Synthesis of a new monomer for sulfonated poly(arylene ether sulfones)

Article abstract of DOI:10.1007/s11172-017-1769-9

4-({2,4-Bis[(4-chlorophenyl)sulfonyl]phenyl}thio)benzenesulfonic acid was synthesized based on the scheme suggested from the results of retrosynthetic analysis. This compound is a new monomer for the preparation of sulfonated poly(arylene ether sulfones) used as a solid polymer electrolyte in fuel cells. The structure of the aromatic disulfone containing a sulfo group was suggested based on the data on the influence of chemical structure of structural elements of polysulfone proton-conducting membranes on their operational characteristics.

Full text of DOI:10.1007/s11172-017-1769-9

Russian Chemical Bulletin, International Edition, Vol. 66, No.3, pp. 545—551, March, 2017
545
Synthesis of a new monomer for sulfonated poly(arylene ether sulfones)
R. S. Begunov,a A. N. Valyaeva,a A. N. Fakhrutdinov,b and S. A. Pirogovaa
aP. G. Demidov Yaroslavl State University,
14 ul. Sovetskaya, 150000 Yaroslavl, Russian Federation.
Fax: +7 (485 2) 79 7751. Eꢀmail: begunov@bio.uniyar.ac.ru
bN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation
4ꢀ({2,4ꢀBis[(4ꢀchlorophenyl)sulfonyl]phenyl}thio)benzenesulfonic acid was synthesized
based on the scheme suggested from the results of retrosynthetic analysis. This compound is
a new monomer for the preparation of sulfonated poly(arylene ether sulfones) used as a solid
polymer electrolyte in fuel cells. The structure of the aromatic disulfone containing a sulfo
group was suggested based on the data on the influence of chemical structure of structural
elements of polysulfone protonꢀconducting membranes on their operational characteristics.
Key words: poly(arylene ether sulfones), retrosynthetic analysis, aromatic nucleophilic
substitution, sulfonation.
At the present time, fuel cells (FCs) are considered as
an alternative to traditional sources of energy. Among
them, great attention is attracted by FCs with solid polyꢀ
mer electrolyte, which is a polymeric film, protonꢀconꢀ
ducting membrane (PCM) used for the selective transport
of protons from the FC working space, thus providing
continuos work of the FCs.
governed by the following ideas. First, the presence of two
highly active reaction centers for the reaction of aromatic
nucleophilic polysubstitution should facilitate preparation
of highꢀmolecularꢀweight polymers. Second, the protogeꢀ
nic group should be, if possible, in the side substituent,
since its presence in the fragments of the main polymeric
chain can impair physicomechanical properties of the obꢀ
tained membranes.4 Therefore, for the sulfo group to be
introduced by the electrophilic substitution reaction the
side fragment of the monomer should contain a highly
active center. Third, it is desirable that the side group
would have been bonded to the main chain through bridging
atoms or groups, which would have decreased the rigidity
of the macromolecules and improved their solubility.5
Fourth, the presence of two sulfone groups in the elemenꢀ
tary unit can increase the stability of the obtained polyꢀ
meric material to oxidation.6
Analysis of literature data1 showed that one of the
promising classes of aromatic condensation polymers for the
development of PCM are the sulfonated poly(arylene ether
sulfones) (HSO3ꢀPAESs). Two approaches are used for their
preparation: 1) the synthesis of PAESs from bisꢀphenols
and aromatic dihaloꢀ or dinitrosulfones by the reaction of
nucleophilic polysubstitution with subsequent electrophilic
introduction of a sulfo group in the polymer;2 2) the preparaꢀ
tion of HSO3ꢀPAESs directly from monomers containing
a sulfo group.3 The second approach is more convenient
for the preparation of polymers having a strictly ordered
structure and a certain amount of protogenic groups.
It is known that the operational characteristics of polyꢀ
mers depend on chemical structure of repeating units and
on their distribution pattern in the chain. The purpose of
the present work is the synthesis of a new highly active in
SNAr reactions aromatic sulfone monomer containing
a sulfo group and suitable for development of HSO3ꢀPAESs.
