Phthalocyanines and related compounds: XLV. Nucleophilic substitution of chlorine in tetrachlorophthalonitrile: Synthesis of aryloxy-aubstituted phthalonitriles and phthalocyanines derived from them

Article abstract of DOI:10.1134/S1070363207060308

Nucleophilic substitution of chlorine in tetrachlorophthalonitrile by the reaction with aryloxy anions is studied. Depending on the reactant ratio, the products of substitution of one, two, and/or three chlorine atoms are formed. Their tetramerization giv

Full text of DOI:10.1134/S1070363207060308

ISSN 1070-3632, Russian Journal of General Chemistry, 2007, Vol. 77, No. 6, pp. 1126 1133.
Pleiades Publishing, Ltd., 2007.
Original Russian Text K.A. Volkov, G.V. Avramenko, V.M. Negrimovskii, E.A. Luk’yanets, 2007, published in Zhurnal Obshchei Khimii, 2007, Vol. 77,
No. 6, pp. 1040 1047.
Phthalocyanines and Related Compounds:
XLV.1 Nucleophilic Substitution of Chlorine
in Tetrachlorophthalonitrile:
Synthesis of Aryloxy-Aubstituted Phthalonitriles
and Phthalocyanines Derived from Them
K. A. Volkova, G. V. Avramenkob, V. M. Negrimovskiia, and E. A. Luk’yanetsa
a Research Institute of Organic Intermediates and Dyes,
ul. Bol’shaya Sadovaya 1/4, Moscow, 123995 Russia
e-mail: rmeluk@co.ru
b Mendeleev Russian University of Chemical Technology, Moscow, Russia
Received December 19, 2006
Abstract Nucleophilic substitution of chlorine in tetrachlorophthalonitrile by the reaction with aryloxy
anions is studied. Depending on the reactant ratio, the products of substitution of one, two, and/or three
chlorine atoms are formed. Their tetramerization gives aryloxychloro-substituted phthalocyanines having the
absorption band in the near-IR range.
DOI: 10.1134/S1070363207060308
We have studied previously the reaction of tetra-
chlorophthalonitrile I with thiols [2]. We found that
substitution of chlorine is regiospecific, with the 4-Cl
atom replaced first and the 5-Cl atom, second. Depend-
ing on the reactant ratio, products with various
degrees of substitution, up to tetrasubstituted com-
pounds, can be prepared.
Proceeding with studies of the nucleophilic substi-
tution in tetrachlorophthalonitrile, we examined its
reactions with some O-nucleophiles, namely, with
aryloxy and alkoxy anions at varied molar ratios of
the reactants. The results of the reactions of dinitrile I
with the above nucleophiles are shown in Scheme 1
and in Table 1.
Scheme 1.
OR
Cl
OR
Cl
Cl
Cl
Cl
CN
CN
RO
RO
CN
CN
CN
CN
Cl
CN
CN
CN
CN
RO
RO
Cl
Cl
Cl
nRONa
+
+
+
DMF, 50 C
RO
RO
Cl
Cl
Cl
I
II, V
III, VI
VII
IV, VIII
OR
OR
CN
CN
RO
RO
nRONa
DMF, 50 100 C
R = Ph (II IV), Py (V VIII), Py = 3-pyridyl.
1
For communication XLIV, see [1].
1126

PHTHALOCYANINES AND RELATED COMPOUNDS: XLV.
1127
The reaction of dinitrile I with sodium phenolate
was carried out at 50 C in DMF for 3 h at the reactant
molar ratio varied from 1:1 to 1:4. In all the cases,
the reaction mixture contained several products. All
of them were isolated pure and characterized.
Table 1. Yields of the aroxychloro-substituted phthalo-
nitriles at various molar ratios of reactantsa
Dinitrile I:RONa molar ratio
RONa
Product
1:1
1:2
1:3
1:4
At 1:1 molar ratio, the conversion of phthalonitrile
is incomplete. About 1/2 of the starting compound
was recovered from the reaction mixture, and 30% of
phenoxytrichlorophthalonitrile, the product of substi-
tution of one chlorine with phenoxy group, was ob-
tained. At 1:2 ratio, the amount of the recovered start-
ing product I decreased to 7%. The major reaction
product was dinitrile II (53%), and only an insignif-
icant amount ( 10%) of the expected product of sub-
stitution of two chlorine atoms III was obtained.
