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[19581 Conjugated Macrocycles. Part X X X I . 3879

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789. Conjugated Macrocycles. Part X X X I . * Catalytic Hydrogenation

of Tetrazaporphins, with a Note on its Stereochemical Course.
By G. E. FICKEN,R. P. LINSTEAD,EDITHSTEPHEN,and MARGARETWHALLEY.
Hydrogenation of tetrazaporphins in the presence of very active catalysts
gave substances easily decomposed to the imides of dibasic acids. With
palladium black as catalyst, tetrazaporphin (I; R = R’ = H) and three of
its alkyl derivatives gave reasonably stable, coloured tetrahydro-derivatives.
The hydrogenation level of these substances w a established by degradation
to saturated imides, by quantitative dehydrogenation, and by spectral
evidence.
The dehydrogenation of tetracyclohexenotetrazaporphin (I; RR‘ =
-[CH,],-) with quinones is described.
CATALYTIChydrogenation of tetrazaporphin 1 (I; R = R’ = H) (now more accessible
because of an improved method for preparation of maleinitrile 2), of its tetramethyl (I;
R = H, R’ = Me), octamethyl4 (I; R = R‘ = Me), and tetracyclohexeno- (I; R R =
-[CH,],-) derivatives and of the corresponding magnesium complexes (11) has been
R’ R R’ R

investigated. The met al-f ree pigments in pyridine, chlorobenzene, or 2-ethoxyet hanol
and the magnesium pigments in pyridine were rapidly destroyed over active catalysts such
as Adams platinum oxide or W-4 Raney nickel. I t seems likely that hydrogenation at
* Part XXX, J., 1957, 2882.
t A preliminary account appeared in Special Publication No, 3, The Chemical Society, 1955, p. 98.
Linstead and Whalley, J., 1952, 4839.
Woods, Imperial Chemical Industries Limited, personal communication ; cf. U.S.P. 2,447,810/
1948.
Brown, Spiers, and Whalley, J., 1957, 2882.
Baguley, France, Linstead. and Whalley, J., 1955, 3521.
ti Ficken and Linstead, J., 1952, 4846.
 View Article Online
3880 Ficken, Linstead, Stephen, and Whalley:
the p-positions of the pyrrole rings is accompanied by hydrogenolysis of the macrocycle,
the linear, possibly polypyrrolic, intermediates then being hydrolysed. The only products
isolated from the magnesium complexes of tetramethyl-, octamethyl-, and tetracyclo-
hexeno-tetrazaporphin were saturated h i d e s , vix., methylsuccinimide, &-dimethyl-
succinimide, and cis-hexahydrophthalimide. Under similar conditions phthalimide was
obtained from magnesium and zinc phthalocyanine.6
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Controlled hydrogenation was possible by using palladium black. With the metal-
free pigments hydrogenation was slow and considerable loss was caused by over-hydrogen-
ation. With the more soluble magnesium pigments in pyridine, preparative hydrogen-
ation was practicable. The magnesium derivatives of tetramethyl-, octamethyl-, and
tetracyclohexeno-tetrazaporphin gave, after 2 mols. of hydrogen had been absorbed,
royal-blue solutions which did not show the strong visible and ultraviolet fluorescence
characteristic of the parent pigments. The spectra of the blue solutions were of the
metal-tetrazaporphin type: in each case hydrogen caused a bathochromic shift of ca. 30 mp
in the position of the longest-wavelength band. The blue pigments, either solid or in
solution, were readily oxidised in air, to the starting materials contaminated with traces
of unidentified pigments which absorbed a t longer wavelength (663, 665, and 666 mp
severally). Under the same conditions, hydrogenation of magnesium tetrazaporphin
(I1 ; R = R' = H) gave very small yields of a blue pigment (A,. 608, 454 mp in pyridine)
which was rather more stable to atmospheric oxidation. Magnesium phthalocyanine in
dilute solution in pyridine slowly formed a blue pigment (Amax. 709, 570 mp) which in air
gave instant and quantitative recovery of magnesium phthalocyanine.
In acetic acid the reduced magnesium pigments from tetramethyl-, octamethyl-, and
t etracyclohexeno-tetrazaporphin gave purple microcryst alline, sparingly soluble (6-
8 mg./100 C.C.of chlorobenzene) metal-free compounds. These pigments were reasonably

