Phthalocyanines and related compounds: XLIII. Synthesis of poly[phenyl(alkyl)sulfanyl]-substituted phthalonitriles and some phthalocyanines based thereon

Article abstract of DOI:10.1134/S107036320706028X

Nucleophilic substitution of chlorine atoms in tetrachlorophthalonitrile by benzene- and alkanethiols in the presence of a base was studied at different reactant ratios. The substitution is characterized by complete regioselectivity: the chlorine atom in

Full text of DOI:10.1134/S107036320706028X

ISSN 1070-3632, Russian Journal of General Chemistry, 2007, Vol. 77, No. 6, pp. 1108 1116.
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. 1022 1030.
Phthalocyanines and Related Compounds:
XLIII.1 Synthesis of Poly[phenyl(alkyl)sulfanyl]-Substituted
Phthalonitriles and Some Phthalocyanines Based Thereon
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 July 13, 2006
Abstract Nucleophilic substitution of chlorine atoms in tetrachlorophthalonitrile by benzene- and alkane-
thiols in the presence of a base was studied at different reactant ratios. The substitution is characterized by
complete regioselectivity: the chlorine atom in position 4 of tetrachlorophthalonitrile is replaced first; next
follows replacement of the 5-chlorine atom. The reactions of tetrachlorophthalonitrile with nucleophiles at
ratios of 1:2 and 1:4 lead to the formation of the corresponding 3,6-dichloro-4,5-bis[phenyl(alkyl)sulfanyl]-
and tetrakis[phenyl(alkyl)sulfanyl]phthalonitriles. The latter were converted into metal complexes of [phenyl-
(alkyl)sulfanyl]-substituted phthalocyanines which absorb in the red and near-IR regions of the electronic
spectra.
DOI: 10.1134/S107036320706028X
In the recent years phthalocyanines attract increas-
ing attention as subjects for study due to continuous
extension of the scope of their application in various
fields of science and engineering. For example, tradi-
tional uses of phthalocyanines as dyes and pigments
[2 4], catalysts of chemical reactions [5 7], photo-
and electrocatalysts [8 10], semiconducting materials
[11, 12], heat-resistant polymers [13, 14], laser dyes,
and optical filters [15] were supplemented by their
application as active media in sensors for various
gases [16, 17] and data storage and display devices
[18, 19]; studies on liquid crystalline properties of
phthalocyanines are in progress [20, 21]. At present,
phthalocyanines attract much interest as photo-
sensitizers for photodynamic therapy of cancer [22
24]. Therefore, numerous studies on the synthesis of
new phthalocyanine structures have been stimulated.
[35], and amino groups [36, 37] were introduced into
the benzene ring of phthalonitrile and, in the next
step, into the phthalocyanine macroring. For this
purpose, 3-nitrophthalonitrile [38] and especially
4-nitrophthalonitrile [39, 40] are used most frequently;
in some cases, monohalo-substituted phthalonitriles,
e.g., fairly exotic 3-bromo-5-tert-butylphthalonitrile
[36], are appropriate; these starting compounds make
it possible to obtain unsymmetrical mono- and di-
substituted phthalonitrile and finally unsymmetrically
substituted phthalocyanines as randomer mixtures.
Phthalonitriles having two replaceable groups
possess a great synthetic potential. For example,
symmetric 4,5-dichloro- [41, 42] and 3,6-bis(trifluoro-
methylsulfonyloxy)phthalonitriles [34] make it pos-
sible to introduce eight symmetrically arranged sub-
stituents into a phthalocyanine macroring. The nitro
groups in 3,5-dinitrophthalonitrile can be replaced in
succession by two different nucleophiles; however,
the regioselectivity of the first replacement is not high
[43]. 4-Bromo-5-nitrophthalonitrile [44, 45] is free
from this disadvantage: the bromine atom in its
molecule is replaced first [46], and the remaining nitro
group can also be replaced by the same [47] or dif-
ferent nucleophile [48, 49].