Compound III becomes the major product at 1:3
molar ratio of the reactants (yield 45%). In this case,
the monosubstituted product II and a new product
IV containing phenoxy groups (19 and 10% yields,
respectively) were also obtained. We failed to obtain
tetraphenoxyphthalonitrile, the product of complete
substitution, at 1:4 molar ratio and the chosen tem-
perature of 50 C. Although the yield of triphenoxy-
phthalonitrile increased considerably (up to 37%),
product III with two phenoxy groups was isolated in
this experiment in almost the same yield (31%).
R = Ph
I
II
48.3
29.2
6.7
d
53.4c 19.2
10.5c 45.3
10.0
III
IV
V
VI
VII
VIII
30.5c
36.5c
R = Pyb
13.0c
e
e
d
22.0c
16.2c
9.1c
7.8
5.2
49.9c
a
In all the cases, unless otherwise indicated, the yields of the
products after their separation by preparative column chro-
matography (silica gel, elution with 1:2 benzene hexane for
R = Ph, with 2:1 benzene ethyl acetate for R = 3-pyridyl) are
b
c
presented.
d
Py = 3-pyridyl.
After crystallization from
e
ethanol. Traces, according to TLC. The products were not
isolated.
taminating the target product. Our attempt to substitute
the last chlorine atom in dinitriles IV and VIII at
50 C led only to the recovery of the starting product,
whereas at the solvent boiling point ( 150 C) ex-
tensive tarring was observed.
An increase in the reaction temperature to the DMF
boiling point at 1:4 molar ratio did not lead to the
formation of the tetrasubstituted product either, al-
though the yield of the trisubstituted product IV in-
creased to 65%.
For all the compounds obtained, we recorded the
13C NMR spectra. In the spectra of disubstituted com-
pounds III and VI, as expected, the number of the
carbon atom signals was twice smaller, which cor-
responds to the symmetric substitution. Similarly to
4,5-bis(phenylthio)-3,6-dichlorophthalinitrile formed
regiospecifically from dinitrile I and thiophenol under
the same conditions [2], we assumed that phthaloni-
triles III and VI were products of the substitution of
two chlorine atoms in the symmetric positions 4 and
5 of tetrachlorophthalonitrile I. For the pyridyloxy-
substituted dinitrile VI, this assumption was con-
firmed by single crystal X-ray diffraction.2
The reaction of dinitrile I with potassium 3-pyrido-
late in 1:2 molar ratio was carried out at 50 C for 3 h.
However, contrary to the results obtained with thiols
and phenol, four products were isolated and charac-
terized in this case.
The major products were disubstituted compounds
VI and VII isolated by column chromatography in a
total yield of 38%. The monosubstituted product V
was isolated in 13% yield, and the trisubstituted prod-
uct VIII, in 9% yield (Table 2).
As already noted, the reaction of arylate ions,
contrary to that of thiolate ones [2], does not lead to
substitution of all the four chlorine atoms, which is
evidently associated with a significant decrease in the
electron deficiency of the phthalonitrile ring due to
the effect of the already introduced three phenoxy
groups and with the lower nucleophilicity of arylates
as compared to thiolates. In the reactions with I, all
the arylates under study, taken in any ratio to I,
When dinitrile I and pyridolate were taken in 1:4
molar ratio, the same substances as in the previous
case were isolated, but the major product was the tri-
substituted compound VIII, whereas the content of
disubstituted compounds VI and VII decreased con-
siderably, and only traces of the monosubstituted
compound were obtained. An increase in the tempera-
ture to 100 C, similarly to the case of phenolate, led
to an increase in the yield of the trisubstituted product
VIII to 60%. However, this was accompanied by a
considerable increase in the amount of tars con-
2
Detailed X-ray structural data will be published separately.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 6 2007

1128
Table 2. Melting points, elemental analyses, and IR and mass spectral parameters of the phthalonitriles obtained
Found, % Calculated, %
Cl Cl
VOLKOV et al.
