Nucleophilic substitution in 4-bromo-5-nitrophthalodinitrile: IV. 5-nitro-4-(phenylthio)phthalodinitrile and octa-substituted metal phthalocyanines based thereon

Article abstract of DOI:10.1023/A:1012351405780

5-Nitro-4-(phenylthio)phthalodinitrile was obtained by nucleophilic substitution of the bromine atom in 4-bromo-5-nitrophthalodinitrile. The product was used to prepare copper(II) and cobalt tetra(5-nitro-4-phenylthio)phthalocyanines, and their spectral p

Full text of DOI:10.1023/A:1012351405780

Russian Journal of General Chemistry, Vol. 71, No. 2, 2001, pp. 243 245. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 2, 2001,
pp. 271 273.
Original Russian Text Copyright
2001 by Shishkina, Maizlish, Shaposhnikov.
Nucleophilic Substitution in 4-Bromo-5-nitrophthalodinitrile:
IV.1 5-Nitro-4-(phenylthio)phthalodinitrile and Octa-substituted
Metal Phthalocyanines Based Thereon
O. V. Shishkina, V. E. Maizlish, and G. P. Shaposhnikov
Ivanovo State University of Chemical Engineering, Ivanovo, Russia
Received December 17, 1999
Abstract 5-Nitro-4-(phenylthio)phthalodinitrile was obtained by nucleophilic substitution of the bromine
atom in 4-bromo-5-nitrophthalodinitrile. The product was used to prepare copper(II) and cobalt tetra(5-nitro-4-
phenylthio)phthalocyanines, and their spectral properties were studied.
The present work is a continuation of studies in
the field of disubstituted phthalodinitriles with peri-
pheral substituents of various nature ((R1, R2) and of
the corresponding octasubstituted metal phthalocyani-
nes MPc(4-R1)4(5-R2)4 [1 5] and deals with synthesis
and properties of (5-nitro-4-phenylthio)-substituted
phthalodinitrile and metal phthalocyanines based
thereon.
was performed by the latter procedure but with
another reactant ratio (thiophenol and triethylamine
were taken in a double excess; otherwise, complete
bromine substitution could not be attained.
Copper and cobalt tetra(5-nitro-4-phenylthio)phtha-
locyanines (III, IV) were synthesized by the reactions
of phthalodinitrile (II) with the corresponding metal
acetates at 220 225 C.
5-Nitro-4-(phenylthio)phthalodinitrile (II) was
prepared by nucleophilic substitution of the halogen
in 4-bromo-5-nitrophthalodinitrile (I). Compound I
was obtained by the procedure in [2].
Complexes III and IV were extracted with benzene
and purified by column chromatography on silica gel
(eluent chloroform). Metal phthalocyanines and their
derivatives are frequently purified by reprecipitation
from concentrated sulfuric acid; therewith, however,
metal tetra(4-phenoxy)phthalocyanines [6], as well
as metal tetra(5-nitro-4-phenoxy)phthalocyanines
MPc(5-NO2)4(4-OPh)4 [8] underwent sulfonation. The
same proved also true of metal complexes III and IV,
and thus we could prepare sulfonic acid V. We sup-
pose that the sulfo group enters the para position of
the phenyl substituents, as with octaphenyl-substituted
tetraazaporphines [9].
It is known that phenyl substitution in metal
phthalocyanines endows the latter with solubility in
organic solvents, thus making them convenient
objects for studying various properties in solutions,
including reactivity and catalytic activity in homo-
geneous reactions [6].
We earlier showed [1, 3, 4] that the halogen atom
in compound I is more mobile than the nitro group,
and thus it is the first target for nucleophilic substi-
tution.
The purity of the synthesized compounds was con-
firmed by elemental analysis, as well as by IR and
electronic spectroscopy. The IR spectrum of nitrile II
shows, along with bands characteristic of substituted
Attempted synthesis of 5-nitro-4-(phenylthio)phtha-
lodinitrile under the conditions we used earlier for
preparing 5-nitro-4-phenoxyphthalodinitrile [1], i.e.
by the reaction of phthalodinitrile I with a nucleo-
philic agent (thiophenol) in the presence of lithium
hydroxide in DMSO has not met with success.
1
phthalodinitriles [10], bands at 1528 and 1344 cm
due to NO2 stretching absorption and bands at 1088
1
1112 cm due to Ar S Ar absorption [11]. The IR
spectra of metal phthalocyanines III and IV show,
like with phthalodinitrile II, bands due to Ar S Ar
and NO2 absorption.
It is known that a halogen substituent in phthalo-
dinitrile can be substituted by a phenylthio group in
DMF in the presence of triethylamine [7]. The syn-
thesis of 5-nitro-4-(phenylthio)phthalodinitrile (II)
The presence of phenylthio substituents endows
phthalocyanines III, IV with solublity in benzene,
chlorobenzene, and chloroform. The compounds are
also soluble in DMF and concentrated sulfuric acid
1
For communication III, see [1].
1070-3632/01/7102-0243$25.00 2001 MAIK Nauka/Interperiodica