Most substituted phthalocyanines were synthesized
by tetramerization of the corresponding substituted
phthalonitriles [2, 3]. The latter are often obtained via
aromatic nucleophilic replacement of halogen atoms
or nitro group in halo- or nitrophthalonitriles. Follow-
ing this approach, such substituents as alkoxy [25 28],
aryloxy [29 32], alkylsulfanyl [33, 34], arylsulfanyl
From the viewpoint of synthetic applications, quite
interesting substrates are tetrahalo-substituted phth-
1
For communication XLII, see [1].
1108

PHTHALOCYANINES AND RELATED COMPOUNDS: XLIII.
1109
onitriles, in particular, commercially available tetra-
chlorophthalonitrile. Theoretically, all four chlorine
atoms therein may be replaced by the same or (in suc-
cession) by different nucleophiles in various ratios,
which could give rise to a diversity of structures.
However, it was surprising that, except for several
patents [50 55], we found no publications on syste-
matic studies on nucleophilic substitution of halogen
atoms in tetrahalophthalonitriles. The above patents
described substitution of halogen atoms in perhalo-
genated phthalonitriles, including tetrachlorophthalo-
nitrile, by sulfur-centered nucleophiles, and the result-
ing substituted phthalonitriles were then converted
into polysubstituted phthalocyanines.
Table 1. Yields of sulfanyl-substituted phthalonitriles (%)
at different molar reactant ratiosa
Molar ratio I: RSH
R in RSH
R = Ph
Product
1:1
1:2
1:3
1:4
I
II
III
IV
V
0.0
b
28.0
20.6 92.0c 25.2
b
b
b
26.7
36.4
28.7
93.0d
R = t-Bu
I
b
VI
VII
VIII
IX
X
XI
XII
XIII
29.1
23.4 91.4d 22.7
b
b
b
It should be noted that exhaustive replacement of
halogen atoms in tetrahalophthalonitrile should give
only one product. If only two halogen atoms are re-
placed, four isomeric products can be obtained via
replacement at positions 3,5, 4,5, 3,6, and/or 3,4.
Only symmetric disubstituted phthalonitriles and
phthalocyanines derived therefrom were described in
[50 55], e.g., 3,6-difluoro-4,5-bis(phenylsulfanyl)-
phthalonitrile [52, 54] was reported; however, no
rigorous proofs for their structure were given.
26.3
40.0
90.2d
e
e
e
b
R = n-Bu
91.0
87.4
95.0
e
b
R = n-C10H21
89.3
a
Unless otherwise stated, the yield refers to the product isolated
by preparative column chromatography on silica gel (eluent
b
c
benzene). Traces according to TLC. After crystallization
d
from benzene hexane (2:1).
e
After crystallization from
The products were not isolated.
Taking into account the lack of sufficient informa-
tion on nucleophilic substitution in tetrahalophthalo-
nitriles, we examined reactions of tetrachlorophthalo-
nitrile with some S-nucleophiles. Here, the main goal
was to elucidate the possibility for directly synthesiz-
ing mono-, di-, tri-, and tetrasulfanyl-substituted
phthalonitriles at different reactant ratios. We per-
formed a series of experiments, where tetrachloro-
phthalonitrile was brought into reactions with thiols
(benzenethiol, butane-1-thiol, 2-methylpropane-2-thiol,
and decane-1-thiol) whose amount was varied. The
reactions were carried oy by gradually adding triethyl-
amine (as a base) to a suspension of tetrachlorophtha-
lonitrile and a required amount of the corresponding
thiol in DMF. Nucleophilic replacement occurred
even at room temperature, as followed from the brown
color of the reaction mixture and heat evolution. The
ethanol.
reaction time generally did not exceed 1 h, and it
depended on the rate of addition of triethylamine. The
progress of reactions was monitored by TLC. After
appropriate treatment of the reaction mixture, the
products were either purified by crystallization or
separated by column chromatography. The results of
the reactions of tetrachlorophthalonitrile (I) with
thiols at different reactant ratios and the yields based
on the initial dinitrile I are given in Table 1
(Scheme 1).
In the reaction of phthalonitrile I with benzenethiol,
butane-1-thiol, 2-methylpropane-2-thiol, and decane-
1-thiol in a ratio of 1:1, the reaction mixture con-
tained three compounds, one of which was initial
Scheme 1.