1
Product mp,
C
Formula
, cm
M+
C
H
N
C
H
N
II
215 216 51.92 1.57 32.77
52.01 1.60 32.85
131 133 62.91 2.62 18.56
62.99 2.63 17.63
8.61 C14H5Cl3N2O
8.67
7.30 C20H10Cl2N2O2
7.36
6.37 C26H15ClN2O3
6.44
51.97 1.56 32.87 8.66
63.01 2.64 18.60 7.35
2241
2240
2239
2241
2240
2242
2230
322
380
438
323
382
382
441
III
IV
V
162 164 71.09 3.44
71.15 3.47
8.00
8.11
71.16 3.45
8.08
6.38
218 219 48.02 1.19 32.75 12.87 C13H4Cl3N3O
48.10 1.23 32.83 12.94
260 262 56.43 2.06 18.48 14.61 C18H8Cl2N4O2
56.48 2.10 18.55 14.67
252 253 56.36 2.05 18.45 14.59 C18H8Cl2N4O2
56.45 2.08 18.55 14.65
48.11 1.24 32.77 12.95
56.42 2.10 18.50 14.62
56.42 2.10 18.50 14.62
VI
VII
VIII 201 202 62.45 2.70
7.96 15.81 C23H12ClN5O3
8.07 15.90
62.52 2.74
8.02 15.85
62.50 2.74
Table 3. 13C NMR parameters of some phthalonitriles obtained (DMSO-d6)
Product
II
C, ppm
155.3 (CAr O), 151.7 (CAr O), 136.6 (CAr Cl), 134.9 (CAr Cl), 132.1 (CAr Cl), 130.2 (CAr H), 123.8
(CAr H), 117.2 (CAr CN), 115.5 (CAr CN), 114.9 (CAr H), 112.8 (CN), 112.5 (CN)
156.1(CAr O), 152.6 (CAr O), 135.8 (CAr Cl), 131.0 (CAr H), 124.8 (CAr H), 116.4 (CAr CN), 115.8 (CAr
H), 113.5 (CN)
III
V
152.4 (CAr O), 150.6 (CAr O), 143.0 (CAr H), 136.9 (CAr Cl), 135.3 (CAr H), 134.7 (CAr Cl), 131.8 (CAr
Cl), 126.2 (CAr H), 125.8 (CAr H), 117.4 (CAr CN), 115.7 (CAr CN), 112.7(CN), 112.5 (CN)
152.1(CAr O), 148.3 (CAr O), 145.4 (CAr H), 137.7 (CAr H), 132.6 (CAr Cl), 124.6 (CAr H), 122.7 (CAr H),
115.6 (CAr CN), 112.9 (CN)
VI
VII
152.9 (CAr O), 152.8 (CAr O), 152.2 (CAr O), 152.0 (CAr O), 145.6 (CAr H), 145.3 (CAr H), 137.9 (CAr H),
137.4 (CAr H), 130.7 (CAr Cl), 130.1 (CAr Cl), 125.0 (CAr H), 123.1 (CAr H), 122.4 (CAr H), 117.2 (CAr
CN), 112.9 (CAr CN), 111.7 (CN), 110.5 (CN)
formed mixtures of substitution products, one of them
being major. The necessity of the chromatographic
separation significantly decreases the synthetic value
of the reaction under investigation. An exception is
the process carried out at 1:4 (or higher) molar ratio
and elevated temperature, yielding tris(aryloxy)phtha-
lonitrile, the product with the highest possible degree
of substitution. Unfortunately, under more severe
conditions (heating above 100 C), the specific reac-
tivity of the o-located cyano groups toward nucleo-
philes causes the formation of significant amounts of
oligomeric products.
As follows from the above data, the phenolate and
3-pyridolate ions also substitute the first chlorine atom
in position 4 exclusively. This is also proved by the
formation of only one monosubstituted product and
of 4,5-bis(aryloxy)dichloro-substituted products III
and VI. Substitution of the second chlorine atom with
the phenoxy group, similarly to the reaction with
thiolate anions, proceeds regiospecifically and yields
symmetrical 4,5-diphenoxy-3,6-dichlorophthalonitrile
III. At the same time, 3-pyridolate reacts to form both
symmetrical and unsymmetrical disubstitution prod-
ucts. Presumably, this pattern is due to the steric hin-
drance to the attack of the adjacent position, created
by the solvated nitrogen of the pyridyloxy group al-
ready introduced into phthalonitrile, but it does not
alter the regioselective character of substitution.
In the case of thiolate anions [2]. substitution of
two chlorine atoms proceeds regiospecifically in posi-
tion 4 and then in position 5 of the phthalonitrile ring.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 6 2007

PHTHALOCYANINES AND RELATED COMPOUNDS: XLV.
1129
Scheme 2.
