed seven times with successive amounts of 150 e.c. of water, pressed, and dried at 100 to 105 until of constant weight. If the latter is 0-95, then 2 grins, of moist silk -= 1*8 grm. 0-85 0-95 dry silk, and J-8 (weighting).

818
hyde bisulphite

ORGANIC CHEMISTRY

(1 to 5 per cent, bath) to check this corrosion, while Berg and Janhoff (1911) prefer the use of hydoxylamine. The use of a diastofor bath (see p. 140) after dyeing has also been proposed. Silk weighted with ZnCl 2 is preserve I in a thiosulphate bath

(Herzig, 1908).

STATISTICS. The world's production of raw silk (excluding the local consumption of the Far East, this being valued at about 55,000 quintals for China and 47,000 for Japan, in 1906, and about one-third more in 1907) is shown in quintals by the following Table (the pre-war value of raw Italian silk may bo taken as 32s. to 36s. per kilo)
:

increases in 1904.

In China the Exportation of real silk tends to diminish, but that of wild silk (or tussah) this is produced by Anterea mylitta and is readily recognised under the micro1,325,000 in 1903, and 2,000,000 scope (Fig. 488). China exported 1,260,000 kilos in 1900
;
;

To the quantity of raw silk produced in Italy from home-grown cocoons must be added 7320 in that obtained from cocoons imported from abroad, viz., 3000 quintals in 1893 1898; 11,000 in 1903, and 13,000 in 1906. The mean annual importation from 1901 to 1905 of cocoons (calculated dry) was 37,736 quintals (46,000 in 1906) with a mean yield of
;

Hence, if the raw silk is calculated to lose 24 per cent, oil stripping, the weighting will bo 76 x (76 is the percentage of silk remaining after stripping) and * ^- 08 ; hence 0-95 0-85 the dyed dry silk contains 76 parts of dry stripped silk (or 100 of raw silk) and 68 of weighting, The silk was hence weighted 44 per cent, (lianoli and Colombo (1907) snowed, total 144. however, that in some cases when metastannie acid is formed on the iibre, e.g., by the fixation of tin salts with sodium carbonate, the whole of the weighting is not eliminated by hydrofluoric more certain result is then obtained by acid, even when this is followed by a bath of HC1. the old method (see above) or by using first soda and then potassium hydrogen oxalate. P. Heermann (1909) proposes to modify the alternate treatment with hydrochloric acid and caustic potash (Ristenpart, 1908) of black on tin salt and catechu, by replacing the caustic potash with a solution of normal caustic potash and concentrated glycerine (28 Be.) in equal parts, the latter preserving the silk, readily dissolving Vrussian blue (by treatment for an hour in the cold or 10 minutes at 80"), but leaving the oxide and tannate of iron unchanged. 1 In Japan a second crop of cocoons (bivoltino) is gathered in summer, and a third (trivoltine) in autumn. About 60 per cent, of the total crop is obtained in the spring, 12 per cent, in tho summer, and 28 per cent, in the autumn. Japan also produces a considerable amount of green wild silk- -of Kvmbyx yamamai, which feeds on chestnut and oak leaves (the wild silkworm of India eats castor oil leaves).
:
:

SILK STATISTICS
]

819

kilo of silk per

kilos of

dry cocoons (at

7,9.

to 9s. 6d. per kilo) or per 11-5 kilos of fresh

cocoons. To the 50,000 quintals of raw silk yarn produced in Italy must be added 24,000 quintals of silk simply treated aiifl imported from the Far East to be spun and twisted, but only about 10,000 quintals are woven in Italy, the rest being exported (50,000 quintals, besides 39,000 of twisted).

The Italian weaving industry is capable of considerable extension, its produce being valued at only 3,200,000, while Switzerland 1 (with 35,000 looms) produces silk fabrics to the value of 5,600,000, France 3 (with 140,000 looms) 19,600,000 England about 13,600,000 (importing 8,800,000) with 87,000 looms, and about the same for Germany. If Italy were to weave the 8,000,000 worth of yarn which it exports, the value would be increased to 16,000,000 (a kilo of fabric? costs about double as much as a kilo of yarn) while 200,000 more workpeople would ho employed. The Italian silk industry has passed through various crises, not on account of excessive production since working on stock is not usual with silk articles and the demand is often greater than the supply but owing to various circumstances, not the least among which are the
;

tariffs raised

against Italy as retaliation for the protection of many by the tariff of July, 1887. Tho most acute crises of the Italian silk industry were those of 1893 and 1903, which were the
Italian industries

cause of numerous financial disasters, and that of 1907 1908, the effects of which are still felt, and which resulted from tho groat American
crisis

Fw.

488.

and is now being aggravated by French and Japanese competition. The quinquennial average price of raw Italian silk fell gradually from 62-1*. per kilo in 1876-1880 to 38-ls. in 1901-1905, mainly owing to increase in the world's production (see Table, In 1906 and 1907 a rise in price of raw silk occurred thus, that of organsine p. 818). sublime (count -J JJ) was 40,s. per kilo at the end of 190*5, and rose to 49,s. 6rf. towards the end of 1906 and to 60s. 6rZ. in August, 1907, after which a *all took place owing to the American
;

crisis.

Silk-twisting in Italy in 1910 employed 800,000 spindles (four- fifths in Lombardy and the remainder in Piedmont), which produced 4,500,000 kilos of organsine and tram, about

one-half from imported raw silk. 1 Switzerland has two very important centres at Zurich and Basic, where the output of silk goods is continually increasing, although the production of cocoons is gradually diminishing fn the canton of Ticino, where the silkworm is reared, the cocoons produced have diminished from 187,500 kilos in 1872 to 58,000 in 1901, while there has been a corresponding increase in the importation of raw silk from China, Japan, and Italy. Tho importation rose from 514,400 kilos in 1893 to 037,000 (worth 960,000) in 1902, but ubput one-third of this, after being twisted in the iSwiss factories, is exported to Germany, Russia, and Italy. In the canton of Zurich alone in 1900 there were at work about 21,000 hand-looms and 13,330 power-looms for silk and mixed
silk fabrics.

The Swiss exports of pure silk tissues in 1893 were 906,700 kilos (2,506,100), those of mixed tissues being valued at 580,000. In 1903 the exports of silk fabrics were 1,760,300 kilos, worth 3,780,000, while the total imports in the same year were 149,000 kilos (330,800) of silk fabrics and also mixed fabrics to the value of 112,000. One-half of the exports goes to England. The silk ribbon and embroidery industry of Switzerland is steadily advancing. Germany is a largo importer of raw silk (about 3,000,000 kilos, largely Italian), and, besides supplying home demands, exports considerable quantities of manufactured goods (ser Table later). Russia consumes about 1,500,000 kilos of raw silk annually. 2 None the less interesting is the condition of affairs in France, although the production of fresh cocoons is only 8,000,000 kilos ( 1905). The, imports of raw silk are^-alculated to be about 9,000,000 kilos, and the silk industry (almost entirely concentrated in the city of Lyons) occupies one of the foremost positions among .French industries. The province of Lyons contains more than 25,000 power-looms for silk-weaving, in addition to a larger number of hand-looms. In order to reduce the importation of raw silk and increase that of cocoons, and so encourage the direct spinning of the latter, the French Government in 1892 offered a premium of 16 for every new four-threaded basin established, but the results did not come up to expectations. While in 1893 the production of silk goods was valued at 15,150,000, in 1902 it reached The French exportation of silk wares of all kinds amounted in 1896 to 4,220,000 17,800,000. kilos, worth about 10,000,000, while in 1904 it rose to 5,700,000 kilos, of the value of 13,200,000
(including about 1,200,000 worth despatched by parcel post). The value of the products woven in Lyons in 1904 was 16,360,000, in 1905 15,040,000, and in 1906 17,040,000. In tho department of Saint-Etiemio the output of silk ribbon in 1906 was valued at 3,760,000, one-third of it for export. The French home consumption of silk wares is about 4,000,000 kilos, this large amount helping considerably to maintain the silk industry in an active condition.

820
The
silk-waste

ORGANIC CHEMISTRY
which was produced in Italy in 1910 (and was exported to the extent was worked up in Italy) amounted altogether to 5,300,000
500,000.

of two-fifths while the remainder

kilos of the value of
Silk,

carded and combed in Italy, amounts to about 1,500,000 kilos and the chappe yarn to almost 900,000 kilos, of which 200,000 kilos are consumed in Italy and the rest Six thousand workpeople are employed in the treatment of waste, the ten exported. establishments in this trade containing about 80,000 spindles in 1912. During the past twenty-five years the silk weaving industry has become of considerable importance in the United States, where raw silk is almost f-ee from customs duty, while the manufactured products (yarn and fabric) are very heavily taxed. These conditions, have led to the rapid development of American spinning and weaving. 1 The importation of raw silk into the United States shows continuous and rapid increase, the annual averages being: 1881-1885, 15,300 quintals ; 1886-1890,23,100; 1891-1895,31,300; 1896-1900, 43,500; 1901-1905, 65,300 quintals, which is about one-third of the world's production (excluding the local consumption of the Far East). The countries with large outputs of cocoons are not always large con,-!ners of silk wares, while in general large consumers are not producers. Italy has a total iiitei nal consumption of 6500 to 7500 quintals of silk articles, and the relation between home consumption and exportation for the principal countries in 1899 was as follows
:

Homo
consumption. IVr rent.

Export*
J'or rout.

Homo
cotiHiiniption.

Export*
IVr rent.

IVrrent.

France

61

Germany
Austria
Italy
.

60
88-5

39 40
12-5

Switzerland

United States China

.

20

80

Japan

5 95 -100 about 50 50

95 5 about 50 50

As regards the quantity of raw silk passing through their conditioning establishments, the two principal silk markets in tho world arc Lyons and Milan, which together receive about two-thirds of all the silk conditioned in Europe, the separate amounts being as
follow
:

1881 1890 1900 1903 1905 1906 1908

..... ..... ..... ..... ..... ..... .....

;

Milan

LyoiH
.. ..

36,652

43,477
72,335 83,725
94,391 101,484

53,480 44,072
60,418 66,508

..
.. .. .. ..

70,102 71,719
73,728

95,293

In 1908 13,186 quintals arrived at Lyons from Europe, 7561 from the Levant, and and at Milan, 67,187 quintals from Europe, 1477 from the 50,000 from the Far East Levant, and 36,530 from the Far East. During recent years Milan has lost ground compared with Lyons. SEA SILK (Ryfiws) is found in tufts protruding from the shells of a mollusc (Pitinus

The protective duty on manufactured wares was 50 per cent, ad aalorem in 1883, while it In 1882 there were only 8000 power-looms rose to 75 per cent, in 1897, and later to 90 per cent. (including 2500 for ribbon) and 3100 hand-looms for silk in the United States, while in 1901 the and that of hand-looms was reduced to 800. number of power-looms was 52,000 (7000 for ribbon) In the same period the number of spindles for twisting and spinning increased from 450,000 to The output of silk gloves was 2000 dozens in 1887 and more than 180,000 dozens 1,900,000. (200,000) in 1901. The production of silk articles increased sixtyfold during the latter half of the nineteenth century. The output in America is, however, not equal to the consumption, the proportion between them being 67-3 per cent, for silk fabrics, 85 per cent, for ribbons, and 53 per cent, for velvet. In 1901 the United States imported silk wares to the value of 5,700,000, later diminished 'to 3,200,00043 per cent, from France, 18 per cent, from .Japan, 17 per cent, from Germany, and The American Government have several times, by otfcring 16 per cent, from Switzerland. prizes, attempted to initiate the cultivation of mulberries and the rearing of silkworms, but with poor success, probably because skilled agricultural labour is lacking and is not easy to form rapidly, and also because labour is expensive. The attempts which have been made in the Argentine have been somewhat more successful but not altogether satisfactory. To the 800,000 mulberry-trees planted during the course of 20 years, 4,000,000 have been added during the past four years, and in 1907 the crop of cocoons
1

was 250

quintals,

ARTIFICIAL SILK

821

nobilis), 30 to 40 cm. long and 15 to 20 cm. bioad, attached to the rocks of the Red Sea and the Mediterranean (Sicily, Sardinia, Elba). It has a pale golden, more or less brownish colour, and sometimes shows greenish reflection. After being washed with soap and water and dried in the shade, it is combed and spun like other textile fibres. Although sometimes

regarded as an abundant product, it is in reality rare, at least in Italy, and figures rather in museums than on the market. ARTIFICIAL SILK is the inaccurate name given to the product which has been for some time on the market in competition with natural silk. There is, indeed, no chemical relation between the two products. In place of the fibroin and sericin produced by Bombyx mori, the new silvery thread contains merely cellulose, as is the case with so many other vegetable products. It has, however, the lustrous appearance of natural silk and only by 1 reason of this property does it compete with the latter. The struggle between the natural and the artificial product has scarcely begun and it is not easy to foretell within what time and what limits the one or the other will t e victorious. We are certainly on the eve of neither a serious convulsion in the agricultural industry nor the disappearance of the mulberry and silkworm, but it may be affirmed that artificial silk has established a position in the making of certain fabrics formerly obtained solely from the natural product. The new artificial fibre has still, however, many defects which limit its use, for the, present, to definite branches of the textile industry, and time is thus given to the producers of natural silk to repair the grave error, committed in the past, of spoiling their valuable

product by excessive weighting, and HO injuring its sale. The first beneficial effect of the appearance of artificial silk should hence be t9 bring the silk industry to the sound basis on which it was built, and which would enable it to withstand any artificial competitor for many years to come. The prime material for the preparation of artificial silk is cellulose, that remarkable subbut so complex stance which has so simple a composition carbon, hydrogen, and oxygen and highly polymerised a molecule (see p. 51)8), and already yields so many most important industrial products from mercerised cotton to celluloid and pegamoid, from guncotton to collodion, from explosive, smokeless gelatines to alcohol, and finally to artificial
silk.
2

struggle between the various types of market has resulted in victory for viscose silk,

The

artificial silk

this,

which have been placed on the owing especially to its low cost, having
from
cellulose,

practically displaced all others. Of the hundreds of patented processes for preparing artificial silk 1 are of no practical importance and but few require mention/

most

1 As early Artificial silk, although of recent preparation, has already an interesting history. as 173-1 Reaumur foresaw the possibility of preparing lustrous fibres, similar to silk, from gummy or adhesive substances, and in 1885 Audemars (of Lausanne) attempted but with imperfect suet-ess to put Reaumur's idea into practice. Expectation of success in the solution of this important problem arose only later when it was found possible to prepare slender collodion fibres for the manufacture of the carbon filaments In 1885 Count Hilaire He Chardonnet of Besancon, then a of incandescence electric lamps. student at the Paris Polytechnic, filed a patent for the manufacture of artificial silk by spinning collodion solutions, and at the Paris Exhibition of 1889 he showed his iirst machine working. Swan, in London, had previously obtained fibres of artificial silk, but these were without practical

industrial results. a When cellulose

the is in the form of wood for fuel, 1 cu. metre cost (pre-war) about (w. same cubic metre of wood, when boiled with lime, soda, and sulphite gives a paper pulp worth about 32*. and yielding paper valued at 5(>s\, or more. If this pulp is transformed into artificial
;

silk, its

value

may

be as high as

80 to

240, according to the articles prepared (artificial hair

and
3

silk, cellulose acetate).

the dcnitration of collodion cotton previously dissolved (1) Nitrocellulose #i7X*, obtained by mixture of alcohol and ether and then reduced to very fine fibres by means of special spinning machinery (de Chardonnet, Lehner, Viviers). In 1891 de Chardonnet formed a company at Besancon with a capital of 240,000, for the manufacture of this new product on a large scale, but for some years de Chardonnet silk could not be used, as it was composed of nitrocellulose, and hence highly dangerous to the wearer and to warehouses in which it was stored, owing to its inflammability. Attempts to render the silk harmless by the addition of various substances proved futile, and the problem was solved subsein a

way it burns almost like other cotton. After denitration, hydrated oxycellulose remains. To obt^iirtJhardormct silk, collodion-cotton is prepared in the way described in the section

822
VISCOSE SILK.

ORGANIC CHEMISTRY
;

In 1892 (Eng. Pat. 8700 Ger. Pat. 70 ,999, of Jan. 13, 1893) E. J. Bevan, 0. F. Cross and G. Beadle, by treating ordinary paper cellulose with caustic soda
on Explosives (pp. 286, 294), and after elimination of the acid by thorough washing, the cotton pressed hydraulically or ceiitrifuged to reduce the moisture-content to 25 to 30 per cent. In this condition it is dissolved in 5 to 10 times its weight of a mixture of 3 parts of ether and 2 of alcohol, with which it is shaken for a couple of hours in revolving iron drums do Chardonnet first prepared solutions of collodion with dried nitrocellulose, but found later (Ger. Pat. 16,932, 1910) that moist nitrocellulose also dissolves in alcohol and ether, avoiding the danger of drying and also giving a more homogeneous fibre. If a little mineral acid is added to the collodion solution (Lehner) the mass becomes much more fluid and requires less pressure for spinning [according to Kng. Pat. 16,932 of 1910, acetylene tetraehloride (see p. 122) is an excellent solvent for nitrocellulose]. The dense collodion solution is passed under a pressure of 40 atmos. through a cotton- wool filter, then left for a couple of days for the air-bubbles to escape, and finally forced first through cotton- wool and then through capillary glass tubes having a bore of 0-2 to 0-08 mm., under a pressure of 60 to 80 atmos. The slender threads issuing from the capillary tubes under pressure and in a closed-in machine, through which a current of air passes to carry off the alcohol and ether vapour (recovered as described in Note, p. 231), are united in a number varying from 6 to 20, and under a water-jet are wound on glass spools in a coagulated condition, but still somewhat adhesive owing to the moisture left in the nitrocellulose. After a short time on these spools the fibre solidifies comIt is then combined, pletely and can be manipulated without danger of the filaments adhering. twisted, and reeled in the same way as silk. Denitration is effected by treating the moist skeins with hydrosulphides of calcium (0-4 to 0-5 per cent, solution) or magnesium, or, better, with dilute sodium sulphide solution for three
is
;

B
crossed (Pauly) fibres ; .tf, striation ; 6, air-bubbles ; </, fine transverse at nations ; J1, sections
d, sign of

FIG. 489.

FIG.

490.
;

(Chardonnet)
sections of fibres.

a,

bubbles

J5,

of

fi

bres.

to four hours in the cold. The dcnitration must be carried out with great care since otherwise can be In practice all but 0-05 per cent, of irregular stria tions are obtained on dyeing. eliminated ; this small amount of nitrogen is detectable by the diphenylamine reaction (Vol. 1., p. 234, footnote), and thus allows of the distinction of this artificial silk from other silks, both artificial and natural. Artificial silks may also be distinguished from natural silk by microscopic

examination (SRC, Figs. 489, 490). In 1921 the most important factory in Europe making Ohardonnet silk was that of Tubizo (Belgium), with a production of more than 3000 kilos per day. It is possible that this works may continue to flourish, as it produces excellent silk, especially for weaving, and also fine yarns further, its plant is written (50 denari, whereas 1 20 denari is a common count for viscose silk) If, however, the off, it has cheap alcohol and ether at its disposal, and it obtains high prices. latter fell, it could not survive. (2) (ilanzstoff, prepared by passing hydrocellulose (mercerised cotton) dissolved in ammoniacal copper oxide solution, through very line capillary glass tubes so as to obtain after complete coagulation in a bath of sulphuric acid at 16 to 20 Be. or one of 5 per cent, caustic soda filaments so slender that 225,000 metres do not weigh 1 kilo (Pauly or Fremery and Urban
;

silk).

patent for this process was that of Despeissis in 1890, but this was not renewed The process was improved and rendered practicable by Pauly, Bronnert, Fremery, and Urban, and the manufacture was undertaken by the Vereinigten-Glanzstoff Fabriken of Elberfeld. Well defatted, bleached cotton waste is lixiviated with sodium carbonate and hydroxide in an autoclave for 3 to 4 hours, rinsed, bleached with cold hypochlorite The mass is then treated with concentrated caustic solution, well washed and centrifuged.

The

first

in a year's time.

VISCOSE SILK
1

823

C 6 H 10 O 5 + 2NaOH + CS 2 = H 2 + NaS CS or sodio-cellulose dithiocarbonate C H 9 O 4 NaOH, the composition of wjiich is analogous to that of sodium xanthate formed when sodium alkoxide is treated with CS 3 OS 2 -}- 2 H5 ONa = NaS OS OC2 H 6
:
fl :

dissolving in carbon disulphide, obtained a (which produces sodio-cellulose), dense, viscous, orange-yellow solution of cellulose sodioxanthate or sodio-cellulose xanthate

and then

but the molecule gradually polymerises and peonies continually poorer in sulphur owing to the separation of the complexes S SNa and the formation of more and more highly condensed mole*
:

In alkaline solution

this substance constitutes the so-called viscose,

cules,

NaS CS O(C 6 H 9 O4 2 OH, NaS CS 0(C

)

H9

4 )3

(OH) 2 NaS CS O(C 6 H 9

-

4 )4

(OH) 3 ,

(Ger. Pat. 187,369 of 1904; 92,590 of 1896, and Fr. Pat. 2 After 24 hours 334,636 of 1904). This process is the so-called maturation of the viscose. at 15 the cellulose complex C 12 ... is formed and the viscose is soluble in water; after and the viscose is then soluble no longer in 6 to 7 days the complex becomes C^
.
.

and even higher polymerides

water but only in excess of alkali, and is readily coagulable on neutralisation with dilute acid ; with less dilute acid or after the lapse of a longer time the viscose decomposes giving These last changes occur readily and rapidly during the insoluble cellulose hydrate. spinning process, so that there remains finally a slender thread of lustrous cellulose, moderately strong and elastic. During the coagulation (see later) of the filament, the impurities remain dissolved and are eliminated.
.

(Ger. Pat. 108,511 of 1898) used a solution of an ammonium Numerous mixtures of salts were subsequently patented, salt, particularly the chloride. the problem being solved by the use of more or less acid solutions of sodium sulphate or

For the coagulation, Stcarn

soda to mercerise

ammuniacal

it and form sodio-cellulose, which is more soluble than cellulose in the cuproThe latter is prepared liquid (0 to 7 kilos of* cotton per 100 litres of solution). beforehand in large tanks (in cellars) containing scrap copper and concentrated ammonia solution kept in circulation by a pump which also injects air until each litre of solution contains about 15 grms. of dissolved copper. 'In this liquid, stirred now and then, cellulose dissolves in six to eight days, the solubility increasing as the amount of copper present increases and as the and 4). As soon as the cellulose has dissolved and the mass temperature is lowered (between become dense and stringy it must be filtered under pressure, since if this is delayed two or three days the cellulose begins to undergo depolymerisation (especially in a warm place), and the mass loses its viscosity, with the result that the silk obtained is of poor quality, irregular and weak. Spinning follows closely on filtration. The threads from the capillary glass tubes were at one time coagulated by passing them into sulphuric acid of about 20 Be., but there is then danger of weakening of the fibre owing to excessive hydra tion, which is facilitated by the rise of temperature caused by the neutralisation of the ammonia. On this account it is now preferred to produce coagulation by means of 5 per cent, caustic soda, this giving a softer and more lustrous silk from which a very weak sulphuric acid bath readily eliminates the traces of copper hydrate precipitated by the soda. According to Ger. Pat. 221,041 (1908) coagulation with alkaline or solution sulphite bisulphite appears advantageous. Glanzstoff competed for some years with nitrocellulose silk, but it has now succumbed in favour of viscose silk, which is cheaper and possibly superior.

(3) The silk prepared from cellulose, acetata by Cross and Bevan seems to be free from the defects mentioned above and to be superior to all other artificial silks in its strength, which is equal to that of natural silk. The manufacture of this was started some years ago by Count Donnersmark, using acetic anhydride and chloroform, but it is too costly to compete with other Excellent solvents for silks, arid is dyed only in dilute alcoholic solutions (Ger. Pat. 152,432). cellulose acetate have been found in tetrachloroethane and formic acid (Ger. Pat. 237,718 of 1907). (4) Millar and Hummers Vandiira &ilk t obtained from gelatine solution and now from casein
is

not used practically.

(5) K. Hofmann (Ger. Pat. 227,198 of 1909) obtains artificial silk and also hair and films dissolving cellulose at 220 in a mixture of concentrated phosphoric and acetic acids, and then precipitating with water or salt or alkali solution. (6) According to a Dutch patent of 1911 (No. 431,052), part of the casein suited to the manufacture can be separated by precipitating the unsuitable casein (which gives brittle products) from skim-milk by means of sodium pyrophosphate solution (3 grms. of the salt per litre of milk). From the decanted liquid, the soluble part of the casein is then precipitated by means of dilute acid. This precipitate is pressed, dissolved in a little dilute ammonia, filtered, reprecipitated

by

insoluble

with acid, again pressed, rendered plastic with a little ammonia, and spun ; the thread is rendered by means of dilute formaldehyde solution. 1 Treatment of cellulose with a solution containing more than 12 per cent, of NaOH gives sodio-cellulose in the ratio (C H 10 O 5 ) 2 2NaOH, which is decomposed by excess of water, giving cellulose hydrate and caustic soda if the sodio-cellulose is treated with absolute alcohol, 1 molecule of the alkali separates, leaving semisodio-cellulose, (C 6 10 5 ) 2 ,NaOH. 2 That the sodium atoms of the sodio-cellulose take part in the formation of viscose is shown by the fact that the sodium atoms of viscose may be eliminated by treatment with iodine solution, in accordance with the equation
:

2NaS CS 0(C 6 H 9

4)W

1,

2NaI

(C e

H O4
9

n -0

824
which gave a

ORGANIC CHEMISTRY

bisulphate (Miiller, Cer. Pat. 187,947, 1905). Later patents improved Miiller's solution, silk of poor lustre, owing to its excessive acidity (up to 20 per cent, of free

acid). The acidity necessary to produce coagulation is 1 to 5 per cent., and the greater or less rapidity of the insolubilisation depends on the quantity of sulphate, the duration of

the action, and the temperature, these factors also affecting the lustre and the stickiness of the fibres (Ger. Pat. 267,731, 1911; 287,955, 1912; Fr. Pat. 449,563, 1912, etc.).

In general, the acidity must be less than that of the bisulphafoe. The presence of glucose in the spinning bath is also advantageous. The industrial manufacture of viscose silk is now carried out approximately as follows Cellulose in sheets, as used in making paper (see p. 605), 1 is dried at 50 and then immersed in about 18 per cent, caustic soda solution (45 kilos or more of the solution per 15 kilos of cellulose). After 8 to 10 hours the soaked and swollen sheets are pressed hydraulically to eliminate the excess of soda, broken into lumps, and reduced in a toothed pulper to a flocculent mass. This is kept in cylinders away from the air for 4 or 5 days at 26 to J 28 to allow of the complete conversion of the cellulose into sodio-cellulose. Dithiocarbonatioii is effected in mixers of the Werner and Pfleiderer type (p. 472), either
:

Fits.

491.

Fiu. 492.

of iron or nickel-lined, with a tight-fitting cover and with a jacket for the circulating cold water. For 15 kilos of cellulose 10 to 11 kilos of pure, washed carbon disulphide is required.

2 to 3 hours, the orange-yellow, spongy, clotted mass obtained being mixed vigorously in a vertical drum with about 45 kilos of 15 per cent, sufficient water is mixed in to give a final solution of density about caustic soda solution 1-13, corresponding with about 7-5 per cent, of cellulose and an alkalinity of about 12 per

Mixing proceeds slowly for

;

cent., expressed as

NaOH. The

degree of maturation required

may be determined

in the

laboratory. In these maturation vessels the mass (sometimes filtered beforehand through filterpresses with cloths stuffed with cotton-wool) is left at 14 to 15 for 3 to 4 (sometimes 6)

days, air-bubbles and excess of carbon disulphide being expelled by prolonged evacuation of the vessels. The matured viscose solution is filtered and, clear and air-free, is conveyed to the tanks which feed the spinning machines through a pipe A (Fig. 491, transverse
section
1
;

Fig. 492, view of front part), kept at constant temperature

cellulose should contain as little hemiccllulose as possible (less

by means

of a jacket.
cent.), since

The
is

than 18 per

this

not coagulated by the acid bath and is lost. The hemicellulose is determined by heating the cellulose for an hour with 18 per cent, caustic soda solution, washing it thoroughly with hot water, drying and weighing the residual cellulose the loss is principally hemicellulose.
;

SPINNING OF ARTIFICIAL SILK

The

825

pipe, A, runs horizontally along the whole %f the double bench carrying the two long and 1 9 containing the coagulating solution of density about 1 -38 (at 20) and troughs, temperature at most 55. If the temperature in the troughs is kept between 50 and 55 the viscose filament coagulates and becomes insoluble during its passage from the mouth of the capillary tube, 6', to the spool, O, which is partially immersed in a trough, //, containing bisulphate solution of density about J -15 and acidity 8 per cent, at 15. From the main pipe, A, the viscose solution is pumped into the tubes, K and B l , carrying thick glass tubes, C terminating in a point closed with a platinum disc having 18 capillary perforations (Fig. 493). From the latter issue the slender threads (becoming far

more slender on

drying), which are collected into a single thread, this passing through the 1 eye, E, at the rate of 40 to 50 metres per minute. The waste yarn and the lumps forming at the orifices of the capillaries when the thread

breaks are thrown into the troughs, and N*. The threads arc freed from part of the acid solution they hold during their passage? in a stretched state past the fixed glass rods, V and F1 The alteration of the acidity of the solution in the troughs by the alkaline viscose is
.

counterbalanced by addition of fresh solution. spools to diminish their tendency to adhere.

air at 65

The threads

are

wound

crosswise on the

The wound silk is washed in running water for 2 or 3 days, dried in circulating to 70, steamed to fix the twisting, skeined, and treated in hot dilute sodium sulphide solution to remove adherent traces of sulphur from the coagulating bath. Finally the skeins are washed in running water, bleached with dilute (e.g., 015 per cent.) tepid calcium hypochlorite solution, softened and rendered more lustrous in a dilute sulphoricinate bath, ceatrifuged, and dried in a current of air at 50 to 60. The dry skeins are beaten by band and sorted into skeins of equal weights and hence of equal counts, those differing by more than 8 to 10 grms. per 250 grins. with good working those discarded in this way being discarded should amount to less than 7 to 8 per cent., but with bad working
;

they
silk

may

exceed 20 per cent.

Properties, advantages

qualities of artificial silk, the strength is considerably less in the moist state ;

and defects of artificial silk. shows diminished strength and, as with other
it

Drnitratcd

A &**
p I(}
.

under such conditions

natural
silks.
2

can

still

compete with heavily weighted

493.

In general a fibre of artificial silk can be distinguished from one of natural silk owing to the small resistance of the former to tension when in the moist condition. Artificial silk is now rendered resistant to moisture and to water treatment with formaldehyde, but this

by

diminishes to some extent the softness and elasticity. A further disadvantage of artificial silk is its high specific gravity, the same weight of yarn of the same size giving a larger quantity of fabric in the case of the natural silk than
1 The machinery used in spinning artificial silk has now undergone further improvements which permit of the production at once of bundles of threads, these being subjected during their development to rapid rotation so that the completely twisted yarn is obtained in a single There are also machines which give two bundles of threads twisted in opposite operation. directions and at the same time wind the two bundles one on the other so as to produce finished organsine of two threads. 2 According to Ilassack the strengths are as follow
:

Natural
,,
,,

silks boiled
,, ,,
,,

and lustred

red, slightly

weighted blue-black, 100 per cent, weighting black, 140 per cent, weighting 500

Cellulose acetate silk

White Chardonnet silk Lehner (Frankfort) silk Pauly (Elberfeld) silk

Viscose silk

Cotton thread

the elongation exhib ted by 100 cm. of the fibre before breaking. The tenacity or strength of natural silk is 3 to 13 grms. for the single thread (bava). Echallier (Lyons) has in a bath containing recently increased the strength of viscose in the moist state by treating it 15 per cent, of lactic acid. formaldehyde, 5 per cent, of alum and 5 per cent of 5% VOL. ji.

The

elasticity is

826
with the
artificial.

ORGANIC CHEMISTRY
But
cent., the difference is

while, with the first artificial silks, tho excess of specific gravity now reduced to 7 to 8 per cent., and further progress in this direction is not improbable. Natural silk has the sp. gr. 1 -36 and cellulose acetate

was 15 to 20 per

silk 1-251, while

other artificial silks show values exceeding 1-5. Marked advances have been made also in the count of the

thread.

Until a few years

ago, only yarn of 120 denari (75,000 metres per kilo) could be made, but nowadays counts of 80 denari (112,000 metres per kilo) are regularly spun, and in some cases, with Ohardonnet These are still far from the silk, 40 denari (225,000 metres per kilo) lias been reached. fineness of natural silk (10 to 20 denari, i.e., 6 to 7 million metres per kilo), but represent

an appreciable step forward. Viscose silk of 160 or even 120 denari is commonly spun. Considerable difficulty was at first encountered in the dyeing of artificial silk, but 1 nowadays the ordinary methods are used. Artificial silk of cellulose hydrate is somewhat hygroscopic and in the air absorbs 1 per
1

cent, of moisture, whilst that with esteritied hydroxyls (cellulose nitrate or acetate), like natural silk, absorbs only 3 to 5 per cent.

By

In its behaviour towards polarised light, artificial silk shows itself doubly refracting. a red ammoniacal solution of ruthenium oxychloride, denitrated C hardonnet silk and viscose silk are coloured red, but non-denitrated and ammoniacal cupric oxide silk are not
1

coloured.

When
little

heated in a closed tube at 200,

artificial silk

chars but natural silk undergoes

is its

change.

USES OF ARTIFICIAL SILK. The most

lustre,

which exceeds that of natural

Beautiful

silk

and permits

valuable property of artificial silk of its use for a large

great
of

number

new effects are obtained by using it as weft in figured textiles with warp of natural silk, a new opening being thus provided for the latter. It is also used with advantage as weft in silk ribbons. For some years it has held almost undisputed sway in the lace industry. Fringe and cord for ornamenting garments, lace, embroidery, etc., are now largely made from artificial silk. Special articles which cannot be obtained with natural silk are made from the artificial product. 'There is now a large consumption
different articles.

by fusing together several thin fibres so as to form a single large compact filament which, unlike large fibres obtained directly by spinning, is flexible and resistant. This artificial white hair, which can be dyed various colours, is in great demand as a substitute for horsehair, which is difficult to bleach and also rather expensive owing to the increased demand for horses for military purposes. This hair is used for various ornaments but mostly for making wigs for ladies, and artificial bristles. Another interesting application of artificial silk is in the manufacture of incandescent such mantles are more resistant to shock gas-mantles according to Plaissetty's patent even after burning, and can be used in trains. Largely used also is a new product obtained from viscose, namely, a kind of ebonite, which serves well for the manufacture of artistically worked and coloured umbrella handles, knife handles, etc., and resists the action of the acids and alkalis with which it is likely to
:

of artifrial hair prepared from artificial silk

come

into contact.

