Allyl Compounds 1

Allyl Compounds
Ludger Krähling, Deutsche Solvay-Werke GmbH, Rheinberg, Federal Republic of Germany (Chaps. 1, 6)
Jürgen Krey, Deutsche Solvay-Werke GmbH, Rheinberg, Federal Republic of Germany (Chaps. 1, 6)
Gerald Jakobson, Deutsche Solvay-Werke GmbH, Rheinberg, Federal Republic of Germany (Chaps. 1, 6)
Johann Grolig, Bayer AG, Leverkusen, Federal Republic of Germany (Chaps. 2 – 5)
Leopold Miksche, Bayer AG, Leverkusen, Federal Republic of Germany (Chap. 6)
1. Allyl Chloride . . . . . . . . . . . . . . 1 2.5. Uses . . . . . . . . . . . . . . . . . . . . . 11
1.1. Physical Properties . . . . . . . . . . . 1 2.6. Methallyl Alcohol . . . . . . . . . . . . 11
1.2. Chemical Properties . . . . . . . . . . 2 3. Allyl Esters . . . . . . . . . . . . . . . . 11
1.3. Production . . . . . . . . . . . . . . . . 3 3.1. Properties . . . . . . . . . . . . . . . . . 11
1.3.1. Chlorination of Propene . . . . . . . . . 3 3.2. Production . . . . . . . . . . . . . . . . 12
1.3.2. Other Production Processes . . . . . . 5 3.2.1. Oxidation of Olefins . . . . . . . . . . . 12
1.4. Handling, Environmental Protec- 3.2.2. Esterification . . . . . . . . . . . . . . . 13
tion, Storage, and Transportation . 6 3.2.3. Transesterification . . . . . . . . . . . . 13
1.5. Quality and Analysis . . . . . . . . . . 7 3.2.4. Other Production Methods . . . . . . . 13
1.6. Uses . . . . . . . . . . . . . . . . . . . . . 7 3.3. Uses . . . . . . . . . . . . . . . . . . . . . 14
1.7. Economic Aspects . . . . . . . . . . . . 7 3.3.1. Polymer Production . . . . . . . . . . . 14
2. Allyl Alcohol . . . . . . . . . . . . . . . 7 3.3.2. Other Uses . . . . . . . . . . . . . . . . . 15
2.1. Physical Properties . . . . . . . . . . . 8 4. Allyl Ethers . . . . . . . . . . . . . . . . 15
2.2. Chemical Properties . . . . . . . . . . 8 4.1. Properties and Uses . . . . . . . . . . 15
2.3. Production . . . . . . . . . . . . . . . . 9 4.2. Production . . . . . . . . . . . . . . . . 16
2.3.1. Hydrolysis of Allyl Chloride . . . . . . 9 5. Allylamines . . . . . . . . . . . . . . . . 16
2.3.2. Isomerization of Propene Oxide . . . . 9 5.1. Properties and Uses . . . . . . . . . . 16
2.3.3. Hydrolysis of Allyl Acetate . . . . . . 10 5.2. Production . . . . . . . . . . . . . . . . 17
2.3.4. Hydrogenation of Acrolein . . . . . . . 10 6. Toxicology and Occupational Health 17
2.4. Quality and Analysis . . . . . . . . . . 11 7. References . . . . . . . . . . . . . . . . . 19

1. Allyl Chloride 1.1. Physical Properties

Allyl chloride [107-05-1], the only chloro- Allyl chloride, 3-chloropropene, CH2 =CH-
propene of industrial importance, was first pro- CH2 Cl, is a colorless, mobile liquid with a pene-
duced in 1857 by A. Cahours and A. W. Hof- trating, pungent odor, M r 76.53, mp −134 ◦ C, bp
mann by reacting phosphorus chloride with al- (101.3 kPa) 44.4 ◦ C, n20 25
D 1.416, nD 1.413 [1–5].
lyl alcohol. The name allyl is derived from the Temperature-dependent physical data are given
latin allium, meaning garlic. Inhalation of even in Table 1.
small amounts of allyl chloride produces, after Expansion coefficient 0.0041 K−1
a short time, the characteristic odor of garlic on (0 – 30 ◦ C)
the breath. Heat of combustion
(CH2 =CH-CH2 Cl (g), HCl (g), 1846 kJ/mol
At the end of the 1930s, IG Farbenindustrie CO2 (g), H2 O (g))
and the Shell Development Co. developed the Latent heat of vaporization at bp 26 kJ/mol
high-temperature chlorination of propene, per- Critical temperature, t crit 240 ◦ C
Critical pressure, pcrit 4.79 MPa
mitting large-scale production of allyl chloride Ratio of specific heat capacities 1.137
with good yields. A significant part of the de- cp /cv
(at 14 ◦ C)
velopment was done by the Shell Chemical Co.
when erecting a commercial plant in 1945. Dow, Vapor pressure equation
Solvay, and Asahi-Kashima developed their own log p = 19.1403 − 2098.0/T − 4.2114·log T ;
processes.
(pinkPa, T inK) [3].

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a01 425
2 Allyl Compounds
Table 1. Temperature dependence of the physical properties of allyl chloride

Temperature, t, ◦ C

10 15 20 25 30 40 50
3
Density,
4 , g/cm 0.950 0.944 0.938 0.931 0.925 0.911 0.898
Specific heat capacity 1.633 1.666 1.700 1.733 1.771
−1
(of liquid), cp , kJ kg
K−1 at 101.3 kPa
Viscosity, η, µPa · s 368 347 336 315 307 282
Surface tension, mN/m 28.9 23.1 21.8
Solubility in 15 % 0.120 0.176
hydrochloric acid, wt%

Allyl chloride is miscible with most solvents glycerol dichlorohydrins (which are then dehy-
in general use (e.g., octane, toluene, acetone); drochlorinated with alkali to give epichlorohy-
the solubility (mass fraction in %) of allyl chlo- drin), is of great industrial importance. Allyl
ride in water at 20 ◦ C is 0.36, that of water in allyl chloride reacts with hydrogen halides to form
chloride, 0.08. Azeotropic data for allyl chloride 1,2-dihalogeno compounds. In the presence of
are presented in Table 2. peroxides, the reaction with hydrobromic acid
yields 1-bromo-3chloropropane (Kharasch ef-
Table 2. Azeotropes of allyl chloride
fect), but in highly concentrated hydrogen per-
Component bp at 101.3 kPa, ◦ C Allyl chloride, mass oxide solution, 1,2-dibromo-3-chloropropane is
fraction, % formed [6]. Addition reactions of silanes [7],
Water 43 97.8 boranes [8], carboranes [9], and phosphorus
Methanol 40 90 trichloride [10], as well as cycloadditions of
Ethanol 44 95
2-Propanol 45 98
allyl cations with alkenes [11], are known. Al-
Formic acid 45 92.5 lyl chloride polymerizes with sulfur dioxide to
form polysulfones [12].

Flash point (closed cup) − 27 ◦ C Reactions of the Chlorine Atom. For-

Autoignition point 392 ◦ C merly, the most important reaction industri-
Flammability limits in air 3.28 and 11.15 vol%
ally was hydrolysis to allyl alcohol, in which
small amounts of diallyl ether formed as byprod-
uct. However, today allyl alcohol is produced
increasingly by the isomerization of propene
1.2. Chemical Properties oxide (see Section 2.3.2). The chlorine atom
is replaced easily by iodide, cyanide, isothio-
Allyl chloride is a very reactive compound un- cyanate, sulfide, polysulfides (giving rubber-
dergoing the usual addition and polymerization like condensation products [13]), and alkyl thi-
reactions at the double bond. Also, because the ols [14]. The salts of carboxylic acids yield
chlorine atom can be exchanged readily with allyl esters (e.g., diallyl phthalate), which are
other groups, allyl chloride is a suitable start- easily polymerized to allyl resins or are copoly-
ing material for the synthesis of a wide range of merized with other monomers. Sodium allyl
allyl derivatives. sulfonate is obtained on reaction with sodium
sulfite [15]. The reaction of allyl chloride with
Reactions of the Double Bond. The reac- ammonia yields a mixture of mono-, di-, and
tion of allyl chloride with oxygen in the liq- triallylamines [16], [17], and the reaction with
uid phase at ca. 120 ◦ C and in the presence primary and secondary amines makes the corre-
of metal acetates or hydrogen peroxide yields sponding alkylallylamines [18]. Organic poly-
glycerol monochlorohydrin. Halogens add read- carbonates are formed from a mixture of tertiary
ily to the double bond yielding the corre- amines, sodium carbonate, alkylene glycol, car-
sponding trihalogeno compounds. The reaction bon dioxide, and allyl chloride [19]. Phase-trans-
with hypochlorous acid, yielding 2,3- and 1,3- fer-catalyzed carbonylation (e.g., with Ni(CO)4
 Allyl Compounds 3