CN
CN
CN
CN
CN
OCH2R
OCH2R
CN
RCH2O
N
N
N
N
N
N
N
N
N
N
RCH2O
N
N
N
N
N
N
HN
RCHO
N
N
N
N
N
It is known that addition of the alkoxide anion to
o-located cyano groups of phthalonitrile leads to the
formation of isoindole structures. Their oligomeriza-
tion leads, in particular, to the formation of phthalo-
cyanine [3] (Scheme 2).
hexanol and 2-dimethylaminoethanol, traces of
phthalocyanines were also obtained.
So significant difference between the results ob-
tained for tetrafluorophthalonitrile [4, 5] and our data
for tetrachlorophthalonitrile is apparently due to
significantly stronger electron-acceptor power of fluo-
rine compared to chlorine. This factor favors the suc-
cessful competition of the aromatic nucleophilic sub-
stitution with alkoxides in tetrafluorophthalonitrile
with the attack on cyano groups. In the reactions of
tetrachlorophthalonitrile with alkoxides, the attack on
cyano group evidently prevails.
However, it was shown recently that all the four
fluorine atoms of tetrafluorophthalonitrile can be
substituted with alkoxy groups, in particular, with
neopentoxy and hexoxy groups, under the action of a
large excess of aliphatic alcohols in presence of potas-
sium carbonate [4, 5]. Using the similar procedure,
we performed the reaction of tetrachlorophthalonitrile
with hexyl alcohol. An unseparable mixture of pro-
ducts formed. The same result was obtained when
sodium alcoholates prepared beforehand (from hexa-
nol, benzyl alcohol, and 2-dimethylaminoethanol)
were brought into the reaction with I in 1:2 or 1:4
ratio in DMF at 50 C (no reaction was observed at
lower temperature). According to the mass-spectral
data, at 1:2 molar ratio the major component of the
reaction mixture was the starting compound. It also
contained unidentified products with high molecular
weights and insignificant amounts of the mono-
substitution products. Di- and trisubstituted products
in 1:4 molar ratio were detected by mass spectrom-
etry, in addition to large amounts of oligomers and
products of addition to cyano groups (Scheme 2). In
the IR spectra of the latter products, the absorption
bands of cyano groups were absent (though we failed
to obtain analytically pure samples). In the case of
The aryloxychloro-substituted phthalonitriles were
used for preparing the substituted phthalocyanines
under the standard conditions of template synthesis.
They were fused with metal salts (cobalt chloride and
zinc acetate) in the presence of ammonium molybdate.
A small amount of o-dichlorobenzene was added to
the reaction mixture for better homogenization. The
reaction was carried out in the temperature range 140
210 C for 3 h with cobalt complexes and for 6 h with
zinc complexes. Based on the structures of the starting
phthalonitriles and the elemental analysis data, the
compounds obtained were identified as IX XV
(Scheme 3, Table 4).
The complexes obtained IX XV were purified first
by multiple sequential extraction of impurities with
boiling ethanol, benzene, and distilled water, and then
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 6 2007

1130
VOLKOV et al.
Scheme 3.
R2 R3
R1
N
Cl
N
R1
Cl
Cl
Cl
N
R2
R3
R3
R3
R2
M2+, (NH4)2MoO4
CN
CN
M
N
N
N
R2
R1
N
R1
N
R1
II VIII
Cl
R2
R3
IX XV
R1 = R2 = Cl, R3 = PhO (II, IX), PyO (V, XII); R1 = Cl, R2 = R3 = PhO (III, X), PyO (VI, XIII); R2 = Cl, R1 = R3 = PyO
(VII, XIV); R1 = R2 = R3 = PhO (IV, XI), PyO (VIII, XV); M = Co (a), Zn (b). Py = 3-pyridyl.