1 When the artificial silk factories supply a /horn O<JP neous product, dyeing is usually accomThe methods of plished without difficulty on skeins of yarn, just as with cotton and silk. dyeing are those used for cotton or, more exactly, for mercerised cotton, which is also cellulose. The dyeing can be carried out without special mordants if substantive dyestuffs (diamine, benzo, eongo, etc.) are used in a hath of sodium sulphate and a little sodium carbonate at the temperature of 50" to 60, various precautions being taken in the manipulation. With basic dyes, a tannin or tartar emetic mordant is used, just as with cotton, the dyeing being commenced in the cold and terminated at a gentle heat in presence of 2 to 3 per cent, of acetic acid. Certain basic colours dye Chardonnet silk even without mordanting. The new sulphur colours are also used. These different processes give all colours, from the pale and more delicate ones to black, in all shades. One merit of artificial silk is that it cannot be weighted so heavily or so easily as natural silk. Only when black can it be relatively heavily weighted. Cellulose acetate t-ilk is not readily dyed by aqueous solutions of colouring-matters, but as it easily fixes phenols even from dilute solution, a line paranitraniline red can bo obtained by passing the silk into a hot 0-5 per cent. j8-naphthol bath and then into a 1-5 per cent, ^-nitraniline bath hydrochlorido containing sodium acetate. Cellulose acetate silk acquires increased affinity for colouring-matters if treated with ammonium thiocyanate. Scroop or rustle may be conferred on artificial silk'by treatment in a bath of glycerine and and then in one of acetic or It is freed from polysulphides by means of glucose tartaric acid. sodium thiosulphate,

USES OF ARTIFICIAL SILK

fixing of the bristles.

827

Casein products, which have also been suggested for these purposes, cannot compete with viscose ebonite, which exhibits marked advantages over bone and horn in the manufacture of brushes, as it can be more easily worked and more easily pierced to allow of the

As hair-ornaments
showing

for ladies, great use

is

made

of artificial silk in thin sheets or ribbons

used in large quant.ity for tapestry, upholstery, neckties, hat-linings, etc., with which no resistance to the action of water is required. With zinc salts viscose* smeared on paper or fabric shows fine silky effects and fine results are also obtained with bronze powder made
brilliant colours

and

sparkle.

Artificial silk is also

making materials

for

into a paste with viscose and spread on different cloths. Important new outlets would offer themselves for artificial silk

if the resistance to the action of water could be improved. It seems to be a question of saturating the hydroxyl groups of hydrocellulose so as to render the latter stable towards water, ami the most

promising attempt yet made is that with cellulose acetate, which gives a silk highly resistant but as yet too expensive, since acetic anhydride is used in its manufacture, while the celluIn America this new product is lose acetate must be dissolved in chloroform to be spun. used as an electrical insulator (its dielectric constant is 4 and that of viscose 7, compared with 5-6 for porcelain). Other uses of cellulose acetate were mentioned on p. 599. Numerous patents have been granted during the past ten years for the manufacture of cinenmtogrnph flmtt, first from cellulose acetate- (which, is, however, too elastic.) and then from viscose, which is less inflammable than celluloid. Viscose has been largely used in recent years to prepare cellophane, which is obtained hy rendering sodium xanthate solutions insoluble by means of ammonium chloride and forming thin films (0-02 mm. thick and up to 2 kilometres in length), which on* as transparent and 5 to 600 grrns. colourless as water even when superposed to form sheets weighing from
1 1

per sq. metre.

are increased
effects.

Cellophane

is

highly elastic, and

by treating it with glycerine. Considerable use is made of it as wrapping for sweetmeats, perfumed substances, It resists alcohol and etc., which are thus protected against water, fatty matters and gases. water even at 100 , and has been proposed as a suitable material for making cinematograph
IJ

tenacity and impermeability It can be stamped so as to produce artistic

its elasticity,

and for rendering faimed waterproof. STATISTICS. The world's production of artificial silk was about 2,500,000 kilos in 1005 more than 0,000,000 kilos in 191 (about 2,500,000 being nitrocellulose silk, an equal amount ammoniacal copper oxide silk, and nearly 1,500,000 kilos viscose silk) 7,000,000 kilos in 1013; 9,000,000 kilos (2,000,000 in France) in 1914; and probably more than 12,000,000 kilos in 1921. France exported 63,700 kilos in 1908, 78,500 in 1909, 161,700 in 1910, and 179,200 in 191 1. Italy consumes large quantities of artificial silk. Before* the war the three large Italian factories (Padua, Pa via, and Turin) were working under adverse conditions owing to the excessive cost of patents and the keen foreign competition, but in 1920 and 1021 two new factories for making, like the others, viscose silk were started, with potential outputs of 3000 and 2000 kilos respectively per day. Large quantities of artificial silk are also
films
; 1 ;

imported.

The United States began to produce artificial silk in 101 (150,000 kilos), and prior to the war imported large amounts from Europe. During and after the war new factories were erected, the output being 4,500,000 kilos in 1920 new plant capable of doubling this output is either complete or in course of construction. Artificial silk, which was sold at 285. to 32$. per kilo in 1903 and 1904, could be bought at 20*. in 1905, while the price fell to 16. in 1906, 13*. 6r/. in 1908, and 12*. in 1910, the
1

poorer qualities being sold at 65. to 8s. per kilo. The price again fell when viscose silk was put on the market and reached 8s. in 1 013. Even before the war many artificial silk works realised enormous profits (the dividends being 30 to 60 per cent, for some years), in spite of the huge royalties paid. Since almost all the more important patents have now expired, it is probable that this industry
will

undergo

still

greater development.

CHEMICAL TESTS FOR THE RECOGNITION OF DIFFERENT TEXTILE FIBRES

The commonest
a thread
;

test for distinguishing animal from vegetable fibres consists in burning the former burn slowly, giving an odour of burnt nails and forming a round

532

828

ORGANIC CHEMISTRY
:

combustion ceases, while vegetable fibres granule of carbon at the point of the thread where burn more rapidly, are converted into ash and give but little smell, which recalls that of
Other reactions are as follow Hemp, jute, flax, cotton, and artificial silk are Boiling 10 per cent, caustic potash insoluble and are not coloured (excepting jute, which becomes yellow) ; wool, silk, and artificial gelatine silk dissolve after a few minutes.
burnt paper.
:

Cold cone, sulphuric acid (after two hours) Hemp, flax, jute, cotton, unweighted silk, artificial silk arc soluble or almost so, hemp being coloured brownish yellow, jute brownish black, and mercerised cotton yellowish, while the rest remain colourless. Wool
:

and

and weighted

silk

do not

dissolve.
:

Flax, hemp, jute, and cotton are insoluble, jute alone Boiling zinc chloride (60 Be) soluble. being coloured a faint brown. Wool, silk and artificial silk arc Schweitzer's reagent (see p. 599), after two hours in the cold, dissolves more or less comif freshly prepared), hemp, flax, jute, cotton, unweighted silk (in less than an hour) and artificial silk. Wool is insoluble. Millons reagent (solution of mercury in an equal weight of nitric acid of sp. gr.. 1-41, first cold, then heated gently, diluted with double the volume of water and decanted after Cotton, flax, hemp, and Chardonnet-Lehner artificial silk are not coloured standing) is turned yellow, wool and p|p*e silk violet-red, and weighted silk and tussah silk

pletely (better

jute ochre-red.

Wool and silk arc coloured red, Cone, aqueous magenta (just decolorised with NaOH) uncoloured. remain flax and cotton whilst Wool is coloured violet to black, whilst cotton and flax are not Silver nitrate solution
:

coloured.

30 fused ZnCl 2 {- 14 water) in the 5K1 lodo-zinc chloride solution (I part iodine Flax, hemp, cotton, and artificial silk are coloured violet-brown (mercerised cotton and with time become almost black) jute, wool, and tussah silk are turned yellowish colourless ; true silk is not coloured. Lowe's reagent (shake 10 grms. copper sulphate, 100 c.c. of water, and 5 grms. of pure sufficient to redissolve the precipitate glycerine and add caustic potash in quantity scarcely in the cold dissolves only natural silk arid is used for the quantitative separation
cold
: ;

formed)

of natural

from

artificial silk.
(1

Diphenylawine sulphate

grm.
;

in

100

c.c.

cone.

H 2SO 4

in the cold

Hemp,

flax, jute,

more or less intense brown colorations (flax dissolves silk cotton and wool dissolve with yellow coloration less easily and is less coloured) artificial silk assumes an intense, dissolves, giving a colourless or faintly brown solution

and tussah

silk arc dissolved, giving

characteristic blue colour.

by dissolving 15 grins, of a-naphthol in 100 c.c. alcohol) sodium carbonate purified by boiling with 2 per cent, One centigramme of the fibre is treated solution and washing thoroughly with water. all the vegewith 1 c.c. of water, 2 drops of Molisch's reagent, and 1 c.c. of cone. H 2 S0 4
the
Molisch's reagent (obtained fibre, dyed or otherwise, is
:

first

table fibres, including artificial silk, dissolve with a violet-blue coloration ; wool is insoluble and is coloured reddish silk is dissolved, giving a reddish (or, if weighted, an intense red)
;

tussah silk dissolves, yielding a yellowish solution. and excess of iodine) 0-1 grm. of the white Iodine solution (1 grm. KI, 100 c.c. 2 O, is treated with a few drops of iodine solution, sodium with as above carbonate, fibre, purified the excess being removed by means of filter-paper hemp, flax, cotton, and artificial silk are coloured blackish brown (flax more intensely than hemp and unmercerised cotton
solution
;

reddish brown)

wool and

silk

become orange-yellow and jute reddish

yellow.

QUANTITATIVE ANALYSIS OF MIXTURES OF TEXTILE FIBRES

It is often of importance for trade or fiscal purposes to determine quantitatively substances extraneous to textile fibres in order to ascertain their commercial weight. This is determined by means of the so-called conditioning. In conditioning, which is now carried out officially, the moisture is estimated by drying in an oven with automatic regulation,- and thus determining very exactly the amount of

dry

fibre (absolute weight)

remaining after

silk

has been heated at 120 or wool and cotton

ANALYSIS OF MIXED FIBRES

at 105
is

829

increased by the to 110. To obtain the commercial weight the absolute weight normal moisture which the hygroscopic fibre absorbs from the air, this being fixed at 12 per cent, tor flax and hemp, 13-75 per cent, for jute, 8-5 per cent, for cotton, 18-25 per cent, for combed wool, 17 per cent, for spun and carded wool, and 11 per cent, for silk (120) ; also the amount of dressing in the fibre must be deducted. It is, however, to be noted that usually wool has only 11 per cent., silk 8-5 per cent., and cotton 7-5 per cent, of

moisture

in ordinary surroundings. 5 grms. of the fabric are well washed with water, wrung out, boiled for 15 minutes in 150 c.c. of 0-1 per cent, sodium carbonate solution, washed in water and rubbedall the fibres being grasped heated to boiling with 150 c.c. of 1 per cc>nt. HCl and kept on the steam-bath for 15 minutes, again washed and rubbed, boiled for 15 minutes with distilled water, washed with cold water, pressed in a towel, washed two or three times with alcohol and two or three times with ether, dried in the air and then in an oven to

when
:

Dressing

constant weight. The loss in weight, after allowing for the moisture (see preceding determination) represents the dressing and colouring-matter ; the latter is almost always a negligible quantity, but in the case of black may be taken at about 0-3 per cent, of the weight of the pure
fibre.

Mixed Cotton and Wool Fabric. 'After the moisture and dressing have been determined, may be estimated and the wool deduced by difference or vice verm. The cotton is determined by boiling 3 grms. of yarn or fabric with 100 c.c. of 10 per cont. caustic potash solution, the wool quickly dissolving the residue is well washed with water, boiled for 15 minutes with distilled water, squeezed, washed with alcohol and with ether, and In cotton. finally heated at 100 to 105 until of constant weight, representing the dry reducing this to percentage, account is taken of the moisture and of the dressing. If, however, the wool is to be determined directly and the cotton by difference, 3 grms. of the fabric are boiled for 15 minutes with 0-1 per cent, sodium carbonate solution, rinsed in water, well wrung out in a towel and left for two hours in cold sulphuric acid of 58 He. ; it is then washed in a large amount of water care being taken that the remaining wool does not become heated boiled for 15 minutes in distilled water, squeezed, washed with alcohol and with ether, and dried at 100 to 105 until of constant weight, which
the cotton
;

After the moisture and dressing have been determined the same piece of dried fabric is immersed for a minute in a boiling solution of zinc chloride (60 Be.) and washed first with water slightly acidified with 3 and then with pure water until the wash water gives no zinc precipitate with ammonium sulphide, the remaining vottoti being washed with alcohol and with ether and dried at 100 to 105 In the case of tussah silk, until of constant weight ; the silk is calculated by difference. the action of the zinc chloride is prolonged somewhat. In order that no loss may occur
(see above),

represents the dry wool. Mixed Cotton and Silk Fabric.

HNO

with a heavily weighted silk, the dressing is eliminated by means of sodium carbonate; alone, treatment with hydrochloric acid being omitted.

Mixed Wool and Silk Fabric. The silk is dissolved in zinc chloride and the residual wool weighed, the silk being determined by difference (see above). Natural and Artificial Silk Fabric. The natural silk is dissolved in Lowe's reagent (see
above).

Cotton and Linen Fabric. As a rule the different fibres can be separated by hand, but this is not possible the cotton (after the moisture and dressing have been determined on the same piece of fabric) is dissolved by immersing the tissue for 1 to 2 minutes in con-

when

centrated sulphuric acid ; the fibro is washed well with water being rubbed meanwhile then with water and ammonia, and again with water, the linen remaining being dried and weighed. The cotton is obtained by difference. Different Artificial Silks. Those from nitrocellulose (Chardonnet, Lehner, etc.) contain traces of nitro-derivatives and with diphenylamine and sulphuric acid give a blue reaction, which is not shown by other silks. P. Maschner (1910) distinguishes different silks by treatment with concentrated 2 80 4 ; that from nitrocellulose colours the liquid a faint yellow only after 40 to 60 minutes ; ammoniacal copper oxide silk is coloured yellow or brownish yellow immediately, while the liquid becomes brownish yellow after 40 to 60 minutes ; viscose is at once coloured carmine-red, the liquid turning brown after 40 to 60 minutes.

The

fibres dissolve after

about 20 minutes and then carbonise.

830

ORGANIC CHEMISTRY
DYEING AND PRINTING TESTS ON TEXTILE FIBRES

tests which admit of the classification of colouring-matters according to their basic, acid, neutral, or mordant character. To this end, dyeing or printing tests are made on a small scale with wool and cotton (nee also p. 795 et seq.). Tests made with colorimeters, which compare the intensities of coloration of solutions in tubes

Of some importance are the

of equal lengths or vessels of equal thickness, are of little practical value. Hence to ascertain the dyeing power of any commercial product, the latter is compared with a standard colouring-matter by weighing out equal quantities (0-1 to 1 grm. per litre of water) of tho two, and dyeing equal weights of wool, cotton, or silk fabric with definite volumes of tho more or less diluted solutions. The quantity of dye used is always referred to the weight

wool

of the fabric, independently of the dilution of the bath ; this is especially the case with (0-1 per cent, of the dye for pale colours and 2 to 4 per cent, for dark colours). The

dyeing tests are made on 1 to 2 grins, of wool or cotton yarn or tissue in glass or porcelain beakers of 150 to 250 c.c. capacity, these being heated in a bath of concentrated sodium sulphate solution or of glycerine giving a temperature of 101 to 102 in the dye-bath (see
Fig. 494).
If the bath retains much colour after the dyeing, a second portion of tho textile is dyed without adding fresh dye. If the cotton is raw it must first be boiled for an hour in a 0-5 per cent, caustic soda solution, and then thoroughly rinsed with water. If light colours are used, the cotton is also bleached in calcium hypochlorite solution (less than Be.) at 25 to 35 for an hour, washed with water, immersed in a 1 per cent, sodium bisulphite bath
1

if

(antiMor), and well rinsed in water. Wool, impure, is heated at 60 for 10 minutes

with a solution containing 0-5 per cent, and 0-1 per cent, of sodium carbonate, and then well rinsed with water. Also silk, if not already discharged, is washed with hot soap solution. -.1 The comparative dyeing tests should ?... be made on equal quantities of textile fibre wetted uniformly before introduction into FIG. 494. the dyeing bath. Silk is dyed like wool, but tho bath is made less acid and the temperature rather lower. Wool is dyed in an aqueous bath containing 10 to 15 per cent, of sodium sulphate and 5 per cent, of sulphuric acid (or 6 to 7 per cent, of sodium bisulphate- the German \Yeinsteinpreparnt in place of the sulphuric the bath is stirred continually with a glass rod and acid) calculated on the weight of fibre heated gently to toiling, being kept slowly boiling for 20 to 30 minutes ; the- wool is then rinsed and dried either in the air or in a water-oven. The above procedure is followed more with basic dyes, one-quarter of the amount of sulphuric acid is especially for acid dyes sufficient. When wool is dyed with acid dyes, it is not merely necessary to acid to the dyebath the quantity of sulphuric acid required to liberate the acid residue of the dye so that this can be fixed on the wool, but in order that the latter may be dyed intensely and well, 20 to 30 times the theoretical amount of sulphuric acid must be added (E. Knecht, 1888). With mordant dyes, the wool w -mordanted with 3 per cent, of potassium dichromate and 2-5 per cent, of cream of tartar (on the weight of wool) and about 100 times the weight of water, heating gradually to boiling and maintaining this for nearly an hour, the water evaporated being gradually replaced ; the wool is then rinsed and dyed in the dye-bath, which contains a little acetic acid (1 per cent, on the fibre), and is mixed continuously and brought slowly to the boil, boiling being maintained for about an hour. Knecht and Hibbert (1903-1905) determine the concentration of the colouring-matters in the different solutions by reduction with standard titanium trichloride solution ; crystal violet, for example, fixes 2H, giving the colourless leuco-derivative. Cotton is dyed with substantive dyes in more concentrated baths (50 of water to 1 of cotton) containing 30 to 50 per cent, of sodium chloride or sulphate and I to 2 per cent, of sodium carbonate (on the weight of fibre) ; this is heated slowly and kept boiling for 30 to 40 minutes ; in general the bath is not exhausted and can be used for a second portion of cotton. In the case of sulphur colours, 20 to 30 per cent, of sodium sulphide are added to the bath and in some cases 2 to 3 per cent, of glucose, and during the dyeing the cotton is kept immersed and out of contact with the air. When basic colouring-twitters are used the
of soap
; ;

PRINTING TESTS

831

cotton is previously mordanted with 2 to 4 per cent, of tannin dissolved in water, being left in contact with this solution for 6 to 7 hours (overnight) at 50 to 60 (the tannin is fixed more slowly in the cold) ; the cotton is then wrung, immersed for 10 minutes in a bath containing 2 per cent, of tartar emetic (antimony potassium tartrate) at 40, rinsed with water and dyed in the tepid (30 to 40) dye-bath' for 20 to 30 minutes. Dyeing on a large scale is carried on under the same conditions, but the calculations are made on a longer time, and great precautions are taken in the moving of the fibre and in raising the temperature, so as to obtain uniformity. For dark colours, the tannin is
fixed with ferric nitrate instead of with tartar emetic.

Industrial dyeing apparatus is

shown more

in detail later (p. 841).

PRINTING TESTS. The object of printing is to colour the fabric or yarn in a definite pattern or with different colours, part of the fibre being possibly left unaltered. In the first rudimentary printing processes, the fabric was printed with resin or a kind of cement, the uncovered parts being dyed as usual and the preserving substance subsequently
removed. It is now usually regarded as preferable to stamp, i.e., to print, on the fabric or yarn the colour mixed with thickening (gum, dextrin, gum tragacanth, etc.) by means of metal rolls on which the desired pattern is engraved. The engraved roll is coated with the pasty colour by rotating against a rubber or cloth roller (furnisher), one-half of which dips in a vessel containing the thickened colour ; a knife (tlorfar) Ls arranged so as to scrape the excess of colour from the metal roll, and the yarn or fabric then passes over the latter under In order to fix the colour and prevent it from spreading, the fibre is subjected pressure. for 30 to 60 minutes to the action of steam at about 105 (see Fig. 552, p. 855). By this means the colour is fixed without immersing the printed fibre. The latter is subsequently washed with an abundance of cold water (or with tepid soap and water), which removes all excess of colour and thickening agent. In other cases similar effects are obtained by dyeing uniformly in the ordinary way and then printing on the dyed fabric reagents which decolorise (corrode) the dye at the points of contact. Sometimes other colours are introduced with the corroding agent, so that the white parts are dyed a lighter or darker shade or a different colour from the foundation. A kilo of thickened colour for printing wool black the wool having been previously subjected to slight chlorination to make it take np the colouring-matter better (by immerJ sion in a cold calcium hypoehlorite bath at 0-5 Be. and then in very dilute HCl, washing, and drying) may be obtained as follows: 750 c.c. of water, 100 grms. of gum, and 100 grnis. of British (/tun (dextrin) are heated in a jacketed vessel by means of indirect steam and kept well mixed, 60 grms. of anthracite* black E (4 and 10 grms. of milling yellow O (and, in some cases, 8 grms. of acid anthracene brown II) being added. When the paste is boiled uniform, it is allowed to cool, and before it is used a solution containing 80 c.c. of water, 120 c.c. of acetic acid (6 Be.), and 40 grms. of sodium chlorate is well mixed in. For printing cotton textiles, colours are used which form insoluble lakes with tannin or metallic oxides such are basic and mordant colouring-matters (alizarin, etc.). The former are dissolved in acetic acid and tannin, (or a solution of 50 parts of tannin, 50 of water, and 5 of tartaric acid) and the latter (alizarin, etc.) in chromium (or iron,
;

aluminium, etc.) acetate, dextrin, gum, etc., being added in either case. Fabrics treated with tannin, after being stemmed at the ordinary pressure and before being washed, are passed into a bath containing 5 to 10 grms. of tartar emetic per litre at 60. FASTNESS TESTS. The fastness of a colour is only relative and must be considered for example, it would with reference to the purposes for which the dyed fibre is required be superfluous to require fastness against light in dyed fibres or fabrics to be used for underclothing, linings, etc. The dyed specimen is mixed with similar undyed fibre and sub jectcd to the following tests, as required. Mordanted colours answer all these tests fairly
;

but in other cases more or less of the colour is given up. Fastness against Water. The sample is immersed in 50 times its weight of cold water for 12 hours or for 1 hour in water at 60 to 70 (and is left to cool in the bath) and is then dried in the oven. Note is taken of the colour assumed by the water and by the white fibre, especially where the latter comes into contact with the dyed fibre. Fastness against Soap, Alkali, and Washing. The skein of white and dyed fibre is immersed iiv 50 times its weight of an aqueous solution containing 10 grms. of Marseilles allowed soap and 10 grms. of soda per litre. The bath is heated at 60 for 30 minutes and to cool, the skein being then removed, well rinsed, and dried. The changes in colour of the bath and the white and dyed fibres are observed.
well,

832

ORGANIC CHEMISTRY

Fastness against Milling. This test is carried out with a soap and soda solution, of double the above concentration, at 40, the skein being continually rubbed between the hands for 30 minutes, and then well washed and dried in the oven. Colours fast to milling should not soil the white portion of the skein and should give up only a minimal amount of colour to the bath. Fastness against Bleach. If the colour is on wool or silk it is immersed in a 2 per cent, sodium bisulphite bath acidified at the moment of using with a few drops of hydrochloric acid, and, after 30 minutes, washed and dried. When the colour is on cotton, the test is made with a calcium hypochlorite bath at 0-5 Be. for half an hour. Fastness against Scouring. Indigo, Turkey-red, and all basic dyes on cotton mordanted with tannin, even when dry, give up a little colour to a white handkerchief with which they are scoured. Other dyes should not soil the white. Fastness against Acid. The test is carried out for an hour with 1 per cent, sulphuric
acid at
J

(>0'

to

70.
In some cases this test is made with a 1 per cent, acetic 40, the skein being dried at 60 under slight pressure, and after thorough rubbing. In others, an alkaline test is made as in against washing but the unrinsed skein is subsequently scrubbed and

Fastness against Perspiration. acid solution for 30 minutes at

without rinsing

testing fastness dried at 60 under slight pressure.

Fastness against Ironing. The dyed fabric or yarn is ironed with a very hot iron (130 to 140), note being taken whether, after cooling and exposure to the air for 15 minutes the fabric resumes its original colour. Many colours are changed by ironing hot, but return
to their initial state in the cold.

10

Fastness against Steaming. The yarn is paused for two or three minutes.

is

placed in a glass tube, through which steam at

Fastness against Light. One half of a skein of yarn or of a strip of fabric is tightly enclosed between two pieces of card, while the other half is left free ; the whole is then hung in the open air exposed to the sun and weather. For pale colours, an exposure of at
least two days, arid for dark colours, one of at least four days, is necessary in summer, while in winter or in cloudy or rainy weather (the skein must be sheltered from rain), at least double or even treble these exposures are necessary. The covered and uncovered portions

are subsequently compared. Fastness of the Dressing against Rain.

A few drops of water are sprinkled on the fabric,

especially finer woollen ones, and after exposure to the air it is noted whether the drops have left faint spots. In some cases the fabric is scratched with the thumb-nail ; a paler

This test is not applied to cotton fabrics strongly dressed, since the nail will sometimes detach the dressing itself. THEORY OF DYEING. The phenomenon of dyeing was at one time thought to be due to the porosity and capillarity of fibres which were thus enabled to absorb and become impregnated with dyes. The possibility of chemical combination between the dye and the fibre was regarded as excluded, it being asserted that in such case the fibre would undergo marked change. The different colouring powers of substances were explained Even at the beginning of last century, in as due to different molecular magnitudes. Chevreul's time, these ideas prevailed, and only in the case of mordant dyeing was any chemical fixation of the dyestuff assumed. Later on, Bergman, J. Persoz, etc., arrived at a purely chemical conception of the phenomenon of dyeing, but when in 1885 substantive cotton dyestuffs of almost neutral character made their appearance, the chemical theory, which was based mainly on the basic or acidic nature of the dyestuffs, was in some degree shaken. Many then accepted a new theory in harmony with the osmotic phenomena of solutions, the more readily because no definite and constant relation between the amount The chemical theory was of fibre and that of dyestuff combined had been established. and is still, however, upheld by many authorities on the subject, more particularly by Noelting, by Knecht, and by Vignon, who have pointed out that alloys form well characterised compounds which exhibit no definite chemical relations between the components and may be regarded as true solid solutions of one substance in excess of the other. Further, they were able to show that silk and wool, in combining with colouring-matters, set free the acid united with the base of the dyestuff, this acid being found in the dye-bath. Also, with certain acid dyestuffs (e.g., naphthol yellow), Knecht and Appleyard found a constant
streak should not result.
relation between fibre

Jacquemin

and dyestuff. asserts that if there

were no question of chemical combination, the dry

THEORY OF DYEING
have the colour of the dry colouring-matter, whereas it has the same dyed colour as the dissolved colouring-matter. Nietzki finds that with certain highly basic colours (e.g., methyl green), wool cannot of itself displace the mineral acid of the colouring base, the addition of ammonia being necessary while, with the same colouring-matters the more markedly acidic silk is dyed without any addition. An interesting fact, which supports the chemical theory, is that the base of rosaniline is colourless and becomes red a (magenta) only when converted into a salt with HC1 similar change is produced if wool is immersed in a colourless rosaniline (base) bath, the wool being dyed red owing to the formation of a salt. If the dyeing is effected directly by rosaniline hydrochloride, the bath ultimately contains the hydrochloric acid which is displaced by the acid of the wool fibre ( Jacqucmin and Knecht, 1888). Moreover Richard (1888), Vignon (1890), and Nietzki (1890) showed that silk and also wool are active both towards acids and towards bases, so that in chemical characters they are comparable with the ammo-acid*. The fibre may even be replaced by albumin, which is dyed by the same dyestuffs as wool, etc. According to W. Suida (1907) the dyeing of wool is accompanied by liberation of the base of the dyestuff which combines (or forms salts) with the textile fibre, the latter functioning as a polybasic acid in virtue of its guanidyl and iminazole groups. Also Vignon showed that when wool and silk are dyed with basic or acid colouring-matters heat is developed, so that the dyeing may be regarded as a true, exothermic chemical reaction. According
tissue should
; ;

to Vignon cotton is not dyed directly by basic or acid dyestuffs (which are usually salts) since it has not the reactive force to decompose them, but if it is previously oxidised or animated, it fixes these dyestuffs partially with development of heat. Further, the difference in fastness against light of the same colouring-matter (e.g., mcthylene blue) fixed on cotton (with tannin) and on wool or silk would appear to favour the chemical hypothesis of

the

phenomenon

of dyeing.

In 1889 O. N". Witt advanced a new theory, which explains also the dyeing of cotton with substantive and mordant dyes. According to Witt, dyeing consists merely of a solution of the colouring-matter in the fibre, analogous to that of solution of coloured metallic oxides in glass, so that the colouring-matter passes from a liquid solvent (dyebath) to a solid one the fibre itself just as occurs with alloys or in the extraction with ether of a substance dissolved in another solvent in which it is less soluble than in ether

assuming that the two solvents are mutually insoluble. Dyeing on mordants is similarly explained as due to the solvent properties of the fibres for the metallic salts, these then fixing the colouring-matter from the dye-bath. The dyeing of cotton with substantive dyestuffs is regarded as the result of the marked solvent power of cotton (cellulose) for these dyes. In support of his theory, Witt cites the fact that silk dyed with magenta gives up its colour to alcohol, which is a better solvent for magenta than is silk, while if the alcohol is then diluted with water, the colour is again
fixed

by the

silk.

Knecht (1902) made the reply that, with substantive colouringmatters lanuginic and sericinic acids form insoluble lakes, i.e., true compounds, while with magenta they form lakes soluble in alcohol ; it is therefore to be supposed that the magenta extracted by Witt with alcohol is in reality the soluble lake formed by the magenta with the components of the fibre. Rosenstiehl (1894), Reisse (1896), and Gillet (1898), after various quantitative dyeing tests, decided in favour of the chemical hypothesis. In 1894-1895 Georgievics advanced a number of arguments in favour of a purely mechanical theory of dyeing (his predecessors of a century earlier being Hellot and Le Pileur d'Apligny, and those of more recent times Walter Crum, Spohn, and Hwass). Comparing the latter with occlusion of gases by solids or with the mechanical fixation of dyes on sand or on powdered charcoal, etc., he maintained that colouring-matters fixed on fibres have the same properties as those not so fixed, and that there can hence be no question of a chemical reaction (but see above, Knecht's experiment), since some dyestuffs fixed on fibres can be separated by mere sublimation, while in other cases (with methylene blue and indigo carmine) the coefficient of distribution of the colouring-matter in the fibre and in the solution is constant. According to Krafft (1899), dyeing generally consists in a deposition, on or in the fibre, of adhesive and resistant colouring salts in the colloidal
this observation
state.

To

Biltz (1905) has succeeded in producing true dyeing

fibre (cotton)

phenomena by replacing the textile by aluminium hydroxide or other hydroxides which behave as hydrogels

884
(see Vol.

ORGANIC CHEMISTRY

L, p. 106) towards the- colouring-matter, which is regarded as a colloid (benzopurpurine and sulphur dyes). Freundlich and Losov (1907) have shown that carbon not only fixes colouring- matters but decomposes basic colouring-matters, fixing the coloured base in the colloidal state and leaving the acid in solution, in the same way as happens with wool or silk. Knecht has recently (1909) found that the amount of colouring-matter fixed by charcoal is related to the quantity of nitrogenous matter remaining in the charcoal even after ignition, so that- here a true chemical reaction occurs ; this investigator has also shown that colon ring- matters cannot be regarded as colloids, since they are electrolytes
diffuse through membranes. Tn 1009 Dreaper and Davis demonstrated that basic colouring-matters are fixed in constant quantity on calcined sand, and in increased quantity if the dye solution contains sodium chloride. Rosenstiehl assumes that the phenomenon of dyeing is explainable by the cohesive force between the colouring-matter and the textile fibre, this force varying with the liquid or gaseous medium in which the dyeing takes place and depending on or being produced by the osmotic pressure of this medium. According to Miiller (1909) dyeing may be regarded as a phenomenon of adsorption of the colouring-matter by the colloid, i.e., the textile fibre. There is hence not chemical combination, but fixation under definite conditions (of moisture and temperature). Mercerised cotton fixes colouring- matters better on account of its more marked colloidal character. The process of fixation or adsorption may also be reversible and all the pheno-

and

mena

of direct dyeing

depend on the relative

coefficient of adsorption of the colloid (fibre)

Freundlich and Losev and Pelet-Jolivet attribute dyeing to for the colouring- matter. adsorption* because the fixation of the colouring-matter from solution by any textile fibre

P
the formula, obevs J
A"
ni
('

jc

(where

denotes the ratio between the quantity of colour ^

of the textile absorbed and the weight fc

final

fibre,

and

are constants,

and

indicates the

by

solid substances

concentration of the colouring-matter), which also regulates the adsorption of gases and that of various dissolved substances by animal charcoal. It

cannot, however, be denied that certain limited chemical processes also correspond with this formula, and that many phenomena accompanying dyeing are most simply explained
chemically. Indeed,

W.

artificial silk,

J. Miiller and Slassarski (1910), by means of experiments on the dyeing of show that the absorbed colour varies in quantity with the chemical properties

of the cellulose (raw, oxycellulose, hydrocellulose).

Every hypothesis is supported by some experimental fact, and it would seem that, according to the nature of the fibre, of the colouring-matter, and of the dyeing process, the phenomenon is explainable either on purely physical or on purely chemical grounds,
but more generally on both. O. Weber (1891, 1899) and (Jnehm (1898) explain the various phenomena of dyeing of lakes in the following way (I) Dyeing on mordanted cotton is due to the formation between the colouring*mattcr and the mordant precipitated mechanically on the cotton. or pigments held by it (2) Azo-eolouring-matterd formed direutly on the fibre (we p. 781) are Guinea cinnabar, deposited mechanochre, etc.) merely precipitates green, (ultramarine, concally in the pores of the fibre. (3) The direct dyeing of cotton with substantive dyes
:

sists in dissolution of

the colouring salt in the

roll juice,

and the marked

fastness against

washing of these colours on cotton is due to their slow diffusion with the juice (MiillerJacobs and Weber). (4) Dyeing of tannin-mordanted cotton with basic or indigo colours fibres is a true mechanical occlusion. (5) Direct dyeing of wool and silk and other animal with basic or acid colouring-matters is due partly to mechanical absorption, and partly to chemical combination, of the colouring-matter by the fibre. -(6) The dyeing of mordanted animal fibres is explained by the formation of insoluble lakes, partly by the mordant fixed chemically by the fibre, and partly by that fixed mechanically within the fibre, but is never caused by combination of the unchanged fibre with the colouring-matter. Pelet-Jolivet's eollmdal theory of electric contort, based on Perrin's law of contact electhe fibre in an alkaline bath is negatricity also finds support According to this theory
neutralisation of the charges resulttively charged and the basic colouring matter positively, other (the colouring-matter being the on one colloid of in ing precipitation (adsorption)

assumed to be
charged by

In dyeing with acid dyestuffs, the fibre becomes positively colloidal). addition of acid to the bath and adsorbs the negative acid colouring-matter.

