Synthesis of aryl 3,5-dinitrophenyl sulfones and sulfoxides. Transformations of 3,5-dinitrodiphenyl sulfone in reactions with O- and S-nucleophiles

Article abstract of DOI:10.1023/A:1022563529344

1-Arylthio-3,5-dinitrobenzenes are selectively oxidized to the corresponding sulfones and sulfoxides by the action of hydrogen peroxide. Reactions of 3,5-dinitrodiphenyl sulfone with O- and S-centered nucleophiles (RXH, X = O, S) in dipolar aprotic solven

Full text of DOI:10.1023/A:1022563529344

Russian Journal of Organic Chemistry, Vol. 38, No. 12, 2002, pp. 1758 1763. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 12, 2002,
pp. 1819 1824.
Original Russian Text Copyright
2002 by Serushkina, Dutov, Sapozhnikov, Ugrak, Shevelev.
Dedicated to Full Member of the Russian Academy of Sciences
V.A. Tartakovskii on the 70th Anniversary of His Birth
Synthesis of Aryl 3,5-Dinitrophenyl Sulfones and Sulfoxides.
Transformations of 3,5-Dinitrodiphenyl Sulfone in Reactions
with O- and S-Nucleophiles*
O. V. Serushkina, M. D. Dutov, O. Yu. Sapozhnikov, B. I. Ugrak, and S. A. Shevelev
Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences,
Leninskii pr. 47, Moscow, 119991 Russia
e-mail: shevelev@mail.ioc.ac.ru
Received April 25, 2002
Abstract 1-Arylthio-3,5-dinitrobenzenes are selectively oxidized to the corresponding sulfones and sul-
foxides by the action of hydrogen peroxide. Reactions of 3,5-dinitrodiphenyl sulfone with O- and S-centered
nucleophiles (RXH, X = O, S) in dipolar aprotic solvents in the presence of K2CO3 result in replacement of
the nitro group by the RX fragment; the reaction with methanol occurs in aqueous medium in the presence
of NaHCO3. Substitution of the nitro group in 3,5-dinitrodiphenyl sulfone by phenylthio group, followed by
oxidation of the sulfur atom to SO2 and further replacement of the remaining nitro group yields 1,3,5-tris-
(phenylsulfonyl)benzene. The phenylsulfonyl group in the latter is replaced by phenylthio group by reaction
with PhSH in the presence of K2CO3. Mononitrosulfones obtained by nucleophilic substitution in the title
compound can be reduced to the corresponding anilines.
1,3,5-Trinitrobenzene usually reacts with various
nucleophiles to give stable anionic -adducts [1 3].
However, we previously found conditions under
which arenethiols and their heteroaromatic analogs are
capable of replacing one nitro group in 1,3,5-trinitro-
benzene to give the corresponding 1-aryl(hetaryl)thio-
3,5-dinitrobenzenes I. These conditions include the
use of dipolar aprotic solvents [such as N-methylpyr-
rolidone (NMP), DMF, etc.] and alkalies or alkali
metal carbonates (K2CO3 is the most convenient) at
50 80 C. Under more severe conditions (150 C), two
nitro groups can be replaced [4 6].
We have studied transformations of 3,5-dinitrodi-
phenyl sulfone IIa in reactions with O- and S-nucleo-
philes (RXH, X = O, S) in the presence of bases with
the goal of synthesizing new polyfunctional meta-
substituted benzene derivatives. Sulfone IIa can be
regarded as an analog of 1,3,5-trinitrobenzene; there-
fore, the reactions of IIa with nucleophiles were
performed under conditions ensuring nitro group
Scheme 1.
We have found that sulfides I undergo selective
oxidation by the action of H2O2 in AcOH, affording
the corresponding sulfones or sulfoxides. Sulfones
IIa IIc are formed in the presence of a larger excess
of H2O2 on heating under reflux. When the amount
of hydrogen peroxide is close to equimolar and the
reaction is carried out at room temperature ( 20 C),
sulfoxides IIIa and IIIb are obtained (Scheme 1).