244
SHISHKINA et al.
NO2
SPh
PhS
O2N
N
M
N
N
N
N
N
Br
CN
CN
PhS
CN
PhSH, Et3N, DMF
(AcO)2M
N
N
O2N
O2N
CN
I
II
PhS
O2N
NO2
SPh
III, IV
NO2
HO3SH4C6S
O2N
SC6H4SO3H
N
N
N
H2SO4
N
M
N
IV
N
N
HO3SH4C6S
O2N
N
NO2
SC6H4SO3H
V
M = Cu (III), Co (IV).
Position of the first band in the electronic absorption
spectra of cobalt phthalocyanines
Comparison of the electronic absorption spectra of
complexes III and IV and the corresponding metal
tetra(5-nitro-4-phenoxy)phthalocyanines reveals
a
max, nm
bathochromic shift of the Q band. The same was
earlier observed with metal tetra(phenoxy)- and tetra-
(phenylthio)phthalocyanines [6]. The possible reason
is the lower electronegativity of S compared with O
(2.5 and 3.5, respectively) [14].
Refe-
rence
Compound
DMF H2SO4
CoPc
660
680
678
698
790
773
786
846
[13]
[5]
[8]
CoPc(4-Br)4(5-NO2)4
CoPc(5-NO2)4(4-OPh)4
CoPc(5-NO2)4(4-SPh)4 (IV)
As evident from the electronic absorption spectrum
of complex V in DMF, sulfo substitution in the bulky
phenyl substituent, like with the tetrasulfonic acid
derived from cobalt tetra(5-nitro-4-phenoxy)phthalo-
cyanine, produces a slight bathochromic shift of the
Q band compared with the parent compound IV. In
aqueous solution, the Q band is broadened because of
molecular aggregation.
CoPc(5-NO2)4(4-SC6H4SO3H)4 (V) 694
and insoluble in water, alcohols, and aqueous alkalis.
Sulfonation of compound IV makes it soluble in water
and aqueous alkalis and reduces its solubility in DMF.
The electronic absorption spectra of complxes III,
IV in organic solvents contain a Q band at 698 718
nm. In going from DMF to chloroform (benzene,
chloroform), the Q band shifts slightly red in the
order: benzene, chlorobenzene, chloroform.
EXPERIMENTAL
The electronic absorption spectra were measured
in DMF, chloroform, benzene, chlorobenzene, and
concentrated sulfuric acid on a Specord M-40 spec-
trometer at room temperature in the range 300
900 nm.
Compared with the corresponding unsubstituted
[12] and tetra(4-bromo-5-nitro)phthalocyanines [5],
the Q band is shifted red both in organic solvents and
in concentrated sulfuric acid (see table).
The IR spectra were obtained on a Specord M-80
spectrophotometer in the range 4000 400 cm in KBr.
1
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 2 2001

NUCLEOPHILIC SUBSTITUTION IN 4-BROMO-5-NITROPHTHALODINITRILE: IV.
245
The melting point was determined on a Boetius hot
stage with an RNMK-05 observation device (Boetius
microscope).
collegiate Scientific Program of the MInistry for
Education of the Russian Federation (project no. 411).
REFERENCES
5-Nitro-4-(phenylthio)phthalodinitrile (II). Thio-
phenol, 0.7 ml, and 0.78 ml of triethylamine were
added to a solution of 0.6 g of nitrile I in 20 ml of
DMF. The mixture was vigorously stirred at 20 25 C
for 4 h and then poured into 50 ml of water. The
precipitate was filtered off, washed with 5% aqueous
sodium bicarbonate, and then with distilled water to
neutral medium. The reaction product was dried in
air. Yield 0.42 g (62%), mp 130 132 C. Found, %: C
57.9; H 2.7; N 14.7. C14H7N3O2S. Calculated, %: C
59.8; H 2.49; N 14.9.
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spectrum, max, nm (log ): DMF 710 (4.81), 334
(4.86); chloroform 718 (4.82), 342 (4.97); benzene
716 (4.82), 334 (4.99); concentrated sulfuric acid 853
(4.74), 334 (4.64). Found, %: C 54.8; H 2.5; N 13.9.
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N 14.2.
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Cobalt tetra(5-nitro-4-phenylthio)phthalo-
cyanine (IV), yield 0.11 g (42%). Electronic absorp-
tion spectrum, max, nm (log ): DMF 698 (4.52), 334
(4.48); chloroform 704 (4.81), 327 (4.64); benzene
706 (4.83), 317 (4.81); concentrated sulfuric acid 846
(4.99), 321 (4.90). Found, %: C 54.9; H 2.5; N 14.0.
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ACKNOWLEDGMENTS
The work was financially supported by the Univer-
sitety Rossii fundamental’nye issledovaniya Inter-
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 2 2001