Cl
Cl
Cl
SR
Cl
CN
CN
CN
CN
CN
CN
Cl
CN
CN
RS
RS
RS
RS
RS
RS
CN
CN
Cl
Cl
nRSH
+
+
+
Et3N, DMF
RS
Cl
Cl
SR
SR
Cl
I
II, VI
III, VII, X, XII
IV, VIII
V, IX, XI, XIII
II V, R = Ph; VI IX, R = t-Bu; X, XI, R = n-Bu; XII, XIII, R = n-C10H21.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 6 2007

1110
VOLKOV et al.
Table 2. Melting points, elemental analyses, and IR and mass spectra of phthalonitriles II XIII
Found, %
Cl
Calculated, %
Cl
49.51 1.48 31.32 8.25
mp,
C
,
Formula
M+
CN
cm
1
C
H
N
S
C
H
N
S
II
>232a
2239 49.70 1.50 31.37 8.18 9.18 C14H5Cl3N2S
9.44 338
49.74 1.51 31.43 8.21
9.24
III
IV
V
154 155b 2232 58.32 2.54 17.07 6.91 16.32 C20H10Cl2N2S2 58.11 2.44 17.15 6.78 15.51 412
58.38 2.56 17.15 6.99 16.28
147 148c 2229 64.23 3.33 7.15 5.48 19.67 C26H15ClN2S3 64.12 3.10 7.28 5.75 19.75 486
64.29 3.37 7.21 5.54 19.72
152 153c 2218 69.16 3.62
69.22 3.63
4.90 22.54 C32H20N2S4
4.98 22.60
68.54 3.59
5.00 22.87 560
VI
210 212c 2237 44.94 2.82 33.49 8.93
45.00 2.88 33.54 8.97
9.80 C12H9Cl3N2S
9.85
45.09 2.84 33.27 8.76 10.03 318
VII 146 148c 2231 51.46 4.90 18.72 7.50 17.26 C16H18Cl2N2S2 51.47 4.86 18.99 7.50 17.18 372
51.53 4.93 18.81 7.58 17.35
VIII 159 161c 2233 56.32 6.31 8.52 6.47 22.19 C20H27ClN2S3 56.24 6.37 8.30 6.56 22.52 426
56.40 6.37 8.59 6.55 22.26
IX
141 142c 2228 59.80 7.46
5.89 26.67 C24H36N2S4
5.93 26.74
59.95 7.55
5.83 26.68 480
59.91 7.57
d
X
2234 51.51 4.84 18.91 7.52 17.03 C16H18Cl2N2S2 51.47 4.86 18.99 7.50 17.18 372
51.60 4.95 19.02 7.60 17.14
d
d
d
XI
2228 59.90 7.50
60.02 7.53
5.73 26.65 C24H36N2S4
5.86 26.78
59.95 7.55
5.83 26.68 480
XII
XIII
2232 62.15 7.71 12.92 4.92 12.13 C28H42Cl2N2S2 62.08 7.82 13.09 5.17 11.84 540
62.22 7.78 13.05 4.97 12.22
2225 70.29 10.29
70.35 10.31
3.41 16.01 C48H84N2S4
3.49 16.12
70.53 10.36
3.43 15.69
a
b
c
d
Sublimation point.
From benzene hexane (2:1).
From ethanol.
Yellow viscous oil.
dinitrile I and the two other were products of replace-
ment of one and two chlorine atoms in molecule I
by phenylsulfanyl or alkylsulfanyl group. It is notable
that each thiol gave rise to only one monosubstituted
product (these compounds were isolated and character-
ized in the reactions with benzenethiol and 2-methyl-
propane-2-thiol) and one disubstituted product, i.e.,
the reaction was highly regioselective.
twice as low as the number of carbon atoms in the
substituted dinitrile (Table 3), which indicates sym-
metric replacement of chlorine in molecule I. The
structure of the disubstituted products was proved by
the X-ray diffraction data for compound III2 (Fig. 1,
Table 4). It was found that benzenethiol replaces
chlorine atoms in positions 4 and 5 of tetrachloro-
phthalonitrile (I). Therefore, we can assume with a
high probability that the reactions with the other thiols
occur just at the same positions in molecule I. On the
other hand, these data indicate complete regioselec-
tivity in the replacement of the first chlorine atom at
C4.