or (Me4 N)2 [Ni6 (CO)12 ]) in the presence of The most important variables in the industrial
sodium hydroxide leads to the sodium salt of chlorination process of propene to allyl chloride
vinylacetic acid [20], [21]. In the presence of are the temperature and the ratio of propene to
alkalis, allyl chloride reacts with polyols to form chlorine, whereas pressure and residence time
the corresponding allyl ethers. Further reactions have only a slight effect on the allyl chloride
are described in [22]. yield [24]. Because the dominant reaction be-
low 200 ◦ C is addition to form 1,2-dichloropro-
pane, the mixing temperature of propene and
1.3. Production chlorine must be kept above 250 – 300 ◦ C. The
best yields of allyl chloride in industrial reactors
1.3.1. Chlorination of Propene are obtained at a maximum reaction temperature
of 500 – 510 ◦ C. If the reactor temperature is in-
Allyl chloride is produced on a large scale by the creased further, spontaneous pyrolysis occurs,
high-temperature (300 – 600 ◦ C) chlorination of with the formation of soot and high-boiling tars.
propene: Under laboratory conditions and temperatures
of ca. 600 ◦ C, benzene is formed and the yield
CH2 =CH-CH3 + Cl2 → CH2 =CH-CH2 Cl + HCl of allyl chloride decreased [24], [25].
∆H 0298 = − 113 kJ/mol The maximum reaction temperature can be
influenced by the temperatures of propene and
At these temperatures, chlorination proceeds by chlorine entering the reactor and by the ratio of
a free-radical chain mechanism, whereby the hy- propene to chlorine. In general, only the propene
drogen atom in the allyl position is substituted is preheated. If the chlorine is also preheated,
preferentially by the chlorine, giving allyl chlo- expensive construction materials must be used
ride [23]. to avoid the danger of a “chlorine fire.” For
a given propene: chlorine ratio, the preheating
Byproducts. Below 200 ◦ C propene reacts temperature of the propene is fixed; for exam-
with chlorine mainly by addition to the dou- ple, for C3 H6 : Cl2 = 3 the temperature is set at
ble bond to give 1,2-dichloropropane; above ca. 300 ◦ C and for C3 H6 : Cl2 = 5, at ca. 400 ◦ C
300 ◦ C, this reaction is suppressed and the for- [24].
mation of allyl chloride predominates so that
1,2-dichloropropane is only a byproduct. The Propene : Chlorine Ratio. The formation
compounds cis- and trans-1,3-dichloropropene of byproducts decreases with increasing propene
arise from a secondary reaction of allyl chloride, excess [26]. On the other hand, the cost of
in which a further hydrogen atom is substituted processing the propene rises simultaneously.
by chlorine. Small amounts of other chlorination The optimum reaction conditions are therefore
products are formed also: strongly influenced by economic considerations,
including the demand for the dichloride byprod-
CH3 –CH=CH2 + Cl2 → CH3 –CHCl–CH2 Cl ucts as nematocides [27]. The byproducts can
∆H 0298 = − 184 kJ/mol be employed also as starting material for the
production of C1 - or C2 -type solvents.
ClCH2 –CH=CH2 + Cl2 → CH2 Cl-CH=CHCl + HCl The pressure in the reactor has little influence
∆H 0298 = − 101 kJ/mol on the yield or the distribution of products and
is determined only by the pressure drop in the
CH3 –CH=CH2 + Cl2 → CH3 –C(Cl)=CH2 + HCl
propene circulation system of the plant.
The residence time has only a small effect on
∆H 0298 = − 121 kJ/mol
the yield of allyl chloride. At high temperatures
(300 – 600 ◦ C), the chlorine has completely re-
CH3 –CH=CH2 + Cl2 → CH3 –CH=CHCl + HCl
acted after 1 – 3 s [24]. Too long a residence time,
however, leads to thermal decomposition of the
allyl chloride [25].
4 Allyl Compounds

Reactor Construction. Industrial-scale re- raw materials must contain as little water as pos-
actors mainly operate adiabatically, even though sible. This is a particularly important condition
higher yields would be expected when operating for the choice of materials for the various stages
isothermally. Because the reaction is rapid and of the plant (see below).
exothermic, the amount of heat lost through the A process similar to that employed by
reactor wall is not significant. Shell, for example [24], [40], is shown in Fig-
The technically simplest and oldest reactor ure 1. Liquid propene is vaporized, then pre-
type is the tube reactor, which sometimes is heated to 350 – 400 ◦ C (b), and fed, together with
equipped with facilities for gas distribution and gaseous chlorine, into the reactor (c) via a mix-
soot removal [25]. Many other reactor designs ing jet. The chlorine reacts completely, thereby
are known [26], [28–35], but all reactors are de- increasing the temperature to 500 – 510 ◦ C (un-
signed to achieve the mixing of the two reactants der optimum conditions). Even under the best
as rapidly and as thoroughly as possible in order conditions, small amounts of carbon are formed;
to reduce the secondary reaction to form 1,3- these catalyze the chlorination. A protective film
dichloropropene. Under the good mixing condi- of vitreous carbon deposits on the reactor walls.
tions obtained in a highly turbulent flow, propene This material, which also contains highly chlo-
and chlorine are fed into the reaction zone at rinated materials and tar, must be cleaned from
velocities up to 300 m/s. The importance of op- the reactor walls at intervals of 4 – 8 weeks. Two
timum mixing conditions is demonstrated by a parallel reactor chains often are in use so that
cyclone reactor, in which, at a molar ratio of partial production can be maintained during the
3 : 1, similar yields are obtained as at a ratio of cleaning. Another possibility is alternate opera-
5 : 1 with other designs [36]. Many reactors are tion of the two chains.
equipped with a cooling jacket. The gas stream leaving the chlorination reac-
If the chlorine is distributed among several tor is precooled (d) and led to a prefractionator
reactors arranged in a cascade, a chlorine con- (e), the overhead temperature of which is main-
version of up to 86 % can be achieved [37], tained at ca. − 40 ◦ C by feeding liquid propene.
[38]. With this arrangement, higher preheating This effectively separates all chlorinated hydro-
temperatures are possible because of a higher carbons; the bottom product is free of propene
propene : chlorine ratio in the first reactor. and hydrogen chloride.
In another design of a cascade of reac- The gaseous mixture drawn off overhead
tors only the first reactor is charged with pre- is separated by absorption with water (i) into
heated propene and chlorine. Liquid propene aqueous hydrogen chloride of commercial qual-
and gaseous chlorine (molar ratio of 1 : 1) are ity and propene. Then the propene is washed
fed into the other reactors. The advantages of with caustic soda in a scrubber (k) to remove
this procedure are the cooling of the reaction gas traces of hydrogen chloride. After compression
and a quasiconstant ratio of the reactants over all to 1.2 MPa (12 bar), it is liquefied in a condenser
stages. At an overall molar ratio of 3.2 : 1, the (l, q). Water is separated (m) and liquid propene
same yield is achieved as at a ratio of 7 : 1 in a is dried by adsorption (n) and returned to the
single reactor [39]. storage tank (a).
The bottom product of the prefractiona-
Feed Preparation. The purity of the tor contains 80 % allyl chloride, 3 % 2-
propene and the chlorine is important. Organic chloro-1-propene [557-98-2] and other low boil-
impurities in the propene cause the formation of ers, 16 % dichlorides (mainly 1,2-dichloro-
byproducts and loss of chlorine. Especially pro- propane [78-87-5] and cis- and trans-1,3-
pane leads to the formation of chlorine deriva- dichloro-1-propene [542-75-6]), and 1 % 1,2,3-
tives (1-chloropropane, 2-chloropropane) which trichloropropane [96-18-4] and other heavy
are difficult to separate. Polymer-grade propene boilers [40]. These four fractions are separated
with a purity of 99.5 % often is employed as by distillation (f, g, h).
the feedstock. The use of revaporized chlorine The basic principle of most production pro-
insures adequate purity. Small amounts of inert cesses is as shown in Figure 1, although it has
gases are thereby introduced into the process, been modified for the synthesis and the fraction-
the venting of which means propene losses. Both ation processes [41–44]. For example, cooler (d)
 Allyl Compounds 5

in Figure 1 can be replaced by quench cooling Oxychlorination. Oxichlorination was de-

