Nucleophilic substitution in 4-bromo-5-nitrophthalodinitrile: X. Synthesis of 4-(1-benzotriazolyl)-5-(1(2)-naphthyloxy)-phthalodinitriles and related phthalocyanines

Article abstract of DOI:10.1134/S107036320908026X

4-(1-Benzotriazolyl)-5-[1(2)-naphthyloxy]phthalodinitriles were obtained by nucleophilic substitution of bromine and nitro group in 4-bromo-5- nitrophthalodinitrile. These compounds were used for the synthesis of the corresponding octa-substituted phthalo

Full text of DOI:10.1134/S107036320908026X

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 8, pp. 1735–1740. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © S.A. Znoiko, A.S. Kambolova, V.E. Maizlish, G.P. Shaposhnikov, I.G. Abramov, S.I. Filimonov, 2009, published in Zhurnal
Obshchei Khimii, 2009, Vol. 79, No. 8, pp. 1376–1381.
Nucleophilic Substitution in 4-Bromo-5-nitrophthalodinitrile:
1
X. Synthesis of 4-(1-Benzotriazolyl)-5-(1(2)-naphthyloxy)-
phthalodinitriles and Related Phthalocyanines
a
a
a
S. A. Znoiko , A. S. Kambolova , V. E. Maizlish ,
a
b
b
G. P. Shaposhnikov , I. G. Abramov , and S. I. Filimonov
a
Ivanovo State Chemical Technological University
pr. F. Engel’sa 7, Ivanovo, 153000 Russia
e-mail: ttoc@isuct.ru
b
Yaroslavl’ State Technical University
Moskovskii pr. 88, Yaroslavl’, 150023 Russia
e-mail: abramovig@ ystu.ru
Received December 30, 2008
Abstract—4-(1-Benzotriazolyl)-5-[1(2)-naphthyloxy]phthalodinitriles were obtained by nucleophilic
substitution of bromine and nitro group in 4-bromo-5-nitrophthalodinitrile. These compounds were used for the
synthesis of the corresponding octa-substituted phthalocyanines. Spectral data of the compounds obtained were
examined.
DOI: 10.1134/S107036320908026X
Phthalocyanines and related compounds for a long
time have been used as high-grade organic dyes and
pigments [2] and catalysts for various processes [3].
There are some approaches to their practical use as
photosensitizers for tumor photodynamic therapy [4],
mesomorphic materials [5], photoconverters [6] and in
others branches of science and technology [7].
benzotriazole fragment protons (positions 3, 4, 5 and
6) respectively. Signals of 1-naphthol protons are
registered as a triplet at 8.17 ppm (position 13),
multiplets at 7.28 (position 7), 7.04 (position 8), 7.45
(position 9), 8.43 (position 10) and a doublet at
7.55 ppm (positions 11, 12).
Signals location for benzotriazole and phthalo-
dinitrile aromatic protons in the spectrum of 4-(1-
benzotriazolyl)-5-(2-naphthyloxy)phthaloditrile IVb do
not sufficiently change in comparison with the
spectrum of 4-(1-benzotriazolyl)-5-(1-naphthyloxy)
phthalodintrile IVa. 2-Naphthol fragment protons give
a triplet signal at 7.33 ppm (position 13), multiplets at
This report deals with synthesis and study of
physicochemical properties of 4-(1-benzotriazolyl)-5-
[1(2)-naphthyloxy]phthalodinitriles and phthalocyanines
based on them.
In the first stage we synthesized the target phthalo-
dintriles IVa and IVb using the known procedure [8,
7
9
7
.16 (position 7), 7.67 (position 8), 7.68 ppm (position
) and 7.45 ppm (position 10) and a doublet at
.87 ppm (positions 11, 12).
9
], by successive nucleophilic aromatic substitution of
the bromine atom and nitro group in 4-bromo-5-
nitrophthaloditrile I.
1
In the IR spectra of IVa and IVb an absorption
The compounds obtained were identified using H,
–
1
band at 2231 cm was observed belonging to CºN
bond vibrations [10]. Absorption bands in the range of
IR spectroscopy and elemental analysis data.
1
In the H NMR spectrum of phthalodinitrile IVa
–
1
1
200–1210 cm are characteristic of Ar–O–Ar bonds
there are signals at 8.73 and 8.14 ppm belonging to
aromatic protons (positions 1 and 2) of phthalodintrile
and in the region of 8.23, 7.81, 7.55 and 8.08 ppm, to
–1
vibrations, at 1040–1050 and 470–475 cm , of
benzotriazole C–N and N=N bonds [11].
Compounds Va–VIa free of metal were prepared
by heating of the corresponding phthalodintriles at
1
For communication IX, see [1].
1735