Surprisingly, in the reactions of compound I with
all the examined thiols in a ratio of 1:2 we isolated
in high yields only the corresponding disubstitution
products III, VII, X, and XII, while only traces of
mono- and trisubstituted compounds were detected.
Analogous patterns were observed at reactant ratios of
1:3 and 1:4. In the former case, mixtures of three
compounds (di-, tri-, and tetrasubstituted) were
formed, and in the latter, only tetrasubstituted com-
pounds V, IX, XI, and XIII (Table 2).
Insofar as symmetrically substituted disulfanyldi-
chloro- and tetrasulfanylphthalonitriles turned out to
be most accessible from the preparative viewpoint,
just these compounds were used to synthesize sulfanyl-
The number of signals in the 13C NMR spectra of
disubstituted compounds III, VII, X, and XII was
2
Detailed X-ray diffraction data will be reported elsewhere.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 6 2007

PHTHALOCYANINES AND RELATED COMPOUNDS: XLIII.
1111
c
C12
C18
0
C13
C14
a
C17
C16
S2
C19
C20
C11
C9
C10
C15
S1
C5
C4
C3
C6
Cl2
C1
C2
C8
C7
N1
b
N2
Fig. 1. Structure of the molecule of 3,6-dichloro-4,5-bis(phenylsulfanyl)phthalonitrile (III) and its crystal packing according
to the X-ray diffraction data.
substituted phthalocyanines (their tetramerization
should produce individual compounds rather than
mixtures of randomers). Metal phthalocyanines were
synthesized under standard conditions of template
synthesis, by heating the corresponding substituted
phthalonitrile with a metal salt in the presence of
ammonium molybdate. The reaction mixtures (in
some cases, o-dichlorobenzene was added to ensure
homogeneous conditions) were gradually heated from
140 to 210 C and were held for about 3 h at that
temperature. We thus obtained a series of poly[phe-
nyl(alkyl)sulfanyl]-substituted complexes XIV XXIII
in 20 40% yield (Scheme 2, Table 5).
The following differences in the reactivity of
phenylsulfanyl- and alkylsulfanyl-substituted phthalo-
nitriles should be noted. Both bis(phenylsulfanyl)di-
chloro and tetrakis(phenylsulfanyl) derivatives III and
V smoothly afforded the corresponding polysubsti-
tuted phthalocyanines XIV XVII and XXII, XXIII
which were isolated in about 40% yield (after purifica-
tion). The yields of phthalocyanine metal complexes
from bis(alkylsulfanyl)dichloro-substituted phthalo-
nitriles X and XII having linear alkyl groups were
much poorer: they did not exceed 20%. We succeeded
in effecting tetramerization of tetrakis(alkylsulfanyl)-
phthalonitriles XI and XIII only in an inert atmos-
Table 3. 13C and 1H NMR spectra of some phenylsulfanyl-substituted phthalonitriles
Comp.
no.
13C NMR spectrum, C, ppm
1H NMR spectrum, , ppm
IIIa
147.9 (CAr S), 141.2 (CAr Cl), 133.6 (CAr S), 129.8 (CAr H), 129.6 7.09 7.18 m (4H), 7.22 7.35 m (6H)
(CAr H), 128.1 (CAr H), 117.8 (CAr CN), 112.5 (C N)
7.02 d (8H, JHH 8 Hz), 7.18 7.40 m (12H)
150.3 (CAr S), 144.4 (CAr Cl), 116.0 (CAr CN), 114.5 (C N), 56.1 1.27 1.36 m (9H), 1.42 1.38 m (9H)
(C CH3), 55.7 (C CH3), 32.2 (CH3), 32.1 (CH3), 31.9 (CH3)
Vb
VIIb
IXb
Xb
1.25 s (18H), 1.40 s (18H)
149.1 (CAr S), 140.8 (CAr Cl), 117.3 (CAr CN), 114.1 (C N), 36.9 0.88 t (6H), 1.30 1.54 m (8H), 3.10 t
(CH2 S), 32.0 (CH2), 22.0 (CH2), 14.1 (CH3)
(4H)
XIb
0.80 0.90 m (12H), 1.30 1.52 m (16H),
3.05 3.20 m (8H)
XIIb
149.2 (CAr S), 139.8 (CAr Cl), 117.9 (CAr CN), 114.1 (C N), 37.2 0.86 t (6H), 1.40 1.54 m (32H), 3.10 t
(CH2 S), 32.0 (CH2), 29.8 (CH2), 29.6 (CH2), 29.4 (CH2), 29.2 (4H)
(CH2), 28.7 (CH2), 28.5 (CH2), 22.8 (CH2), 14.6 (CH3)
a
b
In CDCl .