TEXTILE MACHINERY
it

835

has been shown that when this is boiled with As regards the mordanting of wool, metallic salts, it fixes not only the basic part but also the acid part of the salt (only of unstable salts, e.g., sulphate of Al, Cr, Cu, or Fe, and not sodium sulphate or chloride) ; the latter part is eliminated to some extent by water, but the basic part is fixed more
stably.

MACHINERY USED

IN

DYEING AND FINISHING TEXTILES

The limits of this treatise do not allow of the inclusion of a complete description of all the machinery used in works where textile fibres are dyed and finished. We shall hence confine ourselves to illustrating some of the principal washing, dyeing, and dressing machines.

WASHING AND PREPARATION. At

textile fibres

the dye-house,

raw (cotton and wool in flock) or combed (wool in skeins or tops) or spun in skeins or on bobbins (wool, cotton, silk), or more commonly woven in pieces 30 to 100 metres long and 60 to 140 cm. wide (woollen, cotton, silk, or mixed fabrics). Wool is sometimes supplied free from its natural fat (see p. 805) but, whether as fabric or as yarn, contains the fat or dressing used in weaving or spinning. Cotton is still in the raw state, and, in order that the
arrive either

may be fixed well it is subjected to energetic boiling under slight pressure with water and with soda. With either flock or skein cotton, this treatment is carried
out in large, closed, iron or copper boilers (Fig. 495), provided with pumps or steam-injectors for circulating the liquid, the textile material not being moved as it might be

colouring- matter

from

damaged. As a rule the boiler is either evacuated or freed by a current of steam, since air damages the fibre owing to formation of oxycellulose, and also gives dark lye along with the caustic soda, vigorously frothing
air
;

Fio. 495.

soap (from castor duced.

oil,

for

example)

is

intro-

The washing

of cotton goods to rid

them

of

the starch with which the weft was charged for weaving purposes was at one time carried out by heating them with milk of lime, but
better results are obtained
dilute caustic soda solution in

by heating with an autoclave

under steam -pressure. Nowadays the goods are often passed through a lukewarm bath of
diamalt
diastase)

or

and

diasto/or (malt extracts rich in left in heaps overnight, the starch

being thus transformed into soluble dextrin and maltose. The latter products are removed by thorough rinsing in water the material
:

passes between the two rollers A and B (Fig. 496) into the water, round the roller (7, up

between
it

and B, down again and so on until reaches the middle, where it is removed, together with a similar piece introduced at the other end of the machine ; the pieces of
material
are
;

tied end to end and passed an abundant supply of water enters the through this washer in a continuous length vessel at D and is drawn off through another pipe. When washed the goods are soured with a solution of sulphuric acid (0-5 Be.), either the cold or tepid (with the latter the action is very rapid, even with more dilute acid) pieces may be tied together in cords and passed through this solution (see Fig. 496). Bleachthis occupies some ing is then effected in a clear chloride of lime -bath (0-5 to 0-75 Be) hours in the cold, or, if the liquid is lukewarm, the material may be passed continuously
;
;

FIG. 496.

836
through
it

ORGANIC CHEMISTRY
as
before.

Then

follows rinsing

and treatment with antichlor (sodium

bisulphite),

Skeins of cotton yarn may- also be bleached with chloride of lime in an apparatus with automatic circulation of the liquid, as is shown in Fig. 495, while the rinsing may be effected in rotating machines (Fig. 497), where each skein rotates on a wheel and all the reels rotate
horizontally in a circulation vessel,

a water-spray being
while.

used mean-

According to Pick and Erban

FIG. 497.

Fio. 498.

be bleached in the cold, without preliminary boiling with alkali, by means of in this way, the strength of ; the fibre is retained better, while time is saved (Ger. Pat. 176,609 of 1906). Cotton or cotton and wool fabrics may be bleached by passing them repeatedly into a sodium permanganate bath (0-6 to 0-7 per cent, of the permanganate on the weight of fibre) until
cotton

may

sodium hypochlorite solution mixed with sulphoricinate

the bath is almost decolorised and the fibre turned brown, then into a sodium sulphite or

FIG. 499.

FIG. 500.
fibre)

sodium] nitrite bath (0-6 to 0-7 per cent, on the

(4 per cent,

and

finally into sulphuric acid

on the

fibre).

The Washing of skeins of wool yarn in a tepid bath (50 to 6G) is carried out by passing the skein for a minute between two rolls (Fig. 498 )> then twisting the skein and again squeezing it. Subsequent thorough washing with water in the vessel shown in Fig. 497,
for example renders the skein of wool ready for dyeing. In all these operations and in those which follow, woollen yarns are treated with greater care than cotton ones, it being necessary to manipulate, press, and rub them as little as possible and only very slowly,

in order to avoid felting.

Bleaching of washed woollen yarns or fabrics (wrung out uniformly by means of centri-

BLEACHING, WASHING
f uges
:

837
in tightly closed

see p, 566)

by sulphuring

is

effected

by

stretching

them out on rods

situate in

chambers in which sulphur has been previously burnt in a cup by a furnace outside. Here the wool is left overnight, and in the morning the windows are opened and the wool dried and deodo-

an angle heated

The amount of sulphur burnt is 2 to 3 per cent, on the weight of the wool, or less if the chamber is a small one, and deficiency of air is maintained in order to avoid sublimation of the sulphur and its deposition as a yellow powder in the
rised in the air.

wool.

Bleaching with Hydrogen Peroxide, is carried out in the cold or at a gentle heat, and for woollen yarn, paraffin waxed

cement troughs, Woollen or silk fabrics are wound into a vessel similar to that used for dyeing (see later), or, better, on a FIG. 501. jigger (see later). The bath is prepared by diluting commercial 10 to 12 vol. H 2 2 with 8 to 10 times its volume of water, and rendering it slightly alkaline with ammonia After use the bath is preserved by acidification with sulphuric acid. (see Vol. I., p. 267).

wooden
are

vessels, or, better,

used.

FIG. 502.

More economical bleaching is obtained with sodium peroxide, which; however, must be better results are obtained with sodium ised with great caution (see Vol. I., p. 553) of a bath in Vol. containing, say, 200 litres of water, 600 grms. I., p. 605) perborate (see mlphuric acid of 66 B6., and 1-8 kilo of sodium silicate at 40 Be.
;

X
*

p. .*

n
vfcv'b/

****

Fin. 503.

Washing of Woollen Fabrics is carried out in various ways, A number of the pieces, two ends of each being tied together, are wound round in a trough fitted with a pair and soda solution. >f pressure rollers, A and B (Figs. 499, 500), and containing hot soap Seneath the rolls is a wooden channel, 0, to collect the expressed liquid, which for some ime is allowed to run back through r but when dirty is run off outside, Thorough rinsing dth water is carried out in the same vessel. It must be noted that almost all washing
/he
t

838

ORGANIC CHEMISTRY

and dyeing machinery is fitted with arrangements for obtaining different velocities of the moving parts, with pipes for water and steam, etc. Very heavy woollen fabrics are more easily washed at their full width in vessels (Fig. 501 ) similar to the preceding, but the lighter ones are most conveniently dealt with by joining the pieces end to end so as to form a single piece, which is treated in the machine shown
in Fig. 502, and, in diagrammatic section, in Fig. 503.

This

is

furnished with three pairs

Fie. 504.
of rolls,

FKS. 505.

A, B, and 6*, which press the pieces in their passage from one vessel to the next, while a slow current of water enters at E and takes a zigzag course through the succeeding vessels ; a little soap and soda solution is gradually addecl in vessels 1, 2, and 3, which are heated by

steam -pipes, while the dirty water is discharged continuously from 8. For making certain articles, woollens must be subjected to Milling, which transforms

them

into

more

or less close cloth.

When

the pieces are rolled up, moistened with soap solution, and then continually compressed and rubbed together, the

and cloth formed in the The milling machine in which this is effected is shown in Figs. 504 and 505. The material is caught between the three wooden rollers, A, B, and (7, which compress them and force them into the wooden channel, R S, where the
wool
is

felted

course

of

a few hours.

pressure of the plate, R, maybe increased by the spring, A ; the expressed liquid collects in the channel, E, and is at first

returned but later discharged. If any knots were formed they would stick at P and raise a spring, T, thus stopping
FIG. 506.
.

tne driving-belt. With certain heavy fabrics already soaked with oleine,

milling
acid.

is carried out with addition of a little soda solution, which saponifies the oleic In some cases dilute sulphuric acid is used, but better results are apparently obtained

with

1 per cent, lactic acid solution, the wool then retaining greater lustre and elasticity (G. Ita, Gcr. Pat. 236,153 of 1910). Some fabrics which are required to take bright designs and a smooth and

very

shiny

surface (tatin, etc.) are freed from the

down always accompanying

textile fibres

especially

after washing, etc. by passing them, quite taut, quickly over a row of gas-jets (or over a sheet of heated copper or a strip of metal heated electrically) which bum the hair on the

CARBONISATION
face

839
where the gas-jets run

and sometimes on the reverse horizontally from A and B).

of the fabric too (see Fig. 506,

The removal

of cotton fibres or bits of vegetable

matter (which would become more

Fw.

507.

noticeable after dyeing) from woollens may be effected by hand, but is more commonly attained by Carbonisation. In this the fabric is impregnated uniformly with sulphuric acid of about 4 Be. (or aluminium chloride solution), centrifuged and heated at 125 to 135

FIG. 508.

over a series of tinned sheet-iron or copper rollers (similar passed at width either woven for used goods after dyeing) through which steam at 2 to 3 atmos. is to those drying or else slowly through a large oven heated with hot air or 848) 531, p. (see Fig. passed with branched pipes fed with steam under pressure (see Fig, 507). In this way all the

840

ORGANIC CHEMISTRY
and shrink, and these

vegetable fibres are incinerated or carbonised and are eliminated in the subsequent souring, which occupies an hour and is effected by means of a large quantity of water in the washing
vessels already described (Figs. 499, 500). As has been mentioned, woollen fabrics exhibit a tendency to felt

FIG. 509.

very pronounced during dyeing, when the material is kept moving two or three hours. In order to avoid these changes, which likewise often spoil the design, the fabric is subjected to fixing, which consists in heating it in a stretched condition in vigorously boiling water, i.e., at a temperature rather higher than
actions

may become

in boiling baths for

any

it

will experience in

subsequent operations

scalding of the fibres in this

way

causes

FIG, 510. of contraction, and the fabric shrinks less during partial loss of their elasticity and power in the so-called revolver machine (Fig. 508), in which the dyeing. Light fabrics are fixed material is wound in compact rolls on reels dipping into a vessel of water kept briskly

boiling
vessels.

each reel

may have

six rolls

and one

reel

is

arranged in each of two adjacent

axis of each reel revolves during the winding, and when the first reel has received the first six rolls, the first roll begins to unwind to form another on the second reel, so that the part of the fabric which was peripheral on the first roll .becomes central in the

The

roll of

the second

reel.

This procedure prevents any subsequent irregularity of colouring

DYEING PLANT

841

owing to the more ready and more intense fixation of the dye on the parts subjected to the most prolonged action of the boiling water. Each roll may contain from 100 to 3(K) metres of fabric, which is fixed in about an hour. Certain heavy woollens with a satin surface (and also mixed wool and cotton goods unions or cotton goods with a satin foundation) are fixed, and at the same time furnished with a lustre which persists ever; after The dyeing, by so-cajled crabbing. machine in which this is carried out consists essentially of two or three pairs
of superposed heavy rolls of solid iron (Figs. 509, 510). One-half of the lower roll of each pair dips into a long narrow
vessel of water kept boiling by direct steam. The stretched, smooth cloth is

wound
roll,

rolls on the lower then allowed to revolve for 30 to 40 minutes in the boiling water, being pressed by the upper roll, which revolves freely and can be weighted by means of levers. The fabric then passes to the lower roller of the adjacent

in

compact

and

is

vessel

and so

on.

Cotton and wool in flock were at one time dyed by immersing them in cloth or net in open wooden vessels containing the hot dye-bath. Use was afterwards made of mechanical apparatus similar to that shown in Fig. 495, where the material remains stationary on a false bottom, below which the liquid is drawn off and
FIG. 511.

DYEING.

pumped

found that the liquid did not p^ss uniformly through the whole but went more easily through that which was least compressed and which contained channels, thus producing irregular dyeing. Almost universal use is now made of mechanical apparatus similar to the above, but with the fibre highly compressed (see Fig 51 1). In this case the pump, which must be more powerful, causes complete penetration of the
of the fibre
liquid,

to the top. It was, however, often

and much better results are obtained. Skeins of yarn can also be dyed in this appaAfter ratus when they are well compressed. the discharge of the dye-bath (kept, if required, for a subsequent operation), the dyed fibre

may

be washed in the same vessel.

To dye combed wool (tops) wound on to bobbins by suitable machines (Fig. 512), very general use is made of Obermaier mechanical
apparatus of the revolver type, in which the Dobbins are arranged in as many horizontal, cylindrical cases fitting into a vertical cylinder closed at the top and communicating below with the pipe of a pump, which it fits exactly FIG. 512. the mode of action is shown clearly (Fig. 513) by the figure. A more simple apparatus which carries larger charges and is largely used also for yarn on bobbins with crossed thread, is that of Halle shown in Fig. 514, where may be seen the false bottom supporting the bobbins, the pump for circulating the dye solution and the perforated cover pressed down by vertical screws. In these mechanical homoapparatus it is always possible to reverse the sense in which the liquid circulates,
;

geneous dyeing being thus more easily obtained.

in the old method, still skeins of spun fibre, various methods of dyeing are in use sticks so that one-half of the skein round smooth on threaded are skeins the used, largely or inverted on the stick from time is immersed in the dye-bath, the skeins being turned to time by hand (see Fig. 515). The form of the wooden vessel is now simpler, as is seen

With

VOT,.

TT.

54

842
from

ORGANIC CHEMISTRY

Figs. 516 and 517, showing the perforated false bottom below which are the direct or indirect steam-pipes for heating the bath, and the perforated wall, P, outside, of which the colour is gradually added so that it may not come into immediate contact with the neigh-

bouring skeins. A mechanical apparatus for dyeing skeins

is

shown

in Fig. 518.

The

skeins are threaded

FIG. 513.

on rods which are rotated by toothed wheels, while the whole frame can be raised from or lowered into the bath by a toothec} rack. Still better is the Klauder-Weldon revolving on a large bronze wheel, one-half of which dips apparatus shown in Figs. 519 and 520 into a trough while the other half is covered, are fixed axial and peripheral rods, which keep the skeins taut. The wheel revolves slowly in the dye-bath, and the pegs, 6, at the ends
:

FIG. 514.

cf the peripheral rods knock against an iron striker inside the trough, so that the rods hende the skeins threaded on them are moved a few centirevolve slightly each time metres. Two workmen suffice for the charging and discharging of 100 to 200 kilos of wool or cotton, while during the dyeing one man can look after three or four of these machines,
;

adding the necessary colour now and then by means of the copper funnel A. The steam for heating the bath reaches the bottom of the trough by the tube d. At e is an automatic indicator which shows when any particular peripheral rod does not turn

DYEING YARN ON BOBBINS

843

owing to the skein being caught. The rapidity of revolution may be altered, but, as a rule, the movement is slow in order that the wool may not be felted. In recent years a happy solution has been found to the problem of dyeing cotton or woollen yarn while still wound on the tubes of the
spinning machine as spools or cops, thus avoiding the winding into skeins and preserving the fibre better. At first the perforated tubes of the bpbbins were inserted in drums which rotated in the bath and from the interior of which the air or liquid was pumped, the bath being hence circulated from the interior to the exterior of every bobbin and vice versa (Figs. 521, 522). There are various other arrangements, but recently a good reception has been everywhere accorded to an apparatus devised by De Keukclaeres of Brussels. This compresses the skeins or bobbins in a square iron or copper case on to a perforated false bottom, while, before the case is covered with a perforated metal plate, the yarn is covered with FIG. 515. sea-sand, which is forced into all the pores of the mass not occupied by fibre by means of a water- jet. The cover is then fitted and screwed tight, and the bath circulated through the mass of yarn by means of a pump capable of the liquid may circulate from bottom to top and vice developing considerable pressure
;

FiG. 516.

versa and, finding

no channels open, is obliged to traverse the fibre uniformly. When the dyeing is finished, it suffices to place the bobbins in a perforated basket and to shake this in a vessel of water to separate the whole of the sand, which collects at the bottom of the vessel and can be used again. For dyeing skeins of cotton with Turkey red, which is the fastest red for cotton, the latter must be prepared and with It is not bleached mordanted. chlorine but is boiled with a caustic soda solution (0-75 Be".) under pressure When (2 atmos.) for 4 to 5 hours. washed, the skeins of cotton are passed repeatedly into a bath of neutralised

ammonium
;

sulphoricinate (20 kilos of 50

;

per cent, strength per 100 litres of water see p. 390) this operation is readily done with a suitable machine (Fig. 523), which is fitted with ingenious contrivances for pressing, wringing, untwisting, and immersing the skeins in the sulphoricinate bath repeatedly and automatically. When thoroughly soaked, the skeins are dried at 50 to 60, then steamed under an excess pressure of 0-5 atmos. in an autoclave for an hour, and afterwards passed into the mordanting bath, consisting of a

Fia. 517.

542

844
basic
is

ORGANIC CHEMISTRY
;
:

aluminium sulphate solution (7 Be.) at 45 (with an iron mordant, a violet colour obtained instead of red with one of tin an orange colour, and with one of chromium a but these mordants are rarely used in pract ce) they are subsereddish brown colour
;
;

quently dried at 45. Use is often made next of a tepid bath consisting either of a

little

chalk suspended in

FIG. 518.

water or of sodium arsenatc, to remove any sulphoricinatc not stably

fixed,

and hence to

a brighter colour. After this preparation, the skeins arc passed into the give subsequently 1.5 per cent, of alizarin paste, calculated on the weight of cotton) contained to dye-bath (10 the temperature is first kept at in wooden vats and heated by tinned copper steam-coils 25 for an hour and is then raised in 30 minutes to 65 to 70, the goods being manipulated skeins arc dried and are often introduced, without washing, into a an hour. The
;

for

dyed

FIG. 519.
1 atmos. second sulphoricinate bath, being then steamed for an hour in an autoclave at an hour for half material the so made is but by immersing the colour is not very bright in a 0-5 per cent, soap solution heated under slight pressure (0-5 to 0-25 atmos.). Thorough at a gentle heat. Although Turkey red is removed washing with water is followed by drying is the fastest red to a small extent if the material Is scoured with a white fabric, yet it the fastness Kornfeld on cotton. now (1910) regards and prepared light against washing red as due, not to the constitution of alizarin, but rather to the formation of a
;

of

salt of aluminium oleate and the calcium salt of alizarin, and still highly resistant double more to the polymerisation of the fatty acid molecules under the action of steam. to a patent by Kornfeld, Turkey red dyeing may be carried out in the usual

Turkey

According

DYEING OF WOOLLENS
means

845

mechanical apparatus with circulation of the bath, the alizarin being rendered soluble by
of sucrate of lime. Cotton Fabrics are sometimes dyed in ropes with vessels similar to those used for wool (see later), but more usually in the so-called jigger (Fig. 524), which is a rather shallow wooden trough provided with two outside rollers worked alternately by gearing so as to* wind or unwind the pieces (3-4) the latter are sewn end to end and are kept quite taut,
;

Fia. 520.

The dye solution in rollers close to the bottom of the trough. be heated at will by direct or indirect steam. The jigger is often used also for dyeing unions, i.e., fabrics composed of cotton warp and wool weft, since these do not cockle or wrinkle, as all-wool goods would do, when passed under tension from one roll to another. Woollens are usually dyed in wooden vessels provided with one or two reels which raise the goods in ropes from the front part of the vessel and drop them into the bath,
and pass below two small
the bath

may

FIG. 521.

FIG. 522.

the inclined wall at the back forcing them in folds on to the bottom of the vessel
(Figs. 525, 526).

itself

reels can be varied at will, being accelerated introduced into the perforated compartment which admits of its gradual passage into the whole of the bath. The perforated steam-pipe also passes into the bottom of this compartment and is' so anaiged that the steam does not strike against the pieces, as this would result in irregular dyeing. The velocity of the reel must not be too high (20 to 50 cm. per second), as otherwise the wool would felt and the bath cool too rapidly. When the pieces are introduced into the vessel, one end is thrown over the reel and then stitched with twine to the other end (see Fig. 526). In some cases the materials cashmeres) are twisted, by the movement in the trough, into very thin

In some cases the velocity of rotation of the

at the

moment when

the colour

is

(e.g.,

846

ORGANIC CHEMISTRY

cords, into which penetration of the colouring-matter is difficult and irregular ; in order to avoid these disadvantages, such fabrics are first folded in two lengthwise and the selvedges

then stitched together. During the dyeing operation, the dyer cuts off small samples of the fabric from time to time, washes them, dries them in a warm towel and compares them with a specimen, so that fresh addition of colour may be made where necessary. Such fresh colour is dissolved

FIG. 523.

the solution being always apart in a wooden bucket in a few litres of the hot dye-bath, which would passed through a very fine hair-sieve to remove granules of undissolved dye, is closed while the new dye is being gradually added. steam-cock the material the spot The dyeing of woollen fabrics is commenced with a bath of tepid water (40 to 50) with the addition of 10 to 15 per cent, of crystallised sodium sulphate and 2-3 per cent, of concentrated 2 S0 4 (or 5 to 6 per cent, of sodium bisulphate) (these proportions referring to the weight of the fibre). The colouring-matter (a few grams for pale colours and as much
;

Fia. 524.

as 5 kilos of black per 100 kilos of material)

is added in several portions at the beginning of the operation, the goods being slowly moved meanwhile. In the course of an hour the bath is brought to boiling and this may last one or two hours before the dyeing is complete. Finally the steam-tap is shut and the goods discharged into a vessel of cold water. After being rinsed and folded roughly by hand they are left to drip on beams for some time, a further part of their water being removed by two or three minutes' centrifuging (see in the apparatus described later. p. 565). The goods are then ready to be dried When very delicate wool or wool and silk fa.brics (with gathers and embroidery) are to be dyed, they are sometimes wound concentrically on hooks fitted to a frame such as

'DYEING OF TEXTILE FIBRES

fabric

84^

that shown in Fig. 527. In this case the frame may not be injured.

is

only

moved now and

then, so that th<

Textile Fibres in Flock are dried in a series of superposed chambers with perforatec bases on which the moist, centrifuged fibre is spread (Fig. 528, I.). At II. is seen a counter poised elevator on which is placed the charged chamber ready to be introduced into iti position in the series in place of one containing fibre already dried. The air used for the

FIG. 525.

FIG. 526.

drying

is forced in by the fan, A, and is healed in tho tubular steam heater, J5. The lowei chambers are dried first, and when these are discharged, the remaining ones are lowered automatically and fresh ones introduced at the top. Yarn or bobbins or spindles can alsc

be dried in these chambers. Skeins of yarn may be dried by threading them, after centrifuging, on rods and fixing these horizontally in frames in a chamber heated by branched steam-pipes on its base the moist air issues from vent-holes fitted to the ceiling. In some cases the yarn is dried

FIG. 527.

FIG. 528.

in hot chambers, the skeins being stretched over revolving reels furnished with central steam-pipes, as is shown in Fig. 529.

Good results are also obtained with the continuous drying machine, in which the skeins are placed on rods, etc., carried by chains moving in a drying chamber (Fig. 530) supplied at A with hot, dry air. The dry yarn issues continuously at Z, while the moist air finds an outlet at B.
Fabrics as they come from the centrifuge are usually dried by passing them, well stretched, over a battery of seven or nine copper drums, (Fig. 531). These are all moved which is 9 regularly by gearing, the rate being regulated by means of the large disc,

actuated at a point more or latter is turned by the pulley

mission.

less distant

from

its

centre

by the

friction roller,

the

joined

by

belting to the general system of

their entire length

power

trans-

The dried

fabrics are then

examined throughout

and breadth before

848

RGANIC
is

CHEMISTRY
any defects
in dyeing or otherwise,

a well-lighted window in order to ascertain if there are so that these may be remedied before dressing.
Dressing of Fabrics
effected

by impregnating them with solution of gum, bone glue, passed beneath a roller dipping into a vessel containing the solution, and is then pressed by a
starch, etc.

The

fabric

is

second roller superposed to the first in a kind of foulard like that shown in Fig. 532 the vessel may have the section shown in
;

The gummed fabrics are subFig. 533. jected to mechanical treatment varying according to the type required. Dressing

Fie. 529.

Fm.

530.

increases the strength

and weight of the tissue, which is next dried and at the same time pulled out both lengthwise and breadthwise in order to bring it back as nearly as possible to the dimensions it possessed before dyeing. This is effected by means of the socalled tenteriny frame, into which the tissue passes, fixed laterally by the selvedges on two

Fia. 531.

the distance between the two chains is gradually chains carrying clips or needle-points increased to the desired width, which is shown on a graduated iron bar, A (Fig. 534). with the gumming machine, J?, and two operatives fixing Fig. 535 shows a complete frame the selvedges on the points of the chains. The widened cloth is dried throughout its
;

whole length by a current of hot air blown into^a long chamber beneath, and finally by a heated drum, C. These frames are 8 to 12 metres long, but are sometimes constructed

CALENDERS
on several
outline
air is
:

849

stories in order to gave length.

the

gummed,

heated at

T and

Fig. 536 gives a better view of the frame in the centrifuged, and folded cloth lies ready on the two benches, the fan, F, forces the hot air into the long chamber, the cloth ;

enters at

and

issues at C.

Milled fabrics and certain others which are required to present a hairy surface are

FKI. 532.

FKI. 533.

passed to the so-called

numbers

(10 to 20 points just touch the stretched surface of the cloth and draw from it fairly long hairs, which are then rendered uniform by passing the dry cloth to the cutting and brushing machines furnished with cylindrical brushes and with drums fitted with cutting edges arranged helically (see Fig. 539) ; the first brush, A, raises the hair, the cutter, B, cuts or

raising* gigs (Fig. 537), consisting of one or more large drums carrying of metallic points or strings of the spiny capsular heads of Dipsacus fullonum cm. in length, Fig. 538) on spindles. The drums or spindles revolve so that the

crops

it off

uniformly, and the second brush,

sets it regularly all in the

same

direction.

Fio. 534.

similar operation is carried out with velvets, which are, however, woven specially, in two superposed pieces attached by a large number of fibres, which are then cut exactly in two so as to give two separate pieces each with a hairy face. When the fabrics are required to have a very smooth, shiny surface, they are passed

and often

after gumming to the so-called calenders. A common type of the latter for "wool and unions, the cloth is seized by the which require but little pressure, is that shown in Fig. 540 to selvedges by two discs fitted with bands, A (called a palmer), which enlarge the cloth the required size and then pass it on to a continuous felt, C, which transfers it in a wellstretched and compressed condition on to a copper drum, B, heated by steam under slight For cotton or cotton and silk fabrics, use is made of calenders with several pressure. superposed and heated cylinders to which pressure may be imparted by means of suitable levers (Fig. 541) in such a way as to exert a kind of friction on the cloth passing from one
:

850

ORGANIC CHEMISTRY
and one
of

cylinder to the other. When a very high finish is required on certain satin fabrics of cotton, they are passed between two massive steel cylinders which are under very high pressure
(hydraulic)

which

is

fluted with very fine striations (as

many

as 10 to 25 per

FIG. 535.

millimetre, as suggested by Schreiner) ; these leave their stable imprint on the fabric like so many minute, shining cylinders like silk fibres, which reflect light under any angle ; Similar calenders are used for this finish is known as silk finish (or Schreiner finish).

obtaining special watered effects (moire).

Fiu.

53(5.

woollen fabrics calenders generally produce a so-called false finish like that of a This is not regarded as desirable by the merchants, and, further, such a finish will show rain-drops, even after drying. In order to avoid this inconvenience and the better to fix the material in both directions, so that it will not shrink when worn.

On

bright sheet of metal

mm>>

FIG. 537.

FIG. 538.

it is

subjected to so-called steaming, i.e., to the action of steam under a pressure of 2 to 3 atmos. (some colours will not withstand this operation). The fabric is well stretched and wound, together with a cloth, round a perforated cylinder ; the roll of two or three pieces thus obtained is wrapped in cloth fastened by strings, the cylinder being then fixed vertion a steam -cock (Fig. 542). The steam, under pressure, is obliged to traverse the
cally

PRESSING OF FABRICS
whole
of the roll of fabric,

851

it issues in a dense cloud (after a few minutes) the operation is at an end ; the roll is then removed, but is allowed to cool without unrolling, since in that way it acquires a better and more resistant lustre. The latter is also found to

and when

FIG. 539.

be improved by carrying out the steaming in a vacuum, the rolls O (Fig. 543) being introduced into a kind of horizontal jacketed autoclave, X, previously heated by passing steam through the jacket when the cover L has been tightly closed, the autoclave is evacuated by passing steam into it and condensing the steam by a water-spray in the cylindrical chamber, W, which communicates with the autoclave by means of the tap, R. After this
;

Jb'ia.

54U.

the steam
versa,

is

passed through the

roll of fabric, either

from the inside to the outside or

vice

by

fixing the roll in a suitable

manner

to the steam-cock.

Of the various other operations comprised in the finishing of fabrics, only that of pressing between hot card need be referred to ; this gives lustre to cloths which are not subjected to steaming and in general imparts a very soft, pleasant feel, more particularly to the finer
woollens.

In

this operation,

which

is

the last of importance, the best effect

is

obtained

when

OR'GANIC CHEMISTRY
first

10 to 15 per cent, of moisture is present, so that fabrics which are too dry are treated with a slight steam- jet, being meanwhile wrapped on drums in large rolls ; after some

FIG. 541.

FIG. 542.

hours these

rolls are

unwound and

the fabric arranged in regular folds, between each

The whole is then left of hot, smooth card. adjacent pair of which is inserted a piece under pressure in a hydraulic press (Fig. 544) for 10 to 12 hours. In order to obtain uniform

FIG. 543.

double pillars in which heating while the pressure is being exerted, presses are now used with steam circulates (Fig. 545) ; also the pillars are sometimes heated electrically. For the folding or rolling of fabrics, and also for measuring, simple and rapid machines

have been devised. For the Mercerisation of cotton

yam

in

hanks

(see p.

808) a machine such as that

shown

PRESSING AND MERCERISING 'MACHINES

853

FIG. 546.

FIG. 545.

854

ORGANIC CHEMISTRY
A

in Fig. 546 is used. The uniformly moist skeins, as they come from the centrifuge, are stretched in a thin layer between the two cylinders, and J3, the distance between which can be increased so that the skeins are considerably stretched.

Then, when the rollers are revolving, a lever is operated to raise the iron vessel, (7, containing cold caustic soda solution of 25 to 30 Be., one-half of each cylinder dipping into the soda. At the end

few minutes the imbibition is complete, the soda solution is off into a tank provided with a pump, while a copious supply of water is sprayed on to the skeins, which are pressed by

of a

drawn
the

roller,

E.

When

washing

is

complete, the tension

is

relieved

and the skein removed.

There are also other machines for mercerising fabrics, these being kept stretched by contrivances similar to those used in the tentering frame (see Fig. 534), while the caustic soda i s removed from the fabrics by means of suction pumps. The fabric is then washed with a little hot water so as to give a moderately strong

may be used to dissolve solid FIG. 547. with advantage be concentrated in multiple effet evaporators (see Vol. I., p. 567). The caustic soda is removed completely from the fabric by thorough washing in cold water, then in a slightly acid bath and finally in water.
caustic soda or

solution of caustic soda, which

may

FIG. 548.

The
rubber

roller,

Printing of textiles, as indicated on p. 831, is carried out by pressing, with a (Fig. 547), the fabric or yarn against a copper cylinder, B, on which the design is engraved. The copper cylinder receives the pasty

colour from a roller, /, dipping into the vessel, G t containing the thickened colour solution, a blade, Z>, then scraping away the excess of colour so that only the hollows of the design

remained filled. Between the rubber cylinder and the fabric, T, to be printed runs a continuous band, E, which is kept taut by the contrivance, V. The arrangement used, with the adjacent drying chamber, o is shown in Fig. 549: the vessel of colouring- matter is at cd, and the fabric is unwound from g together with the accompanying cloth h, and the continuous
9

pressure cloth * ; the dyed and dry fabric at I, while the cloth h is rewound at r, and
to the printing cylinder.
_._
.p

is
i

collected in folds

When

returns constantly several colours are to be

printed on one and the same fabric, a number of rolls and colour vessels are required, as is shown diagrammatically in Fig. 549.
;

Fig.

highly skilled

550 shows a complex machine for the printing of textiles in twelve colours at once workmen are required to regulate its working with accuracy*

PRINTING
A A

855

simple arrangement for printing yarn in skeins by hand is shown in Fig. 551. The skeins are kept taut between the rods and B, and the printing rollers, which are riot very clear in the figure, are below A. The printed jskeins are hung on rods fitted to a framework, this being introduced into an autoclave to be treated with steam under pressure (Fig. 552).

FIG. 550.

boilers,

Printing colours are boiled with the thickening agents in suitable double-bottomed heated by means* of steam and furnished with stirrers. Fig. 553 shows a battery

of such colour- pans.

When mention was made

of aniline black (p. 768),

it

was stated that the complete

FIG. 551.
this colour is obtained in

FIG. 552.

development of

an oxidation chamber

(Fig. 554).

In the case of

yarn, the method of continuous drying illustrated in Fig. 530 gives good results, but with fabrics use is generally made of a chamber with revolving rollers, where the fabric traverses slowly a very long path and issues completely black ; a hood is arranged to carry off acid

vapours.

Of great importance in

this operation

is

the regulation of the temperature

of

856

ORGANIC CHEMISTRY

Fia. 553.

FIG. 554.

FIG. 555,

PROTEINS

857

the draught and of the velocity with which the fabric pass33 through the chamber. Unexpected stoppages are dangerous, as they may lead to corrosion of the fabric or alteration of the colour. To polish and soften silk, the skeins are stretched, twisted, and rubbed repeatedly on a smooth rod fixed in the wall. But nowadays this is done by machines (Fig. 555), which act automatically and give a large output.