Bearing these reasons in mind, we suggested the strucꢀ
ture 1 as a monomer for the development of HSO3ꢀPAESs.
Results and Discussion
Based on the analysis of literature data on the structure
and properties of sulfone monomers and PAESs obtained
on their basis, we suggested an AAꢀtype monomer not
described in the literature. In its development, we were
To choose the most optimal pathway for the synthesis
of monomer 1, we carried out retrosynthetic analysis,
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0545—0551, March, 2017.
1066ꢀ5285/17/6603ꢀ0545 © 2017 Springer Science+Business Media, Inc.

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Begunov et al.
which is widely used at the present time in the developꢀ
ment of optimal strategies for the synthesis of compounds
with a required structure.7 The retrosynthetic schemes
show possible reagents corresponding to the synthons obꢀ
tained after the virtual cleavage of bonds or functional
group interconversion (FGI).
Compound 2 can be easily obtained by the SNAr
reaction of thiophenol 4 with aromatic disulfone 3 conꢀ
taining a good nucleofuge (R), such as F and Cl atoms or
a nitro group. The presence of two acceptor groups should
considerably facilitate the course of the substitution reacꢀ
tion. Consequently, the step of the "C—S bond cleavage"
can be represented by Scheme 2.
The presence of the protogenic group in the structure
of a monomer can be achieved using two means (Scheme 1):
the introduction of a sulfo group in the thiophenyl radical
of compound 2 by the SEArꢀtype reaction or as a result of
the reaction of compound 3 with 4ꢀmercaptobenzeneꢀ
sulfonic acid. The second method seems less convenient
due to the following reasons: 4ꢀmercaptosulfonic acid is
a poorly available and expensive reagent, while thiophenols
containing strong electronꢀwithdrawing groups are weak
nucleophiles, which would require drastic conditions for
carrying out the SNArꢀtype reactions with their involveꢀ
ment. At the same time, sulfonation is widely used in
organic synthesis and proceeds readily for substrates with
electronꢀdonating substituents. The product is obtained
through the formation of a sulfonyl chloride, which hydroꢀ
lyzes upon treatment of the reaction mixture with water.
Thus, the first step of the retrosynthetic scheme is the
"C—SO3H bond cleavage".
Scheme 2
Scheme 1
The shortest pathway for the synthesis of compound 3
is the Friedel—Crafts reaction of chloroꢀ or fluorobenzene 5
with 4ꢀchlorobenzenesulfonyl chloride 6 (2 equiv.) in the
presence of anhydrous AlCl3 (Scheme 3). A principal disꢀ
advantage of this method consists in the difficulty of the
introduction of the second electrophilic species in the
forming diphenyl sulfone, which does not contain elecꢀ
tronꢀdonating substituents. Using the IFG method, a simꢀ
pler and more efficient pathway can be suggested. It is
known8 that diphenyl sulfones can be obtained easily and
in high yield by oxidation of diphenyl sulfides with the
mixture of H2O2—AcOH. After the cleavage of the C—S
bond, the building blocks can be suggested, from which
the polynuclear structure 7 would be assembled. These are
2,4ꢀdichloronitrobenzene (8) and 4ꢀchlorothiophenol (9),
highly active reagents for the SNAr reaction (see Scheme 3).
The conditions for this process are described in detail in
the literature for the reaction of 4ꢀchloronitrobenzene with
different nucleophiles.9
Thus, using retrosynthetic analysis we have designed
a scheme for the preparation of a new monomer 1 for the
development of PAESs containing a sulfo group (Scheme 4).
Following the Scheme 4, 2,4ꢀdichloronitrobenzene 8
and 4ꢀchlorothiophenol 9 were used to obtain 2,4ꢀbis[(4ꢀ
chlorophenyl)thio]ꢀ1ꢀnitrobenzene 7 in 96% yield. To inꢀ
crease the conversion of the substrate and to decrease the
reaction time, the substitution was carried out upon treatꢀ
ment with ultrasound for 1 h under conditions described
by us in the work.10

New monomer for poly(arylene ether sulfone)s
Russ.Chem.Bull., Int.Ed., Vol. 66, No. 3, March, 2017
547
Scheme 3
The aromatic disulfide 7 was oxidized with 33% aqueꢀ
ous solution of hydrogen peroxide in glacial acetic acid
(see Scheme 4). The data on the influence of temperature
of oxidation on the yield of product 3 are given below.
