Cobalt(II) tetraaminotetranitrophthalocyanine and its N-acyl derivatives

Article abstract of DOI:10.1023/A:1015370001651

The reaction of 4-acylamino-5-nitrophthalocyanines with cobalt(II) chloride was used to prepare for the first time the corresponding cobalt phthalocyanines. Hydrolysis of cobalt(II) tetra-4-acetylamino-tetra-5-nitrophthalocyanine gave cobalt(II) tetra-4-a

Full text of DOI:10.1023/A:1015370001651

Russian Journal of General Chemistry, Vol. 72, No. 1, 2002, pp. 131 132. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 1, 2002,
pp. 140 141.
Original Russian Text Copyright
2002 by Zharnikova, Balakirev, Maizlish, Shaposhnikov.
Cobalt(II) Tetraaminotetranitrophthalocyanine
and Its N-Acyl Derivatives
M. A. Zharnikova, A. E. Balakirev, V. E. Maizlish, and G. P. Shaposhnikov
Ivanovo State University of Chemical Engineering, Ivanovo, Russia
Received March 14, 2000
Abstract The reaction of 4-acylamino-5-nitrophthalocyanines with cobalt(II) chloride was used to prepare
for the first time the corresponding cobalt phthalocyanines. Hydrolysis of cobalt(II) tetra-4-acetylamino-tetra-
5-nitrophthalocyanine gave cobalt(II) tetra-4-aminotetra-5-nitrophthalocyanine. The effect of amino(acyl-
amino) and nitro groups on the properties of the metal complexes, particularly on their electronic absorption
spectra, was demonstrated.
Considerable recent interest has been focused on
octasubstituted metal phthalocyanines. Only a few of
them contained peripheral substituents differing in
electronic nature [1 4]. In partucular, no compounds
have been reported containing in the benzene rings
amino(acylamino) and nitro groups located ortho to
each other.
Complexes I III were reprecipitated from concen-
trated sulfuric acid, washed with organic solvents, and
identified by elemental analysis and vibrational and
electronic spectroscopy.
The IR spectra contain absorption bands characte-
ristic of metal phthalocyanines, as well as bands at
1524 and 1324 [ and (C NO2)] and 1696
1
Earlier we described the synthesis of 4-acylamino-
5-nitrophthalonitriles containing aliphatic or aromatic
acyl residues [5].
1724 cm [ (C=O)].
The presence in the benzene rings of the isoindole
fragments of acylamino groups makes these com-
pound better soluble in DMF than cobalt(II) tetranitro-
and tetraaminophthalocyanines, but still they remain
insoluble in such organic solvents as benzene, acetone,
chloroform, and aliphatic alcohols.
We reacted these compounds with cobalt(II) chlo-
ride at 185 190 C to obtain cobalt 4-acetylamino-
tetra-5-nitrophthalocyanines (I), cobalt tetra-4-cap-
ryloylaminotetra-5-nitrophthalocyanines (II), and
cobalt tetra-4-benzoylaminotetra-5-nitrophthalo-
cyanines (III).
The electronic absorption spectra of cobalt(II) tetra-
4-acylaminotetra-5-nitrophthalocyanines in DMF
characteristically show a hypsochromic shift of the
long-wave band compared with cobalt tetra-4-amino-
phthalocyanine (IV), which is explained by the fact
that the acylamino group has a much weaker electron
donor than the primary amino group; at the same time,
compared with cobalt tetra-4-nitrophthalocyanine, an
inconsiderable bathochromic shift is observed, pro-
duced by the effect of the weakly electron-donor acyl-
amino group on the -electron system of the molecule
(see table). The long-wave band in the electronic
absorption spectra in concentrated sulfuric acid is
hypsochromically shifted by 30 nm compared with
compounds IV and V (see table).
CN
CN
RCONH
O2N
4
NO2
RCONH
O2N
NHCOR
N
N
N
N
CoCl2
Co
N
N
N
N
RCONH
NO2
NHCOR
When heated in 7% aqueous sodium hydroxide on
a boiling water bath, cobalt phthalocyanine I un-
dergoes hydrolysis by acetylmino groups to give
cobalt tetra-4-amino-tetra-5-nitrophthalocyanine (VI).
The hydrolysis progress was followed by spectrophoto-
O2N
I III
R = CH3 (I), C7H15 (II), C6H5 (III).
1070-3632/02/7201-0131$27.00 2002 MAIK Nauka/Interperiodica