DD. PROTEINS

OR ALBUMINOIDS

These are fundamental products in the formation and constitution of animal and vegetable organisms. The protoplasm of vegetable and animal cells, which is the origin of the metabolic processes and hence of the life of the organism, consists of protein substances, which are also indispensable components
of foodstuffs.

nificance,

a physiological point of view they are therefore of the utmost sigbut their chemical nature is very complex and is still little understood, although the investigations of Emil Fischer and a number of able collaborators during the past thirty years have to some extent pierced the veil surrounding this most important group of organic compounds, which had been previously
studied, as regards

From

Iloppe-Seyler,
Sieber, etc.

some of their more superficial characters, by Ritthausen, Hammarsten, Neumeister, Pfliiger, lied in, Kiister, Nencki and

in this group are all composed of their percentage compositions N, and S, with, in a few cases, P 0, 19 to 24 0, 50 to 55 II, 6-9 to 7-3 vary between the following limits N, 15 to 19; S, 0-3 to 24. The heat of combustion of 1 grm. of protein substances varies from about 5000 to 6000 calorirs. The proteins have high refractive indices. Their solutions are Isevo-rotatory, the specific rotation varying with the concentration and with the salt content protein ions have higher rotations than the neutral proteins. The molecular magnitudes of these substances cannot be established with certainty, since it is not easy to isolate single individuals, only very few of them crystallise, none are transformable into vapour, and in no case are true solutions
C, II, 0,
;
:

The numerous substances comprised

obtainable capable of cryoscopic or ebullioscopic measurement their solutions are colloidal. Direct or indirect attempts to determine their molecular weights
;

have given numbers varying from 10,000 to 30,000. Both the sulphur and the nitrogen occur in two groupings, being partly removed by hot potash and partly more stably combined. Absolute alcohol coagulates proteins and precipitates them to some degree unchanged from their aqueous solutions. They are also precipitated unaltered by solutions of sodium chloride, magnesium sulphate or ammonium sulphate of different concentrations, which are characteristic of the various
proteins.

arc coagulated and precipitated from their aqueous solutions quantities of mineral acids (nitric acid may be in excess). They have a feeble acid character and form salts as insoluble precipitates with metallic

Proteins

by small
salts,

and they dissolve small amounts

mercuric chloride, copper sulphate, etc., of freshly precipitated ferric hydroxide. From these metallic precipitates proteins are liberated in a changed form. Less pronounced is their basic character (like the amino-acids, they behave as both acids and bases at the same time), although egg-albumin is completely
e.g.,

ferric chloride, acidified

precipitated
acid.

by weak

acids,

such as tannin, phosphotungstic acid, and picric

Aqueous solutions of the proteins are coagulated on heating to different characteristic temperatures, and the coagulated proteins dissolve only in an
excess of acid or alkali in the hot, their constitution being modified thereby
VOL.
ii.

65

858

ORGANIC CHEMISTRY
:

and H 2S and NH 3 sometimes evolved with alkalis they form acuminates* and with acids Aicd-Albumins (syntonins* see p. 862), both insoluble in water and reprecipitable by neutralisation. By the protracted action of these two reagents (Hydrolysis, see below) or by the action of pancreatic juice, which contains Tryptase (see p. 1 3d), they yield various amino- or diamino-acids glycocoll, alanine, phenylalanine, aspartic acid, glutaminic acid, leucine (in abundance),
:

pyrrolidinecarboxylic acids, tyrosine, serine, triaminotrihydroxydodecanoic acid, )8-indoleacetic acid, arginine, lysinc, ornithine, tryptoghane, cystine (sulphur compound), etc., all of them optically active with the exception of glycocoll. When a piece of boiled egg-albumin is heated at 37 with gastric juice, it rapidly dissolves with formation of Peptones and Albumoses. The peptones, passing into the intestines, undergo further hydrolysis, and as final products yield amino-aeids. The complete hydrolysis of the albumin may be effected more rapidly by means of a concentrated acid (e.g., HCI), which gives amino-acids and also ammonia. By putrefaction various other substances are formed Ptomaines, such as cadaverine (see p. 257), putrescine or tetramethylenediamine, etc. glucosamine, methylamine, ammonia, /3-indoleacetic acid, phenylacetic acid, carbonic acid, hydrogen sulphide, formic to caproic acids, partly of normal structure and partly optically active (valeric and caproic) etc. indole, skatole, phenol, cresol, mercaptan, methane, etc., all of these being oxidation or reduction products of the original compounds obtained. The action of pathogenic bacteria on proteins yields poisonous substances, the Toxalbumins, which are similar in composition to the proteins and lose their toxicity when their aqueous solutions are heated. The following reactions are characteristic of the proteins Protein solutions give a violet coloration (like biuret) with alkali and a few drops of 2 per cent, copper sulphate solution (biurel reaction). With nitric acid in the hot and even in excess a yellow precipitate is formed
: ;
;
:

(xanthoprotein reaction). With Millon's reagent (see p. 828) a red coagulum is formed on boiling. The degradation or hydrolysis of proteins, when it is complete and takes account of all the more or less complex groups composing the protein molecule,
will permit of an attempt, with probability of success, to synthesise these substances completely. Such more or less gradual decompositions are attained by protracted heating (for different times with different proteins and in some cases for 200 hours) in an autoclave, or by means of soda or baryta (Schiit.zenberger), or, better, 25 per cent, solutions of hydrochloric or sulphuric acid. Even under these conditions, however, some of the intermediate compounds cannot be detected, the hydrolysis being in many cases too rapid. Hugounenq and Morel (Intern ational Congress of Applied Chemistry, London, 1909) have obtained a somewhat more gradual hydrolysis by using 15 to 25 per cent, hydrofluoric acid solutions and heating for 100 to 150 hours. Interesting results were obtained by N. Zelinsky (1912) with formic acid (1 to 30 per cent.), best at

a high temperature and pressure.

The separation of the numerous amino-acids resulting from the hydrolysis of the proteins constitutes a difficult problem, which has recently been solved by E. Fischer for the amino-acids and by Kossel for the diamino-acids. Fischer
subjects the esters of the amino-acids to fractional distillation in vacuo and thus determines their separate amounts. It is thought that the amino-acids occur in the proteins in a condensed form similar to Glycylglycine, CH 2 CO -NH CH 2 C0 2H. Indeed, 2 Fischer was able to synthcsise the so-called Pol ypeptides, which contain such groups and in many respects resemble the natural peptones derived from proteins the esters of the amino-acids readi ly give up alcohol and undergo (see later) ketonic condensation to polyanhydrides, and thebe, under the influence of alkali, take up a molecule of water, giving the peptides

NH

ALBUMINS
2NH 2 CH 2
00,0^1.

859

- 2C H OH
2 G
2

-|-

Ethylglycocoll

f Double Anhydride or Diketopiporazinc

2

NH<J

>NH (and this + H 0)

2

NH CH a CO NH CH 2 CO H
Dippptide or (ilycylglyrlnc

By chlorinating thecarboxyl of the dipeptide with PC1 5 in acetyl chloride solution, a second molecule of ethylglycocoll may be caused to react with formation of a tripeptide, and so on, higher polypeptides similar to the natural
ones being ultimately obtained,
'

...

CO

Cl

+ NH CH
2

CH 2

00, C 2 H 5 = HC1 -CO a -C 2 H5

. :

+X

CO Nil

these polypepfides are completely hydrolysed by hot concentrated IIC1, are digested by tryptase, withstand cold alkali, are soluble in water and insoluble in alcohol, and give the reactions of the proteins (see below). These syntheses, which represent the first small step towards the synthesis of the proteins, give an idea of the enormous difficulties to be overcome before the natural proteins can be reconstructed. Indeed, since the dipeptides have molecular weights of about 100, while with the proteins the molecular weight certainly exceeds 10,000, at least 100 of these groups must be present. Also, as several of the amino-acids contain one or more asymmetric carbon atoms, stereoisonierism
is

possible,

and

so likewise

is

tautomerism,

e.y.,

HN-CO
of

N:C(OII)

The investigations of Fischer have resulted in the synthetical preparation more than a hundred of the simpler polypeptides, and of a tetradecapeptide, but on ascending the series the complications and difficulties increase disproportionately. This problem could occupy a whole generation of chemists, and its solution Would be a glorious triumph for the twentieth century, as it would banish for ever the Malthusian threat that one day humanity will be starved owing to the disproportion between the population and the productive capacity
Indeed, while it is not possible to replace the proteins in human nutriment by fats or carbohydrates -these alone leading to rapid decay of the organism and to death proteins of themselves are able to supply all the needs of the organism. So that the insufficient production of proteins in nature at some future time would of a certainty be accompanied by famine, unless a method of synthesising proteins by chemical means had previously been discovered. Berthelot imagined that one day the air would supply the oxygen and nitrogen, and water the hydrogen for this synthesis, and it is not for us to deny that the dream of yesterday may become the reality of to-morrow, if chemistry learns how to imitate the simplicity and economy of the natural synthetical processes best exemplified in plants, which from carbon dioxide, water, and nitrates are able to effect continuous production of carbohydrates, fats, and Our laboratory synthetical methods are still too cumbersome, too proteins.
of the earth.
indirect, and generally too costly. Only when the action of catalysts and light and the laws of colloids have been more closely studied can any hope be entertained of a more rapid progress in the synthesis of such complex organic

substances.

The numerous
groups
:

different proteins are usually classified in the following groups

and sub-

I.

NATURAL PROTEINS

(1) (of eggs or Egg-albumin, of blood serum or serum-albumin, of milk or lactalbumin, of muscles, of plants, etc.). These are the most common and also the best known of the proteins, since they can

ALBUMINS

662

860

ORGANIC CHEMISTRY

be isolated as definite, crystalline, chemical individuals. They are soluble in water, dilute acid or alkali, or neutral solutions of NaCl, MgS0 4 , or (NH 4 ) 2 S0 4 (the globulins being insoluble), but in acid solution these salts precipitate the albumins. In the hot they are
coagulated.

The products

of

OH
by

C 6H 4

CH 2 C0 2H,

the putrefaction of albumin contain also j9-Hydroxyphenylacetic Acid, which occurs likewise in urine (acicular crystals coloured greenish

ferric chloride).

There exists nowadays a considerable trade in dry albumin obtained from the egg and from blood. In various countries, eggs and yolks are preserved in salt and employed in different industries (for tanning, making lecithin, 1 tulinary purposes, etc.), and the fresh white separated is diluted with a little water, beaten until it forms a froth, allowed to stand until the latter is destroyed, filtered through woollen bags, and evaporated in a stream of air at 30 to 40 in large shallow pans after 40 to 60 hours there remains a thin, yellowish, transparent pellicle, which is completely soluble in water and keeps without developing
;

2 any unpleasant odour.

C 42 H^ 6 O NP (see. p. 462), is an ester of choline (p. 267) and of glyctrophosphoric combined as a glyceride of palmitic or stearic acid. When boiled with water or barium hydroxide it decomposes into choline, glycorophosphoric acid (p. 258), palmitic and stearic acids. Its constitution, first studied by Strecker (1868), would therefore be
1

Lecithin,

acid,

CH a r -0-CO-0 17 H 85 CH O CO-C 16 H 31
(

CH 2 -0-] PO(OH)
It is dextro-rotatory,

CH 2 CH a N(OH)(CH 3
-

) 3,

but when heated with 95 per cent, alcohol

is

racemised to the inactive form,

is converted into l-lecithin by the action of lipase (p. 134). Distcaric and dioleic lecithins are also known. Lecithin occurs in the animal kingdom [nerves, brain, blood corpuscles, egg-yolk (9-4 per It forms cent.) ] and in the oils and seeds (0-5 to 2 per cent.) of cereals and leguminous plants. an orange-yellow, waxy, crystalline mass, and is soluble in alcohol, ether, chloroform or glycerine, and slightly so in acetone or ethyl acetate. It is hygroscopic and with water swells and forms an opalescent solution, from which it is separated by various salts (including 1HC1 4 ) ; it combines with both acids and bases, forming salts. Lecithin is decomposed by the pancreatic juice, the resulting products being completely resorbcd by the intestine. It is largely employed as a tonic, either as such or in the form of various salts. It intensifies metabolic processes, causes assimilation of phosphorus and nitrogen, reinvigorates the blood, and results in increase of weight. Industrially lecithin is extracted from egg-yolk, in which it occurs partly combined with albumin as lesithalbumin, which may be isolated unchanged and then decomposed into its components by heating with alcohol. To obtain lecithin, JO kilos of egg-yolk is shaken with 10 kilos of cold methyl alcohol (this dissolves less fat than ethyl alcohol) for three hours, left overnight and filtered, the residue being washed with 10 kilos of methyl alcohol in several portions. The alcohol is then distilled off under diminished pressure and the lecithin thus obtained dissolved in ether and reprecipitated with acetone. According to FT. Pat. 390,683, the fat and cholesterol are dissolved and the lecithalbumin left undissolved when egg-yolk is treated with ethyl acetate. Separation of lecithin as its salt with cadmium chloride is more complicated. Many other processes have been patented. Before the war egg lecithin was sold at 3 to 4 per kilo, but during and after the war the price increased greatly. 2 The eggs produced by hens of different breeds are of varying size and weight (from 45 to 65 grms. ; duck, goose, and turkey eggs weigh from twice to four times as much) and are composed of about 60 per cent, of white, 30 per cent, of yolk, and 10 per cent, of shell (mainly calcium carbonate) ; the white contains 86 per cent, of water and 13 per cent, of albumin, and the yolk about 51-5 per cent, of water, 28-5 per cent, of fats, 15-8 per cent, of proteins (principally vitellin), 2 per cent, of salts, 0-45 per cent, of cholesterol, 1-2 per cent, of phosphoglyceric acid, and 0-4 per cent, of extractive substances. As regards its nutritive value, an egg weighing 60 grms. is equivalent to 50 grms. of meat, while its heat value is about 80 Calories. Continuous* evaporation of water takes place through the shell of the egg, and the volume of the content* diminishes, leaving a free air-space varying in size in different eggs which may be observed the egg at a candle flame in a dark chamber. Fresh eggs are also distinguishby looking through able from stale ones by the specific gravity : fresh eggs sink in a salt solution of sp. gr. 1-078,. those 2 to 3 weeks old in one of sp. gr. 1-060, those 3 to 5 weeks old in one of 1-060, and rotten, eggs in one of sp. gr. 1-015. It has also been observed that fresh eggs float horizontally on a denser liquid, those 4 to 6 days old at an angle of 20, those 8 to 10 days old at an angle o$ about 45, and those 16 to 20 days old at an angle of 60 The preservation of eggs is of considerable importance, since in summer eggs are abundantand cheap, while in winter they are scarce and cost double as much. A common means of preservation formerly employed consisted in immersing the eggs in water saturated with lime* (which partially filled UD the pores of the shell with calcium carbonate), but in this way they

which

GLOBULINS, NUCLEO-ALBUMINS
From fresh
The blood
is first

861

blood (from the butcher's) pure albumin is separated with greater difficulty. allowed to undergo spontaneous coagulation, the blood globules and f ther impurities thus collecting in a compact mass so as to allow of the ready decantation of the faintly coloured liquid serum containing the albumin or, after coagulation, the blood may be introduced immediately into a centrifugal separator (see p. 476). The centrifu^ed or decanted liquid is beaten (without dilution), filtered, decolorised with charcoal, and dried as above. In many cases decolorisation is difficult, and the albumin has to be precipitated the decanted precipitate is washed and suspended in water, which is with lead acetate then saturated with carbon dioxide, the lead carbonate being allowed to settle. The clear albumin solution is treated with a litfle hydrogen sulphide, which removes traces of lead,
; ;

and

filtered, and the pure solution evaporated as with egg-albumin. According to Ger. Pat. 143,042, the serum-albumin is coagulated by means of salt, dissolved in ammonia and treated at the boiling-point with hydrogen peroxide, the excess of

ammonia being subsequently

consists in treating the

driven

off.

The method described

in Kng. Pat. 10,227 (1905)

scrum successively with hydrosulphitc, acetic acid, and sodium acetate, the liquid being then neutralised with ammonia and evaporated as usual. Albumin is used in various industries for photographic papers, in textile printing, in etc. printing titles in gold-leaf on books, as a clarifying agent in wine-making (see p. 260), Egg-albumin cost, before the war, according to its degree of purity, 24 to 28 per the dark at 88s., the quintal. Blackish blood-albumin was sold at 48-s. to 60s. per quintal,
:

pale at
(2)

to

8,

and the pale powdered at

128*. to 208,9.

GLOBULINS

insoluble in water

are (of plants or Phytoglobulins, Serum-globulin, Lactoglobulin, etc.) but soluble in dilute acid or alkali. At 30 they are precipitated unchanged

sodium completely by solutions of ammonium or magnesium sulphate and partly by chloride solution. Their solutions arc coagulated by heat.
are acid in character and decompose (3) NUCLEO-ALBUMINS (Vitellin, Casein, etc.) dissolve with formation of salts in but in soluble are carbonates water, slightly they caustic soda or ammonia and are then coagulated neither by heat nor by alcohol. They contain phosphorus (0-85 per cent, in casein) but arc distinct from the nuclco-proteins, which give xanthine bases among their decomposition products. Casein is found in milk it is soluble in borax or acids at 50 (see p. 643) and is coagulated by rennet or by dilute Converted into salts in potassium carbonate and is rendered insoluble by formaldehyde. various ways, it is placed on the market as a concentrated and readily digestible food to make var(plasmon, nutrose, tropon, etc.) ; it is mixed with mineral colouring-matters The hydrolysis of casein yields various amino-acids and complex tribasic acids nishes.
; ;

(Skraup). Vegetable caseins are also known. To obtain pure casein in the laboratory, diluted skim-milk to which 0-5 per cent, of acetic acid has been added is heated to 55 to 60 and the precipitated casein collected on cloth, washed well with water, redissolved in very dilute ammonia, decanted or filtered to remove

Prepared

the undissolvcd fat and nuclein and then reprecipitated with acetic acid as at first. It is and dried in a vacuum. again collected on cloth, washed with alcohol and then with ether, in this way, it is free from fat, leaves less than 0-5 per cent, of ash and contains

15-5 to 18 per cent, of nitrogen. From ordinary casein a modification known as paracasein, Commercial containing 14-8 to 15 per cent, of nitrogen, may apparently be separated. casein (see p. 643) contains less than 3 per cent, of ash and less than 0-1 per cent, of fat, and costs 64s. to 80s. per quintal. Riegel (Ger. Pat. 117,079 of 1900) precipitates it in a is detected on textiles highly pure state from milk by means of ethylsulphuric acid. Casein or paper by Adamkiewicz's reaction, a drop of a mixture of glyoxylic and sulphuric acids
cent, of sodium chloride acquire an unpleasant taste an improvement is effected by adding 5 per Others preserve them in pounded salt or in salt and bran, pointed end down, to the lime water. while others again smear them with wax, vaseline, and oil or tallow. Largo quantities of eggs are now preserved for some months (May to November) by placing them in thin layers on wooden lattices in cold chambers, which are kept at a temperature of 1 to 2 and a humidity of 70 to 80, and are well ventilated, preferably by means of an apparatus producing ozonised air. In certain cases good results are obtained by preserving the eggs in 10 per cent, sodium silicate solution, of the silicate or of although such eggs often burst during subsequent boiling. A mere coating For transport eggs are arranged in layers, with alternate layers of collodion is of little avail. old straw, in wooden boxes. The value of the eggs imported into England was 80,000 in 1864, 8,000,000 in 1906, and 6,800,000 in 1910 (about 3,300,000 from Russia, 1,750,000 from Denmark, 560,000 from in Austria-Hungary, 420,000 from France, 360,000 from Italy, 200,000 from Germany), addition to 3,800,000 from Ireland.
;

862

ORGANIC CHEMISTRY
:

being placed on the surface, which is then gently heated over a flame the drop of liquid assumes a transitory violet-red colour.

in presence of casein,

(4) PROTEINS WHICH COAGULATE (Fibrinogen, Myosin, etc.) are distinguished by exhibiting a first coagulation under the influence of certain enzymes and a further coagulation by heat or absolute alcohol. (5) HISTONES (Globin, Nucleo-histone, etc.) contain sulphur and are markedly basic

in character

they are precipitated by alkalis, and in acid solution give insoluble compounds with the albumins. Niicleo-histones are obtained from the leucocytes of the thymus gland and from the testes of certain fish. The protein part of the haemoglobin molecule of the rod blood corpuscles consists of a histono, glob in. The histones have certain properties in common with the peptones and albumoses. (6) PROTAMINES (Salmin, Clupein, Sturin, etc.) do not contain sulphur but contain up to 25 per cent, of nitrogen and are composed mainly of diamino-acids (arginine) they
; ;

arc obtained from the spermatazoa of many fishes (salmon, herring, sturgeon, etc.). They and the histones are the least complex proteins. They are still more basic in character than the histones and readily form platinichlorides,
sulphates,
alkalis.

and

picrates,

which are

all

crystalline.

They

arc precipitated

by

dilute

II.
(1)

MODIFIED PROTEINS
are derived from true proteins by various trans-

ALBUMOSES

and

PEPTONES

The albumoses are soluble and cannot- be coagulated, but are precipitable by ammonium sulphate and other salts. The peptones arc regarded as the last decomposiformations.
tion products of the proteins which givo protein reactions (the biurct reaction) ; on decomposition they give amiiio-acids without intermediate products. (2) SALTS OF PROTEINS (Syntonins or Acid-albumins, Albuminates) are markedly acid in character.

III.

CONJUGATED PROTEINS (PROTEIDS)

is

These represent combinations of proteins with other complex substances, and are
coagulable by alcohol.
(1)

HAEMOGLOBIN

the colouring-matter of red blood corpuscles and

is

regarded as

a protein combined with a colouring-matter containing iron, since, when defibrinated blood is heated on a water-bath with sodium chloride and acetic acid, the hspmaglobin is decomposed into albumin and Hsematin, t'3.3H 32 OiN 4 Fe -OH. The latter is a brown substance containing 8 per cent, of iron, and by treatment with sodium chloride is transformed into Haemin, C-ggHgoO.jN^Fe Cl, which forms characteristic, reddish brown, acicular The constitution of luouiatin has been elucidated by the work of Nencki and crystals. Zaleski (1901), Kiister (1901, 1906, 1914), Willstatter, Knorr, Piloty, and H. Fischer (1911, 1912), and that of the haematinic or hsematmiminic acid obtained on oxidation renders

,CO
certain the presence of the pyrrole complex,

CH 2 CH 2 C0 2 H,
||

NH<^ X'O

this yielding

Cl

CH 3
The haemoglobin
of venous

succinic acid

when

oxidised with bichromate or permanganate.

blood

of considerable importance in respiration, as it combines very readily with atmospheric oxygen (when the blood traverses the lungs) forming Oxyhaemoglobin, which is found in arterial blood and carries the oxygen to the tissues, afterwards returning to the
is

Blood-spots (even old ones) may be detected by Teichmann's test : to a solution of the spot in a little glacial acetic acid are added a trace of sodium chloride and then a small quantity of pure concentrated acetic acid, the liquid being heated to boiling on a watchveins.

and one or two drops of the hot solution placed on a microscope slide and allowed to evaporate slowly in the cold ; a drop of water is added, a cover-glass applied, and the slide observed under the microscope. The brown hsemin crystals resemble barley-corns, but are sometimes rhombohedral and generally crossed in groups ( Fig. 556) ; viewed in polarised light between crossed nicols, they appear luminous and golden on a dark ground. They are insoluble in water or cold acetic acid, but dissolve in alkali. also be identified by means of the catalytic action of the haemoglobin, Blood-stains
glass
,

may

BLOOD
by

POT

863

which colours alcoholic guaiacol tincture or alkaline phenol phthaloin previously decolorised
1 zinc dust or, better, the leuco-base of malachite green (F. Michel, 191 1). T. Gigli (1910) states that a very sensitive reaction is given by a fresh mixture of 3 drops of benzidine (5 per cent, solution in acetic acid) and 2 drops of 3 per cent,

hydrogen peroxide given immediately by a trace of blood. Bardach and Silberstein (1910) propose the use of guaiacuin resin and sodium perborate. Oxyhaemoglobin has a composition differing little from that of the proteins, but it contains 04 per cent, of iron combined in the ferric state, as with haoinin and ha?matin, whilst the reduction product of the latter, i.e., hemoglobin, is a ferrous
solution
;

a blue coloration

is

compound

(W. Kttster, 1910). In a vacuum (or under the action of ammonium sulphide) it loses oxygen giving haemoglobin. Haemoglobin forms a red crystalline powder soluble in water and reprecipitable in the Both luemoglobin and oxy haemoglobin give characteristic crystalline state by alcohol.
absorption spectra.

Haemoglobin and also its ash exert a catalytic action in certain combustion phenomena sugar moistened with a little human blood burns with great energy. When a current of carbonic oxide is passed into a solution of red oxyhamioglobin (dofibrinated blood) the oxygen is displaced and the liquid assumes a violet-red colour, carboxyhcBms)globin which can be obtained in bluish crystals
;

e.g. 9

being formed. An aqueous solution o this compound (blood poisoned with carbonic oxide) gives two characteristic absorption bands between the I) and K lines of the spectrum,

and these bands do not unite or disappear as happens in the case of oxy haemoglobin when a few drops of ammonium

55 -Hwmin crystals at *" sulphide are added to the solution. Hemoglo bin itself gives different magnifications. a single absorption band between the 1) and E lines. (2) NUCLEOPROTEINS or Nucleins have a pronounced at-id character and are insoluble
-

and acids, but soluble in alkali. They represent compounds of proteins with a Nucleic Acid, which is phosphoric acid neutralised partially by basic organic groups, such as xanthine, guanine, etc. The nucleins contain 5-7 pe^ cent. P, 41 per cent. 0, and 31 per cent. O, and are hence sharply distinguished from true proteins although they give the same colour reactions. They form the fundamental constituents of cell nuclei.
in water
(3) GLUCOPROTEINS are acid in character and are formed of a protein combined with a sugar derivative. They are insoluble in water and with a little lime-water give neutral, When frothy, and ropy solutions which are not coagulated by heat or by nitric acid. hydrolysed with alkali or acid they yield sugar, peptones, and Syntonins. These compounds, which are poor in nitrogen (11-7 to 12-3 JKT cent.), include tho

Mucins.

IV.

ALBUMINOIDS

Those constitute the fundamental parts of the cartilaginous tissues and epidermis of animals and comprise :
1 Blood-spots may also be detected by means of hydrogen peroxide : it is sometimes sufficient to press a piece of moistened filter-paper 011 tho dry blood-spot and then to immerse it in hydrogen peroxide solution, to obtain a copious evolution of oxygen.

To ascertain from what animal the blood comes, and in general to discover if it^is human blood, Uhlenhuth's test (1909), based on the formation of different antitoxins in different animals Tristovitch and Bordet (1899) showed, indeed, that if an extraneous serum (see p. 138), serves. (e.g., human) is injected in several doses into the blood of an animal (?.</, a guinea-pig), the serum of this animal (antitsemm) ultimately acquires the property of precipitating (or rendering turbid in the case of dilute serum or dilute blood) the blood of the animal which furnished the injected serum (e.g., man). If even a very dilute solution of blood (obtained, for instance, by extracting a dried blood-spot with a little water) is cleared by filtration and- treated separately with different clear antiscra to ascertain with which of them a turbidity is produced, it can be stated with certainty that the blood-spot was derived from the animal whose serum, when injected into the guinea-pig, produced the aiitiserum rendering the blood solution turbid. The test must be applied very carefully and with parallel control experiments ; it does not distinguish between the bloods of similar animals, e.g., hens and pigeons, sheep and goats, apes and men. The difference between various species becomes more evident when dilute solutions or, better, dilute blood and a little concentrated antiserum are employed. All these phenomena, studied by Uhlenhuth, and subsequently by others, are based on the precipitation of the albuminoid substances of the different sera (precipitin*), and they allow of tho determination of the character of blood-spots 60 years old. Clear solutions and sterilised vessels are always used for the test.

864
(1)

ORGANIC CHEMISTRY
ELASTIN, which forms the

elastic pirt of the tendons and ligaments, is insoluble the latterloses the whole of its sulphur. with but or in dilute acid alkali, is the principal constituent of the nails, horns, feathers, epidermis, (2) KERATIN of It is insoluble in water, but when heated under pressure, best in presence etc.

hair,

alkali, it dissolves
is

with partial decomposition. It contains 4-5 per cent, of sulphur, which eliminated to some extent by boiling water. With nitric acid it gives the yellow xanthbprotoin reaction (see alwve, yellow spots on

combine boiling-point not by which is precipitated by tannin or by mercuric chloride acidified with HOI but the extent of mineral acids. They contain stably combined sulphur. They consist, to and Bottcher, 1909-1910), and, like the ,85 cent., of ammo-acids (Skraup, Biehler

skin treated with nitric acid). They are abundant in bones, hair, tendons, and cartilage. (3) The COLLAGENS and dissolve, forming ordinary glue, or gelatine, with water at the

mainly Prolylglycocoll of alkali leads to thiohy drat ion, allows of their differentiation disulphide, which in presence a is not from agglutinating substances (Sadikow, 1910) the agglutination of gelatine only of the side-chains. Gelatine a condensation also but molecule, of the collagen disgregation for which has undergone prolonged exposure to light loses some of its absorptive power water owing to the formation of formaldehyde, which hardens the glue (Meisling, 1909). On hydrolytic decomposition, the collagens give glycocoll (while the albumins give tyrosine, 1 and Very dilute solutions of glue give, with boiling
;

per and azomcthyl-groups. Unlike casein, protamines, are true proteins containing methoxythem with caustic baryta, On on acid hydrolysing little hyd/olysis. glutamic they give as primary E. Fischer and B. Boehner (1910) obtained Proline (pynolidine-a.-carloxylic acid) is also obtained from gelatine, does not which Acid, a-Amino-S-hydroxyvaleric product ; By digesting gelatine with trypsin, Levene (1910) obtained give proline with baryta. The absorptive power of the collagens for carbon Anhydride.

leucine, glutamic acid,

1

asparagine.

and hide waste, Manufacture of Glue and Gelatine. The prime materials are bones From bones the fat is first extracted (see p. 4b lime. generally untanned and preserved with of hours in a large and also Vol. I., p. 047), and the crushed bones then heated for a couple wmn into soluble gelatine autoclave with water and steam under pressure, so as to convert the dilute solutions being used for a this treatment is repeated two or three times, the final more
;

in a Kestner shows 12 to 14 on the glue-densimeter arid is concentrated in a vacuum (e.g., then discharged into zinc moulds surrounded by apparatus Vol. L, p. 563) to 45 to 40, and In some cases, however, the bones and hence also the glue are freed cold water to solidify. cent, hydrochloric 7 from calcium phosphate by treatment with four times their weight of 6 to per JH precipitated trom acid (sp gr 1-05) until complete softening occurs. The calcium phosphate a doublethe solution by means of lime and calcium carbonate, while the osseiii, placed of glue. According to bottomed vessel heated by steam, is rapidly converted into a solution under pressure (only Ger Pat 144,398, the calcium phosphate may be dissolved by aqueous SO 2 are then cut into suitable the 'treatment under pressure is patented). The solid blocks of glue which are placed in chambers through sizes and dried on wide-meshed nets arranged on trolleys, this temperature which air at 25 to 30 is circulated by means of fans. If the air is above this account, and also because the glue will melt, while if it is too dry the cakes are deformed. On in summer. Dry bone-glue contains 15 to 20 per cent, it would readily putrefy, glue is not made

subsequent operation.

Batteries

of autoclaves

arc generally used.

The

solution obtained

When the mineral part of the bones is dissolved drying occupying 10 to 12 clays. a mineral acid, gelatine remains. and also other waste (nerves, cartilage, Skm-glue (leather glue) is prepared from hide-waste or swelling in water, which likewise etc ) by defatting with carbon disulphide and softening milk removes impurities. It is then macerated for three weeks in a series of vessels containing It is then blood, etc. of lime, which is frequently renewed to eliminate any remaining fat, of lime (which would make the glue turbid) thoroughly washed in water and the last traces
of water, the

bv SO o

or

or phosphoric removed by means of dilute hydrochloric acid, or, better, of sulphur dioxide The waste prepared in this way is treated with hot water and stearn in wooden vessels acid the glue-densimeter, with false bottoms, and the first solutions, showing densities -of 16 to 20 on The two or three succeeding extracts, which are more dilute, are solidified in moulds AS above.

a single or multiple-effet vacuum apparatus (seep. 560), discs to break up the froth, and are then allowed to used Good results are now obtained with Kestner concentrators (,w above). The waste set The finer qualities, filtered, decolorised, and of dry glue. gives about one-third of its weight name of gelatine and cost almost double. prepared from pure, fresh, raw materials, bear the untan them In order to utilise tanned hides in the manufacture of glue it is necessary to and lime if chrome tanned, they by successive treatments with dilute alkali solution, water, acid, then with an abundant supply of water and finally treated first with dilute
are concentrated to 20
to 22
in

surmounted by a column with perforated

are

sulphuric of dilute HU, with lime. In either case, the remaining traces of lime are removed by means Pat. 22,738 eliminated latter the by treatment with alkali and washing with water (Eng. being

FM-glue

is

obtained from the well-purified swimming -bladders of various species of Acipenser,

GLU

S I

DES

865
coloured solution, which

ammonium molybdate solutions, a characteristic precipitate and may be applied to quantitative estimations (E. Schmidt,' 1910).
V.
more to those

VARIOUS PROTEINS
;

its hydrolytic products approximate Spongin enters into the formation of sponges of the collagens than to those of the albumins, but they are more resistant Cornein constitutes coral and gives to the action of soda arid baryta than collagens. fibroin leucine on hydrolysis. Fibroin and Sericin are obtained from silk (see p. 813) dissolves in energetic alkalis with elimination of ammonia and formation of Sericoin, and when completely hydrolysed it yields tyrosine and glycocoll but not leucine. The Enzymes (see p. 134) belong to the group of complex albumins.
;

GLUCOSIDES AND OTHER SUBSTANCES OF UNCERTAIN OR UNKNOWN COMPOSITION

Glucosides have been defined and the synthesis of artificial glucosides described on aromatic or aliphatic compounds with carbopp. 530 and 531. They are compounds of to Pfeffer, difficultly hydrates. In vegetable organisms these glucosides form, according dialy sable substances which serve the plants as reserve material, gradually becoming are decomposed by the various enzymes occurring in other cells. This uti Usable as

they

shown by T. Weevers (1903 and 1908) for Salicin, which is decomposed (by cmulsin) into glucose and saligemn (hydroxybenzyl alcohol), the latter being probably further transformed into a final product known as Catechol. The latter is a phenol found throughout the whole plant (e.g., Salix purpurea), and its quantity is inversely proportional to that of
was
well

the salicin present it is possible that it reacts with fresh quantities of glucose, regenerating Whilst the sugars are gradually utilised in the growth of the plant, the aromatic salicin. not for yeasts) is used in the group (which servos as a reserve of carbon for bacteria but continuous reconstruction of the glucoside. Thus plants are able to prepare reserve materials when the carbohydrates arc not udlincd, they are transformed into in different
;

ways

insoluble starch, or into glycogen, or into glucosides. AMYGDALIN, already mentioned on p. 130, has a composition corresponding with and forms colourless crystals which are soluble in water and melt at 200. O C
20

27

in the stones of various fruits (cherries, poaches, bitter almonds, otc.) and in When hydrolysed by acids or enzymes (see p. 134) it yields the loaves of the cherry-laurel. dextrose, prussic acid, and benzaldehyde. SAPONIN, C 32 H 62 O 17 is obtained from Saponaria root, quilaya bark, arid the Indian It is

HN

found

used for washing garments in place of soap, and is also employed to produce a persistent froth (e.g., to give a head to beer). It is soluble in water, has an irritating taste and smell, and dissolves red blood corpuscles (is hence poisonous). It is extracted
chestnut.
Jt is

treatment with acid, lime, steam, water, etc. especially of Aripenser sturio (sturgeon), by be used. Fish-glue costs double According to Ger. Pat. 131,315, the blubber of whales may also or treble as much as the best qualities of other glue. of glue with its own weight of water and Liquid glue is obtained by th protracted heating one-fourth or one-third of its weight of hydrochloric, acetic, or nitric acid (the last at 35 Be. ; the nitrous fumes must be carried a>vay by a good draught). F. Supf ((Jer. Pat. 212,846 of 1908) obtains liquid glue by treating, sa#, 450 kilos of glue with 120 kilos of sodium naphthalene'

Glue is analysed by determining the ash (2 to 3 per cent.) and the increase in weight caused should not dissolve), the best qualities by immersion for 12 hours in cold water (in which it has an almost neutral reaction, and absorbing most water and swelling. The ash of bone-glue The ash of hide-glue does not chlorides and phosphates are found in its nitric acid solution. The aqueous solution acid. melt, ha.8 an alkaline reaction, and contains little or no phosphoric kinds are of pure glue has a neutral or very faintly acid reaction, while those of the more impure sometimes alkaline. Glue should be completely soluble in hot water, any undissolved part The moisture content of dry glue should not exceed 15 to 18 per cent, representing impurity. The best qualities melt at the highest temperatures and the dropping-point (lost at 105). The relative may be determined by Ubbelohde's apparatus (see p. 6), using a larger vessel. adhesive powers of different glues may be estimated by preparing tepid solutions of equal and areas) in them concentrations, immersing pieces of cotton or woollen fabric (of equal weights same centrifuge, ironing for 2 or 3 minutes, centrifuging the fabrics at the same time in the them slightly with a hot iron, drying completely in an oven at 100 and then noting which of the fabrics adheres best and longest to the fingers.

sulphonate.

