Nucleophilic substitution in 4-bromo-5-nitrophthalodinitrile: XV. Synthesis of bis-4,5-(phenylsulfanyl)phthalonitrile, octakis-4,5-(phenylsulfanyl)phthalocyanines, and their sulfo and alkylsulfamoyl derivatives

Article abstract of DOI:10.1134/S1070363217070209

Novel water- and organic-soluble derivatives of octakis-4,5-(sulfanylphenyl)phthalocyanine and its magnesium and aluminum complexes were synthesized starting from 4,5-bis(phenylsulfanyl)phthalonitrile obtained by nucleophilic substitution of the bromine a

Full text of DOI:10.1134/S1070363217070209

ISSN 1070-3632, Russian Journal of General Chemistry, 2017, Vol. 87, No. 7, pp. 1562–1571. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © S.А. Znoiko, E.S. Golovashova, O.V. Potekhina, D.B. Berezin, M.А. Serova, V.E. Maizlish, G.P. Shaposhnikov, 2017, published in
Zhurnal Obshchei Khimii, 2017, Vol. 87, No. 7, pp. 1169–1178.
Nucleophilic Substitution in 4-Bromo-5-nitrophthalodinitrile:
1
XV. Synthesis of Bis-4,5-(phenylsulfanyl)phthalonitrile,
Octakis-4,5-(phenylsulfanyl)phthalocyanines,
and Their Sulfo and Alkylsulfamoyl Derivatives
S. А. Znoiko*, E. S. Golovashova, O. V. Potekhina, D. B. Berezin,
M. А. Serova, V. E. Maizlish, and G. P. Shaposhnikov
Research Institute of Macroheterocyclic Chemistry, Ivanovo State University of Chemical Technology,
pr. Sheteremetevskii 7, Ivanovo, 153000 Russia
*
e-mail: znoykosa@yandex.ru
Received February 15, 2017
Abstract—Novel water- and organic-soluble derivatives of octakis-4,5-(sulfanylphenyl)phthalocyanine and its
magnesium and aluminum complexes were synthesized starting from 4,5-bis(phenylsulfanyl)phthalonitrile
obtained by nucleophilic substitution of the bromine and nitro group in 4-bromo-5-nitrophthalonitrile. Spectral
and luminescence characteristics of the newly synthesized compounds were studied.
Keywords: phthalocyanines, electronic absorption spectra, fluorescence spectra, association
DOI: 10.1134/S1070363217070209
The porphyrin chromophore, which is the key
structural unit of both natural and synthetic tetra-
pyrrole compounds, can be modified by the replace-
ment of the methine by aza bridges, as well as β anneal-
tion of carbo- and heterocyclic fragments and introduc-
tion of various substituents [2–4]. Phthalocyanine (Pc)
and its derivatives and metal complexes are closely
related to porphyrin. Due to their intense blue green
color, high coloring properties, and photo- and che-
mical stability; these compounds are used as dyes and
pigments [2], highly efficient catalysts [2, 5], com-
ponents of lubricant compositions [6], and electro-
chromic materials [4, 7]. Phthalocyanines are also used
in information recording and storage systems [4], as
well as in photodiagnostics and photodynamic therapy
therapeutic window range (630–730 nm), and intense
fluorescence and/or high singlet oxygen quantum yield.
In this connection, Pcs containing peripheral phenyl-
sulfanyl substituents appear to hold great promise,
because such substituents are known to cause a
bathochromic shift of the longwave (Q) band in the
electronic absorption (UV-Vis) spectra [10–12]. The
presence of an aluminum atom in the macrocyclic
core, too, is known to shift the Q band to longer waves
and, in addition, imparts well-defined luminescence
properties to such Pc derivatives [2, 10–12]. For
example, Maevskii et al. [13] have recently reported
the development of a second-generation photosensitizer
Photosense on the basis of a sulfonated aluminium Pc
derivative with combines near-optimal photophysical
characteristics and other necessary properties second-
generation photosensitizer Photosence [13]. Furthermore,
Pc derivatives were proposed as promising candidates
for the development of efficient photosensitizing
agents against bacterial and fungal infections [14, 15].
[8–10].