N- N

s+
H H

stable to oxidation at room temperature but in boiling chlorobenzene or, better, chloro-
benzene-nitrobenzene they oxidised to the parent pigment : this made purification by
crystallisation impracticable. The number and position of the " extra '' hydrogen atoms
in these compounds was still to be determined.
Several coloured hydrotetrazaporphins with the P-positions of one or more pyrrolic
Barrett, Dent, and Linstead, J., 1936, 1719.
' Wieland, Ber., 1912, 45, 489.
 View Article Online
[19581 Conjugated Macrocycles. Part X X X I . 3881
corners reduced, are formally possible. The dihydro-form (111) corresponds to the
relatively stable chlorin 8 in the porphyrin series. The tetrahydro-compound may be
formulated as (IVa) (corresponding to bacteriochlorophyll 9, or (IVb). Formulze (V) and
(VI) represent possible hexahydro-forms. In (11), (111), (IV), and (V) a large conjugated
ring is retained [in (V) by transfer of 2 hydrogen atoms from central nitrogen atoms to
B-pyrrolic carbon atoms]. In the hexahydro-compound (VI) the conjugation of the
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large ring is interrupted.

The more obvious methods for deciding between the possible structures proved un-
helpful. Hydrogen uptake figures suggested a tetrahydro-structure for the magnesium
hydrotetrazaporphins. This made structure (V) or (VI) unlikely for the metal-free
pigments. It was, however, uncertain whether the metal-free pigments were at the
tetrahydro- or the dihydro-level because of the possibility of partial dehydrogenation
during demetallation. Carbon and hydrogen determinations on the metal-free pigments
were inconclusive.
Spcctva of ( A ) tetrahydro-octamethylletrazaporphinand ( B )letrahydrotetrazaporphin in chlorobcnzene.

0.2

W a v e I e n g t A (mp)

Vigorous oxidation of a symmetrically substituted tetrazaporphin (cf. refs. 3, 4, 5)