____________
*
This study was financially supported by the Russian Founda-
tion for Basic Research (project no. 01-03-32261).
Ar = Ph (a), 4-ClC6H4 (b), 2-benzothiazolyl (c).
1070-4280/02/3812-1758$27.00 2002 MAIK Nauka/Interperiodica

SYNTHESIS OF ARYL 3,5-DINITROPHENYL SULFONES AND SULFOXIDES.
1759
Scheme 2.
NMP is N-methylpyrrolidone.
Scheme 3.
replacement in 1,3,5-trinitrobenzene. Both nitro and
phenylsulfonyl groups are good nucleofuges in the
aromatic nucleophilic substitution reactions [7], and
replacement of the PhSO2 group might also be ex-
pected. Although the nitro group is generally believed
[8] to be considerably more labile than PhSO2, it is
known that selective replacement of either NO2 or
PhSO2 group (depending on the substrate structure
and nucleophile nature) can be effected in benzene
derivatives where these group occupy ortho or para
positions with respect to each other [9 11]. As far as
we know, the order of replacement of meta-arranged
nitro and phenylsulfonyl groups was not studied.
Running ahead, it should be noted that in all the
examined reactions only the nitro group was replaced,
while no products of substitution of the PhSO2 group
were detected.
It is known that heating of 1,3,5-trinitrobenzene in
aqueous methanol in the presence of a large excess of
NaHCO3 leads to replacement of one nitro group by
methoxy [12]. Under similar contitions, one nitro
group in sulfone IIa is also replaced by methoxy
group to give 3-methoxy-5-nitrodiphenyl sulfone (IV)
(Scheme 2). The reaction of sulfone IIa with phenol
in the presence of K2CO3 in NMP at 80 C gives
nitro(phenoxy)phenyl sulfone V. Treatment of the
latter with 1 equiv of phenol under more severe condi-
tions (at 150 C) results in substitution of the remain-
ing nitro group with formation of diphenoxyphenyl
sulfone VI. Under the same conditons, one or two
nitro groups in 1,3,5-trinitrobenzene are replaced by
the action of phenol [13, 14].
Sulfone IIa reacts with arenethiols in NMP in
the presence of K2CO3 at 50 C, yielding products of
replacement of one nitro group (Scheme 3). Likewise,
one nitro group in 1,3,5-trinitrobenzene is replaced by
the action of arenethiols under similar conditions
[4 6]. The reaction of IIa with benzenethiol gave
sulfone VII, and with a heterocyclic analog, pyridine-
2-thiol (VIII), sulfone IX was formed. The best
results were obtained in HMPA at 20 C.
By reaction of bis(4-mercaptophenyl) sulfide (X)
with 2 equiv of sulfone IIa we obtained product XI.
All sulfide bridges in the latter were oxidized to SO2
fragments with 35% hydrogen peroxide in acetic acid.
As a result, polysulfone XII was obtained (Scheme 4).
Analogous oxidation of sulfone VII gave bis-sulfone
XIII (Scheme 5). Despite the presence of two PhSO2
groups in XIII, only the nitro group was replaced in
the reaction with benzenethiol (NMP, K2CO3, 50 C).
The substitution product, bis-sulfone XIV was
oxidized with H2O2/AcOH to tris-sulfone XV. On
the other hand, the reaction of XV with PhSH under
the conditions ensuring nitro group replacement in
compound XIII (as well as in 1,3,5-trinitrobenzene
[4 6]) gives bis-sulfone XIV as a result of substitu-
tion of the PhSO2 group. Thus, the nitro group is
always replaced first in aromatic substrates having
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 12 2002

1760
SERUSHKINA et al.
Scheme 4.
Scheme 5.
PhSO2 and NO2 groups in the meta position with
respect to each other. If no nitro group is present,
PhSO2 group is replaced with the same ease. Almost
complete analogy between the transformations of
sulfone IIa and 1,3,5-trinitrobenzene in reactions with
O- and S-nucleophiles should be noted, though com-
pound IIa gives rise to a greater diversity of products.