Research into the photodynamic therapy applica-
tions of these compounds seems to be the most urgent
issue at present [8–10]. Sensitizers for photodynamic
therapy should meet a number of requirements [10]. In
particular, the molecule should have both a hydro-
phobic and a hydrophilic units, peak absorbance in the
The disadvantage of phenylsulfanyl-substituted Pcs
is that they are insoluble in water. The water solubility
of Pc derivatives is generally enhanced via peripheral
sulfo substitution [2].
1
For communication XIV, see [1].
1
562

NUCLEOPHILIC SUBSTITUTION IN 4-BROMO-5-NITROPHTHALODINITRILE: XV.
1563
Scheme 1.
NC
NC
Br
S
S
NO2
1
N
N
N
M
N
HS
S
S
S
S
DMF, K CO ,
N
N
2
3
o
1
00 C, 12 h
N
N
NC
NC
S
S
а, b
2
S
S
3, 4
a, Mg(OAc)
2
·4H
2
O 180–185°C, 2 h; b, AlCl 200°C, 2 h; M = Mg(II) (3), Al(III) (4).
3
The goal of the present work was to synthesize
novel water- and organic-soluble derivatives of a
highly symmetrical octakis(phenylsulfanyl)-substituted
phthalocyanine and its aluminum complex.
Further on we reacted compound 2 with magnesium
acetate tetrahydrate or anhydrous aluminum chloride at
180–200°С for 2 h to obtain highly symmetrical octakis-
substituted metal phthalocyanines 3 and 4 (Scheme 1).
It was found that complex 3 in chloroform under-
went dissociation even upon short standing because of
the presence of traces of HCl in the solvent. As a result,
the UV-Vis spectrum of this phthalocyanine, which
initially showed a single Q-band in the longwave
region (703 nm), later got more complicated and
already showed two of almost equal intensity at 675
and 710 nm. This transformation implied that the sym-
metry of Pc chromophore had changed from D ,
The first stage of the work involved the synthesis of
4
,5-bis(phenylsulfanyl)phthalonitrile 2 via the nucleo-
philic substitution of bromine and nitro group in 4-bromo-
-nitrophthalonitrile 1 [16] by phenylsulfanyl frag-
ments (Scheme 1). The reaction was performed in
aqueous DMF at 80–85°С for 9 h in the presence of
potassium carbonate as a deprotonating agent [17]. The
yield of compound 2 was 85%.
5
4
h
Compound 2 was previously synthesized starting
from 4,5-dichlorophthalonitrile [18, 19]. Tau and
Nyokong [18] performed this synthesis in dry DMSO
at 90°С for 14.5 h, whereas Koptyaev et al. [19] used
dry n-hexanol as a solvent and accomplished the process
at 110°С for 8 h. The yield of the target product 2 was
which is characteristic of metal Pcs, to D , which is
2
h
characteristic Pc ligands [20] and was indicative of
the formation of a metal-free phthalocyanine 3а
(
Scheme 2).
Products 3 and 4 were identified by elemental
analysis, MALDI-TOF mass spectrometry, and UV-Vis
and IR spectroscopy. According to the mass spectral
data, compound 4 contains a chlorine extra ligand on
aluminum. The IR spectra of metal phthalocyanines 3
and 4 no longer show the stretching vibration band of
the cyano groups of the starting phthalonitrile 2 but at
the same time preserve the С–S–С stretching vibration
8
2–83% [18, 19]. Comparing the published and our
own results, we can see that the use of 4-bromo-5-
nitrophthalonitrile instead of commercial 4,5-dichloro-
phthalonitrile allows 4,5-bis(phenylsulfanyl)phthalo-
nitrile to be prepared with a slightly higher yield and in
slightly milder conditions and a shorter time.
–
1
В MALDI
̶
TOF mass spectrum of phthalonitrile 2
band at 695 cm . The IR spectrum of the metal-free
phthalocyanine 3а contains the N–H stretching vibra-
tion bands of the endocyclic imino groups at 3055 and
contained a molecular ion peak at m/z 345.72. The
elemental analysis and IR spectrum were in a good
agreement with those reported in [18, 19].
–
1
1008 cm .
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 7 2017

1
564
ZNOIKO et al.
Scheme 2.
S
S
S
S
N
N
N
N
N
Mg
N
N
N
S
S
S
S
S
S
S
S
CHCl3
N
N
NH
HN
N
N
N
N
S
S
S
S
3
3a
Scheme 3.
