Nucleophilic substitution in 4-bromo-5-nitrophthalodinitrile: VIII. Synthesis of 4-(benzotriazol-1-yl)-5-[4-(1-methyl-1-phenylethyl)phenoxy] phthalodinitrile and phthalocyanines on its basis

Article abstract of DOI:10.1134/S1070363207090216

Nucleophilic aromatic substitution of the bromine atom in 4-bromo-5-nitrophthalodinitrile by a 2-aminophenylamine residue followed by conversion of the resulting compound to 4-(1-benzothiazol-1-yl)-5- nitrophthalodinitrile and nucleophilic substitution of

Full text of DOI:10.1134/S1070363207090216

ISSN 1070-3632, Russian Journal of General Chemistry, 2007, Vol. 77, No. 9, pp. 1623 1627.
Pleiades Publishing, Ltd., 2007.
Original Russian Text S.A. Znoiko, V.E. Maizlish, G.P. Shaposhnikov, I.G. Abramov, M.N. Voron’ko, 2007, published in Zhurnal Obshchei Khimii,
2007, Vol. 77, No. 9, pp. 1551 1555.
Nucleophilic Substitution in 4-Bromo-5-nitrophthalodinitrile:
VIII.1 Synthesis of 4-(Benzotriazol-1-yl)-5-[4-(1-methyl-
1-phenylethyl)phenoxy]phthalodinitrile
and Phthalocyanines on Its Basis
S. A. Znoikoa, V. E. Maizlisha, G. P. Shaposhnikova,
I. G. Abramovb, and M. N. Voron’kob
a Ivanovo State Chemical Technological University,
pr. F. Engel’sa 7, Ivanovo, 153000 Russia
e-mail: ttoc@isuct.ru
b Yaroslavl State Technical University, Yaroslavl, Russia
Received December 19, 2006
Abstract Nucleophilic aromatic substitution of the bromine atom in 4-bromo-5-nitrophthalodinitrile by a
2-aminophenylamine residue followed by conversion of the resulting compound to 4-(1-benzothiazol-1-yl)-
5-nitrophthalodinitrile and nucleophilic substitution of the nitro group by a 4-(1-methyl-1-phenylethyl)-
phenoxy group gave 4-(benzotriazol-1-yl)-5-[4-(1-methyl-1-phenylethyl)phenoxy]phthalodinitrile. The latter
product was reacted with certain metal acetates and chlorides to obtain the corresponding metal complexes of
octasubstituted phthalocyanines. Spectral properties of the complexes were studied.
DOI: 10.1134/S1070363207090216
Phthalocyanines and related compounds have long
been used as high-class organic dyes and pigments
[2] and effective desulfurization catalysts [3]. They
are also known to be applied as catalysts in other
processes, as well as materials for photodynamic
therapy of cancer, optical discs, chemical sensors, etc.
[4 8]. Heterocyclic compounds are of primary im-
portance in many biological processes and are their
key components. In particular, triazoles are bacterial
antagonists that inhibit cell division, and they also
possess herbicidal activity [9]. In view of the afore-
said, synthesis of phthalocyanines (Pc) containing
such small heterocycles holds promise, but only few
such compounds have been synthesized, mostly
pyridyl-substituted Pc [10].
In the present work we made use of compound I to
4-(benzotriazol-1-yl)-5-[4-(1-methyl-1-phenylethyl)-
phenoxy]phthalodinitrile (IV) and metal phthalo-
cyanines on its basis.
The nucleophilic substitution of the bromine atom
in 4-bromo-5-nitrophthalodinitrile (I) on the reaction
of the latter with (2-aminophenyl)amine resulted in
the synthesis of 4-[(2-aminophenyl)amino]-5-nitro-
phthalodinitrile (II) which reacted with sodium nitrite
in the presence of acetic acid to form 4-(1-benzothia-
zol-1-yl)-5-nitrophthalodinitrile (III) [13]. The nuc-
leophilic substitution of the nitro group under the
action of 4-(1-methyl-1-phenylethyl)phenol in the
presence of K2CO3 gave target phthalocyanogen IV.
Compounds II IV were identified by elemental
New substituted phthalocyanines are difficult to
synthesize, not infrequently because of the lack of
difficulties in preparation of starting phthalic acids or
their derivatives, specifically phthalodinitriles. Pre-
viously we reported on a unique source of a variety
of substituted phthalodinitriles, 4-bromo-5-nitrophtha-
lodinitrile (I) [11], which exhibits high reactivity in
aromatic nucleophilic substitution [12 14].
1
analysis and H NMR (the numbering of protons in
the compounds are given in the scheme) and vibra-
tional spectroscopy.
The 1H NMR spectrum of phthalodinitrile IV
contains signals at 7.75 and 8.70 ppm, corresponding
to the protons in the 1 and 2 positions of the phthalo-
dinitrile benzene ring, and signals at 8.16, 7.80, 7.65,
and 7.5 ppm, corresponding to the protons in the 3, 4,
5, and 6 positions of the benzotriazole fragment. The
1
For communication VII, see [1].
1623