[44], whereby the hot reaction gases are cooled veloped for the production of allyl chloride in
by the evaporation of propene or of condensed order to utilize cheaply available hydrogen chlo-
reaction products. ride instead of chlorine as the feedstock [50–
62]. Palladium, vanadium, tellurium, copper,
Construction Materials. The choice of ma- lithium, and manganese, as well as their chlo-
terials in the allyl chloride synthesis (propene rides and oxides and mixtures thereof, have been
circulation) depends on the individual process suggested as catalyst systems.
operations, temperature, and pressure. In prin- Most of these oxychlorination processes start
ciple, normal carbon steel is resistant where from propene [50–60], although two of them
the water content of the product streams is low start from propane [61], [62]. The following pro-
enough. If the chlorine stream is not preheated, cess was tested in a pilot plant by Hoechst [58].
carbon steel also can be utilized in the reactor Propene, hydrogen chloride, oxygen, and
area. However, materials resistant to chlorine 2-chloropropane (either produced in a sub-
at high temperatures (chromium – nickel steels, sidiary reactor or introduced from out-
nickel, cupronickel alloys) often are employed side) react in a main fluid-bed reactor at
in the reactor region. Graphite and PTFE coat- 200 – 260 ◦ C and 0.1 MPa (1 bar) gauge pressure
ings are favored for the absorption of the hydro- (∆H= − 218 kJ/mol). The carrier catalyst con-
gen chloride, whereas rubberized steel can be tains tellurium, vanadium pentoxide, phosphoric
employed for the caustic soda scrubber. Carbon acid, and a nitrogen compound as promoter. A
steel is suitable for the entire chlorinated hydro- part of the catalyst flow is treated in a side stream
carbon fractionation plant. However, in places with air and nitric acid to remove coke and main-
when large amounts of water are present, ex- tain constant reactivity. In a subsidiary reactor,
pensive materials, such as nickel and cupron- 2-chloropropane is produced from propene, hy-
ickel, are necessary [45]. Dry allyl chloride can drogen chloride, and ferric chloride solution.
be stored in steel vessels without any danger of The unreacted propene, 2-chloropropane, and
corrosion. hydrogen chloride are separated and recycled.
The yield of allyl chloride is 88 – 94 % based
upon propene. The purity of the propene is not
1.3.2. Other Production Processes particularly critical.
Some of the suggested oxychlorination pro-
Several other processes have been suggested for cesses have disadvantages. For example, the ac-
the production of allyl chloride, but none of these tivities of the catalysts deteriorate quickly as a
has been operated commercially. consequence of the volatility of the metal salts
employed and large volumes must be passed
Catalytic Chlorination of Propene. This through the reactor because the conversion per
process uses tellurium-containing catalysts [46]; pass is low. Also, it is difficult to remove the
allyl chloride yields of up to 82 % are ob- highly dilute allyl chloride from the reaction
tained. The main organic byproduct is 17 % 2- mixture without excessive loss of propene by
chloropropane (isopropyl chloride). Unreacted reaction with oxygen. A suggestion [60] at-
propene and the hydrogen chloride produced in tempts to avoid these disadvantages by using
the reaction can be converted to allyl chloride in manganese dioxide as both catalyst and carrier
a second reaction step by oxychlorination. for oxygen. The following reactions take place
in the main reactor:
The dehydrochlorination of 1,2-dichloro-
MnO2 + 4 HCl −→ MnCl2 + Cl2 + 2 H2 O
propane [47–49] produces only a 55 % yield
of allyl chloride plus a large amount of C3 H6 + Cl2 −→ C3 H5 Cl + HCl
monochloropropenes. The process is of no com-
mercial interest even though the starting material The catalyst is then reoxidized and activated
is dichloropropane, produced in large quantities with oxygen:
during the production of propene oxide.
MnCl2 + O2 → MnO2 + Cl2
6 Allyl Compounds

Figure 1. Allyl chloride production by high-temperature chlorination of propene

a) Storage vessel for liquid propene; b) Evaporator and superheater for propene; c) Reactor; d) Cooler; e) Prefractionator;
f) Light-ends column; g) Allyl chloride purification column; h) Dichloropropene column; i) Hydrogen chloride absorber;
k) Gas washer; l) Compressor; m) Decanter for removing water; n) Propene dryer; p) Evaporator; q) Condenser; r) Cold
propene storage vessel

The process achieves an allyl chloride yield of contamination must be reported immediately to
between 71 and 81 % based on the consumption the responsible authorities.
of propene. Allyl chloride-containing wastes can be dis-
posed of without difficulty in special incinera-
tors, such as those used for the disposal of sol-
1.4. Handling, Environmental vents, where the combustion gases are treated in
Protection, Storage, and Transportation absorbers or scrubbers to remove the hydrogen
chloride formed.
Handling and Environmental Protection. Because of the high volatility and low flash
Allyl chloride is a highly reactive, highly toxic, point of allyl chloride, plants for its production
easily ignitable substance. Therefore, very strin- and processing must comply with the relevant
gent standards exist in many countries for atmo- standards for fire and explosion protection.
spheric emission. Allyl chloride should be han- Combustion of chlorinated hydrocarbons
dled in closed systems in order to fulfill these produces hydrogen chloride, so that fire fight-
requirements. Gases containing allyl chloride or ers should be equipped with suitable protective
byproducts of the production process must be suits and portable breathing apparatus. Combus-
purified by condensation in cold traps, by ab- tion in the absence of adequate air supplies can
sorption, by adsorption, or in special cases by lead to the formation of carbon monoxide.
combustion before they are vented [63]. The Allyl chloride is highly reactive. Therefore
compensation technique has proved of value contact with other substances can lead to vigor-
during transfer from one vessel to another. ous, exothermic, and even explosive reactions.
Any contamination of the soil, of under- This applies particularly to alkali and alkaline-
ground water supplies, watercourses, or of earth metals, but also to aluminum and zinc and
wastewater must be avoided. Any danger of such to strong oxidizing agents, such as concentrated
sulfuric acid. The anhydrous halides (e.g., chlo-
 Allyl Compounds 7

rides) of the metals mentioned above also react 1.5. Quality and Analysis
vigorously with allyl chloride [5]. In plants pro-
ducing or processing allyl chloride, careful con- Commercial allyl chloride is at least 97.5 wt%
sideration must be given to the safety aspects of pure and contains 1-chloropropene, 1-
these exothermic reactions [64]. In 1996, allyl chloropropane, and 1,5-hexadiene as impuri-
chloride has been classified by the EC as “dan- ties. In addition, it contains a stabilizer, such
gerous for the environment” and “very toxic to as propene oxide, to scavenge any hydrogen
aquatic organisms”. chloride produced hydrolytically on long-term
storage. Allyl chloride containing traces of iron
Storage. Pure, dry allyl chloride (water con- has a pinkish tinge. The quantitative analysis of
tent
200 mg/kg) does not corrode iron and can allyl chloride is performed exclusively by gas
be stored in ferrous containers for months at am- chromatography.
bient temperatures without significant changes
in quality. Lined vessels should be used if traces
of iron chlorides are objectionable. Unwanted 1.6. Uses
coloration can be prevented by the addition of a
suitable stabilizer (e.g., propene oxide). Allyl chloride [22], [66] is an important interme-
diate in the petrochemical industry, used chiefly
Transportation of the highly toxic and for the production of epichlorohydrin, which in
highly flammable allyl chloride is governed turn is used in the production of epoxy resins. Al-
by many regulations [65]. International marine lyl chloride is a starting material in the synthesis
transportation is governed by the IMDG Code, D of various chemicals, such as glycerol, many es-
3108, class 3.1, UN no. 1100; transportation in ters [of which those of phthalic, phosphoric, and
Europe is governed by RID, ADR, and ADNR carboxylic acids are the most important (Sec-
class 6.1, no. 4 a, Rn 601, 2601, and 6601, re- tion 3.2.4)] and some allyl ethers (Section 4.2)
spectively. European Economic Community: and allylamines (Section 5.2).
Yellow Book 78/79, EG-no. 602−029−00-X; Further compounds made from allyl chloride
Great Britain: Blue Book: Flammable Liquid, are: allyl isothiocyanate (synthetic mustard oil),
IMDG Code E 3023; United States: CFR 49: used in plant protection agents and pharmaceu-
172 – 189, Flammable Liquid (DOT Regula- tical preparations; allyl sulfonate, used as an
tions) [5]. electroplating-bath additive [67] and in the pro-
The most important regulations state that: duction of carbon fibers [68]; allylsilane, used
for the production of additives for the rubber in-
1) Vessels may be filled only to a maximum of dustry; and cyclopropane, an anesthetic.
93 % of their volumes or the RID (Suppl. X
and XI) must be complied with.
2) Road transport is allowed (in Germany a
1.7. Economic Aspects
maximum of 3 t per tank container).
3) No pipe ducts or pipe connections are al-
More than 90 % (ca. 800 000 t worldwide in
lowed below the surface of the liquid. Filling
1997) of the allyl chloride produced is used
and emptying connections must be tightly
for the production of epichlorohydrin. Less than
closed and should be additionally secured
55 000 t worldwide went into other applications.
by means of sealed caps. The tanks must be
tested regularly to insure that they withstand
total pressures of 0.6 MPa (6 bar).
4) Welded drums constructed of steel or stain- 2. Allyl Alcohol
less steel must be used for transport in
drums. Frequent changes in regulations are Allyl alcohol was first prepared in 1856 by
recorded. Each transport must be examined A. Cahours and A. W. Hofmann by saponifi-
individually with regard to the countries con- cation of allyl iodide. For general literature on
cerned. allyl alcohol, see [69–74].
8 Allyl Compounds