T/°C
70
75
80
80
83
85
84
90
89
95
97
100
95
Yield (%) 71
At the temperatures below 90 °C, the yield of 2,4ꢀbisꢀ
[(4ꢀchlorophenyl)sulfonyl]ꢀ1ꢀnitrobenzene (3) did not exꢀ
ceed 84%. This can be explained by the poor solubility of
the substrate 7 in acetic acid, as a result, the reaction
proceeded under heterophase conditions. As a result, the
target product 3 contained a considerable impurity of the
starting compound, which cannot be completely removed
by recrystallization. Pure product 3 was obtained by carryꢀ
ing out the reaction at 95 °C for 3 h. After cooling the
reaction mixture, compound 3 crystallized as colorless
crystals and did not require additional purification. The
yield of aromatic disulfone 3 was 97%.
The oxidation of compound 7 resulted in the introducꢀ
tion of two strong electronꢀwithdrawing groups in its strucꢀ
ture, which promote formation of three reaction centers
for the nucleophilic attack.
At first glance, only a nitro group, the nucleofugicity of
which is higher than that of chlorine atoms,11 should unꢀ
dergo substitution in the course of the SNAr reaction at the
stoichiometric ratios of reagents 3 : 4 = 1 : 1. In addition,
the presence in compound 3 of two strong electronꢀwithꢀ
drawing groups at orthoꢀ and paraꢀpositions to the reacꢀ
tion center should also facilitate the nucleophilic attack at
the C—NO2 bond. However, when the process was carried
out at 70 °C and higher (the solvent DMF, the deprotoꢀ
nating agent K2CO3, 1 h), a difficult to separate mixture
of products was obtained. Carrying out the reaction at
20 °C did not give pure target product 2 either, since
Scheme 4

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Begunov et al.
Scheme 5
Scheme 6
about 20—25% of the nitro compound remained unreactꢀ
ed. In this case, an increase in the time of the synthesis did
not lead to any significant change in the conversion of
nitroarene 3.
To identify the side processes proceeding in the course
of the reaction of aromatic nucleophilic substitution in
nitrobenzene 3, the complicated structure of this substrate
was virtually transformed into simpler compounds 10—12
(Scheme 5), containing possible reaction centers for the
nucleophilic attack, and the reactions of these compounds
with thiophenol 4 were studied (Schemes 6—8).
In the reaction of 1ꢀchloroꢀ4ꢀ(phenylsulfonyl)benzene
(10) with nucleophile 4 (DMF, K2CO3) at 70 °C, the
conversion of compound 10 after 1 h was only 21%
(Scheme 6). An increase in the temperature to 100 °C and
the SNAr reaction time to 8 h allowed us to obtain the
Scheme 7
1
individual product in 91% yield. The H NMR spectrum
of compound 13 exhibited the signals for 14 aromatic proꢀ
tons, with the signals for the protons H(2c) and H(6c)
being observed in the more highꢀfield region of the specꢀ
trum (at δ 7.21) as compared to other signals. These data,
as well as the m/z value of 327.0516 [M + 1]+, correspond
to 1ꢀ(phenylsulfonyl)ꢀ4ꢀ(phenylthio)benzene (13). The
formation in this reaction of the only product 13 indicated
the presence in the structure of 10 of only one reacꢀ
tion center.
As it was expected, the reactivity of 1ꢀnitroꢀ4ꢀ(phenylꢀ
sulfonyl)benzene (11) in the reaction with 4 was higher
(Scheme 7). At 70 °C, 36% of the substrate was consumed
in the reaction already after 1 h. However, this reaction
proceeded with the formation of two products. The comꢀ
pound 11 was completely converted when the substitution
process was carried out for 5 h at 100 °C. This resulted in
the formation of a mixture of products 13 and 14 in the
ratio of 3 : 1, which was separated by fractional crystalliꢀ
zation in a binary mixture of solvents PriOH—hexane.