In DMSO-d .
6
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 6 2007

1112
VOLKOV et al.
Table 4. Selected bond lengths and bond angles in the
molecule of 3,6-dichloro-4,5-bis(phenylsulfanyl)phthalo-
nitrile (III) according to the X-ray diffraction data
phere. The zinc complex of hexadecakis(decylsul-
fanyl)phthalocyanine was isolated in an inert atmos-
phere only as a crude product (
750 nm; chloro-
max
form), for it decomposed during chromatographic
purification. Presumably, per(alkylsulfanyl)-substi-
tuted phthalocyanines are very sensitive to atmos-
pheric oxygen. Unfortunately, we failed to synthesize
the corresponding phthalocyanines from symmetric
Bond
d,
Angle
, deg
S1 C4
1.775(5)
1.775(5)
1.772(4)
1.124(5)
1.149(6)
1.374(6)
1.397(5)
1.484(7)
1.424(7)
1.402(6)
1.411(4)
1.374(6)
1.391(6)
1.387(6)
1.375(6)
C4S1C9
101.7(2)
118.4(5)
120.6(5)
121.7(4)
116.6(4)
121.7(3)
119.1(5)
120.8(3)
120.0(4)
176.1(5)
120.3(4)
118.9(4)
119.9(5)
120.0(5)
119.9(5)
S1 C9
C3C2C1
C1C2C8
C2C3C4
C2C3Cl1
C4C3Cl1
C3C4C5
C3C4S1
Cl1 C3
N1 C7
N2 C8
C2 C3
C1 C2
C1 C7
C2 C8
C3 C4
C4 C5
C9 C10
C9 C14
C10 C11
C11 C12
tert-butylsulfanylsubstituted
and IX.
phthalonitriles
VII
Copper and zinc complexes of phenylsulfanyl-
phthalocyanines (XIV, XVII, XXII, and XXIII) and
copper complex XVIII derived from butylsulfanyl-
substituted phthalocyanine are almost insoluble in
most organic solvents, except for such dipolar aprotic
solvents as DMF and DMSO on heating or at the
boiling point. Phenylsulfanyl-substituted chloroalu-
minum and dichlorotitanium complexes XV and XVI
are readily soluble both in DMSO and DMF and in
less polar benzene, chloroform, and methylene chlo-
ride due to the presence of axial ligands deviating
from the macroring plane. Similar dehavior is shown
by decylsulfanyl derivatives XX and XXI due
to the presence of long-chain aliphatic groups. All
zinc complexes are also readily soluble in pyridine
due to coordination of the latter at the central metal
ion.
C5C4S1
N1C7C1
C10C9C14
C10C9S1
C9C10C11
C12C11C10
C11C12C13
Scheme 2.
R1
R2
R3
CN
CN
We have recorded the electronic absorption spectra
of phthalocyanine metal complexes XIV XXIII in
organic solvents (Figs. 2, 3; Table 5). It is known that
R4
III, V, X, XII
M2+, (NH4)2MoO4
XVI
XV
XXII
XVIII
XX
R3
R2
R1
N
R4
R1
N
R1
R4
N
M
N
R2
R3
R2
R3
N
N
R4
N
N
R1
R4
,nm
400
500
600
700
800
Fig. 2. Electronic absorption spectra of 1,4,8,11,15,18,
22,25-octachloro-2,3,9,10,16,17,23,24-octakis(phenyl-
sulfanyl)phthalocyanine complexes with chloroaluminum
(XV, chloroform) and dichlorotitanium (XVI, benzene)
and of copper complexes with 2,3,9,10,16,17,23,24-octa-
kis(butylsulfanyl)-1,4,8,11,15,18,22,25-octachloro-
(XVIII, 1,2-dichlorobenzene), 1,4,8,11,15,18,22,25-
octachloro-2,3,9,10,16,17,23,24-octakis(decylsulfanyl)-
(XX, chloroform), and hexadecakis(phenylsulfanyl)-
phthalocyanines (XXII, DMSO).
