Nucleophilic Substitution in 4-Bromo-5-nitrophthalodinitrile: VII. Synthesis and Properties of Phenylthio-substituted Phthalocyanine Metal Complexes

Article abstract of DOI:10.1023/A:1024760525889

New phenylthio-substituted phthalodinitriles have been synthesized: 5-amino-4-phenylthio-, 5-acetylamino-4-phenylthio-, 5-octanoylamino-4- phenylthio-, 5-phenoxy-4-phenylthio-, 5-(4-carboxyphenoxy)-4-phenylthio-, 5-(4-tert-butylphenoxy)-4-phenylthio-, and 4,5-bis(phenylthio)phthalodinitriles. Their complexes with metals have been prepared and examined by spectral methods.

Full text of DOI:10.1023/A:1024760525889

Russian Journal of General Chemistry, Vol. 73, No. 2, 2003, pp. 292 296. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 2, 2003,
pp. 314 318.
Original Russian Text Copyright
2003 by Balakireva, Maizlish, Shaposhnikov.
Nucleophilic Substitution in 4-Bromo-5-nitrophthalodinitrile:
VII.1 Synthesis and Properties of Phenylthio-substituted
Phthalocyanine Metal Complexes
O. V. Balakireva, V. E. Maizlish, and G. P. Shaposhnikov
Ivanovo State University of Chemistry Technology, Ivanovo, Russia
Received March 11, 2001
Abstract New phenylthio-substituted phthalodinitriles have been synthesized: 5-amino-4-phenylthio-,
5-acetylamino-4-phenylthio-,
5-octanoylamino-4-phenylthio-,
5-phenoxy-4-phenylthio-,
5-(4-carboxy-
phenoxy)-4-phenylthio-, 5-(4-tert-butylphenoxy)-4-phenylthio-, and 4,5-bis(phenylthio)phthalodinitriles. Their
complexes with metals have been prepared and examined by spectral methods.
Among substituted phthalocyanines, those having
phenylthio groups attract certain interest. Such com-
pounds can be used in various fields of science and
technics, specifically as catalysts for homogeneous
reactions [2]. Most data on phenylthio-substituted
phthalocyanines are related to tetrakis- and hexadeca-
kis(phenylthio) derivatives [2, 3]. We previously
reported on the synthesis of tetra(5-nitro-4-phenyl-
thio)phthalocyanines [4]. In continuation of these
studies, we have synthesized other phenylthio-sub-
stituted phthalocyanines with the goal of extending
the series of available synthetic models for examining
the effect of substituent in the ortho position with
respect to the phenylthio group on their physico-
chemical properties. The synthesis of the desired
products required the corresponding phthalodinitriles
to be available; therefore, the first step of our study
included preparation of disubstituted phthalodinitriles,
namely, 5-amino-4-phenylthio- (IV), 5-acetylamino-4-
phenylthio- (V), 5-octanoylamino-4-phenylthio- (VI),
5-phenoxy-4-phenylthio- (VII), 5-(4-carboxy)phen-
oxy-4-phenylthio- (VIII), 5-(4-tert-butyl)phenoxy-
4-phenylthio- (IX), and 4,5-bis(phenylthio)phthalodi-
nitrile (X). As starting compounds we used 5-nitro-4-
phenylthio- (I), 5-nitro-4-phenoxy- (II), and 4-bromo-
5-nitrophthalodinitriles (III), which were synthesized
by known methods [4 6].
PhS
CN
CN
PhS
CN
CN
PhS
CN
CN
PhS
CN
CN
RHN
O2N
4-XC6H4O
H2N
V, VI
IV
I
VII IX
PhS
CN
CN
PhS
CN
CN
PhS
PhS
CN
CN
O2N
O2N
III
X
II
V, R = CH3CO; VI, R = C7H15CO; VII, X = H; VIII, X = COOH; IX = X = t-Bu.