3, 4
o
_
SOCl , HSO Cl 25 C 0.5 1 h
2
3
ClO2S
SO Cl
S
S
SO Cl
HO3S
S
S
SO H
2
3
SO Cl
SO H
2
2
SO H
3
3
N
N
N
N
N
M
N
N
M
N
S
S
S
S
S
S
o
S
S
H O, 100 C
2
N
N
N
N
N
N
N
N
SO Cl
SO Cl
SO
HO3S
3
H
SO
H
3
2
2
ClO2S
S
S
SO Cl
S
S
SO H
2
3
5, 6
7, 8
M = Mg (3), HH (5, 7), AlCl (4, 6, 8).
Compounds 3 and 4 were used as precursors for
their subsequent chemical modification to octakis-4,5-
phenylsulfanyl)phthalocyanine sulfonyl chlorides 5
and 6. To this end, Pc derivatives 3 and 4 were reacted
with a mixture of chlorosulfonic acid and thionyl
chloride (Scheme 3). The reaction time of aluminum
complex 4 was 1 h. Compound 3 underwent
dissociation to form the corresponding metal-free
derivative, and, therefore, it was allowed to react no
longer than 0.5 h, because upon longer reaction time
the reaction product destroyed and the yield was much
lower.
(
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 7 2017

NUCLEOPHILIC SUBSTITUTION IN 4-BROMO-5-NITROPHTHALODINITRILE: XV.
1565
Scheme 4.
ClO2S
SO Cl
S
S
SO Cl
ХO3S
SO Х
S
S
SO Х
3
2
SO Cl
SO Х
2
2
3
3
N
N
N
N
N
N
N
N
(
СH ) СO, HХ
3 2
S
S
S
S
S
S
_
o
S
S
6
0 65 C, 1 h
NH
HN
NH
HN
N
N
N
N
SO Х
3
SO Х
3
SO Cl
SO Cl
SO
ХO3S
3
Х
2
2
ClO2S
S
S
SO Cl
S
S
2
5
9, 10
2 5 2
X = N(C H ) (9), NHC18H37 (10).
The synthesized compounds were characterized by
Н NMR spectroscopy. The Н NMR spectrum of com-
pound 5 displays a downfield singlet signal (δ 7.71 ppm)
from 16 phthalocyanine benzene ring protons. The
signal at 7.54 ppm belongs to the phenyl protons
located ortho to the S bridge, and the signal at
In view of the fact that metal-free alkyl-substitute
Pc derivatives can exhibit liquid-crystalline properties
[21, 22], we synthesized alkylsulfamoyl derivatives 9
and 10, starting from metal-free phthalocyanine
sulfonyl chloride 5 (Scheme 4). The synthesis involved
treatment of solution compound 5 in acetone with a
double molar excess of diethyl- or octadecylamine
under reflux for 1 h. The yields of compounds 9 and 10
were 84 and 67%, respectively.
1
1
7
.63 ppm is assignable to the benzene ring protons
ortho to the sulfo groups.
In the UV-Vis spectrum of compound 5 in chloro-
The synthesized compounds were insoluble in
water, scarcely soluble in DMF, and readily soluble in
chloroform. Solutions of compounds 9 and 10 in con-
centrated sulphuric acid rapidly decolorized, implying
decomposition of the solutes.
form, two longwave bands are observed at 675 and
7
3
10 nm, which suggests dissociation of phthalocyanine
during synthesis and isolation of the resulting
sulfonyl chloride.
Due to their high reactivity, compounds 5 and 6
could be immediately used to synthesize sulfonic acids
and alkylsulfamoyl derivatives. Sulfonic acids 7 and 8
were obtained by hydrolysis of the corresponding sulfonyl
chlorides (Scheme 3). The products were characterized
Alkylsulfamoyl derivatives 9 and 10 were charac-
1
terized by elemental analysis, UV-Vis and Н NMR spec-
troscopy, and MALDI-TOF mass spectrometry. The
mass spectrum of compound 9 contains a signal at m/z
2594.57, corresponding to the molecular ion [M + Na +
1
by elemental analysis, UV-Vis and Н NMR spectro-
+
K] .
scopy, and MALDI-TOF spectrometry. The mass
spectra contain peaks at m/z 2029.79 and 2161.65,
assigned to the [M + Li + 2H] and [M + 2Na] ions.