1
736
ZNOIKO et al.
NH2
NH2
NH
N
N
NC
NC
Br
NC
NC
NC
NC
N
NH2
NaNO2
NO2
NO2
NO2
I
II
III
O
O
5
6
5
6
4
4
N
N
3
2
N
N
3
2
NC
NC
N
NC
NC
N
O
O
1
7
8
1
3
1
9
7
8
12
11
1
3
10
1
2
11
9
10
IVb
IVa
N
N
R
N
N
N
N
N
N
R
R
N
N
i, ii
IVa, IVb
N
M
N
N
N
N
N
N
N
R
N
N
_
_
_
Va Vc VIa VIc
(
i) T = 220°C, urea; (ii) T = 200–210°C, M(OAc)
2 2
·nH O; M = HH (a), Cu (b, n = 1), Ni (c, n = 6); R = 1-naphthol (V), 2-
naphthol (VI).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009

NUCLEOPHILIC SUBSTITUTION IN 4-BROMO-5-NITROPHTHALODINITRILE: X.
1737
2
20ºС for 2 h in the presence of urea (i), since in the
D
absence of the latter reaction proceeds at high
temperature and the target products yields are
approximately three times lower. We emphasize that
the unsubstituted phthalodintrile does not form
phthalocyanine macrocycle under the conditions
mentioned above. Probably, in this case positive result
can be ascribed to the presence of basic benzotriazolyl
groups in the initial precursor molecules. An indirect
confirmation of the validity of this assumption is the
fact that the unsubstituted phthalocyanine was obtained
on the yield over than 50% by heating a mixture of
unsubstituted phthalodintrile with urea in the presence
of 1-benzotriazole in the molar ratio 4:1
1.6
1
.4
1
1.2
1
0
0
0
.0
.8
.6
.4
2
0.2
0
4
00
500
600
700
800
(
phthalodintrile:benzotriazole). However more detailed
λ, nm
investigation is necessary for ascertaining the cause of
this phenomenon.
Fig. 1. Electronic spectra of tetra-4-(1-benzotriazolyl)-
tetra-5-(2-naphthyloxy)phthalocyanine: (1) in DMF (2.20×
Metal complexes Vb, Vc, VIb and VIc were
synthesized by the nitrile method (ii) by reaction of
phthalodintriles IVa–IVb with the corresponding
metal acetates.
–5
–1
–5
–1
1
0 mol l ) and (2) in chloroform (2.12×10 mol l ).
In the electronic spectra (CDCl ) of not metal-
3
containing compounds we observed two intensive
long-wave absorption bands in the region of 671–672
and 707–709 nm that are characteristic of phthalo-
cyanine ligands [7] (Fig. 1).
After the reaction completing, the products were
carefully ground, washed with 5% hydrochloric acid
and then with water to neutral pH, dried at 80°С, and
extracted with chloroform. The final purification was
In DMF, a simplification of the electron spectrum is
observed, which is characterized by the presence of a
single Q-band at 683–684 nm in place of two long-
wave bands. This indicates that phthalocyanine
dianionic form with molecular symmetry D4h is
produced in the medium of basic solvent [13].
carried out by column chromatography using Al O as
2
3
a sorbent and chloroform as an eluent.
The compounds obtained were identified by the
1
data of elemental analysis, H NMR, vibration and
electronic spectroscopy.
Analyzing the electronic spectra of tetra-4-(1-
benzotriazolyl)-tetra-5-(1(2)-naphthyloxy)phthalocyanines
metal complexes Vb, VIc–VIb, VIc (Fig. 2), we
emphasize that in such organic solvents as DMF,
chloroform, and carbon tetrachloride all the com-
pounds are in the non-associated forms. The solvent
nature effects on the first band location appears as a
red shift of the first absorption band by 4–5 nm when
DMF is replaced by chloroform.
1
In the H NMR spectrum of tetra-4-(1-benzo-
triazolyl)-tetra-5-(2-naphthyloxy)phthalocyanine VIa
there is a signal of transannular imino groups protons
at –1.80 ppm, which is absent in the spectrum of
compound VIc. The signals location in the spectra of
benzotriazolyl-substituted phthalocyanines as a whole
practically coincided with the described above
spectrum of the initial phthalodintrile.
The red shift of Q-band by 5–6 nm is also observed
in passing from nickel complexes to copper phthalo-
cyanines.
In the IR spectra of the synthesized compounds the
absorption bands remained belonging to substituents
bond vibrations and to those registered in the spectrum
of the corresponding phthalodinitriles. In the spectra of
metal-free phthalocyanines there are absorption bands
At the comparative analysis of the electronic
spectra for metal complexes Vb, Vc–VIb, VIc and the
corresponding tetra-4-(1-benzotriazolyl)metalphthalo-
cyanines in organic solvents we noted that incur-
poration of 1- or 2-naphthol residue into ortho-position
relative to 1-benzotriazole fragment causes a red shift
of Q-band by 5 nm.
–
1
in the region of 1012–1014 cm characteristic for
–
1
phthalocyanine ligands. Absorption at 3290–3340 cm
originates from NH-bonds vibra-tion of transannular
imino groups [12] and is absent in the spectra of metal
complexes.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009