yields 4 mols. of the corresponding unsaturated imide. The dihydro-derivative (111) and
the tetrahydro-compound (IVa or b) would therefore be expected to yield 1 mol. and 2 mols.
of saturated imide respectively. In fact oxidation of hydro-octamethyltetrazaporphin
gave aa’-dimethylsuccinimide (0.95 mol.) and dimethylmaleimide (1.77 mols.). Allowing
for the (detennined) experimental loss the yield of saturated imide becomes 1.19 mols.
This still takes no account of the loss (unknown) through dehydrogenation of the pigment
before ring scission. It is clear that the true yield of saturated imide is more than 1 mol.
and therefore that the hydro-pigment contains more than one reduced pyrrolic corner.
The hydro-pigment must therefore be at the tetrahydro-level since a higher level was
excluded. This was confirmed by the results of quantitative dehydrogenation described
below.
Similar oxidation of hydrotetracychhexenotetrazaporphin and of hydrotetramethyl-
tetrazaporphin gave cis-hexahydrophthalimide (0.3 mol.) and methylsuccinimide (0.4 mol.).
The low yields of saturated imide in these two cases is not unexpected because of the
greater ease of dehydrogenation of these hydrogenation products which would greatly
increase the extent of dehydrogenation before ring scission. However, the absorption
spectra of hydrot etracyclohexenotetrazaporphin, hydro-oct amethyltetrazaporphin and
hydrotetrazaporphin (Amax. 678, 525 mp in chlorobenzene; obtained in minute yield from
* Cf., e.g., Eisner and Linstead, J., 1955, 3742.
Golden, Linstead, and Whitham, J . , 1958, 1725.
5N
 View Article Online
Ficken, Linstead, Stephen, and Whalley:
magnesium t et razaporphin) resemble so closely that of t etrahydro-oct m e t hylt et raza-
porphin (see Figure) that they too must be tetrahydro-derivatives.
The isolation of succinimide derivatives by degradation of the hydrotetrazaporphins
indicated that the extra hydrogen atoms were on the P-positions of two of the pyrrolic
corners of the macrocycles. It is of special interest that the aa'-dimethylsuccinimide from
tetrahydro-octamethyltetrazaprophin was isolated in the unstable meso-form lo in which
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the hydrogen atoms are cis- with respect to the imide ring. This shows that, as in the
mild catalytic hydrogenation of polynuclear aromatic compounds,11 there is one-sided
addition of hydrogen to the molecule. This in turn would correspond with addition to
each double bond of both atoms of hydrogen during one period of sorption on the catalyst.
There is no evidence from measurements of light absorption during hydrogenation (or
during dehydrogenation with air, boiling nitrobenzene, dilute nitric acid, or quinones) for
the formation of a dihydro-pigment. If it may be presumed from this that all four atoms
of hydrogen are added during a single period of sorption, it may be con-
u (vIII)
cluded that the tetrahydride is not only cis but cis-syn-cis, to apply the
nomenclature used l2 for the hydrides of polynuclear aromatic compounds.
This is represented diagramatically in (VIII).
Indications of the existence of a hexahydro-compound (possibly V or VI) were obtained
only in the tetracyclohexeno-series. The metal-free pigment in pyridine over palladium
black gave, after 3 mols. of hydrogen had been absorbed, an olive-green solution (Amax.
720 my) which was rapidly oxidised in air (with uptake of 0.5 mol. of oxygen) to a solution
of tetrahydrotetracyclohexenotetrazaporphin.
It has not been possible to determine, as yet, whether our products have the structure
(IVa) with opposite pyrrolic corners reduced or (IVb) with adjacent corners reduced.
The simple absorption spectra, however, suggest that they are not mixtures of the two forms
because the two forms of tetrahydroporphins have been shown to have widely differing
absorption spectra.l3914
The hydrogenation level of the hydrotetrazaporphins was also established by quantit-
ative dehydrogenation. Titration methods using potassium dichromate, hydrogen
peroxide, or ferric alum were unsuccessful because ring scission accompanied dehydrogen-
ation; but dehydrogenation with quinones, a method successfully applied to the
dehydrogenation of synthetic chlorins,15 confirmed the tetrahydro-structure for our
products : hydro-octamethyltetrazaporphin in o-dichlorobenzene a t room temperature
was 50% dehydrogenated by 1 mol. of 2 : 3-dichloro-5 : 6-dicyano-1 : 4-benzoquinone and
1000/, dehydrogenated by 2 mols. The product was octamethyltetrazaporphin which was
spectroscopically identical with the pigment prepared from dimethylf~maronitrile.~The
isolation of 2 : 3-dichloro-5 : 6-dicyanoquinol from the reaction indicated that transfer of
the extra " hydrogen atoms to the quinone had in fact occurred. With quinones of
I'

lower potential, e.g., tetrachloro-1 : 2-benzoquinone and chloranil, dehydrogenation was

