7
56
ZNOIKO et al.
synthesized from 127 mg of phthalonitrile 5а. Yield
4
-[(4,5-Dicyano-2-nitrophenyl)sulfanyl]benzoic
–
1
acid (3) was synthesized as described in [10]. Yield
7
1
63 mg (49%). IR spectrum, ν, сm : 1709 (C=O), 1246
–
1
8%. IR spectrum, ν, сm : 2232 (C≡N), 1725 (C=O),
550 [ν (NO )], 1383 [ν (NO )], 1117 (Ar–S–Ar).
(Ar–O–Ar), 1052 (N=N), 744 (C–N). Mass spectrum,
+
m/z: 1585.38 [M + Н] ; calculated М 1584.61. Found,
as
2
s
2
–
Mass spectrum, m/z: 324.71 [M – Н] . Found, %: C
%: C 64.05; H 3.05; N 17.53. C H N O Со.
8
4
47 20 12
5
5
5.25; H 2.02; N 13.00. C H N O S. Calculated, %: C
Calculated, %: C 63.68; H 2.8; N 17.68.
15
7
3
4
5.38; H 2.17; N 12.92. М 325.65.
-(1H-Benzotriazol-1-yl)-5-[(4-carboxyphenyl)-
oxy/sulfanyl]phthalonitriles. а. A solution of 0.68 g
5 mmol) of anhydrous KCO in 4 mL of water was
Cobalt tetra-1-(1H-benzotriazol-1-yl)tetra-5-[(4-
carboxyphenyl)sulfanyl]phthalocyanine (6b) was
synthesized from 131 mg of phthalonitrile 5b. Yield
4
–
1
(
72 mg (52%). IR spectrum, ν, сm : 1711 (C=O), 971
(Ar–S–Ar), 1047 (N=N), 745 (C–N). Found, %: C
63.85; H 3.11; N 17.02; S 7.66. C H N O S Со.
3
added to a mixture of 0.5 mmol of compound 2 and
.06 g (0.5 mmol) of 1H-benzotriazole в 25 mL of
0
84
44 20
8 4
DMF. The reaction mixture was stirred at 70°С for 1 h.
The precipitate that formed was filtered off, washed
with 5% aqueous HCl, and dried.
Calculated, %: C 61.09; H 2.87; N 16.96; S 7.76.
ACKNOWLEDGMENTS
b. A solution of 0.07 g (0.5 mmol) of anhydrous
The work was performed under the State contract
with the Ministry of Education and Science of the
Russian Federation (no. 4.1929.2017.4.6) and with
partial financial support of the President of the Russian
Federation (project no. MK-161.2017.3), using the
equipment of the Center for Collective Use, Ivanovo
State University of Chemical Technology.
KCO in 4 mL of water was added to a mixture of 0.15 g
3
(
0.5 mmol) of 4-(1H-benzotriazol-1-yl)-5-nitrophthalo-
nitrile and 0.5 mmol of the corresponding benzoic acid
in 25 mL of DMF. The reaction mixture was stirred at
5°С for 0.5 H. The resulting precipitate was filtered
off, washed with 5% aqueous HCl, and dried.
2
4
-[2-(1H-Benzotriazol-1-yl)-4,5-dicyano-2-phenoxy)]-
benzoic acid (5а). Yield 0.07 g (38%, route a), 0.16 g
83%, route b). IR spectrum, ν, сm : 2227 (C≡N),
714 (C=O), 1245 (Ar–O–Ar), 1050 (N=N), 744 (C–N).
Mass spectrum, m/z: 383.37 [M + 2Н] . Found, %: C
5.95; H 3.02; N 18.30. C H N O . Calculated, %: C
REFERENCES
–
1
(
1
1
. Znoiko, S.A., Golovashova, E.S., Potekhina, O.V.,
Berezin, D.B., Serova, M.A., Maizlish, V.E., and
Shaposhnikov, G.P., Russ. J. Gen. Chem., 2017, vol. 87,
no. 7, p. 1562. doi 10.1134/S1070363217070209
. Shaposhnikov, G.P., Kulinich, V.P., and Maizlish, V.E.,
Modifitsirovannye ftalotsianiny
+
6
6
21 11 5 3
6.14; H 2.91; N 18.36. М 381.66.
-[2-(1H-Benzotriazol-1-yl)-4,5-dicyano-2-phenyl-
2
4
i
ikh strukturnye
sulfanyl)]benzoic acid (5b). Yield 0.01 g (5%, route
a), 0.17 g (85%, route b). Found, %: C 63.35; H 3.00;
N 17.56. C H N O S. Calculated, %: C 63.47; H
analogi (Modified Phthalocyanines and Their Structural
Analogs), Koifman, O.I., Ed., Moscow: KRASAND,
2
012.
21
11
5
2
3
4
. Choi, Ch.-F., Tsang, P.-T., Huang, J.-D., Cha, E.Y.M.,
Ko, W.-H., Fong, W.-P., and Ng, D.K.P., Chem.
Commun., 2004, p. 2236. doi 10.1039/B405868B
. Kimura, M., Nakada, K., Yamaguchi, Y., Hanabusa, K.,
Shirai, H., and Kobayashi, N., Chem. Commun., 1997,
no. 13, p. 1215. doi 10.1039/A701263B
5. Ikeuchi, T., Nomoto, H., Masaki, N., Griffith, M.J.,
Mori, Sh., and Kimura, M., Chem. Commun., 2014,
vol. 50, p. 1941. doi 10.1039/C3CC47714B
6. Kudrik, E.V., Maizlish, V.E., Tararykina, T.V., Shaposh-
nikov, G.P., Smirnova, A.I., and Usol’tseva, N.V., Russ.
Chem. Bull., 2006, vol. 55, no. 6, p. 1028. doi 10.1007/
s11172-006-0372-2
2
.79; N 17.62.
Octasubstituted cobalt phthalocyanines. Urea,
0 mg (1 mmol), was added to thoroughly mixed
.33 mmol of the corresponding substituted phthalo-
6
0
nitrile and 54 mg (0.20 mmol) of cobal chloride hexa-
hydrate, and the mixture was triturated, placed into a
molybdenum glass tube, and heated at 190–195°С
until solidified. After cooling, the resulting solid was
thoroughly triturated, successively washed with 5%
aqueous HCl and acetone, and subjected to column
chromatography on Silica gel (eluent DMF). The
solvent was removed by distillation, and the residue
was dried at 80–90°С.
7
. Vashurin, A., Maizlish ,V., Kuzmin, I., Znoyko, S.,
Morozova, A., Razumov, M., and Koifman, O.,
J. Porphyrins Phthalocyanines, 2017, vol. 21, no. 1,
p. 37. doi 10.1142/S108842461750002X
Cobalt tetra-1-(1H-benzotriazol-1-yl)tetra-5-[(4-
carboxyphenyl)oxy]phthalocyanine (6а) was
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 4 2018