ORGANIC CHEMISTRY
in various

ways according to Ger.

14

Pats. 116,591, 144,760,

;

and

156,954.

The crude product

,

cost, before the war, 9s. 6d. per kilo

DIGITALIN, C 35 H 6fl

the purified, 20s., and the puriss., 40s.

(?)

the most important constituents of the foxglove (ftigifalis purpitrea) and are used in modiPure digitalin cost, before the war, lOd. per cine, especially for diseases of the heart.

DLGITONIN, C a7 H ?l O lif and DIGITOXIN, C 31 H 64 O n are

gram, and crystallised digitoxin 20s. per gram. SALICIN, C 13 H 1H 7 (see pp. 535, 677), is contained in several varieties of Salix, and on with nitrous acid it forms hydrolysis gives glucose and saligenin (see pp. 641, 677) Helicin, C 13 H 16 7 -f H 2 O, which can also be obtained synthetically from glucose and
;

salicylic aldehyde.

^ESCULIN, C 15 H 18

9,

is

obtained from

horse-chestnut bark, and ,U\\ : CH

|

is

the glucoside
isomeric with

of ^ESCULETIN (a Dihydroxycoumarin),
daphnetin.
salicin

6 H,,(OH)o<

which

is

\0--CO

is a Benzoylsalicin, and is obtained synthetically from occurs naturally in Populus. occurs abundantly in the bitter orange, and on decom, position gives phloroglucinol, glucose, and Ferulic Acid, which is the monomethyl ether of

POPULIN, C 20 H 22O H

-f

2H 2 0,
;

and benzoyl chloride HESPERIDIN, C 22 H 26O 12

it

OH
Caffeic Acid,

H0<^

\-CH

CH CO2 H.

PHLORETIN, C 16 H 14 O 5 and
plants,

its glucoside, PHLORIDZIN, C 21 , 24 O 10 , are found in in cases of glycosuria in animals. IRIDIN, C 24 26O 13 , is found in the roots of the Florentine iris and yields Irigenin and

and

glucose on hydrolysis.

ARBUTIN, C 12 H lflO 7 occurs in the leaves of the bear-berry and gives glucose and hydroquinone on hydrolysis. Methylarbutin gives glucose and methylhydroquinone.
,

in black

of its potassium salt, which occurs mustard seed, gives glucose, potassium bisulphate, and allyl mustard oil. SANTONIN, C ]5 H 1RO 3 its constitution has been studied more especially by Oannizzaro and his pupils. It is a naphthalene derivative and is found in worm-seed (santonica). ALOIN, C 17 H JH O 7 an anthracene derivative, occurs in aloes and is a strong purgative. LECITHIN (composition, see pp. 462, 860) is a characteristic component of egg-yolk and of brain and nerve matter and is a crystalline waxy substance, which dissolves in alcohol or ether and with water forms an opalescent liquid. When hydrolysed it yields glycerophosphoric, oleic, and palmitic acids, together with choline, and it may therefore be regarded as a glyceride (see, pp. 218, 460). Considerable use has been made of it (and also of bromo- and iodo -lecithin) in recent years as a medicine. Lecithin is extracted on the large scale from egg-yolk, and new processes are described in Fr. Pats. 371,391 and 406,634 of 1908. Pure lecithin costs up
; ;
,

CONIFERIN, C 16 H 22 6 8 -f 2H 2O (see p. 678). SINIGRIN (Myronic Acid), C 10 H 17 9NS 2 hydrolysis

to

8 per

kilo.

CEREBRIN, C 17 H 33O 3N,

occurs in the nerves.

I.,

p. 162) is the iodine compound of the thyroid gland. Compounds include TAUROCHOLIC ACID, C 26 H 45 7 NS, and GLYCOCHOLIC ACID, C 2fl H 43O 6N, as sodium salts. When decomposed by alkali, both acids yield Cholic Bile also contains colouringAcid, OH C 21 H 32 (CH 2 OH) 2 (CO 2 H), glycine and taurine. matters such as BILIVERDIN, BILIFUCHSIN, and BILIRUBIN, C 16 H 18 O 4N 2 CANTHARIDIN, C 10 H I2O4 occurring in eantharides, causes blistering of the skin, and
(see Vol.

IODOTHYRIN
Bile

It is insoluble in alkali (unlike keratin) and when hydrolysed by acid gives a glucosamine. Fusion with potash at 184 yields acetic acid and Chitosan, which also forms the glucosamine with acid.

sublimes in thin scales. CHITIN forms the skeletal matter of crustaceans.

CHOLESTEROL, C 27 48O, occurs in many plants and animals (that of plants is called Phytosterol), generally together with fats and oils ; certain physical differences but virtually no differences in chemical behaviour are observable in products of different origin. Its
gations of A. Windaus,
constitution has not been definitely established, but, owing more especially to the investidoubt many of its component groups have been ascertained.

VITAMINS
phytosterols
It

867

whether the complex contained one or two double linkings formerly existed, but the addition of ozone (Molinari and Fenaroli, 1908) shows the presence of two such Unkings in both

and other

cholesterols.

indicates the formula, 20 29 O 9 4 , is soluble in alcohol or water, resists the action of dilute sulphuric acid (even 10 per cent.), dialyses easily, is sensitive to heat (90 or, rarely, 120) or alkali, is absorbed by charcoal and by certain precipitated alumina (in preparing vitamins,

forms shining scales melting at 147, and in constitution it resembles the terpenes more than the substances of any other group, but in all probability it does not contain benzene groups. Minimal quantities of cholesterol may be detected by Tschugajew's reaction, which consists in the formation of a more or less intense red coloration when a small quantity of a substance containing cholesterol is poured into fused anhydrous trichloroacetic acid. In alcoholic solution, cholesterol and phytosterol (but not their ethers) form an insoluble compound with Digitonin this reaction serves for the estimation of these substances and for Iheir separation from other animal and vegetable organic compounds, such a^ hydrocarbons, etc. 1 VITAMINS. The constitution of those compounds has not yet been determined, but they appear to be alkaloidal in character and to contain heterocyclic closed chain groupings. They are obtained from various animal glands, from seeds and bran and from beer yeast (which derives it from the malt) by extraction with alcohol slightly acidified with hydrochloric acid, the extract being concentrated in a vacuum, taken up with hot water and precipitated with phosphotungstic acid. The precipitate is treated with barium hydroxide, and the filtrate concentrated, dissolved in alcohol and precipitated by means of mercuric chloride. Precipitation of the filtrate with silver nitrate then yields a crystallised base melting at 233, which may be resolved by repeated crystallisation into three other bases of different melting-points. The mixture of the throe bases is the most active, and in two or three hours cures pigeons affected with polyneuritis. This mixture, analysis of which
;

these arc separated from the liquids by contrifugation and not by filtration). With phosphotungstic or phospUomolybdic acid, crude vitamins give the reactions of uric acid. They do not usually occur free in nature, but aro liberated on hydrolysis (even with 10 por cent, sulphuric acid) in an active condition. Gaglio found that human urine contains a vitamin

which rapidly cures

pulyiieuritls in pigeons.

hydrolysod, both Funk's vitamin and the oryzaniii separated from rice husks by Suzuki, Shimamura and Odake yield choline, glucose and nicotiiiie acid. Also Drummond and Punk showed that vitamins are pyridino derivatives. In some cases, ?.(/., with hydrogen peroxide, they act as catalysts. Mammals arc incapable of producing vitamins and those present in the milk are derived from the food. Vitamins in OXOPSS are harmless to the human organism. Bottomley and Mockeridge gave the name auximones or oxhnows to species of vitamin which are produced during the fermentation of peat and facilitate the development of the nitrogen bacteria of the soil. The study of vitamins is still in its infancy and many points connected with them

When

remain controversial.
1 ('. Funk gave the name vitamin to a substance which may be extracted from rice bran and beer yeast and is capable of curing the disease known as bcri-beri. In Java in 189H Kijkman found that 28 per rent, of the prisoners fed on decorticated (polished) rice suffered from this disease, whereas the proportion was only 0-0 per cent, among those fed with whole rice A similar phenomenon occurs with fowls, pigeons and rats, which are cured by (see p. 505). administration of either whole rice or its bran. Fii 1910 ftrcaudat and also Htepp simple confirmed Eijkman's results and showed that vitamins and Hpoids (ace p. 740) arc not identical. Mc.CoJlum and Davis (1915) maintained that, for regular and equilibrated growth of the animal organism, the food must contain two special substances which they term factor A, or antixerophthalmic vitamin (soluble in fats, but hydrolysable only with difficulty), and factor II The latter corresponds with Funk's vitamin (insoluble in fats, but soluble in alcohol or water). and occurs moro or less abundantly in animal and vegetable foodstuffs it abounds in milk and its products, egg-yolk, wheat, beans and soja beans, being localised especially in the cuticle or husk of seeds and in the embryo, but lacking in the starch. Want of factor A (normally found in the Hpoids of the glandular tissues, e.g., the testicles, ovary, liver, etc., and in the leaves of cauliflower, clover, etc.) produces in adults xcrophthahma, and in the young ric-kcls. Scurvy is due to lack or deficiency of a specific vitamin occurring largely in fresh or germinating vegetables and in lemon or orange juice (it decomposes on drying at 90 to 100). Funk obtained an anti-scorbutic ritanthi which protects man from scurvy and bcri-beri, and an anti-beri-beri vitamin ; tho latter is possibly formed by scission of the former (less stable), and abounds in oats, wheat and yeast and protects the organism from bcri-beri, but not from scurvy, which is, indeed, the more common. Moist oats (wheat, peas) are anti-beri-berie, and on germination become anti-scorbutic. The relation of vitamins to pellagra is still very uncertain.
1 ;

INDEX
Abriii,

138
prsecatorius, 138

Abrus

Acacia, 690

Acenaphthene, 730 Acer saccharinum nigrum, 540 Acetaldehyde, 250, 670

Estimation, 251
Acetals, 245, 534

Acid, Allocro tonic, 355 Allophanic, 433 Alloxanic, 435 7-Allylbutyric, 357
Allylsuccinic, 373

Amino G, 729 Amino R, 729

Aminoacetic, 379, 385, 423 o-Aminobenzoic, 682 Aminoethylsulphonic, 257 a-Aminoglutaric, 424
o-

Acetamide, 421 Acetamidine, 426

Acetamido-chloride, 425 Acetanilide, 661 Acetate, Amyl, 459
Cellulose, 381,

Amino -j3-hydroxypropionic, 424

864

a- Auiino-5-hydroxy valeric,

590

Ethyl, 459 Acetates, 345348 Acetic anhydride, 380

Acetifiers,

342

Acetimino-chloride, 425 Acetiminothiomethyl hydriodide, 425 Acetins, 257, 274 Acetoacetaldehyde, 399

Acetobromainide, 420 Acetochlorhoxoses, 535 Acetometers, 344 Acetonamines, 252 Acetone, 129, 254 Acetonealcohol, 397 Acetone-chloroform, 119 Acetonitrile, 238 Acctonylacotone, 399 Acetophenone, 675 Acetophenoneacetone, (370 Acetoxime, 253 Acetyl chloride, 379 cyanide, 395 iodide, 380 number, 224 sulphide, 419 Acetylacetone, 398 Acetylcarbinol, 397 Acetylccllulose, 381
Acetylene, 111 hydrocarbons, 110 Acetylethylamine, 420
Acetylglycocoll, 424

Aminonaphtholdisulphonic, 729 Aminonaphtholsulphonic, 729 a-Aminopropionic, 423 Aminosuccinic, 424 a-Amino-#-thiolactic, 396 Amylacetyleiiccarboxylic, 360 Aniyhnalonic, 369 Angelic, 356 AnilidoacetU', 661 Anisic, 681, 687 Ant hraflavi trie, 733 Anthranilic, H82, 762 Arabunic;, 392, 527 Arachidie, 320, 493 Aspartic, 424 Atropic, 681 A/elaic, 365, 372 Azosalicylic, 682 Azulmic, 427 Barbituric, 435, 437 Behenio, 320 Behcnolic, 360, 362 BoMzeiiclicxac.arboxylio, 678, 685 Bon/enestoaroaulphonic, 508 BcnzencsulpKonie, 621, 637, (>40 Bonzhydroxamic, 681 Bcnzilio, 720 Benzoic, 680
Beuzoylacctic, (i81 Benzoylformic, 681
Bornylciiccarboxylic, 717
Brasaidic, 360 Brassylic, 360, 365

a-Aminoisocaproic, 424 Aminonaphthalenetrisulphonic, 729

Aoetylhydrazides, 426 Acetylides, 110, 361

Acetyl-p-phenetidine, 666 Acetylurea, 433

Bromosuccmio, 374
Butylacetylenecarboxylic, 3(50 Butylfuinaric, 373

Aciaminoanthraquinones, 789 Acianilides, 656 Acichlorides, 379 Acid, Abietic, 206, 707 Acetaldehydedisulphonic, 257 Acetic, 328 Acetoacetic, 396 Ace toned acetic, 411 Acetonedicarboxylio, 411 Acetonetricarboxylic, 419 Acetonic, 389 Aceturic, 385, 424 Acetyleneear boxylic, 3 6 1 Acetylenedicarboxylic, 370 Acetylsalicylic, 687
i

Butyl maleic, 373 Butyl rnalwiic, 369 Butyls uccinic, 371 Butyric, 348 Oacodylic, 242 Caffeic, 689, 866 Caffctarmio, 438 Camphoric, 716 Camphoronic, 376, 716 Caprio, 350 Oaproic, 349 r*a])ryli(!, 349 Carbamie, 431
C^arbaminic, 431 Carbolic, 638

Aconitic, 376,411 Acridic, 754 Acrylic, 354 Adipic, 357, 362, 730 Alkylphoflphonie, 242 Allanturic, 435

Allocinnamic. 683

o-Carboxycinnamic, 728 o-Carboxyhydrocinnamic, 730 Carniinic, 793 Cerotic, 351, 462 Cetylinalonic, 369 Chaulmoogric, 473

863

INDEX
Acid, dielidonic, 743 Chloroacetic, 379 Chlorobenzoic, 682 o- (-, 7-) Chlorobutyric, 378 Chlorocarbonic, 431 -, (j8-) Chloropropionic, 378
Cholic, 866

869

>Chromotrope, 729 Cinchomcronic, 743, 755 Cinchonic, 754 Cinnamic, 678, 681, 683
Citraconic, 22, 375 Oitramalic, 400
Citric, 412 Citronellic,

357

Citrylideneacetic, 364 Cleve's, 729

Acid, Dinicotinic, 743 Dinitrobenzoic, 652, 701 Dinitronaphthalenesulphonic, 778 Dioctylmalonic, 369 Diphenic, 719, 736 Diphenylacetic, 720 Biphenylcarboxylic, 676 Bipicolinic, 743 r Dipropylmalonic, 369 Bipropylsuccinic, 371 Dithiocarbamic, 434 Dithiocarbonic, 433 DithiocarbonyUc, 433 Dodccamethylenedicarboxylic, 365 Durenecarboxylic, 681 Durylic, 681
Ela'ostearic, 364 Elaidic, 359

Clupanodonio, 478 Comanic, 743 Coumalinic, 743 Coumario, 681, 688 Coumaririic, 688 Crotonic, 22, 354 Cuminic, 681,683 Cyanic, 427 Cyanoaoetic, 377 Cyanuric, 428, 431 Cyclogeranic, 363 Uahl's, 729 JDecamethylcnedicarboxylic, 365
Decoic, 350

Erucic, 360 Krythric, 392 Ethanetricarboxylic, 411 Ethanthiolic, 419 Ethanthiolthiolic, 419 Ktbylacetylenecarboxylic, 360 Ethylcarbonic, 431

Dchydroundeceiiok 361
1

Desoxalic, 419 Diacetosuccinic, 411 Diacetylcncdicarboxylic, 376 Diacetylglutaric, 41 1

EthyleneaminosuJphonic, 424 Ethylenelactic, 389 Ethylcncsuccinic, 370 Ethylfumaric, 373 Ethylhydroxarnic, 427 Ethylideneacetic, 355 Ethylidcnolactic, 386 Etbylidcnepropionic, 356
Ethylidenesuccinio, 371 Ethylisopropylmalonic, 369 a- (7-) ElhyJitaconic, 373 Ethylmaleic, 373 Ethyimaloiiic, 369 Ethylmetliylacctic, 349 Ethylnitric, 236 Ethylsuccinic, 371

Dialkylphosphonic, 242 Piallylacctic, 363

Dial uric, 435

Diaininoeaproic, 392 DiammostilbenediKiilphoiiir, 722 5-Diaminovaleric, 392 Diatcrebinic, 400 Diazobciizencsulphonic, 671 Dibasic quiiiolink', 753

Ethylsulphonic, 235 Kthylsulphurie, 108, 235 Ethylsulphurous, 235 Euxanthinic, 793

Ferulic, 689, 866 Elavcanhydric, 427 Formic, 324

Dibenzhydroxaniic, 654 jSy-Dibromobutyric, 355 j8j3-Dibromopropk>iik', 378

Dicetylmalonic, 369
Dk-hloracetic, 378
no.-

(a-)Dichloropropionie, 378 Diethylbarbituric, 746 Bictbylmaleic, 373 Diethylmaloiiic, 369 Dietbylsuccinic, 371
Digallic, 689 Diglycollic, 384 00 -Dihydroxy butyric, 355

Dihydroxymalonic, 410

Eormothiohydroxamic, 429 Eorinylacetie, 393 Eulmiiiic, 428 Eumaric, 22, 374 G, 729 Galactoiiic, 392, 534 Gallic, 681, 688 Gallolylgallic, 689 Gallotannic, 689 Geranic, 358, 363 Glucoheptonic, 393
Gluconic, 392, 531 Glutaconic, 375 Glutainic, 424 Glutaric, 366, 372 Glyceric, 220, 392 Glycerophosphoric, 258 Glycocholic, 866
Glycolglycollic, 384 Glycollic, 379, 384

0/8- Dihydroxypropionic,

392

Dihydroxystearic, 359, 390, 392 Pihydroxytartaric, 411 Diisoamylmalonic, 369

Diisobutylmaloriic, 369 Diisobutylsuccinic, 371

Bimethylacetic, 349
ajB-Dimethylaerylic, 356

Dimethylarsenic, 242 Dimethylfumaric, 375 aa- (ay-, 77-) Dimethylitaconk*, 373 Dimethylmaleic, 375

Dimethylmalonic, 369 Dimethyloxaminic, 240 Dimethylparabanic, 436 Dimethylpseudouric, 436 Dimethylsuccinic, 371

Glycolsulphuric, 256 Glycoluric, 433 Glycuronic, 393 Glyoxylic, 393 Gulonic, 392

H, 729 Hsematinic, 862 Hemellitic, 681

Hemimellitic, 685

Dimethyltrihydroxycinnamic, 750

870
Acid, Heptoic, 349 Heptylacetylenccarboxylic, 360 Heptylsuccinic, 371 Hexajiydroxystearic, 364 Hexamethylenecarboxylic, 702 Hexantetroloic, 392 Hexylacetyleneear boxy lie, 360 Hexylsuccinic, 371 Hippuric, 423, 680, 682 Homocamphoric, 716 Hydantoic, 433, 435 Hydnocarpio, 473 Hydracrylic, 389 Hydratropic, 681 Hydrazoic, 426, 434, 671 Hydroehcliclonic, 411 Hydroeinnamic, 681 Hydrocyanic, 427 Hydromellitic, 686 Hydromucic, 373 Hyclromuconic, 375

INDEX
Acid, Isophthalic, 621, 685
Isopropylacetyleriecarboxylic, 360

Isopropylfumaric, ^73
7-lsopropyJitaconic, 373 Isopropylmaleic, 373 Isopropylmalonic, 369 Isopurpuric, 6(55 Tsosaccharinic, 392 Isosuccmic, 371
Jsotrachylolic, IsovaleriV, 349 Itaconic, 374

495

Itamalic, 400
J, 729 Jecorinic,

364

y3-Ketobutyric, 396 Lactic, 383, 386 Lactobinnic, 536

Lanugic, 807
Laurie, 320, 350, 362 Leuciuic, 389 Lcvulinic, 390, 397, 530 Lignic, 602 Lignoceric, 320, 493

Hydroparacoumaric, 681

(-) Hydroxy butyric, 389 a-Hydroxycaproic, 389 o-Hydroxycinnamic, 688 Hydroxycitric, 419 Hydroxyethylsulphonic, 257 Hydroxygallolylgallic, 689 a- (-) Hydroxyglutarie, 400 a-Hydroxyisobutyric, 389 a-Hydroxyisovaleric, 389 Hydroxymalonie, 399 HydroxymcthyJsulphonic, 257 a-Hydroxymyristic, 389 Hydroxyoleic, 390 a-Hydroxypalmitic, 389 j8-Hydroxypelargonic, 390 p-Hydroxypheriylacetic, 687, 860 a-Hydroxypropiouic, 386 j8-Hydroxypropionic, 389 a-Hydroxystearic, 389, 506, 507 Hydroxysuccinic, 399 Hydroxytoluic, 681 a-Hydroxyvaleric, 389 Hypogseic, 358
a-

364 363 Lupulinic, 194 Lutidinic, 743 Lyxonir, 392 Malaniie, 421 JVlaleic, 374 Malic, 399, 421 Malonic, 368, 437 Maltnbionic, 536 Mandelic, 681, 688 rf-Maimonic, 392, 534 rf-Mannosaccharic, 534 Margaric, 350 Mcconic, 713, 750
Linnleiiic,

Linolic,

Melissic, 351 Mollitic, 634,

685
(J85

Mellophanic,

Mesacoiiic, 22, 374

Ichthyolsulphonic, 103
Idonic, 392

Iminodithiocarbamio, 433 Iminodithiocarbonic, 433 Iminothiocarbamic, 433 Induxylic, 756, 762 /3-Iodopropionic, 378 Isatic, 756 Isatinic, 756 Isethionic, 257 Jtioamylmalonic, 369 Isoanthraflavinic, 733 Isobutylaticonic, 375 Jsobutylfumaric, 373 Jsobutylmaleic, 373 Isobutylmalonic, 369 Isobutylsuccinic, 371 Iso butyric, 349 Isocinchomeronic, 743 Isocinnamic, 683 Jsocrotonic, 22, 355 Isocyanic, 427 Isodurenecarboxylic, 681 Jsodurylic, 681
Isoerucic,

Mesitylenccarboxylic, (>8l Mesitylcnic, 681 Mesotartaric, 40 Mosoxalic, 399, 410 MetacryJic, 35(> Mctasaccharinic, 392 Methionic, 228, 257 Metliylacetylenecarboxylic, 360 a-Mothylacrylic, 35(5 ^-Mcthylacrylic, 355
1

Me thy Ibutyl malonic,

1

)8-Mcthyladipic, 372

369 -Methy lcyclohexylideno-4-acctic, 20

MethyJenedi.su Iphoriic, 257 7-Mcthylene-7-inethyJpyrotartaric, 373 Slethylcnesuccinic, 374 Methylethylglycollic, 389 Methy lethvHtaconic, 373 Methylcthylmaleic, 373 Methylethylmalonic, 369 Methylfu marie, 374 Methylisobutylmalonic, 369 MethylisopropylmaJeic, 373 Methylisopropylmalonic, 369 a- (y) Methylitaconic, 373 Methylmaleic, 374 Methyl malonic, 369

Methylmethyleneacetic, 356
Methylpropiolic, 361

360

a-(-)Isofulminuric, 429
Isolinolenic, 364 Isonicotinic, 742 Iso-oleic, 359

Methylpropylmaleic, 373 Methylpropylmalonic, 369 Methylsuccinic, 371 Monochloroacetic, 379, 383 Monothiocarbamic, 433

INDEX
Acid, Monothiocarbonic, 433 Monotbiocarbonylainio, 433 MonothioearbonyKc, 433 Mucic, 410, 527, 534 Muconic, 376 Myristic, 350 Myron ic, 866 Naphtha lenesulphonic, 728 Naphthalic, 730 Naphthionic, 729 Naphtholcarboxylic, 728 Naphtholdisulphonic, 729 Naphtholtrisulphonic, 729 Naphthylaminedisulphonic, 729 Naphthylaminesulphonic, 727, 729 Naphthylenodiamincdisulphonic, 727 Naphthylenediaminetrisulphoiiic, 727 Neville- Win ther, 728 Nicotic, 742 Nicotinic, 742 w-Nitrobenzoic, 682, 701 o-Nitrocinnamic, 761 Nitrohydroxylaminie, 246 0-Nitrophenylacetic, 760 o-Nitrophcnylpropiolio, 684, 761 Noiiok-, 349, 360 Nonylacetylenecarboxylic, 360 Nucleic, 863 (Enanthic, 349 Oleic, 358
Aa/3-Oleio, Orsellinic,

871

Acid, Prehnitylic, 681 as. Propanetricarboxylic, 411 s. Propanetricarboxylic, 376, 411 Propargylic, 361 Propinoic, 361 Propiolic, 361 Propionic, 348 Propylacetylenecarboxylic, 360 Propylfumaric, 373 Propylitaconic, 373 Propylmaleic, 373 Propylmalonic, 369 Propylsuccinic, 371
Protalbinic, 759

Protoeatechuic, 681, 687 Pseudouric, 437 Purpuric, 435 /3-Pyridinesulphonic, 742 Pyrocinch^nic, 375
Pyrogallic, 645

Pyroligncoua, 335

Pyromeconic, 743
Pyromellitic, 685

Pyromucic, 737 Pyrotartario, 372 Pyroterebic, 357 Pyrroglutamic, 739

a-Pyrrolidineuarboxylic, 739, 864 a'-Pyrrolidone-a-carboxylic, 739 Pyruvic, 383, 396 Quinic, 702, 752, 754 Quinolineoarboxylic, 754 Quinoline-a : j8-dicarboxylic, 754 Quinolinic, 743

359 681 Oxalacetic, 410 Oxalic, 366 Oxaluric, 435 Oxamic, 42 1

R, 729 Racomic, 21, 400

o-Oxysodiobenzoie, 686 Palmitic, 350, 506 Parabanic, 435, 436 Paralactic, 389 Parasacchariuic, 392
Paratartaric, 401 Pectic, 555 Pectosinic, 555 Pelargorue, 349

Rhamnohcxonic, 393
Rhoclanic, 429 Rhodinic;, 358 Ribonic, 392
Ricinelaidinic, 390 Ricinisoleic, 494 Ricinuloic, 390, 494

Pentadecoic, 320 Pentamethylbeiizoio, 681 Pentamethyldigallic, 690 Pentaniethyleneacetic, 702

Ricinolcinsulphonic, 390 Roccellic, 365 Rosolic, 721, 765, 784

Pen tame thy leiiecar boxy lie, 702

Pentylmalonic, 369 Pcrinaphthalened icarboxylic, 725 Perthiocyanic, 429
Phellonic, 615

Rubeanhydric, 427 Ruberythric, 734 Rufigallic, 733 Saccharic, 410, 531 Saccharinic, 392
Salicylic, 212, 680, 681,

686

/8-Phenanthrenecarboxylk-, 735 Phenylacetic, 679, 681, 683 Phenylaminoacetic, 661 a-Phenyl-/8-hydroxypropionic, 749 a-Phenyl-o-nitrochmaimc, 735
Phenylglycine-o-carboxylic, 761 Phenylpropiolic, 634, 678, 681, 684 Phenylaulphaminic, 661

Santalic, 793 Sarcolactic, 389 Sativic, 364

Schiiffer's,

729

Seba(;ic, 358, 365,

372

Phenylene - p-dicarboxylic 684

,

Sinapic, 750 Sorbic, 363 Sozolic, 667 Stearic, 350 Stearolic, 358, 362 Suberic, 365, 372, 617

Phenylsulphuric, 643 Phloroglucinoltricarboxylic, 646 Phthalic, 684

Picolinic,

Succinamic, 421
Succinic, 370 Sulphanilic, 637 Sulpho-oleic, 505 Talonic, 392

742 778

Picramic, 665
Picric, 303, 664,

Tannic, 689
Tariric,

Pimaric, 707 Pimelic, 365, 617 Pinonic, 707 Piperic (piperinic), 678, 689, 743
Piperonylic, 687 Pivalic, 349 Prehnitic, 685

362

Tartaric, 21, 400

Artificial,

410

Manufacture, 407 Tartronic, 220, 399

Taurocholic, 257, 424, 866
Telfairic,

364

Prehnitinecarboxylic, 681

Teraconic, 373

872
Acid, Teracrylic, 357 Terebic, 357, 715 Terebinic, 400, 707 Terephthalic, 685, 707 Terpenylic, 357 Tetrabromostearic, 364

INDEX
Acids, Hydroxamic, 246, 427

Hydroximic, 427 Hydroxy, 383 Hydroxybenzoic, 687

Hydroxynaphthalenecarboxylic, Hydroxynaphthoic, 730 Hydroxyolefinecarboxylic, 389 Hydroxypyridinecarboxylic, 743 Insoluble fatty, 461 a-Ketonic, 395 -Ketonic, 395 7-Ketonic, 396 Ketonic dibasic, 410 Lactic, 20, 385 Liquid fatty, 492 Monobasic, 234, 680 Monobasic aldehydic, 393 Monobasic ketonic, 394 Naphthalenesulphonic, 728 Naphthenic, 702 Naphthoic, 730 Naphtholsulphonic, 729, 780 Nitrated benzoic, 701 Olefmecarboxylic, 351 Olcfinedicarboxylic, 373 Pentacarboxylic, 743 Pentoic, 524 Phenolic, 679 Phenolsulphonic, 643, 667 Phthalic, 678, 684 Polybasic aromatic, 684 Polybasic fatty, 364 Pyridinecarboxylic, 742, 743 Pyrotartaric, 372
.

72(5

376 Tetracetylenedicarboxylic, Tetrahyoroxyhexahydrobenzoic, 702 364 Tetrahydroxystearic, Tetrolic, 356, 361 Thioacetio, 419 Thiocyanio, 429 Thiocyanuric, 429 Tiglic, 357 Toluio, 681 Trachylolic, 495 Tricarballylic, 363, 376, 411 Trichloroacetic, 378 Trihydroxybenzoic, 688 Trihydroxyglutaric, 410, 528 Trihydroxyisobutyric, 525 Trimellitic, 685 Trimesic, 393, 685 Trimethylacetic, 349 Trimethylenedicarboxylic, 616 oa^-Trimothyltricarballylic, 376
Trinitrobenzoic, 682, 701 Trithiocarbonic, 433 Tropic, 681, 749

Umbellic, 689 Undecenoic, 358 Undecoic, 350 Undecolic, 361 Uric, 435, 740 Valeric, 349 Vanillic, 687 Veratric, 687 Vinylacetic, 354 -Vinylacrylic, 363 Violuric, 437 Xanthic, 434 Xanthonic, 434 Xylic, 681 Xylonic, 392, 527 Acid-albumins, 858, 862 Acid halides, 379 Acidol, 424
Acids, Affinity constants, 321 Heat of neutralisation of organic, 26 Alkylsulphonic, 233 Alkylsulphuric, 235

Quinolinebenzocarboxylic, 764. Quinolinecarboxylic, 754 Saturated dibasic, 364 Saturated monobasic fatty, 319
Succinic, 370

Sulphobenzoic, 682 Sulphonic, 235, 636

Tartaric, 21, 400 Tetrabasic, 376

Tetrahydroxypentanccarboxylic, 392 Toluic, 683 Tribasic, 234, 376 Trmydroxycmnamic, 689 Unsaturated dibasic, 373 Unsaturated monobasic fatty, 351 Unsaturated monobasic, of the series C,,H 2 ,,- 4 O 2 , 360
Volatile fatty, 460

Amino, 422
Aminobenzoic, 682
Anthracenecarboxylic, 733 Anthracenesulphonic, 733 Anthraquinonesulphonic, 733 Aromatic, 671, 678 Azobenzoic, 682 Benzenedicarboxylic, 678 Benzenetetracarboxylic, 685 Benzenetricarboxylic, 678, 685
Benzoylbenzoic, 720 Diazobenzoic, 682
Dibasic, 234, 684

with two double bonds, 362 with three double bonds, 364 with triple linking, 360 with unsaturated side chain, 679 Xylic, 683 Acoine, 751 Aconitine, 745
.