To decrease the hygroscopicity of sulfo derivative
8, it was converted into ammonium salt 11 (Scheme 5).
+
+
1
The Н NMR spectra of sulfonic acids 7 and 8
One of the important requirements to photo-
sensitizers for photodynamic therapy consists in the
lack of tendency for association in solutions of biocom-
patible surfactants and other model systems, because it
is the nonassociated form that is responsible for the
efficiency of singlet oxygen generation [23, 24]. As
known [25, 26], molecular association is accompanied
display show downfield signals of the protons in
position 3, located ortho to the sulfo groups, at 7.96 (7)
and 8.57 ppm (8), respectively. The signal at 7.63 ppm,
which was observed in the spectrum of the starting
sulfonyl chloride, disappears, and the SO H proton
appears as a singlet at 11.20 (7) or 11.36 (8) ppm.
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 7 2017

1
566
ZNOIKO et al.
Scheme 5.
HO3S
SO H
S
S
SO H
H NO S
S
S
SO NH
3 4
3
4
3
SO H
SO NH
3
3
3
4
SO NH
3
4
Cl
N
Cl
N
N
N
N
Al
N
NH OH
N
Al
N
4
S
S
S
S
S
S
S
S
_
o
9
0 100 C
N
N
N
N
N
N
N
N
SO NH
3
4
SO NH
4
SO H
SO H
3
3
3
HO3S
S
S
SO H
H NO S
S
S
SO Х
3
3
4
3
8
11
by fluorescence quenching because of the increased
probability of intermolecular radiationless transitions
in the associates. As a result, the relaxation of the
excitation state of the sensitizer is complicated by the
vibrational process of internal conversion, thereby
decreasing the fluorescence quantum yield. Therefore,
an aggregated sensitizer exhibits a lower photo-
dynamic activity than a non-aggregated one [27, 28].
The UV-Vis spectrum of aluminum octakis-4,5-(4-
sulfophenylsulfanyl)phthalocyanine 8 in water and
aqueous alkaline solutions provides evidence to show
that, due to the presence of eight strong hydrophilic
centers (sulfo groups), this compound is present in an
associated form, namely, the spectrum displays a
broadened absorption band with its maximum
(678 nm) in the transparency window (Fig. 2), as well
as a shoulder at 710–715 nm. The UV-Vis spectrum of
ammonium salt 11 and the starting sulfonic acid 8 are
identical to each other.
We have analyzed the UV-Vis and fluorescence
spectra of octakis-4,5-(phenylsulfanyl)phthalocyanineа
3
а and its aluminum complex 4, as well as sulfo
Compound 8 is readily soluble in 96% ethanol,
derivatives 7 and 8 (see table). The UV-Vis spectrum
of aluminum phthalocyanine 4 in chloroform displays
a visible absorption band. The extinction coefficient of
this band (ε 98700) and the fact that it follows the
Lambert–Bouguer–Beer law point to the absence of
association in this solvent. It should be noted that, like
all the fluorescence spectra obtained in the present
work, the fluorescence spectrum of compound 4 is a
mirror image of its UV-Vis spectrum (Fig. 1). The
Stokes shift is 9 nm (see table).
where it is also associated, and it is only at the concentra-
tion of 0.5×10 M that the molecule is present in a
completely free form. Therewith, the absorbance at
–
6
6
78 nm decreases and at 715 nm increases. Dilution to
–
7
the concentration of 0.5×10 M leads to an appearance
of bands at 645 and 725 nm, and the first of these
bands is 4 times weaker than the second (Fig. 3).
Figure 4 shows the electronic absorption and emis-
sion spectra octakis-4,5-(phenylsulfanyl)phthalocyanine
Absorption and fluorescence spectroscopy data for compounds 3a, 4, 7, and 8
Comp. no.
Solvent
λ
max, nm
λ
fl, nm
722
Stokes shift, nm
11
Фfl, %
3
4
7
8
а
CHCl
3
(675), 710
725
7.14
32.97
18.46
22.13
CHCl
3
734
724
727
9
9
С
2
Н
Н
5
ОН (aq.)