The structures of compounds 13 and 14 were conꢀ
firmed by 1H NMR spectroscopy and mass spectrometry.
1H NMR spectrum of 1ꢀnitroꢀ4ꢀ(phenylthio)benzene (14)
contains the signals for the nine protons of monoꢀ and
disubstituted benzene rings. A signal with the double inꢀ
tensity attributed to the protons C(2b) and C(6b) was found
in the highꢀfield region of the spectrum at δ 7.27. A signal
at δ 8.11 belongs to the weakly shielded protons H(2a) and

New monomer for poly(arylene ether sulfone)s
Russ.Chem.Bull., Int.Ed., Vol. 66, No. 3, March, 2017
549
H(6a) at orthoꢀpositions to the nitro group. The other five
protons resonate as a multiplet in the region of δ 7.48—7.58.
The high resolution mass spectrum exhibits a molecular
ion with m/z 232.0435 [M + 1]+.
The data obtained allow us to draw a conclusion that
in compound 11 both the nitro group and the phenylsulꢀ
fone fragment can act as a nucleofuge.
The nucleophilic substitution reaction between 1ꢀchloꢀ
roꢀ4ꢀ[(4ꢀnitrophenyl)sulfonyl]benzene (12) and thioꢀ
phenol 4 at 100 °C reached completion within 5 h (Scheme 8).
This resulted in the formation of a mixture containing
three products, which were not isolated in the individual
state, however, diphenyl sulfide 14 was identified as one of
the products by gas chromatography. The retention times
of two other products (X1 and X2; see Scheme 8) are higher
than that of the starting compound 12. Products X1 and
X2 are most likely formed as a result of the substitution of
the nitro group and the chlorine atom in substrate 12. This
indicates a possibility for the SNAr reaction to follow three
directions.
Fig. 1. The Overhauser effects in compound 2 confirming its
structure.
stituted benzene rings. The mutual arrangement of the
rings was determined using the nuclear Overhauser effect
(NOE): the throughꢀspace interaction was found for the
proton H(3a) (a doublet at δ 8.66) with the protons of the
paraꢀsubstituted benzene rings H(2c), H(6c) and H(2d),
H(6d) (Fig. 1). Such interaction confirms the presence of
the 4ꢀchlorophenylsulfonyl fragments at positions 2 and 4
of the central ring of the molecule. Apart from that, the
experiment showed that the proton H(6a) (a doublet at
δ 7.01) is close in space with the orthoꢀprotons H(2b) and
H(6b) of the thiophenyl substituent.
Scheme 8
The introduction of the sulfoxy group in compound 2
was carried out using chlorosulfonic acid, which is widely
used as a sulfonating agent in organic synthesis.12 The
SEAr reaction was carried out for 2 h at 40 °C with a twoꢀ
fold excess of the electrophilic agent. Chloroform was used
as the solvent. A highly pure sulfonated product 1 was
obtained in 86% yield (see Scheme 4).
In conclusion, a successful synthesis of earlier unknown
monomer 1 confirmed the rightful choice of the set of well
studied types of reactions and available reagents suggested
in the course of retrosynthetic analysis. The selection of
conditions and the studies of regioselectivity of several
steps of the process allowed us to obtain 4ꢀ({2,4ꢀbis[(4ꢀ
chlorophenyl)sulfonyl]phenyl}thio)benzenesulfonic acid (1)
with high degree of purity, that is a necessary condition for
the synthesis of highꢀmolecularꢀweight polymers possessꢀ
ing required physicochemical characteristics.
Thus, based on the results of the studies we draw
a conclusion on a possibility of the nucleophilic attack on
several reaction centers of 2,4ꢀbis[(4ꢀchlorophenyl)ꢀ
sulfanyl]ꢀ1ꢀnitrobenzene 3: the chlorine atoms, the
nitro group, and the phenylsulfone fragments can act as
nucleofuges.