Aconitum

napellus, 376, 41 1

Acraldehyde, 251 Acridine, 765 Acridines, 796 Acrolem, 261

Dihydroxybenzoic, 687 Dihydroxycinnamic, 689 Dihydroxystearic, 389 Diofefinedicarboxylic, 376 Diphenylcarboxylic, 719 Diphenylsulphonic, 719 Halogenated, 377 Heptonic, 393 Hexabromostearic, 364 Hexahydroxystearic, 364 Hexonic, 392, 524 Homoaspartic, 425 Hydrophthalic, 701

Acrolemammonia, 252
Acrolemaniline, 753
Acrpse, 393, Activators, 507

526

Adamsite, 660 Adenine, 436, 441 Adonitol, 529

Adrenaline, 745, 746, 751 Adrenalone, 747 Aesculetin, 689, 866 Aesculin, 689, 866 Affinity constants, 321 Agglutinins, 139

INDEX
Agro
Airol, cotto, 414, 415

873
179

688

Alcohol, Rectification, 164 Solid, 131

Statistics,

Alanine, 389, 423 Albanan, 711

Synthetic, 171
Tests, 172, J74

Albumin, Living, 137 Albuminates, 862 Albuminoids, 857, 863 Albumins, 859 Albumoses, 858, 862
Alcohol, Absolute, 130, 172 Acctoisopropyl, 398

Windisch's Table, 175

Yield, 153 Alcohols, 123

Aldehydic, 393

Aromatic ketonic, 674, 677

Constitution, 124 Derivatives of monohydric, 226
of polyhydric, 256 Dihydric, 216

Acetone, 397
Allyl, 216, 327 Amyl, 126, 165,

215

Anisic, 677

Benzyl, 674 Butyl, 125, 126, 214 Caproyl, 215 Capryl, 215 Carnaubyl, 479
Ceryl, 126, 215, 479 Cetyl, 215, 462 Coniferyl, 601, 678

Higher monohydric, 214

Ketonic, 394, 397 Nomenclature, 125 Polyhydric, 217, 224 aldehydic, or ketonic, 523 Primary, 124, 125 Saturated monohydric, 124, 126 Secondary, 124, 125 Tertiary/ 124, 125
Tetrahydric, 224 Tolylene, 674 Trihydric, 217 Unsaturated, 216 Alcoholene, 178 Alcoholism, 130, 184 Alcoholometer, Cay Lussac, 174 Tralles, 174 Alcoholometry, 174

Cumyl, 674
Decyl, 126

Denatured, 176 Dodecyl, 126 Ethyl, 130 Fluorene, 676 Furfuryl, 737
Glucovanillyl, 678 Glycide, 258 Heptyl, 126, 215 Hexadecyl, 126, 215

Hexyl, 215

Hydroxy benzyl, 677 Isobutyl, 126, 215 Isohoxyl, 715 Isopropyl, 126, 214 Lanolyl, 479
Melissyl,

216

Methyl, 127, 173, 794 Monochlorocthyl, 256

Myricyl, 126, 216

Nonyl, 126
Octodecyl, 126
Octyl, 126, 215

Oenanthyl, 215
of crystallisation, 126

Pentadecyl, 126
Phthalic, 674

Propargyl, 216 Propyl, 126, 214

Styryl, 674 Tetradecyl, 126 Tolylene, 674 Tridecyl, 126 Undecyl, 126
Vanillic,

677

Vinyl, 216 Xylylene, 674 Alcohol, Amylo process, 155 Denaturatioii of, 176 Effront process, 167 Fiscal regulations, 179

from from from from from from from from from

beet, 166 calcium carbide, 171 fruit, 167 lees, 169 molasses, 166 sulphite liquors, 169 vinasse, 169 wine, 169 wood, 167 Industrial preparation, 140 meters, 173 motors, 178

Aldehyde- ammonias, 245 Aldehydes, 116, 124, 243, 244 Aromatic, 674 Determination by Straeho's method, 255 Phenolic, 677 SchiU's reagent, 246 with unsaturated radicals, 251 Aldehydine, 741 Aldehydo-catalase, 1 34 Aldims, 677 Aldine, 743 Aldinos, 675 Aldohexoscs, 524, 529 Aldoketeries, 256 Aldol, 393 Aldols, 245 Aldoses, 524 Aldoximes, 246 Alembics, 158 Alfalfa, 607 Alga, 68 Algarovilla, 690 Aliphatic compounds, 29 Alizarin, 733, 778, 783, 787 astrol, 800 cyanine, 787 irisol, 800 saphirol, 800 Alkaloids, 743 Synthesis, 744 Table, 745 Tests, 744 Alkines, 742 Alkoxides, 124 Alkoxy-groups, Estimation, 642 Alkyl halides, 114 Estimation, 120 Alkylanthrahydrides, 733 Alkylenes, 106 Alkylhydrazines, 241 Alkylhydroanthranols, 733 Alkylhydroxylamines, 24 1 Alkylisoureas, 432 Alkyls, 30
Allantoin, 436

VOL.

II.

56

874
Ailene, 109, 374 Alloisomerism, 21, 22 Alloxan, 435, 740 Alloxan thine, 436 Allyl bromide, 123 chloride, 123 iodide, 123 isothiocyanate, 430

INDEX
Anhydride, Butyric, 381 Caproic, 381
Caprylic, 381
Diglycollic, 384

Double (diketopiperazine), 859

Glutaric, 366 Isobutyric, 381 Isovaleric, 381 Laurie, 381 Myristic, 381

mustard

oil,

430

thiocyanate, 430
Allylaniline, 753 Allylene, 110, 375 Almonds, composition of sweet, 482 Aloin, 866 Alypine, 119, 746, 751 Amaranth, 780 Amber, 370 Amidases, 183 Amides, 263, 419 of carbonic acid, 431 of hydroxy- acids, 421 Amidines, 238, 425, 426 Amido- chlorides, 425 Amidol, 664, 666 Amidoximes, 427 Amimides, 425 Amines, 239 Aromatic, 654 Amino-acids, 419 Derivatives of, 422 Aminoanisoles, 666 Aininoazobenzene, 672 Aminoazobenzenes, 668 A minoazo- derivatives, 671 Aminoazonaphthalene, 727 Aminoazotoluenes, 668 Aminocetyl benzene, 655 A mino- derivatives of aromatic hydrocarbons, 654 Aminoguanidine, 434 Aminonaphthols, 728 Amino-oxiiidole, 760 Aminophenols, 665 Aminothlazole, 740 Aminothiophe^ols, 667 Ammelide, 431 Ammeline, 431 Ammonium acetate, 345 carbamate, 431 cyaiiate, 428

(Enanthic, 381 Palmitic, 381 Pelargonic, 381 Phthalio, 684

Prolylglycocoll, 864 Propionic, 381 Pyrocinchoriie, 373, 375 Pyromellitic, 685
Salicylic (internal), Stearic, 381

687

Succinic, 365, 371

Trimethylacetic, 381

Anhydrides, 380 Internal, 380 Mixed, 380 Anilides, 661 Aniline, 657, 669

Homologues
nitrate,
oil,

of,

661

hydrochloride, 659, 670

670
660

659
659

platiiiichloride,
salt,

sulphate, 660 Anisaldehyde, 677 Anisidines, 665, 666 Anisole, 642 Annatto, 477 Anterea mylitta, 818 Anthracene, 731 derivatives, 733 Anthrachrysone, 733 Anthraflavone, 789 Anthragallol, 733

ichthyolsulphonate, 103
picrate, 665

thiocyanate, 429 Amygd^iri, 136, 865 Amyl acetate, 459 Amylacetylene, 399 Amylase, 133, 134 Amylbenzene, 623 Amylene, 109 hydrate, 215 Amylodextrin, 141 Amyloid, 599, 600

Anthrahydroquinones, 733 Anthramine, 733 Anthranil, 682 Anthranol, 733, 734 Anthrapurpurin, 733 Anthraquinon.es, 733, 765 Anthraquinonimide derivatives, 789 Anthrarufin, 733 Anthrols, 733 Anthrone, 733 Antialdoximes, 253 Anti-bodies, 138 Antichlor, 830 Antidiazo-p-chlorbenzene cyanide, 669 Antidiazotates, 669
Antifebrin, 661

Antiketoximes, 253
Antilactase, 138

Amylomyces Rouxii, 155, 156 Amylo process, 155 Anaesthesia, 114, 118, 746 Ansesthesin, 751 Ansesthesiophore, 751 Anesthetics, 118, 746 Mild local, 751 Analgen, 754 Analysis, Elementary, 8
Qualitative, 7 Quantitative, 8

Antimorphine, 138 Antinonnin, 773 Antipepsin, 138

Antipyrine, 673, 739, 745

Antique purple, 788 Antirennet, 138

Antiricin, 138 Antiseptics, 151, 640

Anethole, 644 Anethum fceniculum, 706 Anhydride, Acetic, 380 Benzoic, 680

Antiserum, 863 Antitoxins, 138 Apigenin, 755 Araban, 527 Arabinose, 625, 529 benzylphenylhydrazone, 627 Arabitol, 225, 526, 528

NDEX
Arachis nuts, 466, 500 Arbutin, 866 Archil, 645, 792 Arginine, 392 Aristochin, 753 Aristol, 643
Balata, 711 Balling's Table, 200
Ballistite,

875
300
794

Baphia
29,

nitida,

Barley, 192

Aromatic compounds, Arrack, 190 Arsines, 242 Artificial hair, 826

618

Malting of, 195 Barwood, 794

Bases, Aldehydo-, 657

Aminic, 239

361 ivory, parthenogenesis, 138 Asafcetida, 644 Ascomycetes, 133 Aseptol, 667 Asparagine, 20, 424 Aspartamide, 425 Aspergillus gallomyces, 688 oryzse, 155 Asphalte, 99 Artificial, 99 mastic, 99 Asphaltite, 100 Aspirin, 687 Astatki, 77, 86 Asymmetric syntheses, 137 Asymmetry, Absolute, 22 Relative, 22 Atole, 190
Atractylin, 248 Atropa belladonna, 749

Ammonium, 239
Arsonium, 242 Iminic, 239 Nitrilic, 239 Primary, 239
Quaternary, 239, 657 Secondary, 239 Tertiary, 239 Vegetable, 743 Bathochromes, 764 Beckmann rearrangement, 253, 676
Beer, 191 Alcohol-free, 211 Analysis, 211 Attenuation, 207 Cask pitching, 209

Atropine, 745, 749

Attenuation of fermented Auramine, 720, 784 Aurantia, 660 Aurine, 721, 784
Australene, 707

liquids, 153, 154,

207

Composition, 211 Detection of antiseptics, 212 Fermentation, 204 Mashing, 201 Pasteurisation, 210 Racking, 209 Statistics, 212 Beet, 543
Cultivation, 544 sugar, History of, 539 Beet -pulp press, 551 Benzal chloride, 636 Benzalacetoiie, 676

Auximones, 867 Auxochromes, 766

Axite, 302 Azides, 426 Aziminobenzeiie, 657

Azimino-compounds, 657
Azines, 785

Azobenzene, 667

Azo carmine, Acid, 800

Azocochineal, 665 Azo- derivatives, 667

Azodicarbonamide, 434 Azoeosin, 665 Azoflavine, 799

Azofuchsines, 781 Azoimide, 241, 426, 434, 671 Azolitmin, 792 Azorubin S, 780 Azotoluene, 667 Azoxazole, 740 Azoxybenzene, 667 Azoxy-derivatives, 667 BACILLUS aceticus, 145, 340 acidi Isevolactici, 389
acidificans longissimus, 152 butylicus, 214

Delbruckii, 149 ethaceticus, 392

saprogenes vini, 404

Bacteria, Acetic, 145, 340 Butyric, 145 Chromogenic, 133, 775 Lactic, 145

Pathogenic, 133 Reproduction, 133 Saprophytic, 133 Zymogenic, 133 Bacteriology, 132 Baekelite, 370, 641 Bagasse, 641

Benzalacetophenone, 676 Benzalazine, 677 Benzaldehyde, 674, 680 homologues, 675 phenylhydrazone, 677 Benzaldoxirne, 676 Benzamide, 681 Beiizanilide, 661, 681 Benzanthrone, 789 Benzazide, 682 Benzene, 622, 630 Artificial, 631 Bromo -derivatives, 635 Chloro-derivatives, 635 Cyclic formulae, 618 derivatives, 618, 635 Characters of, 621 Formation of, 622 Isomerism of, 620 from naphtha, 87 lodo -derivatives, 635 Nitration of, 648 Pure, 633 sulphochloride, 637 Testing of, 632 Benzeneozimide, 671 Benzeneazobenzene, 667 Benzenesulphonamides, 637 Benzhydrazide, 682 Benzhydrol, 675 Tetramethyldiamino-derivative, 719 Benzidam, 657 Benzidine, 668. 718, 770, 781 Benzil, 723 dioxamine, 723 Benziminazoles, 657 Benzine, Crude, 84 Benzo-azurin, 719, 784 blue, 801

876
Benzo
blue-black, 801

INDEX
browns, 802
flavine, 781

Bloodstains, Identification, 862, 863 Blue, Acid, 666

Algol, 789 Alizarin, 787 Alkali, 80O

furfuran, 755 orange, 801 purpurin, 719

o-Benzoicsulphimide, 682 Benzoin, 722 Benzonitrile, 071, 679

Benzophenone, 675, 719 oxime, 676 Benzopinacone, 675 Berizopyrrole, 755 Benzoquinone, 647 Benzothiophen, 755, 756 Benzotrichloride, 636
Benzoyl, 15
chloride, 681

Benzoy lace tone, 676

Benzoylazoimide, 682 Benzoylcarbinol, 678 Benzoylsaliciri, 866 Benzoyltropine, 746 Benzyl bromide, 635 chloride, 635, 653 iodide, 635 Benzylamine, 662 Benzylanilirie, 660
Benzylglucoside, 535
Benzylhyclraziiie, 673

Anthracene, 787, 798 Capri, 785 Carmine, 784 Chrome, 728 Ciba, 788 Diamine, 728, 729, 801 Diaminogen, 729, 801 Diamond, 729 Diphenyl, 660 Fine, 787 Immedial, 801 Indanthrene, 789 Indroiie, 79O Janos, 800 Jet, 727 Lanacyl, 800 Meldola's, 796 Methylene, 772, 785, 796 Naphthazariii, 726 Naphthol, 727, 785 Naphthylamino, 781 Night, 727 Nile, 800
801 Oxidation, 787 Patent, 784 Pluto, 801 Sulphur, 801 Victoria, 727
Vidal, 667 Wool, 727, 800 Zambesi, 801

Oxamme,

Benzylphenylamine, 660 Benzylphenylhydrazine, 673 Berberine, 745 Bergamo t, 413 Beri-beri, 867 Beta maritima, 543 vulgaris, 54O, 543 Betaine, 385, 423 hydrochloride, 423 Betol, 728 Bile compounds, 866 Bilifuchsin, 866 Bilineurine, 257 Bilirubin, 866 Biliverdin, 866 Biogen theory, 137 Bisazo-compourids, 668 Bismuth tribromophenoxide, 122 Bisulphite aldehyde compounds, 244 Bitumen, 99, 630 Biuret, 433 Bixa orellana, 477 Black, Acid azo, 798 Alizarin, 787 Aniline, 786, 855 Animal, 568 Anthracene, 798 Biebrich, 729 Bone, 568 Cibanone, 790 Columbia, 801 Cyanide, 104 Diamine, 801

Boghead

coal,

100

Boiling-point, 2, 25 Bombyx mori, 813 Boot-polish, 572, 624 Bordeaux, Ciba, 788
Iriciaiithrcne,

789

Borneo!, 714, 716

Bornesitol, 647 Boudineuse, 284, 300

Bradolytes, 721

Diamond, 728,
Fine, 787

729, 781

Immedial, 801 Naphthazarin, 726 Naphthol, 729, 781 Naphthylamine, 781 Oxidation, 787 Pluto, 801 Sulphur, 664, 791 Vidal, 801 Zambesi, 801 Blankite, 542 Blastomycetes, 133 Blood, 137, 795

Brandy, 190 Brazilein, 793 Brazilin, 793 British gum, 597 Bromoacetylcne, 123 Bromobenzenes, 636 4-Bromomethylfurfural, 528 Bromostyrene, 636 Bronze, Diamine, 802 Brown, Alizarin, 783 Anthracene, 688, 783 Bismarck, 657, 662, 780, 796 Cibanone, 790 Diamine, 802 Indanthrene, 790 Janos, 802 Pluto, 802 Pyrogen, 802 Sulphur, 802 Thiazine, 802 Brucine, 745 Brussels Sugar Convention, 575 Bulgarian ferment, 537 Butandiene, 113 Butandiine, 114 Butandione, 398 Butanes, 37 Butanolone, 398 Butanols, 214 Butanone, 256
'

INDEX
Butantetrol, 225 Butenes, 109 Butter, 474 Analysis, 476
Artificial,

877

470

Cacao, 437 Coconut, 498

Degree of rancidity, 464 Renovated, 477 Butyl iodides, 117, 118 Butylbenzone, 623 Butylenes, 109 Butyramide, 421 Butyroflavine, 471 Butyrolactone, 384 Butyrometer, Gerbcr, 476 Butyrorefractometer, Zciss, 463 Butyryl chlorides, 380 Byssus, 820 CACAO butter, 437 Cachou de Laval, 790 Itnmedial, 802 Sulphur, 802 Cacodyl, 15, 242 chloride, 242 oxide, 242 Cadaverine, 257 Cadmium bromoxylonato, 527 Caffeine, 438, 745 Calcium acetate, 337 bonzoate, 622 butyrato, 348
carbide, 111 citrate, 415, 417

Carbohydrazide, 433 Carbolineum, 630 Carbon, Asymmetric, 19 chains, 16 Estimation, 8 sulphochloride, 433 tetrachloride, 122 Valency, 15
see Phosgene Carbonic acid esters, 431 Carbonisation of textiles, 805, 839 Carbonite, 284, 307 Carbonites, 306 Carbonylquinine, 753 Carbostyril, 754 CarboxyhaBmoglobin, 863 Carboxyl, 124 Carbyl sulphate, 257 Carbylamines, 238, 656 Carone, 706, 714 Carotin, 815 Cart-grease, 98 Carvacrol, 644 Carvacrylamine, 655 Carvene, 703, 705 Carvol, 714 Carvomenthol, 714 Carvomenthone, 714 Carvone, 714 Caryophyllene, 708 Casein, 474, 827, 861 Vegetable, 861 Castor oil, 390, 493 seeds, 482, 507 Catalases, 135 Catalysts, Dry, 458 Inorganic, 136 Moiht, 457 Organic, 136 Catechol, 690, 865 Catechu, 691, 794 Cedreno, 708 Celiase, 134 Cellite films, 599 Cellobiose, 600 Cellophane, 827

Carbon oxychloride,

cyanamide, 430 dilactate, 388 ethoxide, 214 formate, 328 lactate, 388 oxalate, 368 tartrate, 401 Calendars, 849 Calorimeter, Junker's gas, 61 Campeachy, 791 Camphane, 708 Camphene, 708 Campholicle, 716 Camphor, 716 Artificial, 707, 717 Camphors, 714 Camwood, 794 Candelite, 482 Candles, 510 Paraffin, 513 Stoarine, 511 Tallow, 510 Cannabis satim, 812 Cannel coal, 100 powder, 305 Cantharidin, 866 Caoutchouc, 708 Capillarimeter, 176 Caprylene, 109 Caps, 309 Caramel, 531, 633 Carane, 706 Carbamide, 432 Carbamidyl chloride, 432 Carbazide, 433 Carbazole, 630, 719 Carbenes, 99
Carbinol, 125, 127 Carbocyclic compounds, 29

Cellose, 600 Celluloid, 717 Cellulose, 598,

824
of,

acetate, 599

Estimation

605

formate, 600 hydrate, 601

Wood, 603
Centrifuges, 565 Cerasin, 69, 105, 707 Cereals, Starch-content, 141 Cerebrin, 866

Cerotene, 109
Corotin, 215 Ceryl cerotate, 216, 460 Cetyl palmitate, 460

Cetylbenzene, 623 Cevadine, 750 Chalkone, 676

flasks, 147 Chamoising, 698 Champy drums, 272 Chappe (silk), 815 Charcoal, Animal, 568 Vinasse, 571 Wood, 268 Chartreuse, 190 Cheddite, 305 Cheese, 474

Chamberland

Carbodiimide, 18, 430 Carbodiphenylimide, 430 Carbodynamite, 284 Carbohydrates, 523

Filled,

474

Margarine, 471

878
Chestnut, 690, 691 Chica, 190 Chinovose, 529 Chitin, 866 Chitosan, 866

INDEX
Cooa leaves, 751
Cocaine, 119, 745, 750
Cocci, 133

Coccus

cacti,

792

Chlamydomucor

oryzso, 155

Cochineal, 792 Cocoa, 437

Chloracetanilide, 661 Chloral, 251, 746 hydrate, 251, 746

Chloralamide, 421 Chloramides, 238 Chloranhydrides, 379

Chloranil, 648

Chloretone, 119 Chlorhydrins, 107, 217, 257 Chlorimides, 238 Chlorobenzenes, 635 Chlorocruorin, 137 Chloroethane, 117 Chloroform, 118
Pictet, 119 Tests, 120

Coconut, Composition, 482 oil (or butter), 498 Cocoons, 813 Codamine, 750 Codeine, 746, 750 Co-enzymes, 140 Ccerulein, 771, 772 Coerulignone, 719
Coffee, 438 substitutes, 439 Cognac, 19O, 191 Colchicine, 745

Collagons, 864
Collidinos, 742

Collodion, 821 cotton, 285, 294, 821

Chloromethane, 116
ct-Chloronaphthalene, 726 Chloronitroberizenes, 653 Chlorophyll, 133, 794 Chlorophyllase, 794 Chioropicrin, 236 a-Chloropropylene, 123 Chocolate, 437
Cholesterol, 866

Cholestrophane, 436
Choline, 257

Chromatic circle, 774 Chromogens, 764 Chromone, 755 Chromophores, 705, 764, 769 Chromotrop, 781 Chronograph, le Boulenge's, 317 Chrysamine R, 718 Chrysazin, 733 Chrysazol, 733 Chrysene, 736 Chrysin, 755 Chrysoidin, 657, 779 Chrysoidines, 668 Chrysoin, 780 Chrysophenin, 891
Cider, 190 Cinchona alkaloids, 751

Cinchonidine, 752 Cinchonine, 745, 751, 752 Cinene, 704

Cineol, 715

Cinnamaldehyde, 675 Cinnamylcocaine, 750 Cinnamylecgonine, 750 Citral, 216, 252, 416 Citrates, 418 Citrene, 703, 705 Citromyces citricus, 412
Pfefferianus
Citronellal, 252, Citronellol, 216

and

G labor,

412

358

Citrus bergamia, 413 industry, 413 limetta, 413

limonium, 413
Classification of organic substances, 29

Clovene, 708 Clupein, 862 Coagulation, Enzymic, 134 Coal, Cannel, 100 dust in mines, 34
for gas, 39 Coal-gas, 38 Coal-tar, 99

Colophene, 708 Colophony, 518, 707 Colorimeters, 830 Colour theory, Ostwald's, 773 Rosenstiehl's, 774 Colouring-matters, 764 Aci-aminoanthraquinono, 789 Acid, 768, 778 Acridine, 787 Adjective, 772 Aminoazo, 779 Azo, 778, 779, 78O, 796 Basic, 768, 778, 796 Benzidine, 781 Bonzo, 781 Chromotrop, 781 Classification of, 778 Goumarin, 787 Diamino, 781 Dianil, 781 JDiphenylmethaiio, 783 Fastness of, 831 Flavone, 787 Helindone, 789 Hydrazone, 782 Hydroxyazo, 780 Iinmedial, 790 Tndanthrene, 789 Iridigoid, 788 Ingrain, 781 Insoluble, 778 Janos, 781 Katigenic, 790 Kriogenic, 790 Manufacture of, 770 Monoazo, 779 Mordant, 778, 783 Natural, 772, 788, 791 Neutral, 778 Nitro, 778 Oxyketono, 787 Phenolic, 796 Physiological action of, 772 Polyazo, 779, 781 Pyrazolone, 782 Quinolino, 787 Quinono, 783 Quinonimide, 785 Quinonoxime, 783 Recognition on fibres, 798 802 Substantive, 770, 778 Sulphur, 667, 790 Tests, 795 Theory of, 764, 773 Thiazole, 787

INDEX
Colouring-matters, Triphenylmethane, 783 Vat, 788 Water-soluble, 795 Xanthone, 787 Colza seeds, 482 Concentrators, Multiple effet, 560 Condensation, Aldehyde, 245 Aldol, 245 Condenser, Liebig's, 2 Conditioning of textiles, 828 Conductivity, Electrical, 29 Conidia, 133 Coniferin, 534, 678, 866 Coniine, 20, 110, 742, 745, 747 Conylene, 110 Coolers, Wort, 204 Copal, 495 Copellidine, 743 Copper aceto-arsenite, 348 Copra, 498 Cops, 843 Coralline, 784 Corchorus capsularis, 812 Cordite, 287, 302 Corium, 693 Cork, 615 Cornein, 865 Cotarnine, 751 Cotton, 807 Bleaching, 836 Dyeing, 830, 841 Morcefisation, 602, 808 seed, 482 Statistics, 809 Coumalin, 743 Coumarin, 680, 688 Coumarone, 755, 756 Count of yarn, 806 Crabbing, 841 Cracking of oils, 87 Cream of tartar, 401 , 402 Creatine, 435 Creatinine, 435 Cremonite, 305 Creoline, 643 Creosol, 645 Creosote oil, 99 oils, 628 Crcsols, 643 Croceine, 668, 780 Crotonaldehyde, 252 Crotonylene, 110 Crushers, 262, 315 Cruteolin, 482 Cryptopine, 750 Crystalline, 657 form, 24 Crystallisation, 2 Crystals, Hemihedral, 19 Liquid, 139 Mixed, 23 Cudbear, 792 Cumene, 634 Cumidino, 655 Cuminaldehyde,'675 Curainol, 675
Cunerol, 474 Curagao, 191 Curarine, 751 Cutch, 691, 794 Cutin, 598

879

Cyano-acids, 377

Cyanogen, 427 chloride, 427 compounds, 427

of coal-gas, 50 sulphide, 429
trichloride,

427

Cyanohydrms, 238
Cyanole, 800 Cyanoquinolines, 754 Cyanurtriamide, 431
Cyclic compounds, 106, 616

Cycloheptane, 617 Cycloheptanone, 357 Cycloheptatriene, 617 Cyclohexane, 71, 617 Hexahydroxy-, 647 Pentahydroxy-, 646 Cyclohexanol, 641 Cyclohexanone, 617, 641 Cyclo-octane, 618 Cyclo-octatetrene, 618 Cyclo-olefines, 29, 616 Cycloparaflms, 29, 616 Cyclopentadiene, 617 Cyclopentane, 71 Cyclopentanone, 617 Cyclopropane, 106 Cymene, 252, 623, 624 Cymogen, 37 Cynarase, 139
Cysteine, 396, 424 Cystine, 396, 424 Cytase, 134

DAMBONITOL, 647

Dammar, 707
Daphnetin, 689, 866 Daphnin. 689 Datura stramonium, 749 Decahydroquinoline, 1M w Decane, 32 D6gragene, 478 Degras, 478, 699 Artificial, 479 Degree of dissociation, 322 fermentation, 153 mercerisation, 808 rancidity, 462, 464 viscosity, 90 Degrees Brix, 153, 577 Dehusker, 145 Delphinine, 744 Denaturants, 177 Denatured alcohol, 1 76 Densimeter, Brix, 577 Legal, 207 Dephlegmators, 77, 158, 162 Depsides, 690 Derma, 693 Dermatol, 688 Derricks, 66, 74 Desichthyol, 103 Desmobacteria, 133 Desmotropy, 18 Desoxybenzoin, 723 Detonation, 268 Detonators, 309 Developers, Photographic, 666 Dextrase, 147 Dextrin, 596 in glucose, 531 Dextrinase, 134, 204 Dextrose, 531 Diacetamide, 421 Diacetanilide, 661 Diacethydrazide, 426 Diacetyl, 398

Cyamelide, 427

Cyanamide, 18, 430 Cyanamines, 785 Cyanates, 427 Cyanides, Alkyl, 237 Cyanine, 787

Diacctylene, 114 Diacet y Iglycol* 217 J Haretylpropane, 711 DIaldehydes, 393 Diallyl/110 Uiamilt, 140, 590, 835 Diamincs, Aromatic, 657
Diarni no -acids, 424

Dihydrocymene, 703, 706

Dihydropyridines, 742, 743 Dih^ dropyrrole, 739 Dihydroxyacetonase, 147 Dihydroxyacetone, 147, 398

Diamiiioazobenzenes, 008 Diaminobenzenes, ($55 p 7>-Diaminodiphcnyl, 718

:

719 /7-Diaminodipheriylniethane, * Diaminogen, 801

Diaminophenol, 666
p-Diaminostilbene, 722 Diamol, 666
Dianisidine, 719

Dihydroxyanthraquinone, 734 o-Dihydroxybonzophenone, 720 Dihydroxycoumarin, 689, 866 Dihydroxydiaminoarseno benzene, 666 Dihydroxydiethylamine, 257 Dihydroxydiphenyls, 719 p-Dihydroxyhexainethylene, 702 Dihydroxynaphthalcncs, 728 Diliydroxynaphthaquinoiie, 783 Dihydroxy toluene, 645 Di-isobutyramide, 421 Diketobutane, 398
2>-Diketohexamethylenc, 702 Diketohoxane, 399 Diketonaminos, 252 Diketones, 394, 398 Dikctopiperazine, 859 J)imethylacotamide, 420 Dimethylacetol, 398 Dimethylamine, 241 Dimethylaminobeiizene, 668 Dimethyl-p-aminobeiizoyl chloride, 720 Dimethylanilino, 660 Dimethylanthracene, 733 DimethylarHenic acid, 242 chloride, 242 Dimethylarsine, 242 Dimethyl benzenes, 623, 633 Dimethylbutadiene, 712 Dimethylcarbinol, 214 Dimethylcyclo-octadiene, 711 Dimethylethylcarbinol, 126, 215 Dimcthylfulvene, 617, 769 Dimethylglyoxime, 398 Dimethylmethane, 36

Diaiithraquhionedihydroazine, 789
Diastase, 133. 134, 141 Diastofor, 140, 596, 835 wj-Diazine, 743

Diazoaminobenzene, 672 Diazoamino-compounds, 656, 671, 672 Diazoanisole cyanide, 669 Diazobonzeiie bromide, 671 chloride, 671, 673
imide, 671
nitrate, 671

perbromide, 671 sulphate, 671 Diazo black, 801

blue, 801

brown, 802 compounds, 241, 669

scarlet, 665 Diazoguanidine, 434

Diazomethano,
669

2-12

Diazoiiaphthaleiic, 727 Diazonium p] at ini chloride,

salty,

670

Diazotisat.ion, 781

Dibenzamide, 681 Dibeiizopyrrole, 755 Dibenzothiophen, 755 Dibeiizyl, 722 Dibipheiiylenethene, 765 Dibromopyranthrcnc, 789 Oibutyramide, 421 Dicetyl, 32 Dichlorethanc, 118 Dichlorhydrin, 257 Diclilorisopciitaiie, 712 1 Mchloro benzenes, 636 Dichlorom ethane, 118 Dichloronaplithalene, 730 Diclirnio substcances, 764 DickoJ, 495 JMcrucin, 460 l)i (\vaiiodiaruide, 431
Dieline, 122
1

Dimethyloxamido, 24O
Dimethylpheiiylpyrazolone, 739 Dimethylpyridiriea, 742

Dimethylthiophcn, 737 Dimorphism, 24 Dinaphthol, 727 Dinaphthyl, 730 Dinaphthylamine, 727

Dinitroaoetylglycerine, 274 Dinitroaniline, 663, 729 Dinitroanthraconos, 733

Dinitroazoxybenzene, 649 Dinitrobonzeiies, 649

Dinitrochlorobenzene, 653, 664 Dinitrodiphenylamine, 661 Dinitrodurene, 650 Dinitroethano, 237 Dinitroformylglycerine, 274 Dinitroglycerine, 273 Dinitroisodurene, 650 Dinitromesitylene, 650

)iethyla<;ety1urca,

746

Diethylamine, 241
Diethylcarbinol, 126, 243

Die thy Icy an amide, 431 Dicthylehediamine, 257 Diethylmalotiyluroa, 746 Diethylsulphone, 233 Diethylthiouroa, 434 Diffusors, 551 Di^italin, 745, 866 Digitouin, 866, 867 Digi toxin, 866 Di^lyccrol, 218 Diglynollamides, 421 Diglyeollimido, 421 Dihydrazides, 426 Dihydroanthracene, 732

Dinitromethane, 237 Dinitromonochlorhydrin, 274 Dinitronaphthalene, 726

Dinitrophenols, 664 Dinitroprehnitene, 650 Dinitrotoluenes, 651
jS-Dinitrotoluidine, 653

Dinitroxylenes, 650
Diolefines, 109 Dionine, 745 Dioxjdndole, 756

Dioxynaphthaquinones, 730
Dipentene, 704
dihydrochlorides, 705 Dipeptides, 859 Diphenyl, 671, 718

INDEX
Diphenyl derivatives, 718 ketone, 675
Diphenylacetamide, 661 Diphenylacetylene, 722 Diphenylamine, 660 sulphate, 828 Diphenylbutadieno, 769 Diphenylcarbiriol, 719 I)i phony lehloroarsine, 660 Diphenylene iminc, 755 ketone, 676 methane, 720 oxide, 755 sulphide, 755 as. Diphenylethano, 720 as. Diphenylethano, 722 Dipheiiylhexatrione, 769 Diphenylhydrazino, 673 Diphenylmo thane, 719 Diphenylnitrosamine, 673 oy-DiphcMiylpropaiie, 690 Diplococci, 133 Dipropargyl, 114 Dipropionamido, 421 Dipsacus fullonum, 849 Dipyridine, 742 7-Dipyridyl, 742 Diquinoline, 754 Diquinolyl, 754
Disinfectants, (540, (>43 Distillation, Fractional, 2, 75 of fermented liquids, 158

881

Egg-albumin, 859 Eggs, 860

Preservation, 860 Ehrlich's side-chain theory, 138 Eicosane, 32

Rikonogen, 729
Elaine, 517 Elastin, 864 Electrical conductivity, 29

Emeraldinc, 786 EmulHin, 134, 535 Emulsions, Stable, 489 Emulsor, Kuhlmann, 278 Kmulsor-centrifuge, 489 Knaritiomorphism, 20 Enantiotropy, 130 Encaustic, 465 Engenhos, 542 Enzymes, 23, 133, 134, 865 Equilibrated action, 136
Glycolylic, 526 Synthetic action, 136 Kosin, 685 Eosins, 784