ОН (aq.)
(648), 715
716
С
2
5
11
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NUCLEOPHILIC SUBSTITUTION IN 4-BROMO-5-NITROPHTHALODINITRILE: XV.
1567
D
I
rel
D
λ, nm
λ, nm
–
5
Fig. 1. (1) Absorption and (2) emission spectra of com-
Fig. 2. Electronic absorption spectra (0.5×10 M) of com-
pound 8 in (1) DMF, (2) water, and (3) H SO
–
7
pound 4 in chloroform (0.50×10 M).
2
4
.
3
а in chloroform, as well as the spectra of the cor-
Thus, in the present work we synthesized water-
soluble (sulfonic acids and their salts) and organic-
soluble [diethyl and octakisdecylsulfamoyl-substituted]
derivatives octakis-4,5-(sulfanylphenyl)phthalocyanine
and its aluminum complex obtained starting from 4,5-
bis(sulfanylphenyl)phthalonitrile. It was found that the
starting octakis-4,5-(sulfanylphenyl)phthalocyanine and
its aluminum complex, as well as aluminum oktakis-
responding sulfo derivative 7 in 96% ethanol. Unlike
the absorption spectrum of compound 3а, which
displays two strong longwave bands corresponding to
the electronic transitions in the main conjugation
contour of the phthalocyanine chromophore, the
emission spectrum contains a single band at 722 nm
(
Fig. 3, see table).
The fluorescence quantum yields of complexes 4
4
,5-(4-sulfophenylsulfanyl)phthalocyanine exhibit
and 8 are higher than those of the corresponding
ligands 3а and 7 (see table). This fact can be explained
by that the introduction of a metal containing an extra
ligand into compounds 3а and 7 decreases the
tendency of the resulting metal phthalocyanines for
aggregation.
luminescent properties. The fluorescence quantum
yield aluminum oktakis-4,5-(4-sulfophenylsulfanyl)-
phthalocyanine and its sulfo derivative is higher than
The value of the Stokes shift of bands in the UV-Vis
and fluorescence spectra of porphyrins and phthalo-
cyanines relates to the degree of noncоplanarity of the
macrocycles [29]. Thus, the Stokes shift increases
from 6 to 11 nm in going from a tetra-tert-butyl-
substituted phthalocyanine [29] to phthalocyanine 3а
containing eight bulky phenylsulfanyl fragments.
D
2
I
rel
D
Alkylsulfamoyl-substituted phthalocyanines 9 and
1
0, which contain branched or long-chain alkyl
fragments, are associated even in chloroform (Fig. 5),
as evidenced by the broadening of longwave absorp-
tion bands and the presence in the range 615–630 nm
of bands half as intense as the Q band. Therewith, this
intensity ratio does not change via an increase in the
intensity of the Q band even when the solutions are
λ, nm
Fig. 3. (1, 2) Absorption and (3) emission spectra of compound 8
–
7
–5
–7
diluted to a concentration of 10 M.
in ethanol. c, M: (1) 1.2×10 and (2, 3) 0.5×10 M.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 7 2017

1
568
ZNOIKO et al.
1
rel
2
rel
D
2
D
1
I
I
λ, nm
–
7
Fig. 4. (1, 2) Absorption and (3, 4) emission spectra of compounds (1, 3) 3а in chloroform and (2, 4) 7 in ethanol (0.5×10 M).
those of the corresponding ligands, which is explained
by the fact that the metal atom and the extra ligand on
it decrease the tendency of the complexes for aggregation.
solutions in CDCl (5) or DMSO-d (7, 8) were
3 6
obtained on
a
Bruker DRX-500 spectrometer.