1
738
ZNOIKO et al.
D
1
1
0
0
0
0
0
.2
D
.0
.8
.6
.4
.2
2
1
1
2
4
00
500
600
700
800
λ, nm
3
) of: (1) copper 1-tetra-4-
4
00
500
600
700
800
λ, nm
Fig. 2. Electronic spectra (CDCl
(
(
1-benzotriazolyl)-tetra-5-(2-naphthyloxy)phthalocyanine
1.12×10 mol l ) and (2) nickel tetra-4-(1-benzo-
Fig. 3. Electronic spectra of water-soluble product obtained
by sulfonation of copper tetra-4-(1-benzotriazolyl)-tetra-5-
(2-naphthyloxy)phthalocyanine, (1) in water and (2) in
DMF.
–5
–1
triazolyl)-tetra-5-(2-naphthyloxy)phthalocyanine
(
–5
–1
1.50×10 mol l ).
Furthermore, in the electronic spectra of copper and
of the process mentioned above, a mixture of
sulfonation products is formed, containing various
number of sulfo groups, on the average 4–6 per
molecule of the corresponding metal phthalocyanine.
We failed to separate this mixture.
nickel complexes the additional absorption band in the
long-wave region (765–775 nm) is observed. It is
relatively weak in the case of copper phthalocyanines
and more intensive in the case of nickel complexes
(
Fig. 2). This absorption band is absent in the spectra
On studying the color properties of all the
compounds obtained their ability was found to colorize
waxes, fats, and polymeric materials into bright rich
colors [9].
of metal-free compounds and it is its nature currently
difficult to interpret.
On dissolving all the metal complexes in
concentrated sulfuric acid followed by pouring into
water we obtain products of dark green color, which
lose the solubility in chloroform and others organic
solvents except for DMF and acquire a solubility in
water-base media. In DMF, the location and shape of
absorption bands in the electron spectra are practically
similar to the spectra of initial metal complexes. In
visible region of spectrum of the water-based solutions
two diffusion absorption bands are observed, the
location and ratio of intensities of which depend on the
phthalocyanine concentration in the solution (Fig. 3).
This shows according to the published data that the
compounds obtained are in associated forms in the
water-base solutions [14].
EXPERIMENTAL
The electron spectra were recorded on a HITACHI
U-2001 spectrophotometer in DMF and chloroform at
room temperature in the range of 325–900 nm. The IR
spectra were registered on an Avatar 360 FT-IR ESP
–
1
device in the range of 400–4000 cm from films
1
(
chloroform) and pellets (KBr). The H NMR spectra
of phthalodinitriles were taken on a Bruker DRX-500
1
device in DMSO-d relative to internal TMS; the H
6
NMR spectra of benzotriazolyl-substituted phthalo-
cyanines were recorded on a Bruker AMD-200 device
In the IR spectra there are absorption bands in the
in CDCl . Elemental analysis was accomplished on a
CHNS-O FlashEA (1112 series) elemental analyser.
3
–
1
region of 1190–1200 cm belonging to sulfo groups
11]. This suggests that tetra-4-(1-benzotriazlyl)tetra-
-(naphthyloxy)phthalocyanines sulfonic acids are
formed. By the elemental analysis data, in the course
[
5
4-Bromo-5-nitrophthalonitrile (I) was obtained
by the known procedure [15].
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009