slow a t 80" and was accompanied by thermal decomposition of both pigment and quinone.
Dehydrogenation of tetrahydrotetracyclohexenotetrazaporphin with an excess of
chloranil a t 110" gave nearly complete conversion into the parent pigment (11; RR' =
-[CH,],-). With an excess of 2 : 3-dichloro-5 : 6-dicyano-1 : 4-benzoquinone at 80°, the
tetrahydro-pigment gave initially the parent tetrazaporphin but then the cyclohexene rings
were successively dehydrogenated to yield, finally, phthalocyanine (VII). Two of the
intermediate pigments-benzotricyclohexeno- (A,. 647, 571 mp) and tribenzocyclohexeno-
tetrazaporphin (Amax. 680, 610 my)-were identified by comparison of the absorption
lo Linstead and Whalley, J., 1954, 3722.
11 Linstead, Doering, Davis, Levine, and Whetstone, severally, J . Amer. Chew?. Soc., 1942, 64,
1985-2022.
l a Idem, ibid., p. 1985.
1s Dorough and Miller, J . Amer. Chem. Soc., 1952, 74, 6106.
Barnard and Jackman, J., 1956, 1174.
1 5 Eisner and Linstead, J., 1955, 3749; Eisner, Linstead, Parkes, and Stephen, J., 1956, 1655.
 View Article Online
[19581 Conjugated Macrocycles. Part X X X I . 3883
maxima with those of the known pigments.16 The third intermediate (lmaX. 671, 585 mp)
was spectroscopically identical with the pigment obtained by treatment of tetracyclo-
hexenotetrazaporphin with 6 mols. of dichlorodicyanobenzoquinone a t 110" or with an
excess of tetrachloro-1 : 2-benzoquinone a t 80". The spectrum and elementary analysis
of this pigment suggest that it is dibenzodicyclohexenotetrazaporphin. Quinones of lower
potential, such as 9 : 10-anthraquinone and duroquinone, failed to remove the
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- -
" extra " hydrogen atoms from tetrahydrotetracyclohexenotetrazaporphin. The pro-
gressive dehydrogenation of the hydro-derivatives of phthalocyanine can be represented
in the following scheme where the numbers refer to the extra hydrogen atoms on the four
isoindole rings: 6.4.6.4 4.4.4.4 4.4.4.0 -+ 4.0.4.0 +4.0.0.0 +0.0.0.0.

EXPERIMENTAL
Microanalyses were carried out in the Microanalytical Laboratory (hlr. F. H. Oliver and
Miss J. Cuckney) of this Department.
MaZeinitriZe.2-Fumaronitrile (8-5 g.) was heated with iodine (0.5 g.) a t 175-180" for
6-5 hr. The product was dissolved in chloroform (120 c.c.). Sodium thiosulphate (5 g.) was
added and the mixture was kept overnight. The chloroform solution was decanted, and the
residue was distilled to give fumaronitrile, b. p. 90-95120 mm. (5.4 g.), and maleinitrile, b. p.
110-120"/20 mm. (2.75 g., 89% on unrecovered fumaronitrile).
Pyridine for Hydrogenations.-Pyridine (from Messrs. Hopkin and Williams, " pure 'I)