Elemental analysis was per-formed on a Thermo
FlashEA 1112 CHNSO analyzer. Before analysis the
samples were heated at 110°С for 2 h. The MALDI-
TOF mass spectra were measured on a Shimadzu
Biotech Axima Confidence in the positive ion mode,
using 2,5-dihydroxybenzoic acid as a matrix. The
samples were prepared mixing equal volumes of
chloroform or aqueous ethanol solutions of the
EXPERIMENTAL
The UV-Vis spectra were recorded in organic
solvents (DMF and chloroform), aqueous alkaline
media, and concentrated sulfonic acid on a HITACHI
U-2001 spectrophotometer at room temperature in the
range 325–900 nm. The IR spectra were run on an
Avatar 360 FTIR ESP instrument in the range 400–
–4
–5
analytes (10 –10 M) with a THF solution of the
matrix (30 mg/mL). The fluorescence spectra were
measured on a Cary Eclipse Varian spectrofluorimeter
in quartz cells (10×10 mm) for ethanol or chloroform
solutions with the optical density of no higher than 0.1
–
1
4
000 cm for thin films (chloroform, 2–6, 9, 10) and
1
KBr pellets (7, 8, 11). The Н NMR spectra of
D
(
at maximum absorption).
The fluorescence quantum yields were determined
by the comparison method by Eq. (1) using as
reference a solution of PcZn in propan-1-ol (Φ = 0.45,
fl
λeх = 600 nm).
GR n2
G n2
A (λ )
S
1
-prop
ex
R
SH
F
Φ =
Φ .
(1)
F
S
R
A (λ )
THF
ex
Here G is the integrated emission area; n, refractive
index of the solvent; А, optical density (≤ 0.02) at the
excitation wavelength; and Φ Ф, fluorescence quantum
fl
yield.
4
-Bromo-5-nitrophthalonitrile (1) was syn-
thesized as described in [16]. mp 140–142°С. Found,
λ, nm
%
: C 38.10; Н 0.76; N 16.50. C H BrN O . Calculated,
Fig. 5. Electronic absorption spectra in chloroform (с =
8 2 3 2
–
5
0
.65×10 M) of compounds (1) 5, (2) 9, and (3) 10.
%: C 38.16; Н 0.80; N 16.67.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 7 2017

NUCLEOPHILIC SUBSTITUTION IN 4-BROMO-5-NITROPHTHALODINITRILE: XV.
1569
Bis-4,5-(phenylsulfanyl)phthalonitrile (2). A solu-
7.42; S 17.55. C H AlClN S . Calculated, %: C
8
0
48
8 8
tion of 2.76 g (0.02 mol) of potassium carbonate in
66.72; H 3.36; N 7.78; S 17.81.
7
(
0
mL of water was added to a solution of 2.52 g
0.01 mol) of compound 1 and 2.2 g (2.36 mL,
.02 mol) of benzenethiol in 50 mL of DMF. The
Synthesis of octakis-4,5-(phenylsulfanyl)phthalo-
cyanine (5) and its aluminum complex (6). Com-
pound 3 (0.28 g, 0.2 mol) or 4 (0.29 g, 0.2 mol) was
added to a vigorously stirred mixture of 2 mL
reaction mixture was stirred at 80–85°С for 9 h until it
became turbid due to abundant precipitate formation.
The target product was then filtered off, washed first
with propan-2-ol until the odor of benzenethiol
disappeared completely and then with water, and dried
(
18 mmol) of chlorosulfonic acid and 2 mL (18 mmol)
of thionyl chloride. The resulting mixture was stirred
at 20°С for 0.5–1 h and then poured into ice treated
with NaCl. The precipitate was filtered off and dried in
a dessicator over H SO for 3 days. The target com-
–
1
at 80–90°С. Yield 85% (3.00 g). IR spectrum, ν, cm :
231 (CN), 1609 (С–Сskeleton), 1282 (С –H), 691
2
4
2
Ar
pounds were extracted with acetone, and the solvent
was removed by distillation to obtain dark green solids
readily soluble in acetone and DMF and moderately
soluble in chloroform.
+
(
C–S–C). Mass spectrum, m/z: 345.72 [M + H] .
Found, %: C 69.55; H 3.60; N 8.02; S 18.25.
C H N S . Calculated, %: C 69.74; H 3.51; N 8.13; S
1
2
0
12
2 2
8.62.
Octakis-4,5-(phenylsulfanyl)phthalocyanine (5).