NUCLEOPHILIC SUBSTITUTION IN 4-BROMO-5-NITROPHTHALODINITRILE: X.
1739
4
-(2-Aminophenylamino)-5-nitrophthalodinitrile
II) was prepared from 4-bromo-5-nitrophthalodinitrile
I by the known procedure [16].
Yield 91.1 mg (91%). Found, %: С 74.00, H 4.63, N
17.71. С H N O . Calculated, %: С 74.30, H 4.51, N
18.10. Electron spectrum, λmax, nm (log ε): in
(
96
54 20
4
chloroform 708 (4.92), 673 (4.90); in DMFA 681
4
-(1-Benzotriazolyl)-5-nitrophthalodinitrile (III)
1
2
(
8
4.89). H, NMR spectrum, δ, ppm: 8.70 s (4H, H ),
was prepared from compound II by procedure [16].
1
3
4
.13 s (4H, H ), 8.05 s (4H, H ), 7.90 s (4H, H ), 7.57 t
5
7–13
4-(1-Benzotriazolyl)-5-(1(2)-naphthyloxy)phthalodi-
(4H, H ), 7.57–7.20 m (32H, H ), –1.80 s (2H, NH).
nitriles (IVa, IVb) were prepared by procedure [9].
General procedure of synthesis of tetra-4-(1-
benzotriazolyl)-tetra-5-(naphthyloxy)phthalocyanines
metal complexes. A mixture of 50 mg (0.12 mmol) of
phthalodinitriles IVa, IVb and 0.03 mmol of the cor-
responding metal acetate was heated to 200–220°С and
kept at this temperature for 1–1.5 h. The phthalo-
cyanines obtained were ground, washed with 5%
hydrochloric acid solution and with water to pH = 7
and dried at 80°С . The target products were extracted
with chloroform and purified by column chromato-
Compound obtained are pale yellow needles,
insoluble in water, well soluble in DMF, chloroform,
acetone and benzene.
4-(1-Benzotriazolyl)-5-(1-naphthyloxy)phthalodi-
nitrile (IVa). Yield 86%, mp 210–212°С. Found, %: C
7
7
8
7.10, H 4.72, N 15.40. С H N O Calculated, %: C
24 13 5 .
1
6.47, H 4.65, N 15.37. H NMR spectrum, δ, ppm:
2
3
1
.73 s (1H, H ), 8.23 d (1H, H ), 8.14 s (1H, H ), 7.81
4
5
6
d (1H, H ), 7.55 t (1H, H ), 8.08 t (1H, H ), 7.28 m
7
8
9
graphy using Al
2
O
3
and chloroform as eluent.
(
(
1H, H ), 7.04 m (1H, H ), 7.45 m (1H, H ), 8.43 m
1H, H ), 7.55 d (2H, H ), 8.15 t (1H, H ).
10
11,12
13
Copper
tetra-4-(1-benzotriazolyl)-tetra-5-(1-
naphthyloxy)phthalocyanine (Vb) was prepared
from 4-(1-benzotriazolyl)-5-(1-naphthyloxy)phthalodi-
ntrile IVa and 6 mg of copper acetate. Yield 31.0 mg
4
-(1-Benzotriazolyl)-5-(2-naphthyloxy)phthalodi-
nitrile (IVb). Yield 87%, mp 209–212°С . Found, %:
C 76.49, H 4.64, N 15.14. С H N O. Calculated, %:
C 76.47, H 4.65, N 15.37. H NMR spectrum, δ, ppm:
.73 s (1H, H ), 8.23 d (1H, H ), 8.16 s (1H, H ), 7.81
d (1H, H ), 7.55 t (1H, H ), 8.08 t (1H, H ), 7.16 m
1H, H ), 7.67 m (1H, H ), 7.68 m (1H, H ), 7.45 m
1H, H ), 7.87 d (2H, H ), 7.33 t (1H, H ).
2
4
13
5
(
66%). Found, %: С 71.11, H 3.33, N 17.52.
1
С H N O Cu. Calculated, %: С 71.49; H 3.28; N
2
3
1
96 52 20
4
8
1
6
7.38. Electron spectra, λmax, nm (log ε): in chloroform
88 (4.93); in DMFA 684 (4.86)
4
5
6
7
8
9
(
(
10
11,12
13
Copper tetra-4-(1-benzotriazolyl)-tetra-5-(2-naph-
thyloxy)phthalocyanine (VIb) was prepared from 4-
General procedure of synthesis of tetra-4-(1-
(1-benzotriazolyl)-5-(2-naphthyloxy)phthaloditrile IVb
benzotriazolyl)-tetra-5-(naphthyloxy)phthalocyanine
ligands (Va, VIa). 100 mg (0.24 mmol) of the
corresponding phthalonitriles was heated to 220°С for
and 6 mg of copper acetamide. Yield 34.2 mg (71%).
Found, %: С 70.01, H 3.37, N 17.95. С H N O Cu.
9
6
52 20
4
Calculated, %: С 71.49; H 3.28; N 17.38. Electron
spectra, λmax, nm (log ε): in chloroform 688 (4.97);
DMFA 684 (4.90).
2
h in the presence of 5 mg of urea. Purification of the
target products was carried out by extraction with
chloroform and then by column chromatography using
Al O and chloroform as eluent. The product was dried
Nickel tetra-4-(1-benzotriazolyl)-tetra-5-(1-naph-
thyloxy)phthalocyanine (Vc) was prepared from 4-(1-
benzotriazolyl)-5-(1-naphthyloxy)phthalodintrile IVa
and 8.5 mg of nickel acetate. Yield 12.3 mg (25%).
Found, %: С 73.22, H 3.77, N 18.05. С H N O Ni.
2
3
in a vacuum at 70ºС. The compounds obtained are
powders of bright green color insoluble in water and
well soluble in organic solvents.
96
52 20
4
Tetra-4-(1-benzotriazolyl)-tetra-5-(1-naphthyloxy)-
phthalocyanine (Va) was prepared from 4-(1-benzo-
triazolyl)tetra-5-(1-naphthyloxy)phthalodinitrile (IVa).
Yield 89.6 mg (90%). Found, %: С 73.71, H 4.80, N
Calculated, %: С 71.71; H 3.33; N 17.53. Electron
spectra, λmax, nm (log ε ): in chloroform 681 (4.80),
7
81 (4.36); in DMFA 681(4.83), 766 (4.27).
Nickel tetra-4-(1-benzotriazolyl)-tetra-5-(2-naph-
thyloxy)phthalocyanine (VIc) was prepared from 4-
1
7.86. С H N O Calculated, %: С 74.30, H 4.51, N
96 54 20 4.
1
8.10. Electron spectrum, λmax, nm (log ε): in chloro-
(1-benzotriazolyl)-5-(2-naphthyloxy)phthalodintrile IVb
form 707 (4.90), 673 (4.88); in DMFA 681 (4.82).
and 8.5 mg of nickel acetate. Yield 14.3 mg (29%).
Tetra-4-(1-benzotriazolyl)-tetra-5-(2-naphthyloxy)-
phthalocyanine (VIa) was prepared from 4-(1-benzo-
triazolyl)tetra-5-(2-naphthyloxy)-phthalodinitrile (IVb).
Found, %: С 71.78; H 4.08; N 17.80. С H N O Ni.
Calculated, %: С 73.22, H 3.77, N 18.05. Electron
spectrum, λmax, nm (log ε ): in chloroform 682 (4.86),
9
6
52 20
4
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009