Table 4. Elemental analyses and positions of maxima ( max) of the long-wave absorption bands of the complexes obtained
Found, %
Calculated, %
max, nm
(DMSO)
Product
Formula
C
H
Cl
N
C
H
Cl
N
IXa
49.58
49.66
49.64
49.70
60.82
60.90
60.48
60.56
67.94
69.13
68.59
69.03
46.14
46.26
46.94
47.01
54.37
54.46
54.15
54.21
54.36
54.49
54.16
54.22
60.49
60.58
60.28
50.39
1.41
1.50
1.50
1.53
2.51
2.55
2.51
2.54
3.27
3.33
3.31
3.34
1.11
1.20
1.12
1.17
2.01
2.06
1.96
2.01
2.00
2.05
1.95
2.02
2.64
2.67
2.60
2.68
31.16
31.25
30.92
30.98
17.66
17.74
17.63
17.72
7.65
8.27 C56H20Cl12CoN8O4
8.35
8.24 C56H20Cl12N8O4Zn
8.31
7.00 C80H40Cl8CoN8O8
7.08
7.01 C80H40Cl8N8O8Zn
7.10
6.17 C104H60Cl4CoN8O12 68.85
49.71
49.47
60.67
60.42
1.49
1.48
2.55
2.54
3.33
3.32
1.19
1.18
2.03
2.02
2.03
2.02
2.65
2.64
31.44
31.29
17.91
17.84
7.82
8.31
679
690
690
695
693
700
685
694
687
703
687
698
700
713
IXb
8.24
Xa
7.08
Xb
7.05
XIa
6.18
7.71
7.64
7.73
6.22
XIb
6.18 C104H60Cl4N8O12Zn 68.60
6.21
12.37 C52H16Cl12CoN12O4 46.02
12.45
12.29 C52H16Cl12N12O4Zn 46.80
12.37
14.07 C72H32Cl8CoN16O8
7.79
6.15
XIIa
XIIb
XIIIa
XIIIb
XIVa
XIVb
XVa
XVb
31.00
31.12
30.90
30.98
17.58
17.65
17.53
17.60
17.58
17.66
17.50
17.60
7.63
31.35
31.20
17.82
17.75
17.82
17.75
7.77
12.38
12.33
14.08
14.02
14.08
14.02
15.34
15.29
54.33
54.11
54.33
54.11
14.15
14.08 C72H32Cl8N16O8Zn
14.11
14.04 C72H32Cl8CoN16O8
14.11
14.03 C72H32Cl8N16O8Zn
14.09
15.27 C92H48Cl4CoN20O12 60.51
7.74
7.68
7.71
15.37
15.34 C92H48Cl4N20O12Zn 60.29
15.40
7.74
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PHTHALOCYANINES AND RELATED COMPOUNDS: XLV.
1131
1.0
1.0
0.5
0.0
XIVa
XVa
XIIIa
in DMSO
in 5% HCl
0.5
XIIa
0.0
550 600
650
700
750
800 850
, nm
320 400 480 560 640 720 800
, nm
Fig. 1. Electronic absorption spectra of complex
XIIIa in DMSO and in 5% aqueous HCl.
Fig. 2. Electronic absorption spectra of pyridyloxy-
substituted cobalt complexes XIIa XVa in DMSO.
by precipitation from DMSO with water in the case of
phenoxy-substituted complexes IX XI, or from 10%
hydrochloric acid with ammonium hydroxide in the
case of pyridyloxy-substituted phthalocyanines XII
XV, followed by washing of the precipitates with hot
ethanol and water.
cyanines, which completely dissolved in DMF at
50 C. Tetrakis(aryloxy)dodecachlorophthalocyanines
were the least soluble.
For all the complexes IX XV, we recorded the
electronic absorption spectra in DMSO (Figs. 1, 2).
The electron absorption spectra of the pyridyloxy-
substituted phthalocyanines were also recorded in 5%
HCl. The general view of the electronic absorption
spectrum in the range 300 850 nm is presented for
XIIIa in Fig. 1. Similarly to all the other phthalo-
cyanine complexes, two strong absorption bands are
observed. The long-wave band (Q band) is located in
the range 680 715 nm, and the short-wave band
(Soret band), at about 350 nm. Note that the Q band
of complex XIIa is poorly resolved, evidently
because of the partial aggregation of molecules.
When purifying complex XIIa, we failed to dis-
solve the product obtained in 10% hydrochloric acid.
The product was partially soluble only in 17% hydro-
chloric acid. In 36.5% acid, approximately 2/3 of the
product dissolved. This solution was treated with
ammonium hydroxide to precipitate the compound.
The insoluble part of the reaction mixture was washed
with concentrated hydrochloric acid and water to
neutral pH and then was dissolved in hot DMSO and
precipitated with water. As a result, two fractions of
the product were obtained. Their analytical data were
similar, which allowed us to consider them as two
randomers of the cobalt complex XIIa.