To increase the selectivity of the reaction of nitro comꢀ
pound 3 with Sꢀnucleophile 4, the temperature of the proꢀ
cess was varied in the range 30—60 °C with a 5 °C step.
The nucleophilic agent was added to the reaction mixture
gradually.
Experimental
Product 7 was synthesized using an S 10 H Elmasonic ultraꢀ
sonic bath (37 kHz, temperature range 30—80 °C, Elma Schmidꢀ
bauer GmbH production, Germany). 1H and 13C NMR spectra
were recorded on a Bruker DRX500 spectrometer in DMSOꢀd6
at 24—27 °C (500.13 and 125.76 MHz, respectively). Chemical
shifts are given relative to the signal of residual protons (δ 2.5)
and the signal of 13C atoms of the solvent. The signals in the
2,4ꢀBis[(4ꢀchlorophenyl)sulfonyl]ꢀ1ꢀ(phenylthio)ꢀ
benzene (2), the product of the substitution of the nitro
group containing no impurities, was obtained in 92% yield
by a dropwise addition of a solution of thiophenol 4 in
DMF to the reaction mixture over 30 min at 35 °C. The
1
structure of compound 2 was confirmed using H NMR
1H and 13C NMR spectra were assigned based on the 2D 1H—13
C
spectroscopy. The splitting patterns of the signals confirm
the structure of the fragments composing this compound,
namely, the paraꢀsubstituted, monosubstituted, and trisubꢀ
HMBC spectroscopy data. The concentration of the samples for
recording the NMR spectra was within the recommended

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Begunov et al.
range.13 Electrospray ionization (ESI) high resolution mass
spectra were recorded on a Bruker micrOTOF II instrument.
Elemental composition was determined on a Carlo Erba 1106
elemental analyzer (Italy). The course of the SNAr reactions
involving compounds 10—12 was monitored by gas chromatogꢀ
raphy on a Krystallyuksꢀ4000 M chromatograph (MetaꢀKhrom,
Russian Federation).
H(2b), H(6b), J = 7.4 Hz); 7.44 (t, 2 H, H(3b), H(5b), J = 7.4 Hz);
7.49 (t, 1 H, H(4b), J = 7.4 Hz); 7.68 (d, 2 H, H(3d), H(5d),
J = 8.6 Hz); 7.71 (d, 2 H, H(3c), H(5c), J = 8.6 Hz); 8.02 (d, 2 H,
H(2d), H(6d), J = 8.6 Hz); 8.04 (dd, 1 H, H(5a), J = 8.5 Hz,
J = 1.8 Hz); 8.10 (d, 2 H, H(2c), H(6c), J = 8.6 Hz); 8.66 (d, 1 H,
H(3a), J = 1.8 Hz). 13C NMR (DMSOꢀd6), δ: 146.8 (C(1a));
139.5 (C(4c)); 139.3 (C(4d)); 138.8 (C(1d)); 138.0 (C(2a)); 137.3
(C(1c)); 136.6 (C(4a)); 134.8 (C(2b); C(6b)); 132.7 (C(5a)); 130.4
(C(3b), C(4b), C(5b), C(6a)); 130.2 (C(2c), C(6c)); 130.0 (C(3d),
C(5d)); 129.53, 129.50 (C(3c), C(5c), C(2d), C(6d)); 128.7 (C(1b));
128.4 (C(3a)). Found (%): C, 53.11; H, 2.86; S, 17.99; Cl, 13.32.
C24H16Cl2O4S3. Calculated (%): C, 53.83; H, 3.01; S, 17.96;
Cl, 13.24.
4ꢀ({2,4ꢀBis[(4ꢀchlorophenyl)sulfonyl]phenyl}thio)benzeneꢀ
sulfonic acid (1). Compound 2 (5.4 g, 0.01 mol) was dissolved in
chloroform (70 mL) with stirring at 30 °C. Then, chlorosulfonic
acid (1.32 mL, 0.02 mol) in chloroform (10 mL) was added
dropwise to the homogeneous solution with vigorous stirring.