Yield 0.39 g (85%). IR spectrum, ν, cm : 3530 (ОН),
Magnesium octakis-4,5-(phenylsulfanyl)phthalo-
cyanine (3). A mixture of 0.345 g (1 mmol) of 4,5-bis-
sulfanylphenyl)phthalonitrile and 0.107 g (0.05 mmol)
–1
3
1
152 (NH), 1612 (С–Сskeleton), 1521 (–N=), 1323 (S=O),
289 (С –H), 1012 (NH ), 721 (С–Н ), 695 (C–
(
Ar
endocycl
def
of magnesium acetate tetrahydrate was heated for 2 h
at 180–185°С. The reaction mixture was then cooled
down, dissolved in chloroform, filtered, and subject to
column chromatography on M60 silica using toluene
1
S–C). Н NMR spectrum, δ, ppm (CDCl ): 7.71 s
3
1
3
(
(
16Н, Н ), 7.63 d (16Н, Н , J = 8.2 Hz), 7.54 d
НН
2
16Н, Н , J = 8.2 Hz).
НН
–
1
Complex 6. Yield 0.37 g (78%). IR spectrum, ν,
as an eluent. Yield 0.29 g (84%). IR spectrum, ν, cm :
577 (С–Сskeleton), 1507 (–N=), 1257 (С –H), 690
–
1
cm : 3541 (ОН), 1616 (С–Сskeleton), 1532 (–N=), 1320
1
(
[
Ar
(
S=O), 1289 (С –H), 711 (С–Н ), 692 (C–S–C).
C–S–C), 645 (С–Н ). Mass spectrum, m/z: 1402.86
Ar def
def
+
M] . Found, %: C 68.25; H 3.81; N 7.61; S 18.05.
Synthesis of octakis-4,5-(4-sulfophenylsulfanyl)-
C H MgN S . Calculated, %: C 68.53; H 3.45; N
8
0
48
8 8
phthalocyanine (7) and its aluminum complex 8.
Compound 5 or 6 (0.2 g, 0.1 mmol) was heated until
dissolution with 10 mL of water in a porcelain dish
and water was then removed. The resulting sulfonic
acid was purified by column chromatography on M60
silica using water as an eluent.
7
.99; S 18.29.
Octakis-4,5-(phenylsulfanyl)phthalocyanine (3а).
Compound 3 (0.1 g, 0.7 mmol) was dissolved in 2 mL
of chloroform, and the solvent was then removed by
distillation. The residue was purified by column
chromatography on M60 silica, using chloroform as an
Octakis-4,5-(4-sulfophenylsulfanyl)phthalocyanine
–
1
eluent. Yield 0.082 g (82%). Mass spectrum, m/z:
(7). Yield 0.17 g (84%). IR spectrum, ν, cm : 3536
(ОН), 3150 (NH), 1612 (С–Сskeleton), 1523 (–N=), 1162
+
1
1
8
380.92 [M] . Found, %: C 69.51; H 3.80; N 8.00; S
8.25. C H N S . Calculated, %: C 69.64; H 3.65; N
(S=O), 1281 (С –H), 1011 (NHendocycl), 722 (С–Нdef),
8
0
50
8
8
Ar
1
.12; S 18.59.
692 (C–S–C). Н NMR spectrum (DMSO-d ), δ, ppm:
6
1
3
1
1.20 s (8Н, SO H), 7.96 s (16Н, Н ), 8.73 d (16Н, Н ,
JНН = 8.2 Hz), 8.52 d (16Н, Н , J = 8.2 Hz). Mass
spectrum, m/z: 2029.79 [M + Li + 2Н] . Found, %: C
3
Aluminum octakis-4,5-(phenylsulfanyl)phthalo-
2
НН
cyanine (4). A mixture of 0.345 g (1 mmol) of 4,5-bis-
sulfanylphenyl)phthalonitrile and 0.066 g (0.5 mmol)
of anhydrous aluminum chloride was heated for 2 h at
90–200°С. The reaction mixture was then cooled
+
(
4
6.75; H 3.26; N 5.42; S 24.89. C H N О S .
80 50 8 24 16
Calculated, %: C 47.56; H 2.49; N 5.55; S 25.39.