2.1. Physical Properties followed by bromination and addition of iso-

cyanates, yields flame-resistant polyurethane
Allyl alcohol [107-18-6], 2-propen-1-ol, foams [78].
CH2 =CH-CH2 OH, C3 H6 O, M r 58.08, mp Hydroxylation. The reaction of allyl alcohol
− 129 ◦ C, bp 96.9 ◦ C (101.3 kPa), is a color- with hydrogen peroxide in the presence of cat-
less, mobile liquid with an irritating odor. alytic amounts of tungstic acid yields glycerol
with excellent selectivity (→ Glycerol). This
Relative density, d 20 25 20
4 0.8520; d 4 0.8476; d 20 0.8535
Refractive index, n20 1.4133; n 25
1.4111; n 30 commercially important process was developed
D D D 1.4090
Critical temperature, t crit 271.9 ◦ C by Shell [79]. The hydroxylation of allyl alcohol
Heat of vaporization at 101.3 kPa 39.98 kJ/mol can be carried out also by organic hydroperox-
Specific heat capacity of vapor,
cp (g), (20 ◦ C and 101.3 kPa) 2.428 kJ kg−1 K−1 ides, such as ethylbenzene hydroperoxide, in the
Specific heat capacity of liquid presence of a vanadium catalyst [80]. Organic
cp (l), (20.5 – 95.5 ◦ C) 2.784 kJ kg−1 K−1 hydroperoxides oxidize allyl alcohol selectively
Heat of combustion at constant p 1853.8 kJ/mol
to glycidol (oxiranylmethanol) [556-52-5] [81].
Glycidol is also obtained by the reaction of allyl
Vapor pressure vs. Temperature alcohol with peracids [82].
Allyl alcohol can be dehydrogenated with
t, ◦ C 20 40 60 80
p, kPa 2.3 7.7 21.6 52.6
air in the gas phase over palladium, silver, or
copper catalysts to give acrolein [83], [84]. The
oxidation of allyl alcohol in the liquid phase
Viscosity (150 – 200 ◦ C, Pd catalyst) yields acrylic acid
at 15 ◦ C 1.486 mPa · s and acrolein with 83 % combined selectivity
at 30 ◦ C 1.072 mPa · s
Surface tension [85].
at 20 ◦ C 25.68 mN/m Catalytic hydrogenation of allyl alcohol
at 60 ◦ C 22.11 mN/m
Dipole moment 1.63 D
gives 1-propanol [71-23-8] [86]. Chlorination
Dielectric constant in aqueous solution yields mono- and dichloro-
at 16.2 ◦ C, λ = 60 cm 20.3 hydrins of glycerol, which can be hydrolyzed
Ignition limits in air
at 100 ◦ C, 101.3 kPa 2.5 – 18.0 vol % to glycerol [87]. Bromination proceeds very
Flash point (closed cup) 22.2 ◦ C selectively in aqueous solution, buffered by
calcium chloride [88]; 2,3-dibromo-1-propanol
Allyl alcohol is miscible with water and or- [96-13-9], used in flame-resistant materials [89],
ganic solvents in all proportions at 20 ◦ C. Table 3 is formed.
contains the most important azeotropic data for Allyl alcohol reacts with allyl chloride to
binary and ternary allyl alcohol azeotropes. give diallyl ether [557-40-4] (bp 94 ◦ C) and with
methallyl chloride to give allyl methallyl ether
[14289-96-4]. Carbon tetrachloride adds to allyl
2.2. Chemical Properties alcohol by radical initiation, leading to 2,4,4,4-
tetrachloro-1-butanol [3290-70-8], which is a
The allylic hydroxyl group and the olefinic dou- useful intermediate in flame-retardant technol-
ble bond can undergo numerous reactions, such ogy [90].
as oxidation, reduction, hydrogenation, conden- Hydroformylation of allyl alcohol in the
sation (formation of ethers and esters), and ad- presence of cobalt carbonyl yields 4-hy-
dition. At room temperature, allyl alcohol is droxybutyraldehyde [25714-71-0] [91] in 30 %
a stable liquid. When heated to temperatures yield. With rhodium-complex catalysts, the 4-
above about 100 ◦ C, allyl alcohol forms water- hydroxybutyraldehyde yield is improved to 80 %
soluble polymers (polyallyl alcohols) that react [92].
with alkenoic acids to give drying oils [75]. The aldehyde then can be hydrogenated
Allyl alcohol also can be grafted to poly- to 1,4-butanediol (→ Butanediols, Butenediols,
imides [76] or copolymerized with styrene in and Butynediols), a useful monomer for the pro-
the presence of oxygen [77]. Condensation of duction of polyurethanes [93]. When the hy-
allyl alcohol with methyl glucoside polyethers, droformylation of allyl alcohol is carried out
in the vapor phase over rhodium triphenylphos-
 Allyl Compounds 9
Table 3. Azeotropes of allyl alcohol

Component bp, ◦ C Allyl alcohol content, wt %

Binary azeotropes
Water 88.89 72.3
Benzene 76.75 17.3
Diallyl ether 89.8 30.0
Allyl chloride 79.9 18
Trichloroethylene 80.95 16

Component I Component II bp, ◦ C Content, wt %

Allyl Component II
alcohol

Ternary azeotropes
Water benzene 68.2 9.1 83.6
Water diallyl ether 77.8 8.7 78.9

phine complexes on porous carriers, tetrahydro- ysis [24] is shown in Figure 2. Water is removed
2-furanol [5371-52-8] is obtained in 94 % yield from the raw allyl alcohol by azeotropic distil-
[94]. Carbonylation of allyl alcohol in acetic acid lation with diallyl ether as entrainer.
solution with a palladium chloride catalyst gives For some reactions, the raw allyl
3-butenoic acid [95]. alcohol – water azeotrope (72 % allyl alcohol)
may be used without further purification.

2.3. Production
2.3.2. Isomerization of Propene Oxide
The raw material in all commercial processes is
propene. However, although allyl alcohol can be The catalytic rearrangement of propene oxide is
made via a variety of intermediates, only the pro- of increasing commercial interest and has par-
cesses proceeding via allyl chloride and propyl- tially replaced the hydrolysis of allyl chloride.
ene oxide are of major commercial importance. The most commonly used catalyst is lithium
phosphate.
2.3.1. Hydrolysis of Allyl Chloride Vapor-Phase Process. Propene oxide vapor
passes at 250 – 350 ◦ C over a lithium phosphate
Allyl alcohol is produced commercially by Shell
catalyst containing up to 30 % inert material.
and Dow from allyl chloride [24], [26]. Allyl
The catalyst is arranged in a fixed bed. Con-
chloride is hydrolyzed by a 5 – 10 % sodium
versions are about 70 – 75 %; allyl alcohol se-
hydroxide solution at 150 ◦ C and 1.3 – 1.4 MPa,
lectivity is 97 %. Space-time yields of 0.5 kg
yielding 85 – 95 % allyl alcohol. Byproducts are
allyl alcohol per liter of catalyst per hour are ob-
diallyl ether (5 – 10 %), chloropropenes, propi-
tained. Olin Mathieson uses a lithium phosphate
onaldehyde, and high-boiling material. In order
catalyst which contains 1 % alkali hydroxide
to obtain commercially satisfactory yields of al-
and which has to be regenerated after 40 h by
lyl alcohol, it is necessary to mix the allyl chlo-
washing with acetone [96]. The catalyst devel-
ride thoroughly with the aqueous alkaline solu-
oped by Chemische Werke Hüls [97], contain-
tion, maintaining a constant pH value. The al-
ing 73.6 % lithium phosphate and 17.5 % silica,
lyl chloride has to be converted nearly quanti-
needs no regeneration. Even after 1200 h, an al-
tatively, because its high corrosiveness does not
lyl alcohol selectivity of 97.3 % is maintained.
allow economical recovery. The reaction there-
Lithium arsenate also has been proposed as an
fore is carried out in a recycle reactor; the most
isomerization catalyst but has no essential ad-
suitable reactor material is nickel.
vantage over lithium phosphate [98]. An older,
A commercial plant for the production of al-
chromium oxide-catalyzed process, developed
lyl alcohol by continuous allyl chloride hydrol-
10 Allyl Compounds