The resulting reaction mixture was stirred for 2 h at 40 °C and
concentrated to 10 mL. The residue after cooling was poured
onto ice. A precipitate formed was collected by filtration and
allowed to stand in 10% aqueous solution of KOH (50 mL), then
treated with 9% aqueous HCl in ice to рH 5—6 and filtered. The
yield was 5.3 g (86%), m.p. >290 °C. Found: m/z 614.9239
[M + H]+. C24H17Cl2O7S4. Calculated: M = 614.9235. 1H NMR
(DMSOꢀd6), δ: 7.01 (d, 1 H, H(2b), J = 8.6 Hz); 7.29 (d, 2 H,
H(3a), H(5a), J = 8.1 Hz); 7.68 (d, 2 H, H(2a), H(6a), J = 8.2 Hz);
7.70 (d, 2 H, H(3d), H(5d), J = 8.6 Hz); 7.74 (d, 2 H, H(3c),
H(5c), J = 8.6 Hz); 8.02 (d, 2 H, H(2d), H(6d), J = 8.6 Hz); 8.08
(dd, 1 H, H(3b), J = 8.6 Hz, J = 1.8 Hz); 8.11 (d, 2 H, H(2c),
H(6c), J = 8.6 Hz); 8.63 (d, 1 H, H(5b), J = 1.7 Hz). 13C NMR
(DMSOꢀd6), δ: 150.1 (C(1a); 146.8 (C(1b)); 139.6 (C(4c)); 139.4
(C(4d)); 138.9 (C(1d)); 138.0 (C(6b)); 137.3 (C(1c)); 136.6
(C(4b)); 134.5 (C(3a), C(5a)); 133.0 (C(3b)); 130.5 (C(2b)); 130.3
(C(2c), C(6c)); 130.1 (C(3d), C(5d)); 129.7 (C(3c), C(5c)); 129.6
(C(2d), C(6d)); 128.8 (C(4a)); 128.5 (C(5b)); 127.7 (C(2a), C(6a)).
Found (%): C, 46.78; H, 2.58; Cl, 11.49; O, 18.22; S, 20.85.
C24H16Cl2O7S4. Calculated, %: C, 46.83; H, 2.62; S, 20.84; Cl, 11.52.
The following reactants purchased from Acros Organics and
Sigma—Aldrich were used in the work: thiophenol (99%), 2,4ꢀdiꢀ
chloronitrobenzene (97%), 1ꢀchloroꢀ4ꢀ(phenylsulfonyl)benzene
(≥97%), 1ꢀnitroꢀ4ꢀ(phenylsulfonyl)benzene (99%). Solvents of
the reagent grade were used without additional purification.
2,4ꢀBis[(4ꢀchlorophenyl)thio]ꢀ1ꢀnitrobenzene (7). Potassium
carbonate (10.76 g, 0.078 mol) and 2,4ꢀdichloronitrobenzene
(8) (5.0 g, 0.026 mol) were added to a solution of 4ꢀchloroꢀ
thiophenol (9) (7.51 g, 0.052 mol) in DMSO (50 mL). The reꢀ
action mixture was sonicated for 1 h at 80 °C, cooled, and
poured into water. A yellow precipitate formed was collected
by filtration and recrystallized from DMF. The yield was
10.18 g (96%), m.p. 139—141 °C. Found: m/z 407.9685
[M + H]+. C18H12Cl2NO2S2. Calculated: M = 407.9687. 1H NMR
(DMSOꢀd6), δ: 6.17 (d, 1 H, H(3a), J = 2.0 Hz); 7.26 (dd, 1 H,
H(5a), J = 8.7 Hz, J = 2.0 Hz); 7.36 (d, 2 H, H(2c), H(6c),
J = 8.5 Hz); 7.42 (d, 2 H, H(3c), H(5c), J = 8.5 Hz); 7.44 (s, 4 H,
H(2b), H(3b), H(5b), H(6b)); 8.20 (d, 1 H, H(6a), J = 8.7 Hz).