Epichlorhydrin, 258 Equilibrium in saponification, 457 Erica B, 802 Eriochromoflavine, 682 Kriocyanine, 800 Eriodendrum anfractuosum, 810 Erythrene, 109, 712
Krythritol, 109, 225

Theory, 3

Vacuum, 4 Wood, 330

Distillery residues, Utilisation, 182

Erythrodextrin, 141 Erythrolein, 792

Erythrolitmiri, 792

Erythrose, 525

Disulphides, 233 Disulphoxides, 233 Ditetralyl, 731

Dithioglyeol chloride, 257 Dithiourethane, 434
Diureides, 435
Divi-divi, 690 Docosane, 32 Dodecanc, 32 Don nar, 305

Erythroxylon cooa, 750 Esterifica I/ion, Laws, 457 Esters, 124,234,457 Ethanal, 250 Kthanamidc, 421 Ethauamidine, 426 Ethandial, 393 Ethandiol, 217 Ethane, 24, 36
Polyrhloro-derivati ves,
Etlianol, 130
1

22

Dorniiol, 119, 746

Dotriacontane, 32 Dropping-point of

fats,

Dryers for

oils,

495

Drying ovens for explosives, 271, 294 textiles, 847 Drying power of oils, 494
Dulcin, 666, 683
Duleitol,

226

Duotal, 644

Durenc, 623, 634 Durra, 141, 182 Dyeing, Theory, 832 Dyestuffs, see Colouring-matters Dyewoods, 791 Dynamites, 273, 282 Analysis, 313 Gelatine, 298 Gelatinised, 299 Gum, 298 Manufacture, 283 Properties, 284 Safety, 284 with active bases, 285 with inert bases, 283 EBONITE, 711, 826 Ebullioscopc, 176 Ecgonine, 751 Echinochrom, 137 Ecrasite, 665 Effusiometer, Bunsen's, 62

Ethene, 108 Ethenol, 216 Etbenylethylenediamine, 740 Ether, 228 Industrial preparation, 230 Petroleum, 37, 76 Properties, 228 Recovery from air, 231 Tests, 232 Uses, 231 Ethers, 226 Ethine, 30, 111 Ethyl, 30 acetate, 395, 459
acetoacetate, 396, 460 ben/oate, 681

bromide, 115 bromopropionate, 369

butyrate, 460 carbonate, 431 chloracetoacetate, 397 chloride, 115, 117 chlorocarbonate, 431 chloroformate, 431 cyanurate, 427
diacetylsuccinate, 397 diazoacetate, 385, 424 diehloroacetoacetate, 397

dihydrocollidinedicarboxylate, 741

diketoapocamphorate, 716

882
Ethyl diketocamph orate, 716 j8 jS-dimcthylglutarate, 716 dimethylmalonate, 460
:

INDEX
Explosion, Velocity of combustion, projectiles, 317 reaction, 263 wave, 262 Volume of gases, 261 Explosive, Favier's, 263, 304 Explosives, 258 Abel's test for, 314 Analysis of, 313 Charging density of, 262
Classification of, 266 Destruction of waste, 312

fluoride, 115, 117 formate, 328, 395, 459 hydrosulphide, 233 hydroxycrotonate, 394 hydro xystearoiiaphthalenesulphon ate, 508 iodide, 115, 117

isocyanate, 428 isocyanurate, 428

malonate, 368

methyl ketone, 256 mustard oil, 430 nitrate, 235 nitrite, 235 oxalate, 240, 716 peroxide, 232 hydrate, 232 phosphate, 234
sodioacetoacctato, 396, 397

Non-congealing, 274, 276 Progressive, 263

Safety, 35, 305 Sensitiveness of, 315

Shattering, 263, 303 Sprengel's, 304 Stabilisation of, 292

sodiomalonate, 369 sodiomethylmalonate, 369

sulphate, 235 sulphide, 234
sulphite, 235

319 312 Theory of, 259 Uses of, 318

Statistics of,
of,

Storage

Extractor, Merz universal, 486 Pallenberg, 486 Soxhlct, 462

sulphoxide, 234 thioacetate, 419 thiocyanate, 419

Wegelin and Hubner, 486

FACTIS, 711 Farin, 570 Fat, Bone, 466, 477
(loose,

Ethylacetamide, 420 Ethylacetamido -chloride, 425

Ethylacetimino-chloride, 425 Ethylacetylene, 110 Ethylamine, 241

466

Hog's, 478 Horse, 466 Marotti, 473

ethyldithiocarbamate, 434 hydrochloride, 420 Ethyibenzene, 623, 633 Ethylcarbinol, 214 Ethylcyanamide, 431 Ethylene, 106, 108 bromide, 118, 217
chloride, 118

cyanide, 256
iodide, 118

monothiohydrate, 257 oxide, 256

Polychloro-derivativcs, 122

Ethylenecyanohydrin, 256 Ethylenediamine, 267 Ethylglycocoll, 859 Ethylhydrazine, 246 Ethylideneacetone, 398 Ethylidene chloride, 118 Ethylidene compounds, 118 Ethylidenecyanohydrin, 238, 256 Ethylmagnesiun bromide, 243 Ethylmercaptan, 233 Ethyl-tt-naphthylamine, 727 Ethylsulphone, 234 Ethyltoluene, 621 Ethylurethane, 432 Etiline, 122 Eucaine, 119, 745, 751 Eugenol, 645 Euquinine, 745, 752 Eurodines, 785 Euxanthine, 793 Euxanthone, 793 Exalgin, 601 Excelsior mill, 200, 269 Exhausters, 53 Explosion, 258 by influence, 265 Determination of, 264 Heat of, 259 Pressure of gases, 261 Velocity of combustion, 263

Ox, 466 Wool, 479 Fats, 457 Acid number of, 464 Animal, 468 Chemical and physical constants of, 4(>6 Consistent, 90 Dropping -point of, 6, 463 Estimation of, 462 Industrial treatment of, 503 et seq. Rancidity of, 464 Saponification of, 467 Fechner's law, 773 Fehling's solution, 255, 400, 582 Felt, 804 Fenchene, 708, 715 Feiichone, 714, 715 Fermentation, Alcoholic, 132, 145, 152, 204 Lactic, 151, 387 Ferrugine, 817
Fibres, see Textile fibres Fibrinogen, 137, 862

Fibroin, 865 Films for cinematographs, 599, 827

Filter-presses, 556 Filters, Charcoal, 568

Mechanical, 558 Firedamp, 34, 305 Fishery statistics, 69 Flavanthrene, 789 Flavin, 755, 793 Flavol, 733 Flavone, 690, 755 Flavopurpurin, 733, 787 Flax, 810 Autumn, 810 March, 810 Fleece, 804 Florentine receiver, 486 Floricin, 494 Floss (silk), 815 Flour, Wheat, 594 Flowers, Essences of, 704

INDEX
Fluavil, 711

883

Geranial, 252

Fluoranthrene, 736 Fluorene, 720 Fluorescein, 685, 722, 784 Fluorindines, 786

Fodder, Molassic, 166 Nutritive value of, 182 Forcite, 298 Forests, 614 Formaldehyde, 247 Formalin (Formol), Analysis of, 247 Formamide, 421 Formanilide, 661 Formates, 327 Formhydrazide, 426 Formins, 257 F.ormolite reaction, 71, 91 Formose, 625 Formula, Constitutional, 15, 17 Empirical, 13 Fleischmann's, 476 Structural, 15 Formulae, Rational, 18 Unitary, 15 Formyl chloride, 379 Formyloxime chloride, 427 Francolite, 104 Fructose, 533 Specific Rotation of, 581 Fruit essences, Artificial, 349, 459 Fuchsine, 721, 784 Fucose, 529
Fulgurite, 284, 304 Fuller's-earth, 80, 89, 490 Fulminate of mercury, 308

Geranine, 802 Geraniol, 216, 252, 715 Gin, 190 Glass, Hardened, 94 Globin, 862 Globulins, 861 Glonoin, 275 Glucoproteins, 863 Glucosarnine, 525, 530 Glucose, 531, 534, 686

Detection of, 532 Estimation of, 631, 581 Granulated, 532 Hydrated, 532 Manufacture of, 532 Glucosides, 530, 534, 865 Glucosone, 533 Glucosoxime, 530 Glucovanillin, 678 Glue, 864 Analysis of, 865 Glutarimide, 422 Gluten, 594 Glyceraldehyde, 393
Clycerides, 218, 460 Glycerol (Glycerine), 36, 146, 217 Industrial preparation, 220
Qualities of, 223

Refractive index, 219

Statistics,

223

Analysis of, 308 Fulvene, 617, 769

derivatives, 769, 770

Tests for, 223 Uses, 220 Glycoroso, 398 Glyceryl trinitrato, 258 Glycine (Glycocoll), 379, 385, 423

Fumaria

officinalis,

374

Furan, 736 Furazan, 740 Furazole, 740 Furfuraldehyde (Furfural), 173, 527, 737 Furfuran, 736 Furfuroids, 528, 598 Furnace, Combustion, 8 Gas, 45 Fusel oil, 109, 146, 165, 172 Fuses, 309 Bickford, 310 Electric, 311 GALACTOSB, 534
Galazin, 191

Glycocyamidine, 435 Glycocyamino, 434 Glycogen, 137, 598 Glycol, 217

acetates, 256}

chlorohydrin, 256

256 Ethyl ethers of, 256 mercaptan, 257 Glycollamide, 421

dinitrato,

Glycollic aldehyde, 393, 525 Glycollide, 384 Glycols, 107, 216

Galbanum, 644
Gallalith, 250, 475 Gall-nuts, 690, 691

Propylene, 217 Glycolsulphuric acid, 256 Glycosine, 393 Glycylglycino, 858 Glyoxal, 393 Glyoxaline, 393, 740
Glyoxiline, 284

Gallocyanine, 688, 785, 797

Galloflavin, 688

Gnoscopine, 750

Gambier, 794 Gas, Air, 60 Blue, 58

Illuminating, 38 mantles, 826
et scq.

Gommeline, 597 Goudron, 99

Grains," 203 Grape-must, 186 Greek fire, 266 Green naphtha, 102 oil, 103 starch, 592 Green, Algol, 789 Alizarin, 787, 799 Brilliant, 799 Diamine, 802 Diamond, 728, 799 Fast, for cotton, 783 Indanthrene, 789 Italian, 802 Janos, 799
Malachite, 720, 784, 799

"

Marsh, 33 meters, 56 Oil, 65, 98

producer, 45, 60 Rich6, 60

Water, 58, 98
Gases, Permanent, 34 Gasolene, 37, 76

Gasometers, 54 Gaultheria procumbens, 127, 686 Gelatine, 864 Blasting, 285 dynamites, 285, 298 Gelignite, 298

Methylene, 785 Naphthalene, 726

884

INDEX
Hesperidin, 866 Hesperidine, 703, 705 Heterocyclic compounds, 29, 616, 736

Groen, Naphthol, 729, 783 Pyrogon, 802 Schweinfurth's, 348 Sulphur, 802 Wool, 720 Grey, Ciba, 788 Grisounite, 307 Guaiacol, 644 Guanamines, 434 Guanidine, 434 Amino- derivative of, 434 Diazo-, 434 nitrate, 434 Nitro-dorivative of, 434 Guanine, 436, 440 Gum, 598 arabic, 598 Artificial, 597 British, 597 dynamites, 298 Kauri, 707 Starch, 597 tragacanth, 598 Vegetable, 597 Guncottou, 285 Compression, of, 293 Manufacture of, 288 Properties of, 287 Pulping of, 292 Stabilisation of, 292 Thomson and Nathan's process for, 290 Uses of, 293 Gunpowder, 266 Manufacture, 267 Gutta, 710 Guttaporcha, 710 HJEMATEIN, 791 Heematin, 862 Hsematoxylin, 791 Hsemin, 862 Hsemocyanin, 137 Haemoerythrin, 137 Haemoglobin, 135, 862 Hair, Artificial, 826 Half -stuff, 605 Halides, Acid, 377, 379 Halogens, Detection of, 7 Estimation of, 12 Hansena fermentation vessels, 208 Hardened glass, 94 Heat of combustion, 25 explosion, 259 formation, 25 of explosives, 259 neutralisation, 26 Hedonal, 119, 746 Helianite, 328 Helicin, 866 Heliotrope, Artificial, 678 Ciba, 788 Heliotropin, 678 Hemicellulose, 598 Hemimellithene, 623 Hemiterpene, 708 Hemp, 812 seeds, 482 Henoicosano, 32 Hentriacontane, 32, 37 Henze autoclaves, 143 Heptachloropropane, 123 Heptacosarie, 32, 37 Heptadecano, 32 Heptaldehyde, 251 Heptane, 32, 37 Heptoses, 526, 534 Heracleum giganteum, 127, 130, 215 spondylium, 215

Hexabenzylethane, 723 Hexabioses, 535 Hexabromobenzeno, 636 Hexacotylmannitol, 224 Hexachlorobenzene, 636 Hexachlorohexahydrobenzene, 636 Hoxacontane, 32/37 Hexacosane, 32 Hexadecane, 32 Hexadione, 399 Hexaethylbonzene, 623 Hexahydrobonzene, 617, 702 Hexahydrocymene, 703, 706 Hexahydrophenol, 702 Hexahydropyridine, 743 Hexahydroxyanthraquiiione, 783 Hexahydroxybonzene, 646 Hexahydroxybenzophonoiie, 689 Hexahydroxycyclohexane, 647 Hexahydroxydiphenyl, 719 Hexamethylbenzene, 111, 623, 631 Hexamethylene, 106, 617, 702 Hoxamethylenetetramine, 187, 248 Hexandiino, 114 Hexanes, 32, 37 Hexanhexol, 225 Hexanitrodiphenylamhio, 660 Hexanitroethane, 237 Hexanol, 215 Hexaphenylethane, 722 Hoxapropylbenzene, 623 Hexatrioses, 524 Hoxine, 110 Hexitols, 524, 531 Hexosaccharine, 53O Hexoses, 529 Constitution of, 530 Hides, Dyeing of, 700 Finishing of, 699 Graining of, 700 Tanning of, 692 Histones, 862
Hollanders, 291, 604, 611) Holocaine, 19, 74(5, 751 Horn oasparagi UPS, 425
1

Ilomooamphoric tiitrile, 716 Homologucs of aniline, 6(51

benzaldehydo, 675 phenol, 643
succinic acid, 371 tcrpones, 708

FTomology, 24 Homophthalimide, 755 Homopyrocatechol, 645 Hoiioy, 533 Hops, 193 Decoction of, 203 Humic substances, 530
lupulus, 193 Hydantoin, 433, 435 Hydracellulose, 601 Hydra mine, 257 Hydrastine, 745, 750 Hydrastiniiie, 75O Hydraulic accumulators, 484 gas main, 45 press, 27O, 483 Hydrazides, 426, 673 Hydrazines, 240, 241, 672 Hydrazobenzene, 667, 668 Hydrazo -derivatives, 668, 765 Hydrazodicarbonamido, 434 Hydrazones, 246, 524 Hydroanthracene, 732

Humulus

INDEX
Hydroanthranols, 732 Hydrobenzamide, 074 Hydrobenzoiii, 722 Hydrocarbons, 29, 31 Aromatic, 622 of petroleum, 71
of the j_ a series, 109 of the C,iH aw _ 4 and C71 2H _ 6 series, 114 Saturated, 29, 31 Unsaturated, 29, 106, 116
}

885

Illuminating gas, Properties of, 40 Purification of, 45 et seq. Separation of naphthalene from, 46
Statistics of,

59

CHo

with triple Unkings, 110 with unsaturated side-chains, 634 Hydrocellulose, 599, 601, 602 Hydrocinchonidino, 752 Hydrocotarnine, 750 Hydrocyanocarbodiphenylimide, 762 Hydrogen, Estimation of, 8 Nascent, 33 Typical alcoholic, 124 Hydrogenated benzene compounds, 701 Hydrolysis, 125, 442, 535 Enzymic, 134 Hydronaphthalenes, 730 Hydropyridines, 743
Hydroquiiiino, 752 Iydro(j[uinone, 645 Hydroxy-acids, Aromatic, 686 Higher, 389 poly basic, 119 Polyvalent dibasic, 399 monobasic, 391 tribasic, 411 Saturated monobasic, 383 Unsaturatod monobasic, 389 Hydroxy-alcohols, 677 llydroxy-aldehydes, Aromatic, 677 Hydroxyaiithraiiol, 733 Hydroxyanthraquinones, 733 Hydroxyazo-compounds, 668 llydroxybenzaldchydes, 677 j8-llydroxybutyraldehyde, 245 Hydroxyethylarnine, 257 Hydroxyothyltriniethylamm oiiium hydroxide, 257 Ilydroxyhydro(j[uinono, 646 Hydroxylaniine, 235 Hydroxylamine derivatives of acids, 427 Hydroxylinolein, 495 Hydroxymethyleneacetone, 396, 399 Hydroxymcthyloiieketones, 399 Hydroxymethylfurfural, 528 Hydroxynitriles, 238 Hydroxypyridines, 742 2-Hyclroxyquiiioline, 754 Hydroxytoluenes, 643 Hygrine, 750 Hyoscyamine, 749 Hyphomycetcs, 133, 155 Hypnone, 675 Hypnotics, 118, 746 Hypoxanthiiie, 436 Hypsoehromcs, 764 IATJROCHEMISTKY, 744 Ichthyoform, 104 Ichthyol, 103 Tchthyolsulphonates, 103
Iditol,

Yield of, 58 Imides, 421 Iminazole, 740 Imiiiocarbamide, 434 Iminocarbamideazido, 434 Tminochlorides, 425 Iminoethcrs, 420, 422
Iininothioethers, 425 Iminourea, 434 Indamine, 765, 785 Indanthrene, 765, 789 Indazin, 800 Indazole, 757 Indeiic, 731

Index

of refraction, 27,

463

Indican, 758
of urine, 756

Indigo, 757, 758

Analysis of, 758 blue, 758 carmine, 760 Colloidal, 759

extract, 800

759 763 Syntheses of, 760 Indigofera erecta, 758 leptostachya, 758 tinctoria, 757 Indigoids, 788 Indigolignoids, 790 Jndigotin, 758 Iiidirubin, 788
Properties
of,

Statistics of,

Indoin, '.80 Indole, 755, 756 Indolignone, 790

Iiidoiiaphthalene, 790

ludophenin, 737 Indophenol, 727, 765, 785 Indophore, 756 Indoxyl, 756, 758, 762 Tmlrenc, 731 Indulines, 786 Infusorial earth, 283 Injectors, Kdrting, 53 Ink, 688 Inositol, 646, 647 Intermediates, 777 Inulin, 533
Invelite, 6-42

Inversion, 531, 538 Invert sugar, 531, 538, 581 Invertase (Invertin), 134, 538

Todobenzene, 635 lodobutane, 117 lodoform, 121

reaction, Lieben's, 131

Tests for, 122

lodol, 738

Todopropane, 117 lodosobenzene, 635 chloride, 635

226 verum, 644 Illuminating gas, 38 Analysis of, 60

Illicium
Calorific value of, 39, 61

lodothyrm, 866
lodourethane, 432 lodylbenzene, 635 loneiie, 713
Ionic concentration, 538 lonone, 713 Irene, 713

Composition of, 40 History of, 38

Lighting power of, 62 meters, 56 Physical and chemical testing Price of, 58

of,

60

866 866 Ironac, 328 Irone, 713

Iridin,

Irigenin,

886
Isatin, 756, 757, 760 chloride, 760 a-Isatinanilide, 762 Isatis tinctoria, 758

INDEX
Kneading machine, Werner-Pfleiderer, 472
Koji, 165

Koumis, 191
Kratites, 305

Isatoxime, 760

Kubierschky column,

77, 631

Isoamyl isovalerate, 400 Isoamylbenzene, 623

Isobutaiie, 37 Isobutyl iodide, 118

Kummel,

191

Isobutylbenzene, 623
Isobutylcarbinol, 126, 215

Isobutyramide, 421 Isocyanates, 427 Isocyanides, 238

Kunerol, 474 Kyanol, 657 LACCASE, 134 Lacs, 495 Lactalbumin, 859 Lactams, 423, 756
Lactases, 134 Lactates, 388 Lactic acid bacillus, 145, 387 Lactides, 384 Lactite, 475 Lactoglobulin, 861 Lactone, Brorno butyric, 355 Isocaproic, 257 Lactones, 355, 377, 384, 526 Lactose, 636 Testing of, 537

compounds, 29 Isocymene, 634 Isodulcite, 529 Isodulcitol, 793 Isodurenes, 623, 634 Isoduridine, 655 Isoeugenol, 645, 678 Isolactose, 535 Isoleucine, 424 Isology, 24 Isoinaltose, 136, 536 Isomelamine, 431
Isocyclic

Lactyl chloride, 389 Lager beer, 203, 205 Lakes, 769, 770, 771

Isomerides, 17 Boiling-points of, 25 Melting-points of, 25 Metameric, 18

Optical, 20 Racemic, 21 Isomerism, 15, 17
Cis-

Lamp,

Carcel,

62

Hefner, Alteneck, 62

and

trans-,

22

Lampblack, 624 Lard, 478 Latex, 708 Laudamine, 750 Laudanidine, 750 l^audanosine, 750
Laurene, 706

Space, 19

427 Isonitrosoketories, 255, 398 740 Iso-oxazole, Isopentane, 37, 712

Isonitriles, 237, 238, 240,

Laurus camphora, 704, 716

Lautopine, 750 Law of Dalton, 5
esterification,

457

Isoprene, 109, 113, 705, 708, 712 Isopropyl iodide, 116, 117 Isopropylacetyleiie, 110

Hess-Berthelot, 25

Lead

refraction, 27 plaster, 351

Isopropylbenzaldehyde, 675 Isopropylbenzene, 623, 634

Isoquinoline, 754

Sugar

of,

347

Leather, 093
Artificial,

Isorhamnose, 529 Isosafrole, 678

Isovaleryl chloride, 380 Isoviolanthrene, 789
Isuret, 427

717 Hardened, 700

Ivory, Artificial, 351

JIGGERS, 845
Jute, 812

KAMPTULICON, 710 Kapok, 499

oil,

810

Kephir, 139, 191, 475 Keratin, 806, 864 Kerosene, 72 Ketenes, 256 Keto-aldehydes, 394, 399 Keto-arabinose, 525 Ketoheptamethylene, 617

Ketohexamethylene, 617, 701 Ketohexoses, 524 Ketoketenes, 256 Ketones, 116, 124, 243, 252 Aromatic, 673, 675 Strache's estimation of, 255 Ketonimides, 243 Ketopentamethylene, 617 Ketoses, 524 Ketoximes, 253, 676

Leben, 191 Lecanora tartarea, 792 Lecithalbumin, 860 Lecithin, 402 Lecithins, 258 Lees, Wine, 170, 402, 408 Lemons, Cultivation of, 413 Treatment of, 414 Leucine, 20, 424, 858 Leuco-bases, 721, 765 Leucocytes, 139 Leucotannin, 689 Levulinaldehyde, 399 Levulose, 633, 581 Lichens, 792 Life, Origin of, 137 Light, Polarised, 27, 395 Sources of, 64 Standards of, 62 Lignin, 698, 601, 605, 608 Estimation of, 605 Ligroin, 37, 76
Lirnonene, 416, 703, 704, 705, 706 Lincrusta, 496

Linoleum, 495, 615 Lixxseed, Composition oil, 679

253, 676

of,

482

Beckmann's transposition
Khaki, 794
Kieselguhr, 275, 283 Kirschwasser, 190

of,

usitatissimum, 494, 810 Lipase, 134, 507 Lipoids, 746

Linum

Lippich polariser, 680

INDEX
Liqueurs, 190 Liquids, Specific gravity
Lithoclastite,
of,

887

284

Lithographers' varnish, 495 Litmus, 792 Logwood, 791 Lupetidine, 743 Lupulin, 193, 203
Luteolin, 755 Lutidines, 742 Lyddite, 303, 665 Lysidine, 740 Lysine, 392, 424 Lysins, 139

Lysochlor, 643

Lysoform, 250 Lysol, 643 Lyxose, 529

MACLUKA

tinutoria,

793

Maclurin, 793

Madder, 734
Magnesia, Effervescent, 413 Magnetic rotation, 28 Maize, 142, 193, 596 Composition of, 482 oil, 499 Malamide, 421 Malaria, 752 Malt, 141, 196 Cleaning of, 200 Diastatic; power of, 199 Evaluation of, 199 Green, 196 Grinding of, 200 Kilning of, 198

Mashing of, 201 Maltase, 134, 141, 535, 581 Malting, 196 Maltodextrinase, 134, 204 Maltol, 600, 687 Maltose, 134, 536, 581

Menthol, 714 Menthone, 714 Mercaptan, 233 Mercaptans, 233 Mercaptide, Mercuric, 233 Sodium, 233 Mercaptides, 233 Mercaptols, 252 Mercerisation, 808 ^ Mercury fulminate, 308 655 Mesidine, Mesitol, 639 Mesityl oxide, 253 Mesitylene, 111, 623, 633 Metaldehyde, 250 Metalepsy, 15 Metamerism, 18, 228 Metastyrene, 634 Meters, Alcohol, 173 Automatic gas, 58 Dry gas, 66 Gas, 56 Methanal, 247 Mothanamide, 421 Methanamidoxime, 427 Methane, 24, 33 Derivatives of, 31 Industrial uses of, 35 Preparation of, 35 Properties of, 34 Methanol, 127 Methanthiol, 233 Methene, 108 Methenylamidoxime, 427 Methoxy methane, 228 Methoxypyridine, 742 Methoxyquinoline, 765 Methyl/ 30
acetate, 459 chloride, 116

Mammoth pump,
Manlianite, 305 Manna, 225 Mannide, 226 Mannitan, 226

278

cyanide, 238
ether, 228 iodide, 117 isothiocyanate, 430

mustard

oil,

Mannitol, 225, 530, 534 Hexacetyl, 224

Ilexanitro, 285

iionyl ketone, succinate, 460 sulphide, 233

430 397

Mannose, 534
Monnotetrose, 585 Mannotriose, 225 Maraschino, 190 Margarine, 470, 680 cheese, 471 Margol, 471 Marmite, 149 Marsala, 190 Mashing apparatus, 201 Massccuite, 564, 565 Masut, 77, 86
Matricaria parthe'aum, 716 Meconidine, 750 Medziankite, 305 Melam, 431 Melamine, 431 Melene, 109
-

Mothylacetanilide, 661 Methylacetylurea, 420 Methylal, 251

Methylamine, 240
hydrochloride, 117, 241 Methylaniline, 660

Melibiase, 134 Melibiose, 58 , Melinite, 301; 665 Melissyl palmitate, 460 Mellite, 685 Mellithene, ')34 Melting point, 5, 25

Menta pulegium, 714

Menthane, 706 Menthene, 706

Methylanthracenes, 733 Methylarbutin, 866 Methylbenzene, 623, 633 Methylbutanol, 215 Methylcyanamide, 431 Methyldihydroiminazole, 740 Methylene, 108 bromide, 115, 118 chloride, 115, 118 glycol, 525 iodide, 115, 118 Methylethylacetyleno, 110 Methylethylcarbiiiol, 214 Methylglyoxal, 399 Methylgranatonine, 618 Methylheptenone, 363 p-Methylisopropylbenzene, 623, 634 Methylisopropylcarbinol, 126 Methylnaphthalenes, 730 Methylpentoses, 529 Methylpropane, 30, 37 Methylpropanol, 215 Methylpseudoisatin, 766

888
Mcthylpyridino, 742 Methylpyridone, 742 a-Methylquinoline, 754 Methylsulphonal, 746 Methyluraeil, 436 Methylurethane, 726 Metol, 666 Michler's ketone, 719 Microbes, 132 Mierococci, 133 Micron, 133 Milk, 134, 474 Analysis of, 475 Coconut, 498

INDEX
Naphthindigo, 788 Naphthols, 727, 728 Naphthosalol, 728 a- (and ft-) Naphthylamine, 727 Naroeine, 745, 750 Narcotine, 745, 750, 751 Natron, 513 Ncosalvarsan, 666 Neradol, 250, 692, 697 Neroline, 728 Neurine, 257 Nicol prism, 579 Nicotine, 745, 747 Nicotyriiie, 747 Nisser powder, 305 Nitracetanilides, 661 Nitriles, 237, 427, 679 Nitroacetins, 274 Nitroanilincs, 663 Nitrobenzaldehyde, 675, 761 Nitrobenzene, 649, 650, 669 Nitrocellulose, 285 constitution of, 286 Nitrochlorhydrin, 274 Nitrochlorobenzoiics, 653 Nitrocymene, 650 Nitro-dcrivatives, Aromatic, 64$ Electrolytic reduction of, 669 Nitrodimethylanilino, 660 Nitroethane, 236, 237 Nitroform, 237 Nitroformins, 274 Nitrogen, Detection of, 7 Estimation by Dumas' method, 10
'

Condensed, 474 Fermented, 191 Skim, 474

Milling of woollens, 838 Mimosa, 69O, 691 catechu, 644

Mirbane, Essence

of,

649

Moellcm, 478 Molasses, 166, 567, 570 Beet-sugar, 166, 570 Lactose, 537 Recovery of sugar from, 571 Spent wash from, 571
Utilisation of,

570

Molecular volume, 25 Monoacotin, 257 Monoacylhydrazides, 426 Monoazo-compounds, 779 Monochlorhydrin, 257 Monoiiitroglycerine, 274 Monosaccharides, 523 Monoses, 523, 524

Kjeldahl\s method, 1 1 Will and Varreiitrapp's method,

Stereoisoinerism, of, 22 Nitroglycerine, 275 Filtration of, 282

Formation of, 525 Mordanting, 830, 834, 835 Mordants, 770 Morin, 755 Morphine, 138, 745, 750 Morpholine, 743 Morphotropy, 24 Morus alba, 813 tinctoria, 793 Motocliemistry, 620 Moulds, 132 Mucins, 863 Mucors, 133, 155, 156, 412 Multiple effet apparatus, 560 Murexide, 436, 437 Muscarine, 257 Muscone, 713 Musk, Artificial, 705, 713 Natural, 713 Mustard, Black, 430 oils, 430 seed, 482 Mutarotation, 28, 581 Mycoderma aceti, 340, 341 vini, 341 Myosin, 862 Myristin, 350 Myrobolans, 690, 691 Myrosin, 216, 502 NAPHTHA, 65 Solvent, 632 Naphthalene, 628, 723, 762 derivatives, 723, 728
Estimation, in coal-gas, 61
coal-gas, 46 tetrachloride, 730

Manufacture
Uses
of,

of,

277

Stabilisation of, 281

282

Nitroguanidirie, 434

Nitrohexane, 236 Nitromesitylene, 650 Nitrornethane, 237 Nitron, 665

Nitroiiaphthaleiies, 726

Nitrophenols, 663 Nitropheiioxides, 663 -Nitrophenylhydrazine, 673 Nitroprehnitene, 650

Nitropropane, 237 Nitrosamines, 240, 656, 660, 669 Nitrosites, 703 Nitrosochlorides, 703
p-Nitrosodimethylaiu'line, 660 Nitrosodiperitene, 705 Nitrosophenol, 648, 660 Nitrosopyrrole, 739 Nitrostarch, 285 Nitrostyreno, 634 Nitrotoluenos, 651 Nitrourea, 432

Nitrourethane, 432 Nitroxylones, 650

from

Naphthamine, 727
a-Naphthaquiiione, 729 /3-Naphthaquinone, 730 Naphthazarin, 783 Naphthenes, 71, 617, 701

Nomenclature, Official, 29 Nonane, 32 Noiiodecarie, 32 Norioses, 534 Nonyl aldehyde, 251 Nubepine, 643 Nuclei, Condensed benzene, 718 Nucleins, 863 Nucleo-albumins, 861 Nucleo-histone, 862

INDEX
NucJeoproteins, 863 Number, Acetyl, 224, 225, 463
Oil, Sanse,

889

492 Sesame, 492, 600

Shale, 102

Acetyl acid, 225 Acetyl saponification, 225 Acid, 105, 464 Butter, 477 Ester, 465 Hohner, 461 Iodine, 463 Kottstorf, 468

Spja-bean, 466, 502 Solar, 72, 98

Sperm, 478
Stillingia ,499

Sulphocarbon, 491

Maumene, 464
477 Reiehert-Meissl-Wolmy, 461, 477 Saponification, 468
Polonaise,

500 Tomatoseed, 502

Teel,

Turkey-red, 390, 490 Turpentine, 703, 706, 707

Walnut, 496

Nutrose, 475, 861 Nux vomica, 751

OCTADECYLBENZENE, 623
Octadierie, 110 Octahydroanthracene, 731 Octahydrophenanthrcne, 731 Octane, 32 Oetanthrene, 731 Octhraccne, 731 Octocosane, 32 Octodeoano, 32 Octoses, 534 Octylbenzeno, 623 Oclylerie, 109 ( Knan th aldehyde, 25 L (Knoxydaso, 134 Oil, Acetone, 255 Allyl mustard, 466 Almond, 466 Aniline, 659 Anise, 644 Anthracene, 628, 630 Arachis, 492, 500 Bitter almond, 674 Boiled Jinseed, 494 Bone, 737 Cardamom, 473 Castor, 390, 493 Chinese bean, 502 Chrysalis, 480 Clove, 645 Coconut, 466, 498 Cod-liver, 466, 478 Colza, 466, 501 Cottonseed, 466, 499 Dipped animal, 737 Ethyl mustard, 430 Fish, 478 for gas, 98 Gaultheria, 687 ( Gelatinised vaseline, 93 Giiigelly, 500 Grapeseed, 502 Hempseed, 466 Kapok, 499 Lemon, 415 Linseed, 466, 494 Maize, 466, 499 Mandarin, 682 Methyl mustard, 430 Oleo, 423 Olive, 466, 490 Orange, 705 Palm, 466, 496
'

Washed olive, 491 Whale, 466, 478 Wood, 503 Wool, 479 Oil-cako, 483, 493, 500 Oil-gas, 64 Oils, Animal, 468 Bleaching of, 490 Blown, 464 Creosote, 628 Deodorisation of, 490 Drying, 363, 462, 494 Engine, 92 for gas, 98
Flash-point
of, 83,

91

Hardening Heavy, 76

of,

480

Lubricating, 627 Mineral lubricating, 86 Mustard, 430

Oxidised, 464 Refining of, 488
Spindle, 92 Tar, 628

Thickened, 495 Vaseline, 89 Vegetable, 482

Viscosity of, 83, 90 Oily seeds, Composition, 482 Olease, 490 Olefines, 106 Constitution of, 108

Palm-nut (Palm-kernel), 466, 497

Paraffin, 76

wax, 94 Pennyroyal, 714 Peppermint, 714 Poppyseed, 466, 494 Propyl mustard, 430 Kavison, 502 Resin, 92, 707
VOL.
II.