(500 c.c.) was refluxed for 4 hr. with W-4 Raney nickel (1 teaspoonful) and then redistilled from
fresh Raney nickel.
Tetrahydrotetracyc!ohexenotetrazaporphin.-(i) A suspension of magnesium tetracyclohexeno-
tetrazaporphin monohydrate monopyridine solvate ti (222 mg.) in pyridine (100 c.c.) was
hydrogenated over palladium black (53 mg.) until 2 mols. of hydrogen had been absorbed.
The solution was filter@ rapidly under nitrogen and the pyridine was removed under reduced
pressure (no air-leak).' Filtered acetic acid (20 c.c.) was added and the mixture was kept a t
room temperature under reduced pressure for 2 hr. Filtered, distilled water was added. Tetra-
hydrotetracyclohexenotetrazaporphin (140 mg., 76%) separated as a dark purple powder (Found :
C, 72.1; H , 6.9; N, 20.8. C,,H,,N, requires C, 71.9; H, 7.2; N, 21.0y0). (ii) TetracycZo-
hexenotetrazaporphin (264 mg.) was suspended in pyridine (50 c.c.) and hydrogenated over
palladium black for 7 days: 2.93 mols. of hydrogen were absorbed. The olive-green solution
was shaken with air: 0.94 atom of oxygen was absorbed. The purple solution was decanted
from the palladium black into 2N-hydrochloric acid (100 c.c.). Tetrahydrotetracyclohexeno-
tetrazaporphin (217 mg., 82%) spectroscopically identical with that prepared from the magnes-
ium pigment was obtained.
Tetrahydro - octamethyZtetrazaporph~n.-Magnesium octamethyltetrazaporphin monopent -
anolate (250 mg.) was hydrogenated in pyridine (100 c.c.) over palladium black (19 mg.).
2.0 Mols. of hydrogen were absorbed. The solution was filtered rapidly and the pyridine was
removed under reduced pressure (no air-leak). Acetic acid (20 c.c.) was added, followed, after
2 hr., by water (20 c.c.). Tetrahydro-octamethyltetrazaporphin(159 mg., 84%) was pre-
cipitated as a purple solid (Found: C, 67-2; H, 6 - 7 ; N, 26.3. Calc. for C,,H,,N,: C,
66.9; H, 7-0; N, 26.0%). The pigment in chlorobenzene passed down kieselguhr or tartaric
acid columns as a single band. Alumina caused dehyrogenation to the ground-level pigment.
TetrahydrotetramethyZtEtraza~or~kin.-This experiment must be completed within 6 hr.
Magnesium tetramethyltetrazaporphin monomethanolate (210 mg.) was hydrogenated in
pyridine (100 c.c.) over palladium black (55 mg.). The solution became brown and then light
green (ca.2 hr.). The reaction was then stopped and the mixture was filtered rapidly under
nitrogen. The royal-blue filtrate was evaporated to dryness under reduced pressure and cold
acetic acid (20 c.c.) was added to the ice-cold residue. After 2 hr. the acetic acid was removed
under reduced pressure and water (20 c.c.) was added. TetrahydrotetramethyZtetraza~orphin
monohydrate (83 mg., 43%) was obtained as a dark purple solid after drying (room
temperature/O-Ol mm.) (Found: C, 6143; H, 5.9; N, 29-1. C,,H2,N,0 requires C, 61.2; H ,
l6 Brown, Linstead, and Whalley, unpublished work.
l7 Org. Synth., 30, 46.
 View Article Online
Ficken, Lirtstead, Stephen, and WhaUey :
6-1; N, 28.6%). Drying the pigment a t slightly higher temperatures invariably caused
dehydrogenation to tetramethyltetrazaporphin.
Oxidation of Tetrahydro-octarnethyZtetrazaporphin.-The pigment (287 mg.) was dissolved in
concentrated sulphuric acid (5 c.c.) a t -5' under nitrogen. 0-Oh-Potassium dichromate
(100 c.c.) was added all a t once. After 2 miii. ferrous sulphate (3 g.) was added and the solution
was filtered to remove octamethyltetrazaporphin (Amax. in chlorobenzene 627, 556 mp) (9 mg.,
3%). The filtrate was extracted continuously with ether for 48 hr. The extract was con-
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centrated to ca. 10 C.C. (inversion of configuration occurs if the ether extract is evaporated to
dryness a t this stage or during extraction) and the solution was chromatographed on silica gel
loaded with water.Is The column was eluted with ether. Twenty-four 4-C.C.fractions were
collected. Fractions 1-6 yielded dimethylmaleimide (136 mg., 1.7 mols.), m. p. 117-119",
fractions 7 and 8 gave a mixture (6 mg.) and fractions 9-23 contained meso-m'-dimethyl-
succinimide (78 mg., 0.95 mol.), m. p. and mixed m. p. 43-45'.*
Oxidation and separation as described above of dirnethylmaleimide (95 mg.) and dimethyl-
succinimide (99 mg.) gave 75 mg. (79% recovery) of the former and 79 mg. (80% recovery) of