13C NMR (DMSOꢀd6), δ: 146.9 (C(4a)), 141.5 (C(1a)), 139.2
(C(2a)), 137.0 (C(2b)), 136.2 (C(2c)), 135.6 (C(4b)), 135.2
(C(4c)), 130.1 (C(3a), 130.0 (C(3c)), 128.0 (C(1a)), 127.2 (C(1c)),
126.4 (C(6a)), 123.1 (C(3a)), 123.1 (C(5a)). Found (%): C, 52.89;
H, 2.63; N, 3.45; S, 15.71; Cl, 17.36. C18H11Cl2NO2S2. Calcuꢀ
lated (%): C, 52.95; H, 2.72; N, 3.43; S, 15.71; Cl, 17.37.
2,4ꢀBis[(4ꢀchlorophenyl)sulfonyl]ꢀ1ꢀnitrobenzene (3). A 33%
aqueous solution of H2O2 (12 mL) was added dropwise to
a solution of compound 7 (8.16 g, 0.02 mol) in glacial acetic acid
(100 mL) at 95 °C over 4 h. The reaction mixture was poured
into a beaker and allowed to stand for 16 h. A white precipitate
formed was collected by filtration. The yield was 9.16 g (97%), m.p.
177—179 °C. Found: m/z 471.9487 [M + H]+. C18H12Cl2NO6S2.
Calculated: M = 471.9484. 1H NMR (DMSOꢀd6), δ: 7.71 (d, 2 H,
H(3c), H(5c), J = 8.7 Hz); 7.74 (d, 2 H, H(3b), H(5b), J = 8.7);
8.05 (d, 2 H, H(2b), H(6b), J = 8.7); 8.14 (d, 2 H, H(2c), H(6c),
J = 8.7 Hz); 8.30 (d, 1 H, H(6a), J = 8.4 Hz); 8.58 (dd, 1 H, H(5a),
J = 8.4 Hz, J = 2.0 Hz); 8.82 (d, 1 H, H(3a), J = 2.0 Hz).
13C NMR (DMSOꢀd6), δ: 149.9 (C(1a)), 144.6 (C(4a)), 140.01
(C(4b)), 139.97 (C(4c)), 137.72 (C(1c)), 137.66 (C(1b)), 135.6
(C(5a)), 133.8 (C(2a)), 130.10, 130.06, 130.02, 129.79 (C(2b),
C(3b), C(5b), C(6b), C(2c), C(3c), C(5c), C(6c)), 129.80 (C(3a)),
127.28 (C(6a)). Found (%): C, 45.69; H, 2.31; N, 2.88; S, 13.58;
Cl, 15.09. C18H11Cl2NO6S2. Calculated (%): C, 45.77; H, 2.35;
N, 2.97; S, 13.58; Cl, 15.01.
The authors of the work are grateful to the specialists
of the Division of Structural Studies of the N. D. Zelinsky
Institute of Organic Chemistry of the Russian Academy of
Sciences (Moscow) for supplying with analytical data.
This work was financially supported by the President
of the Russian Federation Council for Grants (Program
for State Support of Young Russian ScientistsꢀCandidates
of Science (Grant MKꢀ3839.2015.3).
References
2,4ꢀBis[(4ꢀchlorophenyl)sulfonyl]ꢀ1ꢀ(phenylthio)benzene (2).
Potassium carbonate (3.1 g, 0.0225 mol) was added to a solution
of compound 3 (7.08 g, 0.015 mol) in DMF (35 mL), followed by
dropwise addition of a solution of thiophenol 4 (1.54 mL,
0.015 mol) in DMF (10 mL) over 30 min at 35 °C. Then, the
reaction mixture was stirred for 30 min at 35 °C and poured into
water. A white precipitate formed was collected by filtration and
recrystallized from a mixture of isopropyl alcohol—DMF. The
yield was 7.38 g (92%), m.p. 242—243 °C. Found: m/z 534.9664
[M + H]+. C24H17Cl2O4S3. Calculated: M = 534.9667. 1H NMR
(DMSOꢀd6), δ: 7.01 (d, 1 H, H(5a), J = 8.5 Hz); 7.30 (d, 2 H,
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Received July 4, 2016;
in revised form October 5, 2016