R2
R3
XIV XXIII
III, XIV XVII, R1 = R4 = Cl, R2 = R3 = PhS; X, XVIII,
XIX, R1 = R4 = Cl, R2 = R3 = n-BuS; XII, XX, XXI,
R1 = R4 = Cl, R2 = R3 = n-C10H21S; V, XXII, XXIII,
R1 = R2 = R3 = R4 = PhS; XIV, XVIII, XX, XXII, M =
Cu; XV, M = AlCl; XVI, M = TiCl2; XVII, XIX, XXI,
XXIII, M = Zn.
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PHTHALOCYANINES AND RELATED COMPOUNDS: XLIII.
1113
Table 5. Elemental analyses and long-wave absorption maxima in the electronic spectra of phthalocyanine metal
complexes XIV XXIII
Found, %
Cl
Calculated, %
Cl
Comp.
no.
,
max
nm
Formula
C
H
N
S
C
H
N
S
XIV
XV
746a 56.04 2.35 16.70
56.10 2.36 16.76
6.57
6.61
6.57
6.62
6.38
6.42
6.55
6.58
7.27
7.34
7.29
7.35
5.07
5.13
5.01
5.09
4.88
4.93
4.85
4.94
15.00 C80H40Cl8CuN8S8
15.09
14.98 C80H40AlCl9N8S8
15.06
14.58 C80H40Cl10N8S8Ti
14.64
14.02 C80H40Cl8N8S8Zn
14.08
16.54 C64H72Cl8CuN8S8
16.59
16.37 C64H72Cl8N8S8Zn
16.44
11.58 C112H168Cl8CuN8S8 60.43
11.62
11.40 C112H168Cl8N8S8Zn
11.46
22.16 C128H80CuN8S16
22.25
22.13 C128H80N8S16Zn
22.20
55.94
55.99
54.45
55.92
49.48
49.45
2.33
2.33
2.27
2.33
4.64
4.64
7.55
7.55
3.47
3.49
16.55 6.52 14.92
18.63 6.53 14.93
20.14 6.35 14.52
16.54 6.52 14.91
18.04 7.22 16.49
18.03 7.21 16.48
12.59 5.03 11.51
12.58 5.03 11.51
4.86 22.23
750b 55.62 2.35 18.71
55.70 2.37 18.79
XVI
XVII
768c 54.97 2.33 20.00
55.04 2.37 20.10
726a 56.46 2.30 16.69
56.53 2.34 16.75
XVIII 741d 49.38 4.70 17.93
49.42 4.73 17.99
XIX
XX
723e 49.49 4.68 17.91
49.53 4.72 17.98
734b 60.34 7.62 12.51
60.37 7.65 12.55
722e 60.32 7.65 12.48
60.38 7.67 12.53
783a 66.51 3.37
XXI
XXII
60.40
66.67
66.60
66.58 3.42
XXIII 759a 66.49 3.50
4.85 22.22
66.53 3.54
a
b
c
d
e
In DMSO.
In chloroform.
In benzene.
In 1,2-dichlorobenzene.
In methylene chloride.
introduction of both chlorine atoms [56, 57] and
phenylsulfanyl groups [35, 58, 59] into phthalocya-
nine macroring induces a red shift of the Q band. In
fact, the Q band in the spectra of the obtained com-
plexes was considerably displaced to longer wave-
lengths. Comparison of the spectral data for the
copper and zinc complexes with those reported for
octachloro- [56] and octakis(phenylsulfanyl)-substi-
tuted phthalocyanines [35, 59] shows that introduction
of eight phenylsulfanyl groups into the -positions of
the macroring leads to a 45 50-nm red shift of the Q
band and that introduction of eight chlorine atoms into
the -positions induces an analogous shift by about
30 nm. In the spectra of copper complexes XIV,
XVIII, and XX and zinc complexes XVII, XIX, XXI,
each having eight sulfanyl groups in the -positions
and eight chlorine atoms in the -positions, the Q
band is displaced by 60 70 nm toward longer wave-
lengths; i.e., some additivity of the substituent effects
on the position of the Q band can be spoken about.
