Nucleophilic substitution in 4-bromo-5-nitrophthalodinitrile: VI. 4-Dimethylphenoxy-5-nitrophenoxyphthalodinitrile and the copper phthalocyanine derived from it

Article abstract of DOI:10.1023/A:1021698417760

4-(3,4-Dimethylphenoxy)-5-(4-nitrophenoxy)phthalodinitrile was prepared by stepwise nucleophilic substitution of bromine and then the nitro group in 4-bromo-5-nitrophthalodinitrile by the substituted phenoxy groups and was converted to the corresponding o

Full text of DOI:10.1023/A:1021698417760

Russian Journal of General Chemistry, Vol. 72, No. 9, 2002, pp. 1463 1467. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 9, 2002,
pp. 1552 1556.
Original Russian Text Copyright
2002 by Maizlish, Ivanovskii, Shaposhnikov, Abramov, Smirnov, Bykova, Usol’tseva.
Nucleophilic Substitution in 4-Bromo-5-nitrophthalodinitrile:
VI.1 4-Dimethylphenoxy-5-nitrophenoxyphthalodinitrile
and the Copper Phthalocyanine Derived from It
V. E. Maizlish, S. A. Ivanovskii, G. P. Shaposhnikov, I. G. Abramov,
A. V. Smirnov, V. V. Bykova, and N. V. Usol’tseva
Ivanovo State University of Chemical Engineering, Ivanovo, Russia
Yaroslavl State Technical University, Yaroslavl, Russia
Ivanovo State University, Ivanovo, Russia
Received December 28, 2000
Abstract 4-(3,4-Dimethylphenoxy)-5-(4-nitrophenoxy)phthalodinitrile was prepared by stepwise nucleo-
philic substitution of bromine and then the nitro group in 4-bromo-5-nitrophthalodinitrile by the substituted
phenoxy groups and was converted to the corresponding octasubstituted copper phthalocyanine by the reaction
with copper acetate. The spectroscopic and mesomorphic properties of the resulting complex were studied. It
exhibits thermotropic mesomorphism and forms an M phase in the range 85 155 C.
Unsubstituted and substituted phthalocyanines (Pc)
are widely used as pigments and dyes [2, 3]. Active
study of this class of compounds showed that they can
also be successfully used as catalysts, chemical sen-
sors, and liquid crystals, and also as materials for
photoelectric cells, optical discs, photodynamic cancer
therapy, Langmuir Blodgett films, thin-film electron-
ics, etc. [3 11]. Synthesis of new substituted Pc, in
particular, of those containing various substituents is
limited by the lack of required precursors, e.g., of
the corresponding phthalodinitriles. One of the routes
to new substituted phthalodinitriles is replacement of
an existing substituent by another group. We have
already reported on the high reactivity of 4-bromo-5-
nitrophthalodinitrile in nucleophilic substitutions [1,
2, 12 17]. The presence of labile leaving groups (Br,
NO2) makes this phthalodinitrile a unique synthon for
preparing new substituted phthalodinitriles. We found
that the bromine substituent is more reactive and is
relatively readily substituted under mild conditions
with O-, S- and N-nucleophiles, whereas the second
leaving group, NO2, is substituted under more rigor-
ous conditions. Previous reports concerned either nu-
cleophilic substitution of bromine only [1, 12 17] or
substitution of both bromine and nitro group with the
same nucleophiles [17]. Some of the resulting phthal-
odinitriles were converted into the corresponding
octasubstituted metal phthalocyanines [15, 18, 19].
Here we report on synthesis of a phthalodinitrile
containing two differently substituted phenoxy groups
and of the copper phthalocyanine derived from it.
CH3
CH3
CH3
CH3
CH3
CH3
NO2
3
5
2
5
2
7
HO
K2CO3, 20 30 C
HO
NO2
O
O
O
NC
NC
NC
NC
NC
NC
Br
4
6
3
K2CO3, 130 140 C
NO2
NO2
1
4
1
3
4
I
II
III
1
For communication V, see [1].
1070-3632/02/7209-1463$27.00 2002 MAIK Nauka/Interperiodica