Figure 2. Allyl alcohol production

a) Preheater; b) Hydrolysis reactor with recycle system; c) Stripping column; d) Dehydration column; e) Separator; f) Diallyl
ether washing tank; g) Allyl alcohol purification column

by Wyandotte Chemical Corp. [99], gives much The acetic acid is recovered and reused in the
lower conversions and selectivities. oxidation of propene. Therefore, only propene
and oxygen are required as raw materials for the
preparation of allyl alcohol.
Liquid-Phase Process. The Progil process This process needs no chlorine and there-
[100] is carried out with a finely ground lithium fore may be of commercial interest in the fu-
phosphate catalyst suspended in high-boiling ture. Allyl acetate can be hydrolyzed by heating
solvents, such as terphenyl or alkyl benzenes. at about 230 ◦ C and 3 MPa, according to a pro-
Propene oxide is bubbled through the suspen- cess developed by Hoechst [102], [103]. In the
sion at 280 ◦ C. Conversion is 60 %, allyl alcohol Bayer process hydrolysis is carried out catalyti-
selectivity 92 % , and the space-time yield 1 kg cally over an acid cation exchanger (sulfonated
allyl alcohol per liter per hour. Catalyst lifetimes polystyrene) at 100 ◦ C [104], [105]. The over-
of 500 – 1000 h are achieved. Jefferson Chemi- all yield of allyl alcohol, relative to the propene
cal Co. patented a similar process using a mix- feed, is 90 %.
ture of biphenyl and diphenyl ether as solvent
[101].
2.3.4. Hydrogenation of Acrolein
2.3.3. Hydrolysis of Allyl Acetate Allyl alcohol also can be obtained by catalytic
hydrogenation of acrolein in the vapor phase.
Propene, acetic acid, and oxygen react in the Use of cadmium – zinc catalysts gives yields up
gas phase over palladium catalysts to form al- to 70 % [106]. The hydrogenation also can be
lyl acetate, which in turn is hydrolyzed to allyl carried out over silver – cadmium alloys on inert
alcohol: carriers, such as alumina or silica, also giving
yields up to 70 % [107].
Ethanol or isopropyl alcohol can reduce
acrolein to allyl alcohol in the presence of a
mixture of magnesium oxide and zinc oxide
[108], [109]. The reaction takes place in the va-
por phase at 400 ◦ C; allyl alcohol yields of 80 %
have been reported [108].
 Allyl Compounds 11

2.4. Quality and Analysis 3. Allyl Esters

Commercial allyl alcohol has the following 3.1. Properties
specifications: content of allyl alcohol 98.0 wt %
(minimum), content of water 0.3 wt % (maxi- Physical Properties. The lower allyl esters,
mum), boiling range 95 – 98 ◦ C. The purity of such as allyl acetate, methallyl acetate, and al-
allyl alcohol is determined by GC. In the ab- lyl acrylate, are colorless, mobile liquids of low
sence of saturated alcohols, allyl alcohol can viscosity, with pungent odors, which cause vi-
be determined also by acetylation with N- olent irritation of the mucous membranes. The
acetylpyridinium chloride and back titration of higher allyl esters, such as diallyl phthalate, have
the unconverted N-acetylpyridinium chloride. high viscosities and boiling points and are nearly
Water is determined by Karl Fischer titration. odorless. The physical properties of the com-
mercially most important allyl esters are sum-
marized in Table 4.
2.5. Uses
Chemical Properties. Industrially, the most
Allyl alcohol is an intermediate in the produc- important property of allyl esters is their ability
tion of polymerizable allyl ethers and esters, es- to polymerize in the presence of oxygen or per-
pecially diallyl phthalate. The bulk of the allyl oxides. The allyl esters readily undergo hydrol-
alcohol produced commercially is consumed in ysis and transesterification. Allyl acetate can be
the production of glycerol. Polymeric allyl al- oxidized by oxygen and acetic acid over a pal-
cohol reacts with unsaturated fatty acids to give ladium catalyst to 2-propene-1,1-diol diacetate
drying oils [75]. Sulfur dioxide and allyl alcohol [869-29-4] [114].
yield polymeric allylsulfonic acids, which have Addition of chlorine in the presence of
been proposed as intermediates for plasticizers catalytic amounts of transition-metal chlo-
and textile auxiliaries [110]. Allyl alcohol can be rides yields 2,3-dichloro-1-propanol acetate
copolymerized with other monomers [76], [77] [589-96-8] [115]. Acetic acid can add to allyl
and then used as an intermediate in the produc- acetate in the vapor phase (phosphoric acid cat-
tion of flame-resistant materials [78], [89], [90] alyst, 200 ◦ C) [116] or in the liquid phase with
or as a nematocide, fungicide, or preservative. cation exchangers as catalysts [117], yielding
1,2-propanediol diacetate [623-84-7].
Substitution. Hydrogen chloride converts al-
2.6. Methallyl Alcohol lyl acetate to allyl chloride; the reaction takes
place at 100 ◦ C in the liquid phase. A combina-
Methallyl alcohol [513-42-8], 2-methyl-2- tion of copper(I) chloride and iron(III) chloride
propen-1-ol, CH2 =C(CH3 )-CH2 OH, C4 H8 O, which is soluble in allyl acetate, is used as a cat-
M r 72.11, bp 114.5 ◦ C (101.3 kPa), d 20
4 0.8515, alytic system [103], [118], giving conversions
n20
D 1.4255, is only partially miscible with water of allyl acetate up to 94 %, and an allyl chlo-
(19.4 wt % methallyl alcohol in water, 33.8 wt % ride selectivity of 96 %. Over copper catalysts,
water in methallyl alcohol, at 20 ◦ C). The hydrocyanic acid converts allyl acetate to allyl
methallyl alcohol-water azeotrope (bp 92 ◦ C) cyanide (3-butenenitrile) [109-75-1] [119–121].
contains 59.8 wt % methallyl alcohol. Hydroformylation of allyl acetate creates
Methallyl alcohol is prepared by hydroly- a mixture of acetoxybutyraldehydes [91],
sis of methallyl chloride in a 10 wt % aqueous [122], [123], the main product being 4-
sodium hydroxide solution [111], [112]. Pure acetoxybutyraldehyde [6564-95-0] in yields of
methallyl alcohol can be obtained by metha- about 70 %. This aldehyde is an intermediate in a
nolysis of methallyl acetate in the presence of proposed production method for 1,4-butanediol
catalytic amounts of bases [113]. Methallyl al- and butyrolactone.
cohol is used in the preparation of polymerizable
esters.
12 Allyl Compounds
Table 4. Physical data of important allyl esters

CAS Mol. bp, ◦ C/p, kPa d 20

4 n20
D
Registry No. Formula,
Mr

Allyl acetate (acetic [591-87-7] C5 H8 O2 100.12 103.5 – 104.5/101.3 0.9277 1.4050

acid 2-propenyl ester)
a
Methallyl acetate [820-71-3] C6 H10 O2 114.14 124/101.3 0.9239 1.4050
(acetic acid
2-methyl-2-propenyl
ester)
Allyl acrylate [999-55-3] C6 H8 O2 112.13 122/101.3 0.9441 1.4320
(2-propenoic acid
2-propenyl ester)
Allyl methacrylate [96-05-9] C7 H10 O2 126.16 67/6.7 0.9335 1.4358
(2-methyl-2-propenoic
acid 2-propenyl ester)
Diallyl maleate [999-21-3] C10 H12 O4 196.20 114 – 116/0.67 1.0773 1.4699
(cis-butenedioic acid 109 – 110/0.4
di-2-propenyl ester)
Diallyl fumarate [2807-54-7] C10 H12 O4 196.20 142/3.7 93/0.4 1.0768 1.4675
(trans-butenedioic
acid di-2-propenyl
ester)
Diallyl succinate [925-16-6] C10 H14 O4 198.22 105/0.4 1.0510 1.4517
(butanedioic acid
di-2-propenyl ester)
Diallyl adipate [2998-04-1] C12 H18 O4 226.27 141 – 142/1.1 1.0235 1.4540
(hexanedioic acid
di-2-propenyl ester)
Diallyl sebacate [3137-00-6] C16 H26 O4 282.38 163/0.4 0.976 1.4551
(decanedioic acid
di-2-propenyl ester)
Diallyl phthalate [131-17-9] C14 H14 O4 246.26 161/0.55 150/0.15 1.120 1.5190
(1,2-benzene
dicarboxylic acid
di-2-propenyl ester)
Diallyl isophthalate [1087-21-4] C14 H14 O4 246.26 181/0.55 1.124 1.521 c
(1,3-benzene
dicarboxylic acid
di-2-propenyl ester)
Diethylene glycol [142-22-3] C12 H18 O7 274.27 162/0.25 1.143 1.4503
bis(allyl carbonate)
(2,5,8,10-tetraoxa-9-
oxotridec-12-enoic
acid 2-propenyl ester)
Triallyl cyanurate [101-37-1] C12 H15 O3 N3 249.27 162/0.25 1.1133 b 1.540 c
(2,4,6-tris
(2-propenyloxy)-
1,3,5-triazine)
Triallyl phosphate [1623-19-4] C9 H15 O4 P 218.19 108 – 110/1.0 1.0815 1.4500
(phosphoric acid 93 – 94/0.14
tri-2-propenyl ester)
a 20
d 20
b
at 30 ◦ C
c
at 25 ◦ C