Some of the prepared mononitrosulfones was
reduced to the corresponding anilines XVIa XVId
with hydrazine hydrate in the presence of FeCl3 and
charcoal (Scheme 6; cf. [15]).
Among the obtained compounds, only tris-sulfone XV
was reported previously [16].
The structure of the products was proved by ele-
1
mental analyses and H NMR, IR [ as(NO2) 1540,
s(NO2) 1260, (SO) 1340, as(SO2) 1350, s(SO2)
1
1150, (NH2) 3480, (NH2) 1620 cm ], and electron
impact mass spectra (in all cases, the molecular ion
peak was observed).
EXPERIMENTAL
The melting points were determined on a Boetius
device (samples were heated at a rate of 4 deg/min).
The IR spectra were recorded on a Specord M-80
spectrometer from samples pelleted with KBr. The
mass spectra (70 eV) were measured on a Kratos MS-
Scheme 6.
1
30 instrument. The H NMR spectra were recorded on
a Bruker AC-200 spectrometer. The progress of reac-
tions was monitored by HPLC using a Liquochrom
Model 2010 chromatograph (UV detector, 240 nm;
Silasorb C-18 reversed phase; eluent acetonitrile
water, 3:1).
X = PhO (a), PhS (b), 2-C5H4NS (c), PhO2 (d).
Thus, our study of transformations of sulfone IIa
in reactions with O- and S-nucleophiles and sub-
sequent oxidation and reduction of nucleophilic
substitution products resulted in development of
procedures for preparation of new polyfunctional
benzene derivatives substituted in the 1,3,5-positions.
Aryl 3,5-dinitrophenyl sulfones IIa IIc. A mix-
ture of 0.03 mol of 1-arylthio-3,5-dinitrobenzene
Ia Ic, 10.2 ml of 35% H2O2, and 70 ml of glacial
acetic acid was heated under reflux. The mixture was
cooled, and the precipitate was filtered off, dried, and
(if necessary) recrystallized.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 12 2002

SYNTHESIS OF ARYL 3,5-DINITROPHENYL SULFONES AND SULFOXIDES.
1761
4
3,5-Dinitrodiphenyl sulfone (IIa). Reaction time
8.30 t (1H, J = 2.1 Hz). Found, %: C 53.55; H 4.02;
N 4.99; S 10.51. C13H11NO5S. Calculated, %:
C 53.24; H 3.78; N 4.78; S 10.93.
1
2 h. Yield 93%. mp 169 170 C; H NMR spectrum
3
(DMSO-d6), , ppm: 7.71 m (3H), 8.28 d (2H, J =
4
4
8.1 Hz), 8.95 d (2H, J = 2.3 Hz), 9.01 d (1H, J =
2.3 Hz). Found, %: C 47.16; H 2.95; N 9.35; S 10.08.
C12H8N2O6S. Calculated, %: C 46.75; H 2.62; N 9.09;
S 10.04.
3-Nitro-5-phenoxydiphenyl sulfone (V). A solu-
tion of 7.7 g (0.025 mol) of sulfone IIa in 10 ml
of NMP was added to a mixture of 2.35 g (0.025 mol)
of phenol, 3.45 g (0.025 mol) of K2CO3, and 15 ml
of NMP. The mixture was stirred for 6 h at 80 C and
poured into 120 ml of cold water, and the precipitate
was filtered off, dried, and recrystallized. Yield 74%.
mp 119 120 C (from MeOH). H NMR spectrum
(DMSO-d6), , ppm: 7.20 d (2H, J = 8.1 Hz), 7.31 m
(1H), 7.50 m (2H), 7.68 m (3H), 7.86 d (1H, J =
2.3 Hz), 7.98 d (1H, J = 2.3 Hz), 8.09 d (2H, J =
7.9 Hz), 8.20 d (1H, 4J = 2.2 Hz). Found, %: C 61.20;
H 4.02; N 4.24; S 8.80. C18H13NO5S. Calculated, %:
C 60.84; H 3.69; N 3.39; S 9.02.