On the other hand, comparison of the spectra of the
recently reported copper and zinc phthalocyanines
having eight hexylsulfanyl groups in the -positions
XIX
XXIII
XVII
XXI
400
500
600
700
800
, nm
Fig. 3. Electronic absorption spectra of zinc complexes
with 1,4,8,11,15,18,22,25-octachloro-2,3,9,10,16,17,23,
24-octakis(phenylsulfanyl)- (XVII, DMSO), 2,3,9,10,
16,17,23,24-octakis(butylsulfanyl)-1,4,8,11,15,18,22,25-
octachloro- (XIX, methylene chloride), 1,4,8,11,15,18,
22,25-octachloro-2,3,9,10,16,17,23,24-octakis(decylsul-
fanyl)- (XXI, methylene chloride), and hexadecakis-
(phenylsulfanyl)phthalocyanines (XXIII, DMSO).
of the benzene rings [34] (
783 and 781 nm,
max
respectively) with the spectra of hexadecakis(phenyl-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 6 2007

1114
VOLKOV et al.
sulfanyl)phthalocyanine complexes XXII (Cu) and
XXIII (Zn) shows the absence of additivity. Thus, on
the basis of our results and published data, the ex-
amined substituents rank as follows with respect to
their effect on the position of the Q band in the elec-
Synthesis of sulfanyl-substituted phthalocyanine
metal complexes (general procedure). A 10-ml round-
bottom flask was charged with a finely ground mix-
ture of substituted phthalonitrile (0.5 mmol), metal
salt [0.13 mmol; copper(II) chloride, aluminum(III)
chloride, zinc(II) acetate, or titanium(IV) chloride],
and ammonium molybdate (2 3 mg). The flask was
immersed into a metal bath preliminarily heated to
140 C, and the mixture was gradually heated to
210 C and was kept for 3 h at that temperature. In the
synthesis of complexes XIV, XVII, XVIII, XXII,
and XXIII, the resulting melt was cooled, thoroughly
ground, and repeatedly extracted with boiling ethanol
and hot distilled water to remove impurities; the
residue was reprecipitated twice from hot DMF with
ethanol. Complexes XV, XVI, and XIX XXI were
isolated by column chromatography on silica gel
using benzene (XV), chloroform ethanol, 1:4 (XVI),
or methylene chloride (XIX XXI) as eluent. The
yields were 20 40%.
tronic absorption spectrum: ( -Cl)8 < ( -Cl)8 < Cl16
<
( -RS)8 < ( -Cl)8-( -RS)8 < (RS)16 < ( -RS)8. Com-
plexes formed by different metals with phthalocya-
nines having the same substitution pattern give rise to
the series Zn < Cu < AlCl < TiCl2, in keeping with
the position of the Q band in the electronic spectrum.
These results are consistent with the data reported by
other authors.
Thus, the results of our study on the reactions of
tetrachlorophthalonitrile with benzenethiol and alkane-
thiols showed that nucleophilic substitution of chlo-
rine atoms in the former is completely regioselective:
the 4-chlorine atom is replaced first, and the sub-
sequent replacement occurs at the 5-position. The
reactions of tetrachlorophthalonitrile with thiols in
ratios of 1:2 and 1:4 give in high yields the corre-
sponding 4,5-bis[phenyl(alkyl)sulfanyl]-3,6-dichloro-
phthalonitriles and tetrakis[phenyl(alkyl)sulfanyl]-
phthalonitriles which can be converted into a number
of substituted phthalocyanine metal complexes.
ACKNOWLEDGMENTS
The authors thank Dr. K.Yu. Suponitskii (Senior
Researcher at the Nesmeyanov Institute of Organo-
metallic Compounds, Russian Academy of Sciences)
for performing X-ray analysis of compound III.
EXPERIMENTAL
Elemental analysis was performed on a Hewlett
Packard HP-185B C,H,N analyzer. The IR spectra
were recorded in KBr on an FSM 1201 spectrometer
with Fourier transform. The mass spectra (electron
impact, 70 eV) were obtained on an MKh-1321 in-
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