1624
ZNOIKO et al.
4
5
6
3
1
2
2
N
N
NC
NC
NC
NC
NO2
NH
NaNO2 + CH3COOH
N
NO2
1
NH2
III
3
6
4
CH3
5
II
OH
CH3
NH2
NH2
13
11
15
14
H3C
10
CH312
7
9
1
2
Br
CN
O
N
NC
NC
8
N
O2N
CN
N
I
3
4
5
6
IV
signals of the 4-(1-methyl-1-phenylethyl)phenoxy
group appear as a multiplet at 7.20 ppm (positions 7
10 and 15), a triplet at 7.27 ppm (positions 13 and 14),
and a doublet at 7.05 ppm (positions 11 and 12). The
upfield singlet at 1.60 ppm belongs to six methyl
protons.
The purification technique was chosen depending
on the individual features of each phthalocyanine.
Copper tetra[4-(benzotriazol-1-yl)]-tetra{5-[4-(1-
methyl-1-phenylethyl)phenoxy]}phthalocyanine (Va)
is soluble in concentrated hydrochloric acid and was
purified by reprecipitation from this acid. Cobalt and
nickel complexes Vb and Vc, respectively, were pu-
rified by treatment with aqueous acetone to remove
unreacted phthalodinitrile. Final purification was
performed by column chromatography on Al2O3
(eluent chloroform). The complexes were identified
by elemental analysis and vibrational and electronic
spectroscopy.
The IR spectra of phthalodinitrile IV show bands
characteristic of substituted phthalodinitriles [15] and
indicative of the substituents present. The absorption
bands characteristic of the C N bonds are observed at
1
2233 cm , and those of the Ar O Ar bonds, at
1
1208 cm . The stretching vibration bands of the
1
methyl groups appear at 2874 3060 cm [16].
Metal complexes Va Vd were synthesized by the
nitrile method from phthalodinitrile IV and acetates
and chlorides of the corresponding metals.
The IR spectrum of the copper complex contains
almost all bands characteristic of phthalodinitrile IV,
1
except for the C N bands at 2230 2240 cm . The
The presence in the phthalocyanine molecule of
bulky 4-(1-methyl-1-phenylethyl)phenoxy groups
weakens intermolecular interactions and enhances
solubility in DMF and other organic solvents, spe-
cifically chloroform, benzene, and acetone. With this
in mind, the target products were extracted with
chloroform.
same is true of the IR spectra of the other metal
phthalocyanines.
Analysis of the electronic absorption spectra shows
that the solvent (DMS, chloroform) only slightly
affects the position of the first band at 669 689 nm
(see figure).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 9 2007

NUCLEOPHILIC SUBSTITUTION IN 4-BROMO-5-NITROPHTHALONITRILE: VIII.
1625
CH3
H3C
N
N
N
O
H3C
CH3
N
N
N
O
N
N
O
N
Mn+
N
N
N
M
IV
N
170 180 C
N
N
N
N
H3C
CH3
O
N
N
N
CH3
H3C
Va Vd
M = Cu (Va), Co (Vb), Ni (Vc), Er (Vd); n = 2 (Va Vc), 3 (Vd).
The influence of the central metal atom shows up
in a bathochromic shift of the first band, whose
magnitude increases in the series: Co < Ni < Cu < Er
(in DMF) and Ni < Co < Cu and Er (in chloroform).
The Q band in the electronic absorption spectrum
of cooper tetra[4-(benzothiazol-1-yl)]-tetra{5-[4-(1-
methyl-1-phenylethyl)phenoxy]}phthalocyanine (Va)
in DMF is shifted bathochromically compared with
(a)
(b)
log
log
1
4.8
4.6
4.4
5.2
5.0
4.8
4.6
4.4
4.2
4.0
3.8
3.6
2
4.2
1
4.0
3.8
2
3.6
400 500 600 700 800
, nm
400 500 600 700 800
, nm
Fig. 1. Electronic absorption spectra in chloroform. (a): (1) Erbium complex Vd and (2) cobalt complex Vb; (b): (1) copper
complex Va and (2) nickel complex Vc.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 9 2007