5-Amino-4-phenylthiophthalodinitrile (IV) was
prepared by reduction of phthalodinitrile I with tin(II)
chloride in hydrochloric acid. The presence of
a primary amino group in the product was proved by
the diazotization test. Compound IV is a yellow
powder which turns dark on heating above 140 C and
decomposes at 158 160 C. It is soluble in DMF,
acetone, benzene, chloroform, and isopropyl alcohol
1
For communication VI, see [1].
1070-3632/03/7302-0292$25.00 2002 MAIK Nauka/Interperiodica

NUCLEOPHILIC SUBSTITUTION IN 4-BROMO-5-NITROPHTHALODINITRILE: VII.
293
and is insoluble in water. Phthalodinitrile IV was
PhS
R
CN
CN
acylated with acetic anhydride and octanoic anhydride.
The acylation completion was checked by a negative
test for primary amino group.
4
5-Acylamino-4-phenylthiophthalodinitriles V and
VI are cream substances having sharp melting points
which decrease as the alkyl chain extends. 5-Acetyl-
amino-4-phenylthiophthalodinitrile (V) melts at 160
161 C, and the melting point of 5-octanoylamino-4-
phenylthiophthalodinitrile (VI) is 114 116 C. Com-
pounds V and VI are soluble in chloroform, DMF,
DMSO, and in hot benzene and are insoluble in water.
R
SPh
SPh
R
N
N
N
N
M(CH3COO)2
N
N
M
N
N
It was also interesting to obtain phenylthio-sub-
stituted phthalodinitriles having other bulky substit-
uents as well, e.g., p-carboxyphenoxy, tert-butyl-
phenoxy-, or one more phenylthio group. Phthalo-
dinitriles VIII X were prepared by reactions of com-
pound I with the corresponding para-substituted
phenols (or benzenethiol) in DMF in the presence of
potassium carbonate at 130 140 C. We previously
showed the possibility for stepwise nucleophilic sub-
stitution in the molecule of 4-bromo-5-nitrophthalo-
dinitrile (III): the halogen atom is replaced first, and
the nitro group is then replaced [7]. Following the
same procedure, we have synthesized 4,5-bis(phenyl-
thio)phthalodinitrile (X).
R
PhS
PhS
R
XI, R = NHCOCH3; XII, R = NHCOC7H15; XIII, R =
PhO; XIV, R = 4-HOCOC6H4O; XV, R = 4-t-BuC6H4O;
XVI, R = PhS; M = Cu (a), Co (b).
with chloroform; after removal of the solvent, the
complexes were purified by liquid chromatography.
The products are dark green powders. As noted in [4],
introduction of a phenylthio group into phthalocyanine
molecule makes these compounds soluble in chloro-
form, benzene, and chlorobenzene and increases their
solubility in DMF, as compared to tetra(4-bromo-5-
nitro)phthalocyanine complexes. On a qualitative
level, replacement of the nitro group in tetra(5-nitro-
4-phenylthio)phthalocyanine complexes by acylamino
or p-carboxyphenoxy groups reduces the solubility in
organic solvents, while introduction of such groups as
phenoxy, tert-butylphenoxy, and phenylthio instead
of the nitro group increases the solubility.
However, our attempts to obtain 5-phenoxy-4-
phenylthiophthalodinitrile (VII) under the same con-
ditions as in the synthesis of VIII X, i.e., by reacting
phthalodinitrile I with phenol in DMF in the
presence of potassium carbonate were unsuccessful.
Therefore,
5-phenoxy-4-phenylthiophthalodinitrile
(VII) was obtained by nucleophilic substitution of
the nitro group in phthalodinitrile II by benzenethiol
in DMF in the presence of K2CO3 at 90 C. A higher
reaction temperature, as well as the change of the II
K2CO3 PhSH molar ratio from 1:1:1 to 1:3:3 leads
to formation of a mixture of products. Presumably,
both nitro and phenoxy groups in II are replaced by
phenylthio groups, which is supported by the ele-
mental analysis. An analogous replacement of
phenoxy group was also reported in [8].