The general view of the electronic absorption spec-
tra of complexes XIII XV in 5% aqueous HCl is
similar to that in DMSO, but the Q band is signif-
icantly broadened and split in two maxima at
630 nm and 680 nm related to the bands of the
aggregated and monomeric species, respectively.
Zinc complexes XIIb XVb were additionally
purified by column chromatography (silica gel column,
elution with pyridine). After that, the products were
precipitated from pyridine with the benzene acetic
acid mixture, washed with hot benzene, water, and
ethanol, and dried. All the complexes obtained were
blue-green powders insoluble in water and such or-
ganic solvents as hydrocarbons, alcohols, ketones,
ethers, and esters. At the same time, all of them are
soluble in aprotic polar solvents such as DMF and
DMSO, and also in pyridine, due to coordination of
the latter with the central metal atom. The solubility
of the complexes obtained increased with the amount
of the pyridyloxy groups in the macroring. The most
soluble were dodecakis(aryloxy)tetrachlorophthalo-
The Q band in the spectra of all the substituted
cobalt and zinc phthalocyanines is significantly
shifted bathochromically as compared to the unsub-
stituted analogs. In particular, for phenoxy-substituted
cobalt complexes IXa XIa the above-mentioned shift
is 12, 23, and 26 nm, respectively, while for pyridyl-
oxy-substituted complexes XIIa XIVa it is 18 20 nm,
and for XVa, 33 nm.
It is known that introduction of chlorine as well as
alkoxy and aryloxy groups into the phthalocyanine
macroring causes the bathochromic shift of the Q
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1132
VOLKOV et al.
band [6]. Comparing the spectral data for complexes
we obtained with the published data on the octachloro-
[7] and octakis(aryloxy/alkoxy)-substituted zinc,
cobalt, and some other metal phthalocyanines [4, 8],
we can note that eight aryloxy/alkoxy groups in the
-positions of the macroring cause the batochromic
shift of the Q band by no more than 10 nm as com-
pared to the unsubstituted analog, whereas eight chlo-
rine atoms in -positions of the phthalocyanine shift
the band by 30 nm. In the spectra of the complexes
we obtained, each containing eight above-mentioned
groups in the same positions, the Q band is shifted by
only 20 nm, contrary to the phenyl(alkyl)thio groups
shifting the Q band by 60 70 nm [2]. Hence, the
effect of substituents on the location of the Q band
maximum is not additive. At the same time, in going
from unsubstituted phthalocyanines to the analogs
with eight alkoxy groups in o-positions of benzene
rings, the bathochromic shift of the Q band maximum
point is no less than 60 nm ( max 735 760 nm) [9, 10].
These data, together with the published data on hexa-
decakis(alkoxy/aryloxy)phthalocyanine metal com-
was added dropwise in the course of 20 min to a solu-
tion of 1.33 g of tetrachlorophthalonitrile in 30 ml of
DMF at 20 C. The mixture was heated to 50 C and
stirred at this temperature for 3 h. Then the mixture
was poured in a saturated NaCl solution, and the
aqueous layer was extracted with ethyl acetate. The
organic layer was washed twice with 5% ammonia
and then with water to the neutral reaction and dried
over anhydrous sodium sulfate. After that, the solvent
was evaporated in a vacuum and the residue was
chromatographed on a silica gel column, elution with
2:1 benzene-ethyl acetate in the case of 3-hydroxy-
pyridine, and with 1:2 benzene hexane in the case of
phenol. The product obtained was recrystallized from
ethanol.
General procedure for preparing aryloxy-sub-
stituted phthalocyanines. A finely pulverized mix-
ture of substituted phthalonitrile (0.5 mmol), cobalt
chloride or zinc acetate (0.12 mmol), and ammonium
molybdate (2 3 mg) was placed in a bath preheated
to 140 C. The reaction mixture was gradually heated
to 210 C and kept at this temperature for 3 h for the
cobalt complexes and 6 h for the zinc complexes.