1626
ZNOIKO et al.
copper tetra[4-(benzothiazol-1-yl)]phthalocyanine
679 nm).
and dried at 70 C. The precipitate looks like light
yellow needles insoluble in water and readily soluble
in DMF, chloroform, acetone, and benzene. Yield
(
max
It should be noted that the long-wave regions of
1
3.84 g (87%), mp 209 212 C. H NMR spectrum, ,
the spectra of copper complex Va and nickel complex
Vc (765 775 nm) contain an additional absorption
band which is fairly weak for complex Va and stron-
ger for complex Vc (see Fig. 1b).
ppm: 8.70 s (1H, H2), 8.16 d (1H, H3, J 8 Hz), 7.85 s
(1H, H1), 7.8 d (1H, H4, J 7.9 Hz), 7.65 t (1H, H5),
7.5 t (1H, H6), 7.27 t (2H, H13,14), 7.20 m (4H,
H
8 10,15), 7.05 d (2H, H11,12, J 8.1 Hz), 1.60 s (6H).
Found, %: C 76.49; H 4.64; N 15.14. C35H21N5O.
Calculated, %: C 76.47; H 4.65; N 15.37.
EXPERIMENTAL
The electronic absorption spectra were taken in
DMF and chloroform on a UV/VIS Perkin Elmer
Spectrometer Lambda 200 spectrophotometer at room
temperature in the range 325 900 nm. The IR spectra
were obtained on an Avatar 360 FT-IR ESP instru-
Metal complexes of tetra[4-(benzotriazol-1-yl)]-
tetra{5-[4-(1-methyl-1-phenylethyl)phenoxy]}-
phthalocyanine were prepared by the reactions of
phthalodinitrile IV with metal acetates and chlorides.
The mixture was heated at 200 220 C for 1 1.5 h.
The reaction products were thoroughly ground,
washed with 5% HCl, washed with water to neutral,
dried at 80 C, and then extracted with chloroform.
After removal of the solvent the products were pu-
rified with account for their individual features. The
final purification was performed by chromatography
on Al2O3 (eluent chloroform).
1
ment in the range 400 4000 cm in thin films
1
(chloroform) and KBr tablets. The H NMR spectra
were measured in 5% solutions in DMSO-d6 on a
Bruker DRX-500 instrument, internal reference TMS.
Elemntal analysis was performed on a CHNS-O
FlashEA Series 1112 instrument.
4-[(2-Aminophenyl)amino]-5-nitrophthalodinit-
rile (II). A mixture of 2.52 g of 4-bromo-5-nitro-
phthalodinitrile, 1.01 g of triethylamine, 1.81 g of
2-aminophenylamine, and 50 ml of propan-2-ol was
refluxed for 2 h, and the precipitate that formed was
The resulting phthalocyanines are dark green or
bluish green powders insoluble in water and readily
soluble in DMF, chloroform, acetone, and benzene.
1
Copper
tetra[4-(benzotriazol-1-yl)]-tetra{5-[4-
filtered off. Yield 2.55 g (92%), mp 168 170 C. H
(1-methyl-1-phenylethyl)phenoxy]}phthalocyanine
(Va) was prepared from 47 mg of compound IV and
6 mg of copper acetate and purified by reprecipitation
from conc. HCl. Yield 31 mg (60%). Electronic ab-
sorption spectrum, max, nm (log ): in DMF: 613
(4.26), 684 (5.09); in chloroform: 617 (4.46), 688
(5.17), 771 (3.57). Found, %: C 72.26; H 4.18; N
15.00. C116H84CuN20O4. Calculated, %: C 73.85; H
4.46; N 14.85.
NMR spectrum, , ppm: 9.66 s (1H, NH), 8.70 s (1H,
H1), 7.12 t (1H, H3, J 16 Hz), 7.05 d (1H, H6, J 8 Hz),
6.93 s (1H, H2), 6.85 d (1H, H5, J 8 Hz), 6.75 t (1H,
H4, J 16 Hz), 5.15 s (2H, NH2). Found, %: C 60.19;
H 3.12; N 24.76. C14H9N5O2. Calculated, %: C 60.21;
H 3.25; N 25.08.
4-(1-Benzothiazol-1-yl)-5-nitrophthalodinitrile
(III). A solution of 7.60 g of NaNO2 in 50 ml of
water was added to a solution of 31.00 g of compound
II in 300 ml of acetic acid. The reaction mixture was
stirred at 70 C for 3 h. The precipitate that formed
after cooling was filtered off, washed with 20 ml of
acetic acid, and dried at 70 C. Yield 29.64 g (92%),
Cobalt tetra[4-(benzotriazol-1-yl)]-tetra{5-
[4-(1-methyl-1-phenylethyl)phenoxy]}phthalocya-
nine (Vb) was prepared from 47 mg of compound IV
and 7 mg of cobalt chloride and purified by treatment
with aqueous acetone (1:10, v/v). Yield 38 mg
(76.8%). Electronic absorption spectrum, max, nm
(log ): in DMF: 605 (4.51), 669 (4.90); in chloroform:
607 (4.25), 675 (4.90). Found, %: C 70.99; H 4.19;
N 14.87. C116H84CoN20O4. Calculated, %: C 73.87;
H 4.50; N 14.87.
1
mp 234 236 C. H NMR spectrum, , ppm: 9.29 s
(1H, H1), 9.00 s (1H, H2), 8.25 d (1H, H3, J 8 Hz),
8.00 d (1H, H4, J 8,1 Hz), 7.80 t (1H, H5), 7.60 t (1H,
H6). Found, %: C 57.95; H 2.06; N 28.92. C14H6N6O2.
Calculated, %: C 57.94; H 2.08; N 28.95.
4-(Benzotriazol-1-yl)-5-[4-(1-methyl-1-phenyl-
ethyl)phenoxy]phthalodinitrile (IV). Dimethylform-
amide, 30 ml, compound III, 2.9 g, 4-(1-methyl-1-
phenylethyl)phenol, 2.12 g, and 1.38 g of K2CO3 were
dissolved with stirring in 10 ml of water, and the solu-
tion was allowed to stand for 0.5 h at room tempera-
ture. The precipitate that formed was filtered off,
washed with propan-2-ol (50 ml) and water (100 ml),
Nickel tetra[4-(benzotriazol-1-yl)]-tetra{5-[4-
(1-methyl-1-phenylethyl)phenoxy]}phthalocyanine
(Vc) was prepared from 47 mg of compound IV and
7 mg of nickel acetate and and purified by treatment
with aqueous acetone (1:10, v/v). Yield 11.3 mg
(22%). Electronic absorption spectrum, max, nm
(log ): in DMF: 600 (4.57), 679 (4.91), 760 (4.41);
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 9 2007