the latter and 4 mg. of a mixture.
Oxidation of Tetrahydrotetracyc1ohexenotetrazaporphin.-The pigment (305 mg.) was oxidised
as described above. The ether extract was evaporated to dryness, the residue was dissolved
in wet benzene, and the solution was chromatographed on silica gel.ls Fractions 1-17 yielded
3 : 4 : 5 : 6-tetrahydrophthalimide (198 mg., 2-3 mol.), m. p. and mixed m. p. 169-172', and
cis-hexahydrophthalimide l9 (27 mg., 0.3 mol.), m. p. and mixed m. p. 133-137".
Oxidation of TetrahydrotetramethyZtetrazaporfikin.-The pigment monohydrate (165 mg.) was
dissolved in concentrated sulphuric acid (4 c.c.) a t 0" under nitrogen and chromium trioxide
(100 mg.) was added in a little water. The mixture was kept a t room temperature for 5 min.
and excess of ferrous sulphate was then added. The solution was continuously extracted with
ether overnight and the extract was chromatographed on silica gel l8 as above. Fractions 1-7
contained citraconimide (69 mg., 1.5 mols.), fractions 8-10 contained no solute, and fractions
11-15 yielded methylsuccinimide (20 mg., 0.4 mol.), m. p. and mixed m. p. 61-64'.
Hydrogenation of Magnesium Phthalocyanine Monohydrate.-Crude magnesium phthalo-
cyanine 6 was crystallised several times from pyridine t o give the purple monohydrate (Found:
C, 68.7; H, 3-7; N, 19-9; Mg, 4.6. Calc. for C3,H,6NsMg,H20:c, 69-2; H, 3.3; N, 20-2; Mg,
4.4%). A solution of the pigment in pyridine (0.34 mg./100 C.C. ; 20 c.c.) was hydrogenated over
palladium black for 16 hr. The blue solution was shaken in the air and immediately reoxidised
to a solution of magnesium phthalocyanine (0.34 mg./100 C.C. , estimated spectroscopically from
the absorption at 674 mp).
Exhaustive Hydrogenations.-(i) Magnesium tetracyclohexenotetrazaporphin monohydrate
monopyridine solvate (350 mg.) was hydrogenated in pyridine (50 c.c.) over Adams platinum
oxide (50 mg.) until no more hydrogen was absorbed. The pyridine was removed under reduced
pressure and the dark sticky residue was extracted with light petroleum (b. p. 60-80"). cis-
Hexahydrophthalimide (21 mg., 0.25 mol.), m. p. and mixed m. p. 133-135', separated.
(ii) Magnesium octamethyltetrazaporphin monopentanolate (237 mg.) was hydrogenated in
pyridine (35 c.c.) over Adams platinum oxide for 3 days. The dark green solution was filtered
through charcoal and the filtrate was evaporated to dryness under reduced pressure. The
residue was sublimed and the sublimate was crystallised from water to give DL-ad-dimethyl-
succinimide (21 mg., 0.38 mol.), m. p. 99-l0lo, mixed m. p. 101-102" (no precautions were
taken to prevent possible inversion of configuration of the primary product).
(iii) Magnesium phthalocyanine monohydrate (97 mg.) was hydrogenated in pyridine
(50 c.c.) over Adams platinum oxide (23 mg.) for 6 days. 11-5Mols. of hydrogen were absorbed.
The brown mixture was shaken with air; magnesium phthalocyanine (6% of the original
quantity, estimated spectroscopically) was re-formed. The solution was filtered and the
filtrate was evaporated to dryness a t room temperature. The residual solid was extracted
with light petroleum (b. p. 60-80°), and the extract was evaporated to dryness. Sublimation
of the residue gave phthalimide (53 mg., 2-1 mols.), m. p. 224-226" and 229-232" after further
sublimation.
(iv) Zinc phthalocyanine monopyridine solvate * (188 mg.) was hydrogenated as above.
18 Elvidge, Linstead, and Whalley, '' Modern Techniques of Organic Chemistry," Butterworths,
London, 1955, p. 9.
lD Ficken and Linstead, J . , 1954, 3730.
 View Article Online
[1%8] Conjugated Macrocycles . Part X X X I .
10 Mols. of hydrogen were absorbed. The brown solution was filtered through charcoal, and
the filtrate was evaporated to dryness under reduced pressure. The solid was dissolved in a
little ethanol and the solution was diluted with benzene (4 vols.). The solution was chromato-
graphed on alumina (Spence H) and gave (a) a weakly adsorbed green band containing a trace
of zinc phthalocyanine, (b) a yellow band which yielded phthalimide (97 mg., 2.1 mols.), m. p.
229--231", and (c) a strongly adsorbed rose-pink band which was eluted with 50% aqueous
pyridine and gave no identifiable product.
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Dehydrogenation of Tetrahydro-octamethyZtetrazaPor~hin.-(i) The following control experi-