After cooling to room temperature, the solidified melt
was finely ground and extracted to remove impurities
first with boiling ethanol, then with benzene, and
finally with distilled water. After that, the precipitates
were filtered off, dissolved in DMSO (for the phenoxy
derivatives) or in 10% HCl (for the pyridyloxy-sub-
stituted complexes), and reprecipitated with water or
aqueous ammonia, respectively. The solutions ob-
tained were washed three times on the filter with hot
ethanol and distilled water.
plexes (
750 760 nm) [4, 5, 11], indicate that,
with a larmgeax number of alkyl(aryl)thio [2] and alkoxy
(aryloxy) substituents in the phthalocyanine macroring,
the substituent effect is not additive. Thus, the results
of this study, in combination with the previous data,
allow the substituents to be ranked in the following
order with respect to their effect on the location of the
Q band in the electronic spectrum: -Cl8 < ( -RO)8 <
-Cl8 < -Cl8, ( -RO)8 < Cl16 < ( -RO)8 (RO)16.
EXPERIMENTAL
The elemental analysis were performed on a
Hewlett Packard HP-185B C,H,N-analyzer. The IR
spectra were recorded on an FSM 1201 Fourier spec-
trometer from KBr pellets. The mass spectra were ob-
tained on an MKh-1321 mass spectrometer; the ioniz-
Zinc complexes XIIb XVb were additionally
purified by column chromatography on silica gel
(elution with pyridine), and the products were pre-
cipitated from pyridine with a benzene acetic acid
mixture, washed on the filter with hot benzene, water,
and methanol, and dried.
1
ing electron energy was 70 eV. The H and 13C NMR
spectra were taken on a Bruker AM-300 spectrometer
in DMSO-d6 against internal TMS. The electronic
absorption spectra were measured on a Hewlett
Packard HP 8435 spectrophotometer. The composi-
tions of reaction mixtures and purity of the com-
pounds obtained were monitored by TLC on Silufol
UV-254 plates.
All the complexes were blue-green powders; yield
35 40%.
ACKNOWLEDGMENTS
Reaction of tetrachlorophthalonitrile with
phenols (general procedure). To a solution of sodium
methylate (0.005, 0.010, 0.015, or 0.020 mol) in
30 ml of methanol, and equimolar amount of phenol
or 3-hydroxypyridine was added. The solvent was
vacuum-evaporated to dryness, and the residue was
dissolved in 50 ml of DMF. The solution obtained
The authors are grateful to Senior Researcher of
the Nesmeyanov Institute of Organoelement
Compounds, Russian Academy of Sciences, Cand. Sci.
(Chem.) Kirill Yur’evich Suponitskii for performing
the X-ray studies.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 6 2007

PHTHALOCYANINES AND RELATED COMPOUNDS: XLV.
1133
REFERENCES
6. Elektronnye spektry ftalotsianinov i rodstvennykh
soedinenii. Katalog (Electronic Spectra of Phthalo-
cyanines and Related Compounds. A Catalog), Luk’-
yanets, E.A., Ed., Chekassy: NIITEKhim, 1989.
1. Derkacheva, V.M., Mikhalenko, S.A., Solov’eva, L.I.,
Alekseeva, V.I., Marinina, L.E., Savina, L.P., Bute-
nin, A.V., and Luk’yanets, E.A., Zh. Obshch. Khim.,
2007, vol. 77, no. 6, p. 1031.
7. Mikhalenko, S.A., Korobkova, E.V., and Luk’ya-
nets, E.A., Zh. Obshch. Khim., 1970, vol. 40, no. 2,
p. 400.
2. Volkov, K.A., Avramenko, G.V., Negrimovskii, V.M.,
and Luk’yanets E.A., Zh. Obshch. Khim., 2007,
vol. 77, no. 6, p. 1022.
8. Han, K.-J. and Kay, K-Y., Bull. Korean Chem. Soc.,
2005, vol. 26, no. 8, p. 1274.
3. The Porphyrin Handbook, Kadish, K.M., Smith, K.M.,
and Guilard, R., Eds., New York: Academic, 2003,
vol. 15, p. 67.
9. Cook, M.J., Dunn, A.J., Howe, S.D., Thomson, A.J.,
and Harrison, K.J., J. Chem. Soc., Perkin Trans. 1,
1988, no. 8, p. 2453.
4. Bhardwaj, N., Andraos, J., and Leznoff, C.C., Can. J.
Chem., 2002, vol. 50, no. 1, p. 141.
10. Leznoff, C.C. and Sosa-Sanchez, J.L., Chem. Commun.,
2004, no. 3, p. 338.
5. Eberhardt, W. and Hanack, M., Synthesis, 1997, no. 1,
11. Birchall, J., Haszeldine, R., and Morley, J., J. Chem.
Soc., 1970, no. 3, p. 456.
p. 95.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 6 2007