1
740
ZNOIKO et al.
1
7
60 (4.37); in DMFA 678 (4.80), 776 (4.20). H NMR
i
ftalotsianina (Porphirin and Phthalocyanine
2
3
Coordination Compounds), Moscow: Nauka, 1978,
p. 280.
spectrum, δ, ppm: 8.73 s (4H, H ), 8.20 d (4H, H ),
.13 d (4H, H ), 7.83 s (4H, H , J 7.9 Hz), 7.56 s (4H,
H ), 8.05 d (4H, H ), 7.20 d (4H, H ), 7.60 s (4H, H ),
.62 s (4H, H ), 7.45 m (4H, H ), 7.90 s (8H, H ),
1
4
8
5
6
7
8
8. Abramov, I.G., Smirnov, A.V., and Plakhtinskii, V.V.,
9
10
11,12
Panorama sovremennoi khimii Rossii. Uspekhi
neftekhimicheskom sinteze polifunktsional’nykh
aromaticheskikh soedinenii (Panorama of Contemporary
Chemistry of Russia. Progress in Petrochemical
Synthesis of Polyfunctional Aromatic Compounds),
Moscow: Khimiya, 2005, p. 85.
v
7
7
13
.37 s (4H, H ).
ACKNOWLEDGMENTS
This work was financially supported by the Russian
Federation Ministry of Education and Sciences (RNP
.2.1.1.7280 and 2.1.1.1180).
9
. Znoiko, S.A., Maizlish, V.E., Shaposhnikov, G.P.,
Abramov, I.G., and Lyskov, V.B., RF Patent no.
2
2
327720 2006144983; appl. 18.12.06; publ. 27.06.2008;
Byull. Izobret., no. 18.
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