132
ZHARNIKOVA et al.
Long-wave absorption bands in the electronic absorption
spectra of substituted cobalt(II) phthalocyanines, max, nm
Cobalt tetra-4-acetylaminotetra-5-nitrophtha-
locyanine (I), yield 0.8 g (78%). Found, %: C 48.5;
H 2.3; Co 5.8; N 23.3. C40H24CoN16O12. Calculated,
%: C 49.0; H 2.5; Co 6.0; N 22.9.
Comp. no.
DMF
H2SO4
Cobalt tetra-4-capryloylaminotetra-5-nitro-
phthalocyanine (II), yield 0.2 g (65%). Found, %: C
57.9; H 5.2; Co 4.3; N 16.8. C64H72CoN16O12. Cal-
culated, %: C 58.4; H 5.5; Co 4.5; N 17.0.
I
II
III
IV
V
705
700
706
730 [6]
684 [6]
766
725
725
725
755 [6]
755 [6]
722
Cobalt tetra-4-benzoylaminotetra-5-nitro-
phthalocyanine (III), yield 0.14 g (67%). Found, %:
C 58.1; H 2.4; Co 5.1; N 17.8. C60H32CoN16O12.
Calculated, %: C 58.7; H 2.6; Co 4.8; N 18.2.
VI
metry, making use of the difference in the electronic
absorption spectra of compounds I and VI.
Cobalt tetra-4-aminotetra-5-nitrophthalo-
cyanine (VI). A suspension of 0.25 g of compound I
in 10 ml of 7% aqueous sodium hydroxide on a boil-
ing water bath for 6 h, the precipitate was filtered off,
washed with water, and dried at 60 C, yield 0.15 g
(72%). Found, %: C 47.0; H 1.8; Co 7.1; N 27.2.
C32H16CoN16O8. Calculated, %: C 47.4; H 2.0; Co
7.3; N 27.6.
The elemental analysis of compound VI is con-
sistent with calculation. The IR spectra preserve ab-
sorption of the C NO2 bond, while the C=O absorp-
tion band disappears. Compound VI is worth soluble
in DMF and DMSO compared with the parent com-
pound I.
The electronic absorption spectrum of compound
VI in DMF is characterized by a strong bathochromic
shift of the long-wave maximum (by 36 and 82 nm
compared to compounds IV and V, respectively),
associated with the electron-donor effect of the amino
group and the electron-acceptor effect of the nitro
group. Moreover, as would be expected, the Q band
of nitro derivative VI is bathochromically shifted
compared with compound I. The spectra of compounds
I and VI in concentrated sulfuric acid are quite similar
ACKNOWLEDGMENTS
The work was financially supported by the
Program for Support of Basic Natural Science of the
Ministry of Education of the Russian Federation
(project no. 97-0-9.4-381).
REFERENCES
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to each other [
725 (I) and 722 nm (VI)].
max
EXPERIMENTAL
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The IR spectra were registered on a Specord M-80
1
spectrophotometer in KBr in the range 400 4000 cm .
3. Mikhalenko, S.A., Surovtseva, A.P., and Luk’ya-
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in DMF and concentrated sulfuric acid on a Specord
M-40 spectrophotometer at room temperature in the
range 500 900 nm.
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Cobalt tetra-4-acylaminotetra-5-nitrophthalo-
cyanines I III. A mixture of 4 mmol of 4-acylamino-
5-nitrophthalocyanine and 1 mmol of cobalt(II) chlo-
ride was heated at 185 190 C for 1 h until a solid
melt formed. It was cooled, washed with dilute hydro-
chloric acid, water, and acetone, reprecipitated from
concentrated sulfuric acid, and dried at 100 C.
6. Elektronnye spektry pogloshcheniya phthalocyaninov i
rodstvennykh soedinenii: Katalog (Electronic Absorp-
tion Spectra of Phthalocyanines and Related Com-
pounds: Catalog), Luk’yanets, E.A., Ed., Cherkassy:
NIITEKhim, 1989.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 1 2002