NUCLEOPHILIC SUBSTITUTION IN 4-BROMO-5-NITROPHTHALONITRILE: VIII.
1627
in chloroform: 605 (4.46), 676 (4.96), 771 (4.36).
Found, %: C 70.19; H 4.30; N 14.23. C116H84N20
NiO4. Calculated, %: C 74.10; H 4.51; N 13.85.
6. Porfiriny: Spektroskopiya, elektrokhimiya, primenenie
(Porphyrins: Spectroscopy, Electrochemistry, Applica-
tion), Enikopyan, N.S., Ed., Moscow: Nauka, 1987.
7. The Porphyrin Handbook, Kadish, K.M., Smith, K.M.,
Erbium tetra[4-(benzotriazol-1-yl)]-tetra{5-[4-
(1-methyl-1-phenylethyl)phenoxy]}phthalocyanine
(Vd) was prepared from 56.4 mg of compound IV and
14 mg of erbium chloride. Yield 26 mg (48%). Elec-
tronic absorption spectrum, max, nm (log ): in DMF:
621 (4.16), 689 (4.87); in chloroform: 618 (4.21), 688
(4.92). Found, %: C 70.92; H 4.30; N 14.23.
C116H84ErN20O4. Calculated, %: C 68.98; H 4.20; N
13.85.
and Guilard, G., San Diego: Academic, 2003, vol. 16.
8. Zhidkie kristally: diskoticheskie mezogeny (Liquid
Crystals: Discotic Mesogens), Usol’tseva, N.V., Ed.,
Ivanovo: Ivanov. Gos. Univ., 2004.
9. Heterocyclic Compounds, Elderfield, R.C., New York:
Wiley, 1957, vol. 2. Translated under the title Getero-
tsiklicheskie soedineniya, Moscow: Mir, 1965, vol. 2,
p. 408.
ACKNOWLEDGMENTS
10. Gaspard, S. and Tran-Thi, J. Chem. Soc., Perkin
Trans. 2, 1989, no. 5, p. 383.
The work was financially supported by the Mi-
nistry of Education of the Russian Federation (RNP
2.2.1.1.7280) and Russian Foundation for Basic Re-
search (project no. 04-03-32305).
11. Shishkina, O.V., Maizlish, V.E., Shaposhnikov, G.P.,
Lyubimtsev, A.V., Smirnov, R.P., and Baran’ski, A.,
Zh. Obshch. Khim., 1997, vol. 67, no. 5, p. 842.
12. Shaposhnikov, G.P. and Maizlish, V.E., Izv. Vyssh.
Ucheb. Zaved., Khim. Khim. Tekhnol., 2004, vol. 47,
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