Allyl acetate can undergo a metathesis reac- 3.2. Production

tion leading to 2-butene-1,4-diol diacetate (cis-
and trans-isomers) [18621-75-5] and ethylene. 3.2.1. Oxidation of Olefins
With a catalyst system consisting of rhenium
heptoxide on alumina promoted by tetrameth- Vapor-phase oxidation of olefins in the
yltin [594-27-4], allyl acetate conversions of presence of lower alkanoic acids and over palla-
17 % are obtained. The selectivity for 2-butene-
1,4-diol diacetate is 96 % [124].
 Allyl Compounds 13

dium catalysts yields the corresponding alkenyl last of these compounds is obtained from allyl
esters. alcohol and the corresponding bischloroformate
The olefins are attacked in the allylic position. (prepared from diethylene glycol and phosgene).
For example, propene is oxidized in the presence
of acetic, propionic, or butyric acid to give allyl
acetate, allyl propionate, or allyl butyrate, re- 3.2.3. Transesterification
spectively. In a similar way, the methallyl esters Higher allyl esters can be prepared by transes-
are obtained by oxidation of isobutene. terification of the corresponding methyl esters
Allyl Acetate. Propene is oxidized with oxy- with allyl alcohol; sodium methanolate is the
gen in the presence of acetic acid in a tubu- preferred catalyst [131], [132]. Diallyl phthalate
lar reactor [125–127]. The solid catalyst is lo- and diallyl sebacate can be prepared in this way.
cated in a plurality of tubes and contains metal- The transesterification of methyl or ethyl es-
lic palladium, alkali acetate, and promoters, ters with allyl acetate has been proposed [133],
such as compounds of iron or bismuth [125], [134]. This method would be of industrial in-
[126]. The reaction takes place in the vapor terest if allyl acetate were commercially avail-
phase at 50 – 250 ◦ C and elevated pressure. Be- able as a primary product, for example, by ox-
cause of the high exothermicity of the reaction idation of propene [133]. Suitable transesterifi-
(∆H = − 1890 kJ/mol) and to avoid explosion cation catalysts are alkoxides or alkoxide com-
hazards, propene and acetic acid are converted plexes of elements of the first to third main
only partially. The Bayer process [125], [128] groups of the periodic table or alkoxides of ti-
yields allyl acetate with selectivities higher than tanium and zirconium [134]. The ester is mixed
90 mol%, carbon dioxide being the sole byprod- with twice as much allyl acetate and catalytic
uct. amounts of the alkoxides and heated to reflux
Methallyl acetate is produced from temperature. Methyl acetate (bp 57 ◦ C) and ethyl
isobutene, acetic acid, and oxygen by a simi- acetate (bp 77 ◦ C) have the lowest boiling points
lar process [129]. and are removed from the equilibrium by distil-
lation. The desired allyl ester can be isolated in
Liquid-Phase Oxidation. Olefins can be excellent yields and high purity.
oxidized also in the liquid phase with a cata-
lyst system consisting of palladium chloride and
copper(II) chloride (redox system) [130]. This 3.2.4. Other Production Methods
reaction is not selective; major byproducts are
1-propene-1-ol acetate, 1-propene-2-ol acetate, The reaction of allyl chloride with the alkali salts
propionaldehyde, and acetone. of mono- or dicarboxylic acids to give the corre-
sponding allyl esters is well known. These salts
also may be formed during the reaction. In this
3.2.2. Esterification way, diallyl phthalate is obtained from the re-
action of allyl chloride and phthalic anhydride
A general method for the preparation of allyl in the presence of sodium hydroxide, sodium
esters is the reaction of allyl alcohol with the carbonate, tertiary amines, or quaternary ammo-
free acids, acid anhydrides, or acid chlorides. nium salts [135].
Catalysts frequently used are aromatic sulfonic Allyl acrylate is prepared by the pyrolysis of
acids (p-toluenesulfonic acid and naphthalene- allyl lactate, allyl methacrylate in a similar man-
2-sulfonic acid) [128]. Strong mineral acids ner from allyl 2-hydroxyisobutyrate [136]. Sub-
are of less value because they can decompose stituted tetrahydrophthalic acid allyl esters are
the allyl alcohol. Polymerizable acids are es- obtained by Diels-Alder reaction of the cor-
terified in the presence of phenolic inhibitors. responding substituted butadienes and diallyl
The following allyl esters are prepared by this maleate [137]. The best method for the prepara-
method: diallyl phthalate, diallyl isophthalate, tion of triallyl phosphate is the condensation of
diallyl maleate, diallyl fumarate, triallyl cyanu- phosphorus trichloride with allyl alcohol to give
rate (from cyanuric chloride and allyl alcohol), triallyl phosphite [102-84-1] followed by oxida-
and diethylene glycol bis(allyl carbonate). The tion with air [138]. Diethylene glycol bis(allyl
14 Allyl Compounds

carbonate) can be prepared in 87 % yield by technique is first to prepare a prepolymer or

heating allyl chloride, diethylene glycol, and precopolymer in solution. This usually is done
carbon dioxide in the presence of sodium car- by dissolving the diallyl phthalate monomer in
bonate and triethylamine in an autoclave [139]. 2-propanol, adding 50 % hydrogen peroxide
at about 105 ◦ C, and precipitating the prepoly-
mer from the cooled, viscous solution with ex-
3.3. Uses cess 2-propanol. Precopolymers can be prepared
by adding comonomers, such as triallyl cyanu-
3.3.1. Polymer Production rate, acrylates, vinyl compounds, acrylonitrile,
styrene, or diallyl isophthalate. The prepoly-
Polymer production is the most important appli- mers and precopolymers are bulk polymerized
cation of allyl esters. They are especially suit- by mixing the prepolymer or precopolymer with
able as components in copolymers. Some allyl large amounts of free-radical initiators (benzoyl
esters are used for cross-linking or curing of peroxide, tert-butyl perbenzoate) and molding
polyolefins (graft copolymerization). Optimum at temperatures up to 200 ◦ C and 40 – 45 bar for
cross-linking is obtained by adding specific per- about 15 min. Because of their outstanding me-
oxides or by high-energy irradiation. The cross- chanical and electrical properties, copolymers
linked polymers and copolymers of allyl esters containing diallyl phthalate are suitable for spe-
give thermoset articles of excellent heat resis- cialty coating and for embedding, especially in
tance. Other applications of these polymers are the production of electronic devices. For ex-
in the production of casting sheets, molding ma- ample, the moisture-sensitive epoxy compounds
terial, electric and optical devices of high resis- now used in light-emitting diode (LED) displays
tance, and flame-retardant materials. can be replaced by stable diallyl phthalate epoxy
encapsulating resins [144], [145].
Diethylene glycol bis(allyl carbonate) usu- By adding inorganic materials to diallyl
ally is referred to as CR 39 monomer. It is phthalate prepolymer compositions, reinforced
bulk polymerized by the addition of relatively thermosetting molding compounds can be ob-
large (compared to similar polymerizations) tained. Glass cloth or paper can be impregnated
amounts of peroxides. The commercially pre- with a solution of prepolymer, monomer, and
ferred peroxide initiator is isopropyl percarbon- peroxide initiator. After removal of the solvent,
ate [105-64-6]. The homopolymer (CR 39 poly- the glass cloth or paper is cured to give the de-
mer) [25656-90-0] is suitable for the produc- sired film-protected material, which is used for
tion of cast sheets, lenses, and other articles that decoration, stain-resistant overlays for house-
have excellent resistance to scratching, impact, hold articles, and furniture.
and heat as well as outstanding optical properties
[140–142]. This polymer is resistant to common Diallyl isophthalate (DAIP) has the advan-
solvents with the exception of oxidizing acids. tage over the ortho isomer that it polymerizes
It is produced in the United States by PPG Ind. faster and gives polymers of better heat resis-
[140]. Even better qualities can be obtained by tance. The DAIP prepolymer is less stable than
reacting CR 39 monomer with other monomers, the diallyl phthalate prepolymer. Cured mold-
such as methyl methacrylate [80-62-6] or trial- ings from DAIP monomer-prepolymer compo-
lyl isocyanurate [1025-15-6]. These copolymers sitions can be better processed than cured dial-
are used for the production of light-weight lenses lyl phthalate moldings because of their greater
with very hard surfaces and high refractive in- fluidity. Compositions containing DAIP pre-
dices [143]. polymers can be used for the production of
hard, translucent, abrasive-resistant, and laser-
Diallyl phthalate is an important monomer trimmable coatings [146].
for the production of thermosetting molding
compounds, which must have good dimensional Diallyl esters of aliphatic dicarboxylic
stability and electrical properties, and be resis- acids, e.g., diallyl succinate, adipate, and seba-
tant to heat and solvents. Diallyl phthalate can cate, are preferred for the preparation of soluble,
be polymerized or copolymerized. The preferred thermoplastic precopolymers that sometimes
 Allyl Compounds 15