The electronic absorption spectra of complexes XI
XVI in DMF are characterized by strong absorption
in the long-wave region (see table), and in all cases
a red shift of the Q band is observed as compared to
the corresponding unsubstituted phthalocyanines. The
spectral pattern, as well as the shift of the long-wave
absorption band in the spectra of complexes with the
same metal, is determined by the nature of substituent
in the ortho position with respect to the phenylthio
group. In the spectra of phthalocyanines containing
acylamino and carboxyphenoxy groups, the Q band is
broadened, and the absorption maxima are not defined
clearly. Presumably, this is the result of association
of the complexes in solution. The Bouguer Lambert
Beer law is violated at a concentration exceeding
Compounds VII X are yellow powders with sharp
melting points. They are insoluble in water and
soluble in DMF, benzene, acetone, and chloroform.
Phthalodinitrile VIII is soluble in aqueous alkalies
due to the presence of carboxy group.
By reaction of disubstituted phthalodinitriles with
copper or cobalt acetate at 185 190 C we obtained
the corresponding octasubstituted phthalocyanine
complexes.
6
10 M, in keeping with the above assumption. The
other complexes give a narrow Q band in the electronic
absorption spectra, indicating that these compounds
exist in solution predominantly in the monomeric
The target products were isolated by extraction
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 2 2003

294
BALAKIREVA et al.
Positions of the long-wave absorption band in the electron
spectra of phenylthio-substituted phthalocyanine metal
complexes
the molecular fragments due to steric hindrances for
the two ortho-arranged benzene rings. Replacement
of the nitro group in the ortho position with respect
to the phenylthio group by an acylamino group is ac-
companied by a small red shift of the Q band
(2 8 nm); the shift is greater for a longer alkyl chain.
max, nm
Comp. no.
DMF
CHCl3
Some red shift of the long-wave absorption band
of all the examined complexes is observed in going
from DMF to chloroform. This means that the com-
plexes exhibit solvatochromic properties. It is known
that the solvatochromic effect is directly related to
such a generalized physical parameter of a solvent as
its refractive index [9]. The greater the latter, the
stronger the red shift of absorption bands. The results
of our study are consistent with the above statement:
The refractive indices of chloroform and DMF are
equal to 1.59 and 1.430 [10], respectively.
XIa
712
718
686
709
697
700
688
699
716
722
694
XIIa
XIIIa
XVIa
XVIb
XVa
XVb
XVIa
XVIb
708
699
707
694
688
710 [4]
EXPERIMENTAL
form (see figure). According to the red shift of the
Q band in DMF, the copper complexes rank as
The melting points were determined on a Boetius
small-size heating device coupled with an RNMK-05
observation setup (with a Boetius microscope). The
electronic absorption spectra of solutions in DMF and
follows: CuPc(4-SPh)4(5-OPh)4
(5-OC6H4C(CH3)3)4
CuPc(4-SPh)4(5-OC6H4COOH)4
<
CuPc(4-SPh)4-
CuPc(4,5-SPh)8
CuPc(4-SPh)4-
<
<
chloroform were recorded on
a
Perkin Elmer
range from
(5-NO2)4 < CuPc(4-SPh)4(5-NHCOCH3)4 < CuPc-
(4-SPh)4(5-NHCOC7H15)4.
Lambda-20 spectrophotometer in the
300 to 900 nm at room temperature.
Replacement of the nitro groups in tetra(5-nitro-
4-phenylthio)phthalocyanines by bulky substituents
leads to a blue shift of the Q band (up to 24 nm),
which is likely to originate from noncoplanarity of
5-Amino-4-phenylthiophthalodinitrile
(IV).
Tin(II) chloride, 2.78 g, was dissolved in 2.1 ml of
concentrated hydrochloric acid, and 1 g of phthalo-
dinitrile I was slowly added to the solution. The
mixture was heated to 60 C, stirred for 2 h at that
temperature, and poured into 50 ml of an ice water
mixture. The precipitate was filtered off, washed with
water until neutral washings free of of chloride ions
therein, dried at 50 C, and recrystallized from benzene.
Yield 71%, decomp. point 158 160 C. Found, %: C
68.1; H 4.1; N 16.7. C14H9N3S. Calculated, %: C
66.9; H 3.6; N 16.9.