ments showed that Beer's law is obeyed by mixtures of octamethyltetrazaporphin (A) and
tetrahydro-octamethyltetrazaporphin(B) in o-dichlorobenzene.

530 mp 560 mp 63J m p 685 mp

Concn. (mg./100 c.c.) Eobs. Ecalc. Eob4. Ecalc. Eobs. Ecalc. Eobs. Ecalc.
A 0.2295
o.2282}
..................... 0.232 0-231 0.232 0.236 0-391 0.413 0.416 0-422
A 0-1148
o.3400} ..................... 0.262 0-276 0.121 0.131 (3.251 0.252 0.630 0.637
A o.1157}
0.3440 ..................... 0-180 0.189 0.314 0.318 0.540 0.522 0.209 0.213

It was also shown that solutions of octamethyltetrazaporphin and of tetrahydro-octamethyl-

tetrazaporphin in o-dichlorobenzene were essentially unchanged after 4 hr. a t 80" under nitrogen.
Method A . 5-C.C. portions of a solution of tetrahydro-octamethyltetrazaporphin (2-
3 mg./100 C.C. of o-dichlorobenzene) were treated with varying molar proportions of 2 : 3-di-
chloro-5 : 6-dicyano-1 : 4-benzoquinone (11-12 mg. in 25 C.C. of o-dichlorobenzene) at 80" for
2.75 hr. (apparatus 20). Each solution was then withdrawn with a long-necked pipette and the
flask was rinsed several times with o-dichlorobenzene. The combined solution and washings
were made up to 25 C.C. and the resulting solution was examined spectrophotometrically a t 530,
560, 630, and 685 my.
Method B . l-C.c. portions of a solution of tetrahydro-octamethyltetrazaporphin (3.4
mg.1100 C.C. of dry o-dichlorobenzene) were placed in ampoules. To each was added a solution
of 2 : 3-dichloro-5 : 6-dicyano-1 : 4-benzoquinone (11.2 mg./100 C.C. of dry o-dichlorobenzene:
0.5-2.0 mols.). The ampoules were sealed and kept in the dark a t room temperature for 22 hr.
The solutions were then made up to 10.0 C.C. with o-dichlorobenzene and each was examined
spectrophotometrically a t 530, 560, 630, and 685 my.

Unchanged Dehydrogen- De- Unchanged Dehydrogen- De-

Quinone hydro-deriv. ated pigment hydrogn. Quinone hydro-deriv. ated pigment hydrogn.
(mols.) (%I (%I (%) (mols.) (%I (%I (%I
530mp 685mp 560mp 630mp 530mp 685mp 560mp 630mp
Method A Method B
0.5 77 70 34 32 30 0.5 - 70 26 26 27
1.0 52 49 49 50 50 1.0 - 44 47 50 52
1.4 33 32 62 67 67 1-25 35 33 60 59 62
2.0 6 8 95 97 95 1.5 24 29 70 70 72
2.0 3 10 91 94 93

The results tabulated above are each the average of two or more independent experiments.
(ii) Tetrahydro-octamethyltetrazaporphin (14.4 mg.) was heated with 2 : 3-dichloro-5 : 6-
dicyano-1 : 4-benzoquinone (180 mg., 3 mols.) in dry o-dichlorobenzene (100 c.c.) in the dark
for 17 hr. a t 80". The solution was evaporated to small bulk and octamethyltetrazaporphin
(13.7 mg., 95%) then separated. It was washed with ether and twice crystallised extractively
from o-dichlorobenzene (Found: 560 mp, log E 4.58; 630 mp, log E 4-78. Octamethyltetraza-
porphin has log E 4.58 and 4.78 respectively). The combined filtrate and washings were evapor-
ated and gave 2 : 3-dichloro-5 : 6-dicyanoquinol (10 mg., 55y0),m. p. and mixed m. p. 257-259"
(Thiele and Gunter 21 give 265"). The product gave the pink colour characteristic for the
quinol with aqueous ferric chloride.
2o Braude, Jackman, and Linstead, J., 1954, 3548.
21 Thiele and Gunter, Annalen, 1906, 349, 54.
 View Article Online
3886 Conjugated Ma CYOcy cles . Part X X X I .
Dehydrogenation of Tetracyclohexenotetra~o~~hin and its Derivatives.-(i) A solution of
tetracyclohexenotetrazaporphin or of tetrahydrotetracyclohexenotetrazaporphin in o-dichloro-
benzene was boiled with a large excess of 2 : 3-dichloro-5 : 6-dicyano-1 : 4-benzoquinone.
Phthalocyanine (Amax. 698, 665 mp) was the only pigment produced.
(ii) Tetracyclohexenotetrazaporphin (1 mol.) in o-dichlorobenzene was heated a t 110" with
dichlorodicyanobenzoquinone (6 mols.) for 17 hr. in a sealed ampoule. The product was
dibenzodicyclohexenotetrazaporphin (Am. 67 1, 584 mp) containing traces of benzotricyclo-
Published on 01 January 1958. Downloaded by Universiteit Utrecht on 07/08/2013 20:09:49.