contain vinyl monomers. These precopolymers to polyester – styrene or methyl methacrylate

can also be used for graft copolymerization with yields cast sheets of improved mechanical and
preformed polymers; heat- and solvent-resistant thermal stability. Short-term heating of triallyl
adhesives, plastics, and coatings are produced cyanurate with polymers in the presence of per-
by this technique. oxides at 180 ◦ C gives cross-linking; valuable
Diallyl maleate and diallyl fumarate have ad- copolymers are thus obtained from poly(vinyl
ditional activated double bonds and copolymer- chloride) elastomers [154] and fluoroelastomers
ize readily with styrenes, vinyl ethers, and acry- [155]. Ethylene polymers and copolymers also
lates. The less reactive allyl groups remain intact may be cross-linked under similar reaction con-
and can subsequently be cross-linked by heating ditions [156]. High-impact plastics have been
with peroxides or treating with high-energy ra- obtained by grafting butyl acrylate-triallyl cya-
diation. As in the case of the saturated diallyl nurate copolymer with a styrene – acrylonitrile
esters, soluble precopolymers are obtained by mixture [157]. Other examples of peroxide-
heating the appropriate mixture of the monomers initiated curing with triallyl cyanurate (2 – 5 %)
in the presence of peroxides [147]. Preferential at 150 – 160 ◦ C are polyurethanes [158], nylons
uses are castings and moldings, plastisols, and [159], cellulose [160], polyoxyethylene [161],
adhesives. vinyl-substituted polysiloxanes [162], and acry-
late copolymers [163]. Crosslinking of polycar-
The allyl acrylic monomer of most impor- bonate with triallyl cyanurate by UV irradia-
tance is allyl methacrylate; allyl acrylate is of tion in the presence of polythiols gives scratch-
secondary importance. Both are used in small resistant coatings [164].
amounts for the preparation of soluble, fusible
copolymers that can be cross-linked in a subse- Triallyl phosphate can explode on heating
quent reaction to form insoluble, heat-resistant to about 130 ◦ C and polymerizes rapidly on ex-
plastics and coatings. Homopolymers also can posure to air. A possible commercial application
be produced by radical-initiated polymerization of this reactive monomer is the cross-linking
but are too expensive and are of poorer quality with polyolefins in the presence of peroxides
than copolymers. About 10 % of allyl methacry- and, if necessary, in the presence of foaming
late and allyl acrylate is copolymerized with agents [165].
other acrylic esters. Preformed vinyl polymers
can be cross-linked and processed to form graft
polymers. A copolymer of 10 % allyl methacry- 3.3.2. Other Uses
late and 90 % vinyl chloride is a flame-retardant
additive for polypropylene in amounts of up to Some allyl esters find application as plasti-
30 % relative to the polyolefin [148]. Allyl acry- cizers, textile auxiliaries, and insecticides. Al-
late is used in the production of dental plastics, lyl cinnamate [1866-31-5] is a component of
optical lenses, reinforced plastic adhesives, coat- perfumes. 2,3-Dibromopropyldiallyl phosphate
ings, rubbers, and components in printing pro- [33528-41-5] has been proposed as a flame retar-
cesses. It can also be used to modify the proper- dant in poly(ethylene terephthalate) fibers [166].
ties of cotton [149], [150] or nylon 6 [151]. Allyl esters also are suitable as diluents for the
less reactive peroxides and as dispersion media
Triallyl cyanurate is used preferentially as a for pigments and fillers.
cross-linking agent in copolymers. On heating it
may polymerize violently and then isomerize to
the more stable triallyl isocyanurate [1025-15-6] 4. Allyl Ethers
with the allyl groups attached to the nitrogen
atoms [152], [153]. 4.1. Properties and Uses
At 30 ◦ C viscous solutions of prepolymers
form slowly. Triallyl cyanurate is used for the Simple allyl ethers, such as diallyl ether or alkyl
production of heat- and solvent-resistant coat- allyl ethers, have only minor commercial impor-
ings and moldings, reinforced plastics, and ad- tance. Valuable allyl ethers are polyol allyl ethers
hesives. Addition of 5 – 10 % triallyl cyanurate and allyl ethers that contain an epoxy group.
16 Allyl Compounds

Allyl glycidyl ether [106-92-3], (allyloxymeth- heating allyl alcohol or mixtures of allyl alco-
yl)oxirane, M r 114.14, bp 87.5 – 88 ◦ C hol with monoalkanols in the presence of min-
(10.9 kPa), d 20 20
4 0.9678, nD 1.4345, is a toxic eral acids. The more valuable polymerizable al-
liquid used as an additive for epoxy resins and lyl ethers of polyols are prepared by reaction of
as a comonomer in polyglycols and polyolefins. allyl chloride with the polyols in the presence of
Crosslinking is achieved by irradiation or by sodium hydroxide [171], [172] or by treating an
thermally induced peroxide decomposition. aqueous solution of the polyol with allyl chloride
Copolymerization of allyl glycidyl ether with in a two-phase system to which a phase-transfer
acrylamide or N,N  -methylenebis(acrylamide) catalyst has been added. Using tetrabutylammo-
yields water-soluble polymers containing epoxy nium bromide [1643-19-2] as the phase-transfer
groups. These can be condensed with phar- catalyst, up to 99.7 % tetraallyl pentaerythritol
macologically active (controlled-release) com- ether is obtained from the reactants [170].
pounds to form pharmacologically active poly-
mers [167].
5. Allylamines
Ethylene glycol diallyl ether [7529-27-3],
1,2-bis(allyloxy)ethane, C8 H14 O2 , M r 142.20, 5.1. Properties and Uses
bp 35 – 37 ◦ C (0.13 kPa), d 20 4 0.8940, n20
D
1.4340, is polymerized oxidatively with cobalt Allylamine [107-11-9], CH2 =CHCH2 NH2 ,
acetate and air in methanol solution soaked C3 H7 N, M r 57.10, bp 54.5 ◦ C, d 204 0.7621, is
on the surface of filter paper. The resulting a liquid with an ammoniacal odor. It can be
polymeric product confers a high degree of hy- converted to N-allylamides or -imides by reac-
drophilicity to the filter paper [168]. tion with esters, acid anhydrides, or acid chlo-
rides. Allylamine is oxidized at 400 ◦ C on a bis-
Partial allyl ethers of trimethylolpropane muth molybdate catalyst; acrylonitrile and pro-
and pentaerythritol are used to increase the pionitrile are the main products (85 % com-
drying rate of alkyd drying-oil coatings. By bined yield) [173]. Plasma polymerization of
condensing a mixture of various pentaerythri- allylamine gives polymers that can be used as
tol allyl ethers with polyesters and ethylene gly- reverseosmosis membranes. A possible future
col monobutyl ether [111-76-2] and then curing application of these membranes is in closed en-
with cobalt octanoate, a film of high tensile hard- vironmental systems, such as manned spacecraft
ness and flexibility can be obtained [169]. [174], [175]. Allylamine is useful as a corrosion
inhibitor when pickling steel in acid [176]. The
Tetraallyl pentaerythritol ether [1471-18-7], rhodium-catalyzed reaction of allylamine with
C17 H28 O4 , 296.41, bp 124 – 125 ◦ C (0.13 kPa), carbon monoxide at 120 ◦ C and 10 MPa yields
d 20
4 0.9497, n 20
D 1.4595, can be added to lubri- 67 % γ-butyrolactam [616-45-5] [177].
cating oil to improve its viscosity index (i.e., to
reduce temperature effects) [170]. Diallylamine [124-02-7], C6 H11 N, M r
97.16, bp 111 – 112 ◦ C, can be cyclized to give
Allyl Ethers of Carbohydrates. Sucrose substituted pyridines [178]. It is an intermediate
polyethers copolymerize with acrylic acid to in the production of pharmaceuticals and resins.
yield branched, water-soluble polymers. Allyl
ethers of starches have been proposed as air- Triallylamine [102-70-5], C9 H15 N, M r
drying protective coatings and as varnishes but 137.23, bp 150 – 151 ◦ C, has been proposed
have found only limited commercial interest as a catalyst for the production of polyesters
because of their instability and water sensitivity. [179] and as an initiator for the polymerization
of butadiene [180].

4.2. Production Methallylamine [2878-14-0], CH2 =C(CH3 )-

CH2 NH2 , C4 H9 N, M r 71.12, bp 78.8 ◦ C, d 20
4
Allyl ethers of low molecular mass, such as di- 0.782, is dehydrogenated to methacrylonitrile
allyl ether and alkyl allyl ethers, are prepared by
 Allyl Compounds 17

[126-98-7] over a silver catalyst. Copolymer- cause severe liver damage, in contrast to com-
ization of methallylamine with acrylonitrile in- parable alkyl compounds (Table 5). Other target
creases the affinity of polyacrylonitrile fibers for organs are mainly the central nervous system,
dyes [181]. the kidneys, and the hematopoietic system.

