Synthesis and properties of 4-acyloxy-5-nitrophthalodinitriles and copper(II) phthalocyanines derived thereof

Article abstract of DOI:10.1023/A:1023300103961

Acylation of 4-hydroxy-5-nitrophthalonitrile gave 4-acetoxy-5-nitro- and 4-benzoyloxy-5-nitro-phthalonitriles. The products were reacted with copper(II) acetate to obtain the corresponding octasubstituted phthalocyanines.

Full text of DOI:10.1023/A:1023300103961

Russian Journal of General Chemistry, Vol. 72, No. 10, 2002, pp. 1633 1635. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 10, 2002,
pp. 1733 1735.
Original Russian Text Copyright
2002 by Balakirev, Maizlish, Shaposhnikov.
Synthesis and Properties of 4-Acyloxy-5-nitrophthalodinitriles
and Copper(II) Phthalocyanines Derived Thereof
A. E. Balakirev, V. E. Maizlish, and G. P. Shaposhnikov
Ivanovo State University of Chemical Engineering, Ivanovo, Russia
Received December 29, 2000
Abstract Acylation of 4-hydroxy-5-nitrophthalonitrile gave 4-acetoxy-5-nitro- and 4-benzoyloxy-5-nitro-
phthalonitriles. The products were reacted with copper(II) acetate to obtain the corresponding octasubstituted
phthalocyanines.
Synthesis and properties of N-(acylamino)-substi-
tuted phthalocyanines (Pc) and their metal complexes
(MPc) have been thoroughly studied [1 7]. Certain
derivatives are readily soluble in organic solvents and
have found application in science and engineering
[2, 3]. At the same time, the information concerning
O-acyl-substituted Pc is very scarce.
respectively) [8]. The spectra of compounds II and
III no longer show bands corresponding to deforma-
tion and stretching vibrations of the OH group of
compound I [8] and acquire a band at 1760 cm
[ (C=O)].
1
Dinitriles II and III were reacted with copper(II)
acetate at 200 210 C to obtain copper phthalocya-
nines IV and V, respectively.
In this connection and in continuation of our
studies on the effect of substituents of the physico-
chemical properties of octasubstituted Pc, we syn-
thesized copper(II) tetra-4-acyloxytetra-5-nitrophthalo-
cyanines. The starting phthalodinitriles were prepared
by the following scheme.
CN
CN
RCO2
O2N
4
II, III
RCO2
NO2
OCOR
CN
CN
CN
CN
HO
RCO2
O2N
RCOX
N
O2N
O2N
N N
I
II, III
Cu(OAc)2
N
Cu
N
R = Me; X = OAc (II); R = Ph; X = Cl (III).
N
N
Compounds I were O-acylated with excess acetic
anhydride and benzoyl chloride at 110 120 C to ob-
tain 4-acetoxy-5-nitro- and 4-benzoyloxy-5-nitro-
phthalonitriles (II, III). After recrystallization from
benzene, the products are yellow powders soluble in
benzene, acetone, chloroform, and DMF and insoluble
in water and aqueous alkalis.
RCO2
O2N
NO2
N
OCOR
IV, V
R = Me (IV), Ph (V).
Compounds II and III were identified by elemental
analysis and IR spectroscopy, as well as by the
melting points.
The resulting complexes were purified by treatment
with acetone.
Compounds IV and V are powder-like dark blue
substances. They are soluble in DMF and DMSO and
insoluble in water, dilute acids and alkalis, benzene,
acetone, and chloroform.
Comparing the IR spectra of the starting and target
phthalonitriles, we can note preservation of the ab-
sorption bands corresponding to stretching vibrations
1
of C N groups [ (CN) 2240 cm ] and antisymmetric
[
as(NO2)] and symmetric [ (NO2)] stretching vibra-
The IR spectra of complexes IV and V contain
s
1
tions of NO2 groups (1544 1536 and 1368 1352 cm , characteristic phthalocyanine absorption bands at
1070-3632/02/7210-1633$27.00 2002 MAIK Nauka/Interperiodica