1
down, dissolved in chloroform, filtered, and subjected
to column chromatography on M60 silica, using
chloroform as an eluent. Yield 0.24 g (67%). IR
Complex 8. Yield 0.17 g (82%). IR spectrum, ν,
–
1
cm : 3550 (ОН), 1614 (С–Сskeleton), 1532 (–N=), 1164
1
(S=O), 1290 (СAr–H), 712 (С–Нdef), 692 (C–S–C), Н
–
1
spectrum, ν, cm : 1579 (С–Сskeleton), 1506 (–N=), 1257
С –H), 690 (C–S–C), 679 (С–Н ). Mass spectrum,
NMR spectrum (DMSO-d ), δ, ppm: 11.37 s (8Н,
6
1
3
(
SO
H), 8.57 s (16Н, Н ), 8.73 d (16Н, Н , JНН =
3
Ar
def
+
2
m/z: 1441.91 [M + Н] . Found, %: C 66.15; H 3.76, N
8.2 Hz), 8.52 d (16Н, Н , JНН = 8.2 Hz). Mass
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 7 2017

1
570
ZNOIKO et al.
+
spectrum, m/z: 2161.65 [M + 2Na] . Found, %: C
5.95; H 3.06; N 5.24; S 24.34. C H AlClN О S .
Containing Phenylsulfanyl Fragments) and financially
supported by the Russian Science Foundation (project
no. 15-13-00096), on the equipment of the Center for
Collective Use, Ivanovo State University of Chemical
Technology.
4
8
0
48
8
24 16
Calculated, %: C 46.18; H 2.33; N 5.39; S 24.65.
Synthesis of alkylsulfamoyl derivatives of octakis-
,5-(phenylsulfanyl)phthalocyanine (9, 10). Diethyl-
amine (0.07 g, 1 mmol, 0.5 mL, ρ 0.7056 g/cm ) or
octadecylamine (0.27 g) was added to a solution of
4
3
REFERENCES
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0
.22 g (0.1 mmol) of compound 5 in 30 mL of acetone.
The resulting mixture was heated under reflux (60–65°С)
for 1–1.5 h, after which acetone was removed by
distillation, the target product was extracted with
chloroform, and purified by column chromatography
in chloroform.
1
0.1134/S1070363216110165
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cm : 3070 (NH), 1612 (С–Сskeleton), 1520 (–N=), 1160
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6
92 (C–S–C). Mass spectrum, m/z: 2594.57 [M + Na +
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K – 2Н] . Found, %: C 54.67; H 5.25; N 8.40; S 20.80.
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8
1
12 123 16 16 16
5
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1
0.1016/j.molcata.2014.09.003
–
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cm : 3072 (NH), 2919, 2850 (CH , CH ), 1637
2
3
6
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(
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1
174 (S=O), 1006 (NHendocycl), 754 (С–Н ), 696
def
(
C–S–C). Found, %: C 65.75; H 9.06; N 5.49; S 12.49.
C H N О S . Calculated, %: C 66.72; H 8.65; N
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24 346 16 16 16
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.56; S 12.72.
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0
0958972.2015.1077237
Synthesis of ammonium salt of aluminum
8
. Makarov, V.I., Vasil’chenko, S.Yu., Ryabova, A.V.,
Konov, V.I., Shevchenko, E.N., Lukyanets, E.A.,
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S107036321501048X
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Solov’eva, L.I., Yuzhakova, O.A., Donyagina, V.F.,
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octakis-4,5-(4-sulfophenylsulfanyl)phthalocyanine
11). A mixture of 0.10 g (0.05 mmol) of compound 8
(
and 5 mL of 24% aqueous ammonia was heated in a
porcelain dish until the solvent evaporated completely,
and the resulting compound was extracted by DMF
and purified by column chromatography on M60 silica,
using DMF as an eluent. Yield 0.082 g (80%). IR
9
–
1
spectrum, ν, cm : 1615 (С–Сskeleton), 1527 (–N=), 1160
S=O), 1280 (С –H), 723 (С–Н ), 693 (C–S–C).
(
Ar
def
Found, %: C 42.85; H 3.45; N 9.94; S 22.88.
1
1
0. Meerovich, I.G., Volkov, K.G., Meerovich, G.A.,
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N 10.11; S 23.14.
8
0
72
16 24 16
ACKNOWLEDGMENTS
The work was performed under the State contract
with the Ministry of Education and Science of the
Russian Federation (no. 4.1929.2017.4.6, Development
of the Method of Synthesis of 4,5-bis(phenylsulfanyl)-
phthalonitrile from 4-bromo-5-nitrophthalonitrile, as
well as Alkylsulfamoyl Derivatives of Phthalocyanines
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 7 2017

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