1464
MAIZLISH et al.
K2CO3 at elevated temperature (130 140 C). Under
4-(3,4-Dimethylphenoxy)-5-(4-nitrophenoxy)-
these conditions, the nitro group is nucleophilically
substituted to form the desired 4-(3,4-dimethylphen-
oxy)-5-(4-nitrophenoxy)phthalodinitrile (III).
phthalodinitrile (III) was prepared by stepwise nucleo-
philic substitution, first of bromine in 4-bromo-5-
nitrophthalodinitrile (I) under mild conditions and then
of the nitro group in the intermediate dinitrile II under
more rigorous conditions, as shown above.
The phthalodinitriles were identified by elemental
analysis and by H NMR and IR spectroscopy. The IR
spectrum of III is largely similar to those of other
substituted phthalodinitriles [20]. The C N vibration
The stepwise synthesis was performed by the previ-
ously developed procedures [16, 17] with isolation
and identification of each reaction product.
1
bands are manifested at 2240 cm , and the C O
1
(ether) bands, at 1260 cm . The bands at 1340 and
1
1560 cm confirm the presence of nitro groups, and
1
4-(3,4-Dimethylphenoxy)-5-nitrophthalodinitrile II
was prepared by the reaction of dinitrile I with 3,4-di-
methylphenol in DMF in the presence of aqueous
K2CO3 solution at room temperature. After isolation
and purification, compound II was treated with
p-nitrophenol in DMF in the presence of anhydrous
the bands at 2860 and 2970 cm , the presence of
methyl groups [21]. By the template reaction of phtha-
lodinitrile III with copper acetate at 180 185 C, we
prepared copper tetra-4-(3,4-dimethylphenoxy)-5-(4-
nitrophenoxy)phthalocyanine IV (one of positional
isomers is shown):
NO2
H3C
H3C
CH3
O
O
CH3
O2N
O
O
N
N
N
N
Cu(Ac)2
III
Cu
N
N
N
N
H3C
H3C
O
O
NO2
O
O
CH3
CH3
O2N
IV
The target product was extracted with chloroform
and, after removing the solvent, purified by reprecip-
itation from concentrated H2SO4 and extraction of the
residual organic impurities with acetone. Final puri-
fication was performed by liquid chromatography
(Al2O3, eluent chloroform). The resulting compound
IV is soluble in chloroform, DMF, and concentrated
sulfuric acid, sparingly soluble in benzene, and in-
soluble in acetone.
DMF are similar and suggest association of the com-
plex (Fig. 1): The monomer and dimer give bands
with maxima at 682 and 629 631 nm, respectively
[22 24]. The association is proved by the concentra-
tion dependence of the spectrum. When the solution
is diluted threefold, the intensity ratio of the dimer
and monomer bands changes from 1 : 1.25 to 1 : 1.71
(Fig. 1, curves 1 and 2).
The relationship between the structures of phthalo-
cyanine molecules and their properties (in particular,
mesomorphic) is a subject of active research [11, 25
30]. Substituted phthalocyanines and their metal com-
The electronic absorption spectra of IV in organic
solvents are poorly sensitive to the nature of the
solvent. The spectra in chloroform, benzene, and
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 9 2002

NUCLEOPHILIC SUBSTITUTION IN 4-BROMO-5-NITROPHTHALODINITRILE: VI.
1465
plexes exhibit both thermotropic and lyotropic meso-
morphism in binary mixtures with aqueous and non-
aqueous solvents. The mesomorphic properties of
1
these compounds depend on the number, position, and
nature of peripheral substituents, and also on the
nature of the central ion [11, 25 30]. Therefore, it was
interesting to study the mesomorphic properties of IV,
as this complex contains differently substituted peri-
pheral phenoxy groups. Polarization microscopic ex-
amination showed that the compound exhibits ther-
motropic mesomorphism, forming an enantiotropic
columnar phase in the temperature range 85 155 C
(Fig. 2). This fact suggests that the columnar meso-
phase belongs to the disordered type, because dis-
ordered columnar phases exhibiting weak microsegre-
gation do not tend to preserve the column packing and
transform into the isotropic state in solution [31]. No
lyotropic properties were found in binary systems of
IV with organic solvents (dimethyl sulfoxide, chloro-
form, benzene, etc.).
A
2
3
4
600
700
800
, nm
EXPERIMENTAL
Fig. 1. Electronic absorption spectra of IV in various
5
organic solvents: (1) chloroform,
c
1.5 10
M;
The IR spectra were taken on a Specord M-80
5
(2) chloroform,
(4) benzene.
c
4.5 10
M; (3) DMF; and
1
spectrophotometer in the range 4000 400 cm , using
1
KBr pellets. The H NMR spectra (5% solutions in
DMSO, internal reference TMS) were taken on a
Bruker AC-200P spectrometer (Institute of Organic
Chemistry, Russian Academy of Sciences, Moscow).
The electronic absorption spectra were recorded in
DMF, chloroform, or benzene on Specord M-40
UV/Vis and Perkin Elmer Lambda-20 spectrophotom-
eters at room temperature in the range 300 900 nm.
The phase state of copper tetra-4-(3,4-dimethyl-
phenoxy)-5-(4-nitrophenoxy)phthalocyanine was ex-
amined by polarization microscopy with an MIN-8
microscope equipped with a heating stage and a Zorkii
1
camera; the heating rate was 2 deg min .
The texture was photographed with a built-in
camera (24 36 mm) and a Wild MPS-51 camera
( 320 magnification).
Fig. 2. Nongeometric texture of IV at 150 C. Crossed
nicols; 100.
Lyotropic mesomorphism was studied using con-
tact samples.
1
mp 176 178 C. H NMR spectrum, , ppm: 8.82 s
(1H, H1), 7.60 s (1H, H2), 7.26 d (1H, H4, J 8 Hz),
7.01 d (1H, H3, J 2 Hz), 6.93 d (1H, H5, J 8 Hz),
2.30 s (6H, CH3).
4-(3,4-Dimethylphenoxy)-5-nitrophthalodinitrile
(II). A 0.01-mol portion of dinitrile I and equimolar
amount of 3,4-dimethylphenol were added with stir-
ring to 30 ml of DMF. After dissolution of the reac-
tants, a solution of 0.01 mol of K2CO3 in 10 ml of
water was added at 20 30 C with vigorous stirring.
The resulting mixture was stirred at 20 30 C for
0.5 h. The precipitated target product was filtered off,
washed with 10 ml of ethanol and 50 ml of water, and
recrystallized from 2-propanol DMF. Yield 74%,
4-(3,4-Dimethylphenoxy)-5-(4-nitrophenoxy)-
phthalodinitrile (III). Dinitrile II (0.01 mol), anhyd-
rous K2CO3 (0.01 mol), and 4-nitrophenol (0.01 mol)
were added with stirring to 30 ml of DMF. The result-
ing mixture was vigorously stirred at 130 140 C for
3 h, cooled, and poured into 100 ml of water. The pre-
cipitated target product was filtered off, washed with
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 9 2002