Nomenclature of, 106 Preparation of, 107 Table of, 106 Oleine, 358, 517 Catalytic, 518 Distilled, 506, 518 Saponification, 518 Transformation into stearine, 506 Wool, 479 Oleomargarine. 470 Oleum cinae, 704 Olive, Composition of, 482 Opium, 750 Opsonins, 139 Optical activity, 19, 69 antipodes, 23 properties, 26 Orange, Alizarin, 709 Croceiiie, 780 Dimethylnitraniline, 663 G, 780 Indarithrene golden, 789 Methyl, 668 TI, 780 III, 668 IV, 660 Orceine, 645 Orcinol, 645 Organo-metallic compounds, 242 Origanum hirtum, 644 Ornithine, 392, 424 Orthobromobenzyl bromide, 732
57

890
Ortho-ethers, 324 Orthoform, 119, 746

INDEX
Pentadecatetrone, 711

Osamines, 530 Osmophores, 705 Osoncs, 633

Osotriazole, Ossein, 864

74O

Oxalates, 308 Oxarnide, 421

Oxamines, 785
Oxazole, 74O Oxidation, Enzymic, 135 Oxidation chamber, 885 Oximes, Aromatic, 676

Oximide, 422
Oxindole, 756 Synthesis of, 760 Oxy-acetylene blowpipe, 113 OxycelluLose, 601, 602, 8O8 Oxydascs, 134 Oxygenases, 135 Oxyhaemoglobin, 862, 863 Oxynarcotine, 750 Oxyterpeiies, 713

Ozoform, 250
Ozokerite, 31, 69, 94, 104 Ozonides, 359 PAiiM fruit, 482
oil, 496 Palmer, 849 Palm-kernel, 482 oil, 497 Palmitates, 350 Palmitin, 35O Panclastite, 304

Pentaethylbenzene, 623 ^ Pentahydroxycyclohexane, 646 Pentahydroxypentano, 225 Pentaline, 122 Pentamethylbenzene, 623 Pentamethyleiie, 617 Pentamethylenediarnine, 257 Pentamethylpararosanilmo, 72 1 Pentanediene, 110 Pentanes, 37 Pentanol, 215 Pentapheiiyl ethane, 722 Poiitatricontane, 32 Penteiies, 11O Pentitols, 524 Pentosans, 527 Estimation of, 528 Pentoscs, 520 Estimation of, 528 Pentosuria, 529 Peptase, 134 Peptones, 858 Perfumes, 703 Pergamin, 602 Pcroxydases, 135 Peroxyozonides, 356 Pcrsco, 792 PeryleUe, 769
Petrinage, 299 Petrolene, 99

Pentaerythritol, 225

Papaver sormiiforum, 75O Papavoramine, 75O

Papaverine, 745, 75O Paper, 602
Bisulphite process, 608 Boiling, 604 Chlorine process, 610

Colouring, 612 Electric process, 610

Loading, 612 Microscopical testing, 613

Paraffined, 602

Parchment, 602
Sizing, 611, 613 Soda process, 6O7
Statistics, 614 Testing, 612 Para -anthracene, 732

Paracasein, 861

Paracyanogen, 427 Paraffin wax, 94 Analysis, 105 Statistics, 106

Paraffins, 29, 31

Paraformaldehyde, 248
Paraglobului, 137 Paraldehyd.o, 246 Paraleucanilino, 721 Pararosaniline, 721

Parchment,

Artificial, 600,

602

Parthenogenesis, Artificial, 138 Partial pressures, 5 Pasteur flasks, 147 Pasteurisation, 186, 210 Pastinaca sativa, 130
Pellagra, 867

Pegamoid, 717
Penicillium glaucum, 23

Pentabromotoluene, 617

Pentachloroanisole, 643

Pentaeosane, 32 Pentadecane, 32.

Petroleum, 65 coke, 78 Composition, of, 7O Crude, 70 Desulphurising of, 8O Distillation of, 75, 76 ether, 76, 86 Extraction of, 73 Flash-point of, 84 fountains, 73 History, 65 Illuminating power of, 84 Optical activity of, 69 Origin of, 67 Pi pc -lines for, 75 Properties of, 70 Purification of, 78 Refining of, 78 residues, 86 Specific gravity of, 70, 72 Statistics of, 81 tanks, 80 Tests for lighting, 83 Transport of, 75 Uses of, 81 Viscosity of, 83 Petroline, 76 Phoeophytin, 794 Pharaoh's serpents, 429 Phellandrene, 703, 706 Phenacetin, 666 Phenacyl bromide, 678 Phenanthraquinone, 736 Phenanthrene, 63O, 735 Phenazine, 765 Phenetidines, 666 Phenetole, 642, 666 Phenol, 638 Acid derivatives of, 643 Homologues of, 643 Pure synthetic, 640 Testing of, 640 Phenolphthalein, 685, 784 Phenols, 637 Dihydric, 644

INDEX
Phenols, Monohydric, 638 Polyhydric, 646

891

Table

of,

639

Trihydric, 645

Pinacones, 217 Pinane, 706 Pinone, 706 hydrochloride, 707

Phenoxazine, 765 Phenoxides, 638, 641, 642, 679 Phenyl disulphide, 667 hydrosulphide, 666 salicylate, 687 styryl ketone, 690 sulphide, 667 Phenylacetanilide, 661 Phenylacetylene, 634 Phenylamine, 657 Phenylanthracone, 733 Phenylanthranol, 733 Phenylbenzaraide, 661 Phenylbenzofulvone, 769 Phenylchloracetamide, 661 Phenyldiazonium chloride, 670, 671 hydroxide, 672 nitrate, 670, 671 sulphate, 671 Phenyldimethylaminopyrazolone, 740 Phenylenediamines, 649, 655, 662 Phenylglycerol, 674 Phenylglycocoll, 661 Phenylglyoxal, 678 Phenylhydrazine, 673 hydrochloride, 672 Phenylhydroxyanthranol, 733 673 Phenvlhydroxylamine, 667, 669, as. Pnenylmethylhydrazine, 673 Phenyl-a-naphthylamine, 727 Phcnylnitromethane, 653, 669 Phenylosazones, 524, 673 Phenylsuccinimide, 422 Phlegm, 158 Phlobaphenes, 693 Phloretin, 866 Phloridzin, 866 Phloroglucinol, 646, 690 Phorone, 256 Phosgene, 118, 431 Phosphine, 787 Phosphines, 242 Phosphorus, Detection of, 8 Estimation of, 13 Photogen, 98 Photographic developers, 66(5 Photometer, Bunsen's, 63 Lummor and Brodhun'a, 63 Phthaleins, 685, 722, 784 Phthalic anhydride, 684 Phthalide, 684 Phthalideine, 733 Phthalidine, 733 Phthalimide, 685, 761 Phthalophenone, 684, 722 Phthalyl chloride, 684 Phylloxera, 188 Physostigmino, 745 Phytochloriu, 794 Phytoglobulins, 861 Phytol, 794 Phytorodin, 794 Phytosterol, 866 Piazthiol, 790 Picene, 736 Picolino, 262, 742 o-Picolylalkine, 742 Picramide, 663 Picrotoxin, 744 Pierrite, 305 Pigments, 778 Pimpinella anisum, 644 Pinacoline, 217

647 816 Pinnoglobin, 137 Pinus maritima, 707 Pipecoline, 743 Piperazine, 257, 743
Pinitol,

Pink

salt,

Piperidine, 110, 741, 743 Piperidines, 743 Piperme, 743, 745 Piperonal, 678 Piperylene, 110 Pitch, 99, 630 Coal, 99 Mineral, 99 Stearine, 506 Pittacal, 784 Plasnion, 475, 861 Plastering of wines, 187
Plastrotyl, 653

Platmichlorides, 14 Pluszucker, 585 Polarimeters, 28, 579 Polarimctry, 579 Polarisation of light, 27

Polyamines, 661 Polyazo -compounds, 779

Polyglyccrins, 218

Polymerism, 14 Polymethylenes, 29, 616 Polymorphism, 24 Polynitrobenzenes, 649 Polyoses, 523, 585 Polypeptides, 858 Polysaccharides, 523 Ponceau, 729 Poppy, Composition of, 482 Populin, 534, 866 Potatoes, Dry matter in, 588 Starch-content of, 141, 588 Powder B, 296 Black, 266 Powders, Brown prismatic, 273 Chlorate, 304 Chocolate, 273 Mining, 267 Perchlorate, 304 Prismatic, 272 Prometheus, 304
Smokeless, 295, 298, 300, 302, 303 Smokeless sporting, 267
Sporting, 267 Various, 311
Precipitins, 139, 863

Prehnidine, 655 Prehnitcne, 623 Pressed yeast, 149

PrimuUne, 667, 787

Printing of fibres, textiles, yarns, 831, Proline, 864

854

Propaldehyde, 251 Propane, 36 Propanol, 214 Propanone, 254 Propantriol, 217 Propargyl aldehyde, 252 Propene, 109 Propenol, 216 Propine, 110 Propionamide, 421 Propionyl chloride, 380 Propyl iodide, 115

mustard

oil,

430

Propylacetylene, 110

892
Propyl benzene, 023, 634 Propylcarbinol, 214 Propylene, 109 a-Propylpiperidinc, 742 Propylpseudonitrole, 236 Protamines, 862 Proteins, 857 Coagulable, 862 Conjugated, 8(52 Hydrolysis of, 858 Modified, 862 Natural, 859 Various, 865 Proteolytic action, 1 34 Protocatechuic aldehyde, 677, 678 Protococcus vulgaris,* 226 Protol, 218 Protopine, 750 Protoplasm, 137, 857 Pseudo-acids, 653, 669 Pseudocumene, 623, 634 Pscudocumidine, 655 Pseudoindoxyl, 756 Pseudoisatin, 756 Poeudoisomerism, 18, 394 Pseudomorphine, 750 Pseudo -tanning, 693 Ptomaines, 257, 858 Ptyalin, 134 Pulegone, 714 Pulp, Chemical wood, 603, 607 Mechanical wood, 603, 605
Purgatol, 701 Purification by physical methods, 2 Purine, 436

INDEX
Quinine ethyl carbonate, 752 hydrochloride, 752 sulphate, 752 Quinitol, 702 Quinizarin, 733 Quiriol, 645 Quinoline, 753 Sulpho -acids of, 754 Quinonediimides, 648 Qiiinonedioxime, 647 Quinoneimides, 648, 785 Quinonemonoxiine, 648 Quinones, 647 Quinoxaline, 657, 786 RACEMISATION, 23 Rackarock, 304 Radicals and types, Theory of, 15 Raffinose, 581, 584 Rags, 603 Raising gigs, 849 Rancidity of fats and oils, 463 Rapeseed, Composition of, 482 Rasp for beet, 545 potatoes, 589 Ravison seed, Composition of, 482 Reaction, Adarnkiewicz's, 861 Arnphoteric, 474 Baeyer's, 107 Baudouin's, 472 Becchi's, 492 Belliez's, 492 Biuret, 858 Blank arid Fmkeribeiner's, 247 Deniges', 413
Formolite, 71

Purple, Antique, 788 Purpurin, 733 Purpuroxanthiii, 733 Putrcscine, 257

Pyramidone, 740
Pyranthrene, 789 Pyrazine, 743 Pyrazole, 739 Pyrazoline, 739 Pyrazolone, 739 Pyrene, 736 Pyridine, 740, 742 Pyridones, 742 Pyridylpyrroles, 747 Pyrimidine, 743 Pyrocatechol, 644 Pyrocoll, 739 Pyrocomane, 743 Pyrogallol, 645 Pyrolignite of iron, 346 Pyrone, 743 Pyronine, 784 Pyropissite, 95 Pyroxylin, 285, 600 Pyrrodiazole, 740 Pyrrole, 422, 787

468 Oignard's, 33, 243 Halpheri's, 470, 491 Kamarowsky's, 172

Ueitel's,

Kornor and Menozzi's, 375, 423

Hydrogenated derivatives of, 739 Pyrrolidine, 422, 739 Pyrrolilene, 109 Pyrroline, 739
Pyruvic aldehyde, 399 QUEBRACHITOL, 647 Quercetin, 755, 793 Quercitol, 646 Quercitrin, 755, 793 Quercitron, 793 Quinaldine, 754 Quinalizarin, 733 Quinhydrone, 647, 767 Quinidine, 745, 752 Quinine, 744, 745, 751 bisulphate, 752

Lieberi's, 121, 129, 131 Liebermann's, 638, 660 Liebermann-Storch-Morawsky, 468 Melsen's, 339 Perkin's, 352, 679 Riche-Halphen, 83 Rimini's, 131, 172 Romijn's, 524 Sabaticr and Sendcrens', 35, 67, 124 Sandmeyer's, 670 SchiflE's, 246 Schmidt, 734 Scudder and Riggs', 129 Teichm arm's, 862 Tortelli and Ruggeri's, 492 Tschugajew's, 867 Uffelmau's, 386 Uhlenhuth's, 863 Varrentrapp's, 350 Wallach's, 357 Xanthoprotein, 858 Reactions, Reversible, 136 enzymic, 136 Reagent, Barfoed's, 532 413 .Deniges', Erdrnann's, 744 Fehling's, 582 Frohde's, 744 Lafou's, 744 Lowe's, 828 Mandolin's, 744

Marquis's, 744
Millon's, 828, 858 Molisch's, 828

Schardinger's, 134
Schiff's,

172

Schweitzer's, 599, 828

INDEX
lleageiit, Soldaini's,

583

Saccharoiio, 410

Twitchcll'H, 508 Rectification, 3, 158 of alcohol, J58 Rectifier, Hempel, 3 Terrier, 100 Savalie, 159 Keel, Algol, 789 Alizarin, 783

Saccharose, 538

Saecharum officinaruni, 53!), SafraiiiueA, 785 Safrole, 078 Saliein, 534, 077, 080
Salicylaldehydc, (i77 Naligenin, 041, 077, 080 Salin, L83
Naliretin, 041 Naimin, 802 Salol, 087

540

Anthracene, 729 Ciba, 788 Congo, 781 Diamine, 802 Indanthrene, 781) Jamm, 802
/j-Nitraniline, 003, 782,

Salt, Aniline, 059 Kalle's, 701

80 1

rcrmanent, 063 Pyrrole, 738 Ijiiiiiulino, 787 Thia/ine, 802 Thioindigo, 788 Turkey, 391, 843
\Vurster\s, 708

of sorrel, 308 RoeheJle, 401 Salvarsa?i, (>()0

475 Sandalwood, 793 Saiijruenielassa, 100

Sanatf)ju;eii,

Sanse, 491
Saiitalin,

793

Santaline, 750

Keductases, 134 Refraction constant, 27 I'cfractometer, 83

Zeiss, 155 Kefnirerator for wort, 204 llentschelX 144 Itennct, 134, 138, 474

Santonin, SOO
SaponiJlottion, 234 Saponin, 138, 805 Sareositie, 3X5, 423, 435

Sawdust, Utilisation

of,

333

Scarlet, Biebrich's, 008, 781

Resells,

495

Resins, Artificial, 041, 707

Resit,

042

Ciba, 788 Cochineal, 729, 780 IndiUithrene, 789 Palatine, 780

Resorcinol, 044 JlpHoriifin, 700, 785 Reteiie, 730

Thioindigo, 788
Scheclisation, 220

Rhamnosc,

521)

Rhigolene, 37 Rhi/oporus oJigosporns, 155 Uhodamines, 605, 784 Rhodinol, 358 Ribose, 521)
Kic-e, 11)3,

595
of,

Com position
.starch, 51)5

580

Schists Bituminous, 100 Schixomycetos, 132 Schizoswvharomyces Ponibe, 204 Schnapps, 190 Schneider ite, 304 Schiviner Hnish, 850 Scrubbers, 48 Scurvy, 807 Sealing-wax, 707 Substitutes for, 041
Securite, 307

Kit-in,

138

]{ieinus seeds, CuinjioMitioii of, 482

Jlolrin,

Kk-kets, 807 138

Kobinia pseudaeacia, 138 Koburite, 300, 307 Koi-cHIa tiiictoria, 792 Kocelliiie, 780 Rochelle salt, 401 Jiodinal, 000 Kope, 812 Kosanime, 783 Kouaniliiie, 721, 705, 70S Kosanthrene, 802 Rose, Diamine, 802 Jtwin, 707 Gallipot, 707 Kubbcr, 708
711 Methyl, 711. 712 substitutes, 711
Artificial,

Seeds, Composition of oily, 482 Semiearbazide, 24C, 433 Seuiicarbazones, 240, 433 Separators, ( ViitrifugaJ, 475, 489

Naphthalene, 40 Spray, 501 Tar, "40 Scricin, 815, 805

Sericoin, 805 Series, Aliphatic, 29 Ethyleiie, 100

Fatty, 29

Homologous, 24 so logons, 24
1

Paraffin, 3 1 Serine, 424

tti8, 745 Serum, Physiological, 13'.) Serum-albumin, 137, 859

Sero-therapy,

Nttiiim -globulin, 8(il

Synthetic. 109, 113, 711, 712

Rufanthrene, 790 Kufiopin, 733 liufol, 733 Rum, 190, 43 Kusma, 094

Serum-li])ase, 402 seeds, Composition of, 482 Sesainhi, 500

Sesame

SAOOWARIMiTKRS, 25, 579

Saccharin, 082

Sesamol, 50.) Shale, 100 Shalonka, 75 Shimose, 303

Saccharometer, Balling, 153 Brix, I.i3, 577

Shoddy, &)5 Silk, 813

Artificial,

821
of,

Saccharomyces

cereviflite,

134, 137, 145

Composition

8J5
of,

Saccharom>cetes, 133

Crackle (Scroop)

815

894
Silk,

INDEX
Dyeing Sea, 820
of,

815, 830

Starch, Maize, 596

818 artificial, 827 Stripping, 814 Tussah, 814, 818 waste. 814, 820 Weighting of, 810, 817 Wild, 818 Silk finish, 850 Silkworm culture, 81 3 Sinapine, 75O
Statistics of,

Manufacture, 588 Microscopy of, 587 Potato, 588 Rice. 595

Saccha-rificatioii of, Soluble, 59<>

143

Sinignn, 502,

8(i(

Siperite, 3O4 Sitosterol, .500

AVheat, 593 Steam, Superheated, Stearine, 35O, 505 Distilled, 5OO pitch, 507 Wool, 480 Stcarolactone, 507 Stenolytes, 721
301*

4,

77

Skatole. 75(>

Smokeless powders, 295, 2U8, 302, Soap, 350, 358, 513 Alkaline, 7O2 Analysis of, 522 Antiseptic, 79 barring machine, 521 boiling, 517 Eschweg, 520
Figging, 521 Finishing of, 515
Marseilles,

Stcreoiscjmericles, Scparatit^n of,

2$

Stereoisomerism, 19
of nitrogen, 22, 253 Stibines, 242" Stilbene, 722 Still iugia sebifera, 499

Stovaine, 74tt, 751 Streptococci, 133

String, 812 .Strychnine, 745, 751 Sturin, 8(32
Styraciii. 074 Styreiie, 4)34

517

Mottled, 511)
Oleine, 517

Resin, 518

Suberane, 077 Suberin, 598, (515

Seasoning Soft, 520 Transparent, 521.) e, 823

of,

522

Suberone, G17 Sublimation, 2

Substitution,

Sodium

acetonebisiilphite, 253

Succinamide, 421 Succinanil, 422

Theory

of,

15

ethoxide, 131, 214 Soja beans. 5O2 Solanine, 138, 745

Solenite, 302 Solubility of organic compound**, 25 Solvents, Non-inflammable, 122

Sucjcinates, 3(5(3, 371 Succindialdehyde, 73( Succinidialdoxime, 738 Succinimide, 306, 421, 422, 43(> Sucrase, 134, 538
Sue-rates,

539

Somato.se, 475 Sorbitol, 220, 631 Sorbose bacterium, 220

Sucrol, (>(i(> Sucrose, 538

Sorghum, 540
Sorrel, Salt of. 308 Spaniolitmiii, 792

Sugar, Acorn, (4(i Beet, 539, 545

<^ane, 538, 54O Fruit. 533 CJrape, 531 Invert, 531,538, 581

Sparteine, 75O
Specific gravity, 25 refraction, 27 rotation, 28 Spent wash, 157, 182

Maple, 540
Milk, 53 Muscle, 047 of lend, 340 Starch, 531

Spermaceti, 478
Sphserobacteria, 133 Spiraea ulrnaria, 077
Spirilla, 133 Spirit, Crude

Wood, 529
Sugar
(sucrose), Alkalinity,

584

wood, 128 Denatured, 173, 170

Ash, 584 Beet-pulp, 551

boiling,

of s \veet wine, 117 of wine, 1 30 Purification of, 172

504

Wood, 128
Spiritus setheris iiitrosi, 117 Spirobacteria, 133

(Vutrifugation of maasecuite, 565 Chemical determination, 577, 581 ( learing (covering), 666, 569
colouring, 533

Spitzenzuekcr, 585 Spongin, 805 Spores, 132 Stachyosc, 225 Standard scrubber. 48 Standol, 495 St^phyloeoccus, ]33, 151 Stareh, 133, 585

Concentration, 559 Crushed, 570 Defecation, 555 Diffusion process, 548 Estimation, 577
Fiscal regulations, 574, 570

from molasses, 590

History, 545
'utput,

Adhesive power of, 590 Animal, 598 Bleaching of, 592 Estimation of, 141 Ureeri, 592 gum, 597

575 570 lered, 570 s, 575

582

(uotient of purity,

Refining, 567 Rcndemeiit, 568

INDEX
Sugar (sucrose), Saccharimetry, 579
Terpanol, 714
Specific gravity and degrees lirix, 577, 578 Statistics of production, 575 Steffen process, 55,*$, 572 Sugars, Analysis of mixed, 582

895

Sulphamidcs, 637 Sulphobenzide, 637 Sulphocyanine, 800 Sulphonal, 119, 233, 252 Sulphone, 637 Sulphones, 233 Sulphoiiium compounds, 233
Sulphorieinate, 390, 494

Terpanone, 714 Terpenes, 702 Complex, 706 Homologous, 70S Terpeiiol, 715
Terpin, 7I."> hydrate, 715 Terpinene, 7O3, 706 Terpineol. 715 TerpmoIeiH', 706
Test, ace Reaction
1 23 Tetrabroim >fluorcscein, 685 Tetrabn mic >indi ru bin, 788 Tetrachlor< lanisole, 643 Tetrachlon >et haiic, 1 22 Tetrachloromethane. 1 22 Tctracosane, 32 Tetradecane, 32 Tot rahydrotia plithalene, 73< Tetrah ydn ma >ht hy lam ine, 73< > Tetrahydropyridines, 743 Tetrahydro pyrrole, 739 Tetrahydroquinoline, 754
)
|

Analysis of, 391 Sulphur, 'Detection of, 8 Estimation gf, 13

139 Tetrahromoetliane,
Tetaiiolysiii,

Sumac, G9O
Superheated steam,
Suprareniiie, 747 Sylvcstrene, 700
4,

77

Syn-diazobenzeno hydroxide, 672 Syn-diazo-com pounds, 669 Syntaiis, 692 Syntheses, Asymmetric, 137 Syntoniiis, 858. 862 Syphilis, 666 TALQUIN, 482 Talgol, 482 Talitol, 226 Tallow, 635 Chinese, 499 tree, 499 Vegetable, 499 Tamping, 264 Tanks, Muedonald, 69 \Veiss, 69 Tannin, 689 Tanning, 692 Chrome, 698 extracts, 69O, 691 in layers, 696 Infusion, 696
Mineral,
Oil,
(597

Tetrahydroxyanthraquinones, Tetra by ( n > \y ben /.en e, 64( i Tetraliydrt ixylln vi >nol, 793 Tetrahydr< >xyrufenol, 791 Teti-a -iodopyrrole, 738
I

7:}.'{

Tetraline, 122, 731

Tetralkylpbosphonium hydroxide, 242 Tetramcthyl base, 719 Tetramethylarsonium compounds, 242

Tet ramethylbeii/enes, (>34 TetrainethyJdiammotriphenylearbiiiol, 720
Tetramethyldiaminotriplipn.vlnictliaiie, 720

Tetramet

698 Rapid. 697

yleiie, 617 Tetramethyleiiediam ine. 257 Tetramethylinethane, 37 Tetramines, Aromatic, 657 Tetranitrodiglycerine, 218, 274 Tetranitroethane, 237 Tetranitrornethane, 237
1

Theory

of,

692

Tantiron, 328 Tar, 623

Tetrazo-c< >mp uiids, lUiS Tetrazole, 740 Tetroses, 52(>

Tetryl, 663 Textile fibres, 804 Analysis of mixed, 828 Bleaching of, 830, 836, 837

Benzene from, 630

Coal, 99 Distillation of, 88, 97, 625 Lignite, 96, 624

Mineral, 07
oils,

628 105

Statistics of, 100 Statistics of lignite, Wood, 99, 624

Chemical identification of, 827 Commercial weight of, 828 Conditioning of, 828 Drying of, 847

Tartar, 402 Analysis

Dyeing Dyeing

of,

841

tests on,

830

of,

402

Canton i's process, 405

Printing of, 854 Printing tests on. 831

Cream

of, 40], 407 emetic, 401

Tenacity
Dressing

of,
of,

825

Textiles, Carbonisation of,

839

Coldenberg's process, 403

industry, 402

848
845

Dyeing
Fixing

of, 841,
of,

406 TaruhVs method, 404 401 Tartrates, Tartrazine, 411, 782 Tartrazines, 782 Taurine, 257, 424 Tautomerism, 18, 394, 766 Tawing, 697 Tea, 439 Tension theory of valency, 107 Tentering frame, 848 Terebenthene, 706 Terpadienes, 703, 704 Terpane, 703, 714
Statistics of,
.

840
of.

Mercerisation

852

Silk finish of, 850 Thalline, 754 Thebaine, 745, 750

Theine, 438

Theobromine, 437, 745

Theophylline, 436

Thermo -oleometer, TortehTs, 4G4

Thiazimes, 785 Thiazine, 791
Thiazole, 740 Thiazones, 785

Thioaeetamide, 238, 425

890
Thioaoids. 41'J ThioalcohoLs, 233 Thioaldehydes, 240 ThioamidoN, 425, 702

INDEX
Tri-iodomethauc, 121 Triketohexamcthylenc, Trikftonamines, 252 Trilinoleiii, 501
'

(>4(5

Thioanhydrides, 411)
Thiobenzanilido, 660

Triinethylacetyl chloride, 380

Thiocarbamide, 434 Thiocarmine, 796 Thioeyanates 429

Thiod'iphenvlainine, 765, 7S5

Trimethylamiue, 117, 241

r

hydroehloride,
rri methyl benzene,

117 111

Thioethers/233 Thioilavine, 787 Tliioindigo, 788 Thioketones, 253 Thiols, 233 Thionine, 766, 785 Tki'jphen. 737 Thiophonol, (537, 6015 Thio phosgene, 433 Thiosenne, 424 Thiuuroa, 434, 050 Thiourethane, 434 Thioxene, 737 Thymeiiamine, 655 Thymerie., 703 Thymol, 643 Thvmnquinone, 64 S Thyocoll, 645 Thyol, 104 Thyroidin, 74<>
Tintarrori, 7<53 Tcibacow, 748

Trimi'thyl benzenes, (533 Trimethyk-arbinol, 215 Trimet hy Icetylben zone, 623 Triinothylone, 106, (il(5 Trimethyl methane, 37

Trimet hylpheiiylanimoniun hydroxide, 657 Trimethylpyridines, 742 TriniethylsuJphonium iodido, 234 Trinitroanilijie, 663
Trinitro benzenes, 64{)
Trinitrocellnlose, 28(> Trinitroglyc'erine, 258, 275 Trinit rohemellithene, H50

Trinitromesitylene, (>5() Trinitroinethane, 237 Trmitrophenol, 303, (J(>4 Trinilr<pseu(tocumene, 650

TrinitroroHoreinjol,

065

Triiiitrotort.hntyltoliienc,

6oO

Tnnitr<jtert.butylxylcne, (553 Trinitrotoluene, 3()4

TriiiitrotuluenoH, (>52

Trinitroxy leni's,
Trioleiii, 358,

(i5(

>

460

Tolane, 722
o-Tolidine, 718
Tciliicue, (523, (>33

Trional, 110, 7J(> Trioses, 584

rripalmitiii, 460 Tripheiivlainirie, 6(iO
f

Trinxyinothyloiie, 248

Toluidiuey, ()(>l Tnlnquirione, 648 TolyJencdiamiiiRH. 055, 0(52 Tofyl ])hcnyl ketnc*H, 720 y>-Tolyl-o-naphthylainine : 727
i

Triphenylnu'thane, 721

TnphcnyhnethyJ, 722
Tristearm, 220^ 4(i(> Trithioketonos, 253 Tritopino, 75O
Tropaeocaiiio, 716 Tropa>olins, 668, 780

Tolyl))hcnylmethanc, 720

Tomato

preserve, 502

Tomatoes, 502 Tnmatosoed oil, 502 Tousile, 104

Tops,
f

Tropanol, 749
Trop:iie, 750

80f5

J\)urnef*J,

702

Tow, 811 Toxalburnins, 858 Toxins, 137 Velocity of reaction

Triacetaiiilide,
(5(51

of, 13$)

Tropidine, 750 Tropine, 74J> Tropinone, 740 Tropon, 475, 861 Truxillme, 750

Transposition, Theory >f, 7(>7, Traiizl's lead block, 316

Trialkylpho,s]ihine oxide, 242

Tryptaw,

134, 858 TmiieJiiia, 16(> Turkey red, 391

oil, 3<)0

TrialkylphnHphoniuni hydroxide, 242 TriaminoH, Aromatic, (io7

"J'riaminoazobenzRJie, 60S, 771) TriaminotriphciiyloarhiiKil, 72 1

Turpentine, 706

Tussah silk, 814, 818 Tyndall phenomenon,

Types, Multiple, 10 Theory of, 15
Tyrosinase, 138
ITiulecane, 32

0!)

Triazoformoxime, 428 Triazolc, 740 Tribromophenol, (543

Tribromorcsorcinol, (544 Tric-hloromethane, 118 Trifhlorophenol, 643 Trirhloropurinc, 43(5

Uramil, 437
Uraniiie, 784

Urea, 1,431, 432

nitrate,

32 Tridccane 32 Trieline, 122 Triethylamine, 241 Triethylenediamine, 257 Triethylsulphonium hydroxide, 233 iodide, 233 Triformin, 373
Tric-osane,
>

A Jkyl -derivatives
432

of,

432

Xitro-dcrivativa Crease, 13 Ureides, 433, 435 Urcthaiie, 432 Uroacids, 435

'

of,

432

Triformol, 248

tlrotropine, 187, 248 ITsinas 542

Trihydroxybenzenes, 045 Trihy droxybenzophenone, 720 Trihydroxytriothylamiue, 257

VALENCY, 10
Partial, (520

Tension theory

of, 1()7, 306,

617

INDEX
VaJeraldehyde, 251 Valonia, 690 Vanilla, 677 Vanillin, 677

897
of,

Wine, Analysis

188

Statistics of. 188

Woad, 758 Wood, Bar, 794

Brazil, 793

Vapor inictcr,
(bid, 495

Ceissler, 174

Varnish, 462, 495

Lithographers', 495 Vaseline, 93
Artificial,

Cam, 794
charcoal, 268

Cuba, 793
Distillation of, 330 Log, 791 Preservation of, 629 Quebracho, 690, 691 Red, 791 Sandal, 793 Yellow, 793 Wood-pulp, Chemical, 603, 6O7 Mechanical, 603, 605 Wood spirit, 127, 128 Poisoning with, 128 Wool, 804 Bleaching of, 837 Carbonisation of, 805, 839 Carded, 804 Chemical properties of, 806 Combing, 804 Dyeing of, 830, 841 from different sheep, 804 XAHTHINE, 436, 441 Xanthogenamide, 434 Xaiithone, 720 Xeroform, 122 Xerophthalmia, 867 Xylans, 527

93

Gelatinwed, 93 oil, 89 Velocity of esterification, 23

inversion, 538 Veratrine, 745, 750 Vcratrole, 644 Verdigris, 347, 348

Vermouth, 190 Veronal, 119, 746 Vcsuvirie, 780

Vigorite, 307 Vinas.se, 158, 188, 404

Vinegar, 340 Adulteration of, 344 Analysis of, 344

Artificial,

344
^

German process, 341 Luxemburg process, 342

Malt, 344 Michaelis procens, 342 mite, 341

Wine, 344 worms, 341 Violamine, 798 Violanthreiie, 789 Violet, Ac-id, 798 Alkali, 798 Chrome, 784 Ciba, 788 Ethyl, 720
for wool, 663

Xyleiies, 623, (133

Xy Mines,

662

Xylitol, 225, 525, Xyloidiri, 286

528

Xyloquinone, 648 Xylose, 527, 529 YABN, Count of, 806

Yeast, 134, 137, 140, 145, 149, 204 Acclimatised, 151 Frohberg, 204 industry, 149 Logos, 204 Pressed, 149 Pure, 147 Saax, 204 Wild, 204 Yellow, Acid, 779 Acridine, 787 Alcohol, 668
Alizarin, 663, 666, 720, 787, 796

Formyl, 784
Indanthrene, 789 Lanacyl, 727 Lauth's, G62, 785 Methyl, 721, 773, 784 Victoria, 798 Violets, Essence of, 713 Viscometer, Engler's, 90 Viscose, 822
Vital force, 1

Vitamins, 867 Vitellin, 861 Vulcan fibre, 602 WAUaON-STIT.L, 76

Waterproof fabrics, 346 Wax, Algae, 68 Carnauba, 350, 465

Chinese, 216, 351

Japanese vegetable, 350, 465 Mineral, 94 Montan, 95 Paraffin, 94 Sealing, 707

Substitutes for, 641

Anthracene, 787 Carbazolc, 796 Chrome, 665 Ciba, 789 Cibanone, 790 Cuba, 793 Diamine, 801 Diamond, 797 Fast, 668, 779 Ilelindone, 789 Indanthrene, 789
Indian, 779, 788, 793 Indigo, 789 Metanil, 796
Milling, 799

Waxes, 465
Hydrolysis of, 467 Weinsteinpreparat, 830 Westphalite, 306, 307 Wetterdinamit, 284, 307 Wheat, 193

Naphthol, 778
Quinoline, 754, 787 Sulphur extra, 801
Thiazole, 801
Victoria, 778 alkyls, 33, 243 lactate, 388 Zymase, 134, 139, 147

Wheat

Composition flour, 594 starch, 593 Whey, 475 Wine, 184

of,

595

ZINC

Alcohol-free, 185, 186

Zymogen, 205

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A MINE OF INFORMATION

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