1634
BALAKIREV et al.
1612 1624, 1505 1524, 1342 1360, 1246 1288,
1170 1188, 1140 1150, 1116 1130, 1080 1092,
1048 1060, 910 950, 850 880, 770 780, and 734
benzene, acetone, chloroform, and DMF. Yield
0.133 g (86%), mp 119 122 C. IR spectrum, cm :
2240, 2200 [ (CN)], 1760 [ (C=O)], 1544 [ as(NO2)],
1352 [ (NO2)]. Found, %: C 61.1; H 2.3; N 14.0.
C15H7N3sO4. Calculated, %: C 61.4; H 2.4; N 14.3.
1
1
736 cm [9, 10] and preserve the NO (1544 1536 and
1
1
1368 1352 cm ) and ester C=O bands (1760 cm ).
Comparing the electronic absorption spectra in
Copper tetra-4-acetoxytetra-5-nitrophthalo-
DMF of copper(II) tetra-4-hydroxytetra-5-nitrophthalo- cyanine (IV). Dinitrile II, 0.59 g, and 0.02 g of cop-
cyanine and compounds IV, V, we note that the long-
wave absorption maximum in the latter two spectra
are shifted bathochromically by 18 nm and, therewith,
the nature of the acyl residue has no effect on the
position of the Q band, which has already been noted
for acyamino-substituted phthalocyanines [4]. The
spectral curves of the complexes are broadened,
implying association of the compounds in DMF.
per(II) acetate were fused in a quartz ampule at 200
210 C for 1 h. The resulting melt was ground, washed
with 3% hydrochloric acid to colorless filtrates and
then with water to neutral, dried at 80 C, and treated
with acetone. Compound I is a dark green powder
soluble in DMF and DMSO and insoluble in water,
aqueous alkalis, benzene, acetone, and chloroform.
1
Yield 0.22 g (36%). IR spectrum, cm : 1612 1624,
1505 1524, 1342 1360, 1246 1288, 1170 1188,
1140 1150, 1116 1130, 1080 1092, 1048 1060,
910 950, 850 880, 770 780, 734 736, 1760 [ (C=O)],
1536 [ as(NO2)], 1368 [ (NO2)]. Electronic absorp-
tion spectrum, , nm: 714s(DMF). Found, %: C 48.2;
H 2.1; N 17.3. C40H20CuN12O16. Calculated, %: C
48.6; H 2.0; N 17.0.
In going from tetraacylaminotetranitro- to tetra-
acyloxytetranitrophthalocyanines,
the
long-wave
absorption band in the electronic absorption spectra
in DMF is shifted bathochromically by 9 nm, which
is explained by the higher electronegativity of oxygen
compared with nitrogen [6].
EXPERIMENTAL
Copper tetra-4-benzoyoxy-5-nitrophthalocya-
nine (V). Nitrile II, 0.74 g, and 0.02 g of copper(II)
acetate were melted at 200 210 C for 1 h. The result-
The IR spectra were obtained on a Specord M-80
spectrophotometer in the range 400 4000 cm 1 in KBr. ing melt was treated as described above. Compound
The electronic absorption spectra were measured in
DMF on a Specord M-40 spectrophotometer at room
temperature in the range 500 900 nm.
V is dark green powder soluble in DMF and DMSO
and insoluble in water and aqueous alkalis, benzene,
acetone, and chloroform. Yield 0.29 g (38%). IR spec-
1
trum, cm : 1612 1624, 1505 1524, 1342 1360,
4-Hydroxy-5-nitrophthalonitrile (I) was prepared
by the procedure in [11].
1246 1288, 1170 1188, 1140 1150, 1116 1130,
1080 1092, 1048 1060, 910 950, 850 880, 770 780,
734 736, 1760 [ (C=O)], 1544 [ as(NO2)], 1352
4-Acetoxy-5-nitrophthalonitrile (II). A mixture
of 0.1 g of dinitrile I, 0.05 g of sodium acetate, and
0.1 ml 0.2 of acetic anhydride was heated to 110 C
for 2 h and then poured into 20 ml of water. The pre-
cipitate that formed was filtered off, washed with
water to neutral, dried at 50 60 C, and recrystallized
from benzene. The product is a yellow powder in-
soluble in water and aqueous alkalis and soluble in
benzene, acetone, chloroform, and DMF. Yield 0.02 g
[ (NO2)]. Electronic absorption spectrum, , nm: 714
s
(DMF). Found, %: C 58.0; H 2.2; N 13.9. C60H28Cu
N12O16. Calculated, %: C 58.3; H 2.3; N 13.6.
ACKNOWLEDGMENTS
The work was financially supported by the Minist-
ry of Education of the Russian Federation in the
framework of the Program for Support of Basic
Natural Science (project no. 97-0-9.4-381).
1
(16%), mp 127 130 C. IR spectrum, cm : 2240
[ (CN)], 1760 [ (C=O)], 1536 [ as(NO2)], 1368
[ (NO2)]. C10H5N3O4. Found, %: C 51.5; H 2.1; N
18.5. Calculated, %: C 51.9; H 2.2; N 18.2.
s
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SYNTHESIS AND PROPERTIES OF 4-ACYLOXY-5-NITROPHTHALODINITRILES
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