1466
MAIZLISH et al.
water, and recrystallized from 2-propanol DMF.
Yield 56%, mp 151 153 C. IR spectrum (KBr),
7. Velichko, A.V., Maizlish, V.E., Shaposhnikov, G.P.,
and Smirnov, R.P., Izv. Vyssh. Uchebn. Zaved.,
Khim. Khim. Tekhnol., 1993, vol. 36, no. 2, p. 47.
,
1
cm : 2240 (CN); 1260 (C O); 1560, 1340 (NO2);
2970, 2860 (CH3). 1H NMR spectrum, , ppm: 8.28 s
8. Simon, J. and Andre, J.J., Molecular Semiconductors.
Photoelectrical Properties and Solar Cells, Berlin:
Springer, 1985.
(1H, H1), 8.23 s (1H, H2), 7.37 d (2H, H4, J 8 Hz),
7.25 d (2H, H3, J 8 Hz), 6.88 6.75 m (3H, H5, H6,
H7), 2.27 s (3H, CH3), 2.24 s (3H, CH3). Found, %:
C 68.55; H 3.95; N 10.84. C22H15N3O5. Calculated,
%: C 68.57; H 3.92; N 10.90.
9. Loutfy, R.O., Hor, A.-M., Hsiao, C.-K., Baranyi, G.,
and Kazmaier, P., Pure Appl. Chem., 1988, vol. 60,
no. 7, p. 1047.
Copper tetra-4-(3,4-dimethylphenoxy)-5-(4-
nitrophenoxy)phthalocyanine. A quartz ampule was
charged with 1 mmol of dinitrile III and 0.3 mmol of
copper acetate; the mixture was fused at 180 185 C
for 0.5 h. The target product was extracted with chlo-
roform. The complex was reprecipitated from concen-
trated sulfuric acid, and the impurities were extracted
with acetone. The compound was finally purified by
column chromatography (Al2O3, eluent chloroform).
The phthalocyanine was vacuum-dried at 60 C; yield
40%. Electronic absorption spectrum, max, nm: 631,
682 (chloroform); 631, 682 (DMF); 631, 682 (ben-
zene). Found, %: C 72.16; H 4.35; N 11.22. C88H60
CuN12O8. Calculated, %: C 71.55; H 4.10; N 11.38.
10. Porfiriny: Spektroskopiya, elektrokhimiya, primenenie
(Porphyrins: Spectroscopy, Electrochemistry, and
Applications), Enikolopyan, N.S., Ed., Moscow:
Nauka, 1987.
11. Usol’tseva, N.V., Liotropnye zhidkie kristally: Khi-
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Liquid Crystals: Chemical and Supramolecular Struc-
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12. Shishkina, O.V., Maizlish, V.E., Kudrik, E.V., Sha-
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13. Zharnikova, M.A., Balakirev, A.E., Maizlish, V.E.,
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ACKNOWLEDGMENTS
The study was financially supported by the Ministry
of Education of the Russian Federation (project no. 97-
0-9.4-381 in the field of basic natural science) and
Russian Foundation for Basic Research (project
no. 98-03-32084).
15. Shishkina, O.V., Maizlish, V.E., and Shaposhni-
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