D
1.1
2
0.9
0.6
5-Acetylamino-4-phenylthiophthalodinitrile (V).
Acetic anhydride, 0.6 ml, and sodium acetate, 0.33 g,
were added to 1 g of amine IV. The mixture was
heated for 1 h at 120 C, cooled, and diluted with
water, and the precipitate was filtered off, washed
with water until neutral washings, dried at 40 C,
and recrystallized from benzene. Yield 56%,
mp 114 116 C. Found, %: C 66.8; H 4.1; N 14.7.
C16H11N3OS. Calculated, %: C 65.5; H 3.8; N 14.3.
1
0.3
600 700
900
, nm
5-Octanoylamino-4-phenylthiophthalodinitrile
(VI). A mixture of 0.5 g of phthalodinitrile I and
0.9 ml of octanoyl chloride was heated to 160 C, kept
for 1 h at that temperature, and diluted with 10 ml
of a 10% aqueous solution of sodium carbonate. The
Electronic absorption spectra of phthalocyanine copper
5
complexes in DMF (c = 10 M): (1) CuPc(4-SPh)
4
(5-OC H C(CH ) ) ,
(2)
CuPc(4-SPh) (5-OC H
6
4
3 3 4
4 6 4
COOH) .
4
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NUCLEOPHILIC SUBSTITUTION IN 4-BROMO-5-NITROPHTHALODINITRILE: VII.
295
precipitate was filtered off, washed with water until
neutral washings, dried at 50 C, and recrystallized
from benzene. Yield 56%, mp 114 116 C. Found, %:
C 71.5; H 7.0; N 11.3. C22H23N3OS. Calculated, %:
C 70.1; H 6.1; N 11.1.
C 70.2; H 4.0; N 7.9. C20H12N2S2. Calculated, %:
C 69.7; H 3.5; N 8.1.
Tetra(5-R-4-phenylthio)phthalocyanine copper
and cobalt complexes XI XVI (general procedure).
A mixture of 0.9 mmol of phenylthio-substituted
phthalodinitrile and 0.25 mmol of copper or cobalt
acetate was heated for 1.5 h at 185 190 C until a solid
melt was obtained. It was cooled, washed with dilute
hydrochloric acid and then with water until neutral
washings, dried at 50 C, and extracted with chloro-
form. The solvent was removed under reduced pres-
sure, and the residue was purified by column chroma-
tography on silica gel L 40/100 m using benzene
ethanol (3:2) as eluent.
5-Phenoxy-4-phenylthiophthalodinitrile (VII).
Benzenethiol, 0.01 mol, and potassium carbonate,
0.01 mol, were added to a solution of 0.01 mol of
5-nitro-4-phenoxyphthalodinitrile (II) in 30 ml of
DMF. The mixture was heated to 90 C under vigorous
stirring, stirred for 2 h at that temperature, cooled,
and poured into 100 ml of water. The precipitate was
filtered off, washed with water, and recrystallized
from ethanol. Yield 63%, mp 130 132 C. Found, %:
C 74.0; H 6.1; N 8.3. C20H12N2OS. Calculated, %:
C 73.2; H 6.1; N 8.5.
[Tetra(5-acetylamino-4-phenylthio)phthalocya-
ninato]copper(II) (XIa). Yield 16%. Found, %:
C 63.2; H 4.0; N 13.4. C64H44CuN12O4S4. Calculated,
%: C 62.2; H 3.6; N 13.6.
5-(4-R-Phenoxy)-4-phenylthiophthalodinitriles
VIII XI (general procedure). Phthalodinitrile I,
0.01 mol, para-substituted phenol, 0.01 mol, and
anhydrous potassium carbonate, 0.01 mol, were added
with stirring to 30 ml of DMF. The mixture was
vigorously stirred for 3 h at 130 140 C, cooled, and
poured into 100 ml of water. The precipitate was
filtered off, washed with water, and recrystallized
from ethanol.
[Tetra(5-octanoylamino-4-phenylthio)phthalo-
cyaninato]copper(II) (XIIa). Yield 15%. Found, %:
C 68.6; H 6.3; N 10.4. C88H92CuN12O4S4. Calculated,
%: C 67.4; H 5.9; N 10.7.