hexenotetrazaporphin (Amax. 647, 571 mp) and unchanged starting material.

(iii) Tetracyclohexenotetrazaporphin in chlorobenzene was heated with an excess of tetra-
chloro-1 : 2-benzoquinone a t 80" for 2 days. The solution was diluted and was then chromato-
graphed (alumina, Spence H). Three pigments were eluted with chlorobenzene, viz., (i) blue
(Amax. 647, 571 mp), monobenzotricyclohexenotetrazaporphinl6 (traces), (ii) violet (Amax, 67 1,
586 mp) main product, and (iii) blue-green (Amax. 680, 615 mp), tribenzocyclohexenotetraza-
porphin 2 1 (traces). The violet fraction was concentrated and rechromatographed, to give the
violet pigment contaminated with traces of the monobenzo-compound. Repeated extractive
crystallisation of the pigment from benzene gave dark blue needles of dibenzodicyclohexeno-
tetrazaporphin (Found: C, 72.8; H, 5.1. C,,H,,N8 requires C, 73-5; H, 5.0%).
(iv) Dibenzodicyclohexenotetrazaporphin and benzotricyclohexenotetrazaporphin in o-di-
chlorobenzene with a large excess of dichlorodicyanobenzoquinone a t 150" each gave tribenzo-
cyclohexenotetrazaporphin (Amax. 680, 610 mp) and phthalocyanine.
A bsorption Spectra.-For qualitative work a Hilger-Nutting spectrophotometer and a
Hartridge reversion spectroscope were used. Quantitative spectra were obtained on a Unicam
S.P. 500 (250-400 mp) and a S.P. 600 (400-1000 mp) instrument. A reduced pigment (ca.
0-5 mg.) was dissolved in the solvent (100 c.c.) a t room temperature and intensity measure-
ments were completed within 1 hr.

Absorption spectra (mp) and log E.

Tetrazaporphin Solvent
Tetrah ydro-octamethyl ...... PhCl 333 342 526 626 651 687
4.65 4.69 4.48 4-12 4-06 4.75
C,H,CI, 331 346 528 625 650 687
4.62 4-66 4.57 3-98 4-07 4.78
Tetrahydrotetracyclohexeno. .. CHCI, 265 328 343 532 628 653 691
4.03 4.69 4.76 4-45 4.23 4.11 4-78
Tetrahydrotetramethyl ...... PhCl 333 338 526 624 681
4.64 4.65 4.29 4.10 4-61
Octamethyl ..,.................. C,H,Cl, 343 558 630
4.82 4.61 4.82
Dibenzodicyclohexeno ......... C6H,C1, 346 544 586 671
4.78 4.31 4-91 4.83
Magnesium phthalocyanine ... C,H,N 347 668 687 610 64i 674
4-73 3-59 3-79 4-45 4-39 4.94

We are grateful for a maintenance award from the Department of Scientific and Industrial
Research (G. E. F.), for a Union Postgraduate Scholarship, and for a scholarship from the
Royal Commission for the Exhibition of 1851 (E. S.). We thank Imperial Chemical
Industries Limited, Dyestuffs Division, for generous gifts of chemicals and Dr. J. C. Woods of
this Division for details of the preparation of maleinitrile.
DEPARTMENT IMPERIAL
OF CHEMISTRY, COLLEGEOF SCIENCE
A N D TECHNOLOGY,
SOUTH KENSINGTON,
LONDON,
S.W.7. [Received, May 20th, 1958.3