Allyl Chloride [107-05-1].

5.2. Production Acute and Subacute Toxicity. LD50
= 460 mg/kg (rat, oral) [191]; LD50 = 3.7 mg/kg
Allyl chloride reacts with aqueous ammonia at (rabbit, percutaneous) [5]; LC50 = 11 mg/L (rat,
about 100 ◦ C to give a mixture of the hydrochlo- inhalation, 2 h) [191]. The inhalation of 3 ppm
rides of allyl-, diallyl-, and triallylamine, from allyl chloride during 7 h/d on 5 days a week was
which the pure amines are obtained by distil- tolerated by a group of rats, guinea pigs, and
lation [182]. Methallylamine is produced in a rabbits for 180 days without irreversible damage
similar manner [183]. occurring. An analogous test using 8 ppm over a
period of 35 days led to damage of the liver and
Table 5. Hepatotoxic effect ∗ of some allyl and propyl compounds kidneys [192]. Further experiments demonstrate
in rats [190]
a neurotoxic effect of allyl chloride, in particu-
Dosage, mg/kg Degree of lar to the peripheral nerves of cats and rabbits
liver necrosis
[191], [193], [194].
Allyl alcohol 25 1.5 Carcinogenicity, Mutagenicity, Embryotoxi-
Allyl formate 40 2
Allyl acetate 45 2.5
city. So far, little information on the carcino-
Allyl butyrate 85 1.5 genic activity of allyl chloride is available [195–
Allyl caproate 75 2.5 199]. A carcinogenic effect is suspected, al-
Allyl heptanoate 165 3
1-Propanol 2160 0 though a definite statement cannot be made at
Propyl formate 1330 0 present [195]. The mutagenicity of allyl chlo-
Propyl acetate 3120 0
Propyl butyrate 5000 0
ride has been confirmed in various tests [200–
203]. A toxic effect on the development of rat
∗ Degree of macroscopically visible liver necrosis on day 5 after embryos, as well as increased embryo mortal-
oral application of 1/3 of the LD50 for four consecutive days.
Degree 1: just clearly visible; degree 3: severe necrosis. ity, was established in rats that had inhaled air
containing allyl chloride at a concentration of
Pure allylamine can be prepared by hydroly- 3.1 mg/m3 . At 0.29 mg/m3 no negative effects
sis of allyl isothiocyanate [184], thermal cleav- occurred [204].
age of allyl dithiocarbamate [185], hydroly- General Characteristic Effects. Allyl chlo-
sis of diallyl cyanamide [186], or ammonoly- ride causes strong irritation of the skin and the
sis of triallylamine [187]. Allylamine may be mucous membranes. It is absorbed by inhala-
produced also by electroreduction of acryloni- tion, by ingestion, and through the skin. Di-
trile on lead cathodes [188]. Polyallylamines are rect contact and exposure to air – allyl chlo-
readily obtainable by catalytic hydrogenation of ride mixtures lead to strong irritation of the
poly(acrylonitrile) over a Raney nickel catalyst eyes, mucous membranes, and nasopharyngeal
[189]. cavity. Acute symptoms are numbness, uncon-
ciousness, and – particularly upon repeated and
lengthy exposure to higher concentrations – pul-
monary edema. The heart and circulatory sys-
6. Toxicology and Occupational tem, liver, and kidneys are endangered. At longer
Health exposure times and higher concentrations, fatal
poisoning is possible. After prolonged exposure,
Allyl compounds are stronger irritants to the chronic damage of the liver and kidneys occurs
skin and mucous membranes and are more toxic [5], [205], [206].
than the corresponding alkyl compounds (Ta- Occupational Health. Because of its toxic-
ble 5). Many allyl compounds are absorbed eas- ity, allyl chloride is classified as a poisonous
ily through the skin and mucous membranes. material. The threshold limit value (TLV) and
After absorption, aliphatic allyl compounds can the MAK are 1 ppm (8 h time weighted aver-
18 Allyl Compounds

age) [207–209]. The short-term exposure limit is allyl alcohol (4.8 – 6.2 mg/kg) with the drinking
twice as high: 2 ppm [205], [208]. Because of its water was tolerated by rats for 15 weeks without
suspected carcinogenic potential, allyl chloride effect [221]. In cases of skin contamination, the
is classified in group III B by the MAK com- danger of systemic intoxication brought on by
mission [207]. In the former USSR, the maxi- the high absorption rate of allyl alcohol through
mum allowed workroom concentration is set at the skin (one drop of allyl alcohol equals ap-
0.1 ppm [210]. proximately 50 mg) exists in addition to local
The particularly pungent odor of allyl chlo- irritation [218].
ride cannot serve as an adequate warning signal.
The odor perception thresholds, at which 50 and Allyl Esters. The toxicological effects of al-
100 % of exposed persons perceive allyl chlo- lyl esters are quite similar to those of allyl al-
ride vapors in the air, are 3 to 6 and 25 ppm, cohol. Local irritation and damage to the cen-
respectively [5]. These values are considerably tral nervous system and the liver caused by
above the permissible working concentrations. absorption are the main effects. For allyl ac-
So far, few investigations in occupational etate [591-87-7], the dermal LD50 in rabbits is
medicine on the effects of allyl chloride exist 1000 mg/kg and the LC50 in rats is 1000 ppm
[193], [205], [211]. after 1 h of inhalation. Comparable values are
reported for diallyl maleate [999-21-3] [212].
Allyl Alcohol [107-18-6]. With respect to Table 5 shows the hepatotoxicity of simple allyl
its irritating and toxic effects, allyl alcohol is esters, compared with some propyl esters. The
the best investigated aliphatic allyl compound. hepatotoxicity of diallyl phthalate [131-17-9]
The odor perception threshold is approximately is probably in the same range as that of oth-
0.8 ppm [212], and 6 – 12 ppm causes irritation ers in the table, but it causes only slight irrita-
of the nose. At a concentration of 25 ppm, se- tion of the skin or mucous membranes [222].
vere irritation of the eye occurs, with lacrima- Allyl methacrylate [96-05-9] has an oral LD50
tion, photophobia, blurred vision, and retrobul- in rats of 430 mg/kg and the dermal LD50 in
bar pain [212]. Corneal necrosis results in tem- rabbits is 500 mg/kg. Allyl methacrylate is eas-
porary blindness in persons exposed to higher ily absorbed through the skin. The inhalational
concentrations [213]. Sensitive persons may re- LCLo (lowest lethal concentration) in rats has
act with slight irritation of the eyes at concen- been found to be 500 ppm [223].
trations of 2 – 5 ppm [214], [215]. In animal ex-
periments daily inhalation of concentrations be- Allyl Ethers.
tween 2 and 7 ppm (7 h/d) has been tolerated Allyl glycidyl ether [106-92-3] has an LD50
without irritation in dogs, rabbits, guinea pigs, of 390 mg/kg (mouse, oral) and an LD50 of
and rats during periods of up to 6 months [192]. 1600 mg/kg (rat, oral). In rabbits, the dermal
The threshold limit value (TLV) and the LD50 is 2550 mg/kg. Inhalational toxicity has
MAK value are 2 ppm [208], [209]. The short- been estimated: LC50 = 270 ppm (mice, 4 h) and
term exposure limit is twice as high, namely 670 ppm (rats, 8 h) [224], [225].
4 ppm. Allyl glycidyl ether causes only slight irri-
A single oral application of allyl alcohol tation of the skin but is strongly irritating and
(0.02 mL/kg) caused liver necrosis in rats and corrosive to the eye. Following inhalation, the
the death of 7 out of 12 animals [216]. The oral irritation of the respiratory tract can lead to pul-
and cutaneous LD50 for rabbits is 50 – 80 mg/kg, monary edema or to secondary bronchopneumo-
and for rats 64 mg/kg [217], [218]. A single der- nia [224], [225]. After absorption, systemic in-
mal application of allyl alcohol to dogs (approx- toxication with disorders of the central nervous
imately 0.2 mL/kg) caused lethal gastrointesti- system and morphologic damage to the liver,
nal hemorrhages within a few hours [217]. In kidneys, and spleen can occur [224], [225]. In
rats hepatotoxic effects with liver cell necro- humans, dermal sensitization has been observed
sis were observed after a single application of besides the irritating effects [224], [225]. The
62.5 µL/kg by gavage [219] and after a single threshold limit (TLV) and the MAK values are
intraperitoneal injection of 0.5 mL/kg [220]. On 10 ppm or 45 mg/m3 [208], [209].
the other hand, the daily application of 50 ppm of
 Allyl Compounds 19

Diallyl ether [557-40-4] smells like 7. M. Capka, CS 187167, 1979 (M. Capka).
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20 Allyl Compounds

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 Allyl Compounds 21

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Alumina → Aluminum Oxide