[Tetra(5-phenoxy-4-phenylthio)phthalocyanin-
ato]copper(II) (XIIIa). Yield 16%. Found, %:
C 66.6; H 4.1; N 6.9. C80H48CuN8O4S4. Calculated,
%: C 65.0; H 3.1; N 7.2.
5-(4-Carboxyphenoxy)-4-phenylthiophthalodi-
nitrile (VIII). Yield 51%, mp 133 134 C. Found, %:
C 70.1; H 4.0; N 7.2. C21H12N2O3S. Calculated, %:
C 67.7; H 3.3; N 7.5.
[Tetra[5-(4-carboxyphenoxy)-4-phenylthio]-
phthalocyaninato]copper(II) (XIVa). Yield 18%.
Found, %: C 66.2; H 3.1; N 6.7. C84H48CuN8O12S4.
Calculated, %: C 65.0; H 3.1; N 7.2.
5-(4-tert-Butylphenoxy)-4-phenylthiophthalodi-
nitrile (XI). Yield 57%, mp 138 140 C. Found, %:
C 76.3; H 6.0; N 7.0. C24H20N2OS. Calculated, %:
C 75.0; H 5.2; N 7.3.
[Tetra[5-(4-carboxyphenoxy)-4-phenylthio]-
phthalocyaninato]cobalt(II) (XIVb). Yield 17%.
Found, %: C 66.1; H 4.1; N 6.8. C84H48CoN8O12S4.
Calculated, %: C 65.2; H 3.1; N 7.2.
4,5-Bis(phenylthio)phthalodinitrile (X). a. Phtha-
lodinitrile I, 0.01 mol, benzenethiol, 0.01 mol, and
anhydrous potassium carbonate, 0.01 mol, were added
with stirring to 30 ml of DMF. The mixture was
vigorously stirred for 3 h at 130 140 C, cooled, and
poured into 100 ml of water. The precipitate was
filtered off, washed with water, and recrystallized
from ethanol. Yield 67%, mp 147 148 C. Found, %:
C 70.0; H 4.2; N 7.9. C20H12N2S2. Calculated, %:
C 69.7; H 3.5; N 8.1.
[Tetra[5-(4-tert-butylphenoxy)-4-phenylthio]-
phthalocyaninato]copper(II) (XVa). Yield 18%.
Found, %: C 73.2; H 5.5; N 6.8. C96H80CuN8O4S4.
Calculated, %: C 72.0; H 5.0; N 7.0.
[Tetra[5-(4-tert-butylphenoxy)-4-phenylthio]-
phthalocyaninato]cobalt(II) (XVb). Yield 17%.
Found, %: C 73.1; H 5.5; N 6.8. C96H80CoN8O4S4.
Calculated, %: C 72.2; H 5.1; N 7.0.
b. Benzenethiol, 0.02 mol, and a solution of
0.01 mol of potassium carbonate in 10 ml of water
were added to a solution of 0.01 mol of 4-bromo-
5-nitrophthalodinitrile (III) in 30 ml of DMF. The
mixture was stirred for 0.5 h at 30 C, heated to
140 C, stirred for 3 h at that temperature, cooled, and
poured into 100 ml of water. The precipitate was
filtered off, washed with water, and recrystallized
from ethanol. Yield 62%, mp 149 150 C. Found, %:
[Octa-4,5-bis(phenylthio)phthalocyaninato]cop-
per(II) (XVIa). Yields 20%. Found, %: C 67.8;
H 4.1; N 7.6. C80H48CuN8S4. Calculated, %: C 66.7;
H 3.4; N 7.8.
[Octa-4,5-bis(phenylthio)phthalocyaninato]-
cobalt(II) (XVIb). Yield 18%. Found, %: C 70.8;
H 4.0; N 7.6. C80H48CoN8S4. Calculated, %: C 66.9;
H 3.4; N 7.8.
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BALAKIREVA et al.
Khim., 2000, vol. 70, no. 5, p. 815.
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