3,5-Diphenoxydiphenyl sulfone (VI) was syn-
thesized as described above for compound V, but the
mixture was stirred for 4 h at 150 C. Yield 63%.
4-Chloro-3 ,5 -dinitrodiphenyl sulfone (IIb).
1
Reaction time 1.5 h. Yield 89%. mp 140 141 C. H
3
NMR spectrum (DMSO-d6), , ppm: 7.76 d (2H, J =
1
3
4
8.2 Hz), 8.22 d (2H, J = 8.1 Hz), 8.99 d (2H, J =
3
4
2.1 Hz), 9.02 t (1H, J = 2.1 Hz). Found, %: C 42.51;
4
H 2.73; Cl 10.58; N 8.61; S 9.06. C12H7ClN2O6S.
Calculated, %: C 42.06; H 2.06; Cl 10.34; N 8.17;
S 9.36.
4
3
2-(3,5-Dinitrophenylsulfonyl)-1,3-benzothiazole
(IIc). Reaction time 6 min. Yield 35%. mp 158
1
159 C (from MeCN H2O, 3:1). H NMR spectrum
(DMSO-d6), , ppm: 7.72 m (2H), 8.24 m (1H),
4
8.37 m (1H), 9.04 d (2H, J = 2.3 Hz), 9.10 d (1H,
1
mp 87 88 C (from 2-propanol). H NMR spectrum
4J = 2.3 Hz). Found, %: C 43.22; H 2.31; N 11.77;
S 17.05. C13H7N3O6S2. Calculated, %: C 42.74;
H 1.93; N 11.50; S 17.55.
(DMSO-d6), , ppm: 6.78 d (1H, 4J = 2.0 Hz),
7.14 m (8H), 7.42 m (4H), 7.64 m (3H), 7.91 d (2H,
3J = 8.1 Hz). Found, %: C 71.98; H 4.90; S 7.37.
C24H18O4S. Calculated, %: C 71.62; H 4.51; S 7.97.
Aryl 3,5-dinitrodiphenyl sulfoxides IIIa and
IIIc. A mixture of 0.025 mol of 1-arylthio-3,5-dinitro-
benzene IIa or IIc, 2.25 ml of 35% hydrogen per-
oxide, and 45 ml of glacial acetic acid was stirred for
7 days at room temperature. It was then poured into
225 ml of cold water, and the precipitate was filtered
off, dried, and recrystallized.
3-Nitro-5-phenylthiodiphenyl sulfone (VII).
A solution of 7.7 g (0.025 mol) of sulfone IIa in
10 ml of NMP was added to a mixture of 2.55 ml
(0.025 mol) of benzenethiol, 3.45 g (0.025 mol) of
K2CO3, and 15 ml of NMP. The mixture was stirred
for 3 h at 50 C and poured into 120 ml of cold water,
and the precipitate was filtered off, dried, and recrys-
tallized. Yield 75%. mp 89 90 C (from MeOH).
1H NMR spectrum (DMSO-d6), , ppm: 7.53 m (4H),
3,5-Dinitrodiphenyl sulfoxide (IIIa). Yield 80%.
mp 119 120 C (from CCl4). 1H NMR spectrum
(DMSO-d6), , ppm: 7.59 m (3H), 7.73 m (2H), 8.85 t
4
4
4
(1H, J = 2.1 Hz), 8.94 d (2H, J = 2.3 Hz). Found,
%: C 49.93; H 3.09; N 10.01; S 10.21. C12H8N2O5S.
Calculated, %: C 49.31; H 2.76; N 9.58; S 10.97.
7.68 m (4H), 8.00 m (4H), 8.33 t (1H, J = 2.1 Hz).
Found, %: C 58.68; H 3.91; N 4.07; S 16.90.
C18H13NO4S2. Calculated, %: C 58.21; H 3.53;
N 3.77; S 17.27.
2-(3,5-Dinitrophenylsulfinyl)-1,3-benzothiazole
(IIIc). Yield 58%, mp 111 112 C (from CCl4 CHCl3,
3-Nitro-5-(2-pyridylthio)diphenyl sulfone (IX).
A solution of 7.7 g of sulfone IIa in 10 ml of HMPA
was added to a mixture of 2.275 g (0.025 mol) of
pyridine-2-thiol (VIII), 3.45 g (0.025 mol) of K2CO3,
and 15 ml of HMPA. The mixture was stirred for
48 h at 20 C and poured into 225 ml of cold water,
and the precipitate was filtered off, dried, and recrys-
tallized. Yield 57%. mp 106 107 C (from MeCN
1
2:1). H NMR spectrum (DMSO-d6), , ppm: 7.57 m
3
(2H), 8.10 m (1H), 8.21 m (1H), 8.91 t (1H, J =
8.1 Hz), 8.97 d (2H, 4J = 2.3 Hz). Found, %: C 45.05;
H 2.51; N 12.35; S 18.02. C13H7N3O5S2. Calculated,
%: C 44.69; H 2.02; N 12.03; S 18.36.
3-Methoxy-5-nitrodiphenyl sulfone (IV). A mix-
ture of 6.16 g (0.02 mol) of sulfone IIa, 120 ml of
methanol, 7.72 g (0.09 mol) of NaHCO3, and 30 ml
of water was refluxed for 6 h. It was then cooled, and
the precipitate was filtered off, washed with water,
dried, and recrystallized. Yield 72%. mp 127 128 C
1
H2O, 3:1). H NMR spectrum (acetone-d6), , ppm:
3
7.29 m (1H), 7.41 d (1H, J = 8.3 Hz), 7.72 m (4H),
4
8.09 m (2H), 8.41 m (1H), 8.46 t (1H, J = 2.1 Hz),
4
4
8.57 t (1H, J = 2.1 Hz), 8.64 t (1H, J = 2.1 Hz).
Found, %: C 55.25; H 3.77; N 7.94; S 16.98.
C17H12N2O4S2. Calculated, %: C 54.83; H 3.25;
N 7.52; S 17.22.
1
(from MeOH). H NMR spectrum (CDCl3), , ppm:
3
3.94 s (3H), 7.60 m (3H), 7.77 t (1H, J = 8.1 Hz),
4
3
7.87 t (1H, J = 2.1 Hz), 7.98 d (2H, J = 8.1 Hz),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 12 2002

1762
SERUSHKINA et al.
of 35% hydrogen peroxide, and 70 ml of acetic acid
4,4 -Bis(3-nitro-5-phenylsulfonylphenylthio)di-
was heated for 30 min under reflux. The mixture was
cooled, and the precipitate was filtered off and dried.
Yield 68%. mp 222 224 C; published data [16]:
phenyl sulfide (XI). A solution of 3.08 g (0.01 mol)
of sulfone IIa in 4 ml of NMP was added to a mixture
of 1.25 g (0.005 mol) of 4,4 -dimercaptodiphenyl sul-
fide (X) and 1.38 g (0.01 mol) of K2CO3 in 6 ml
of NMP. The mixture was stirred for 4 h at 50 C and
poured into 50 ml of cold water, and the precipitate
was filtered off, dried, and dissolved in 1,2-dichloro-
ethane. The solution was filtered through a layer of
silica gel ( 10 g), the solvent was removed, and the
residue was recrystallized. Yield 32%. mp 138 140 C
1
mp 218 C. H NMR spectrum (DMSO-d6), , ppm:
7.69 m (9H), 8.09 m (6H), 8.28 s (1H), 8.60 s (2H).
Found, %: C 58.23; H 3.98; S 18.87. C24H18O6S3.
Calculated, %: C 57.81; H 3.64; S 19.29.
Reaction of 1,3,5-tris(phenylsulfonyl)benzene
(XV) with benzenethiol. A solution of 4.98 g
(0.01 mol) of compound XV in 4 ml of NMP was
added to a mixture of 1.02 ml (0.01 mol) of benzene-
thiol, 1.38 g (0.01 mol) of K2CO3, and 6 ml of NMP.
The mixture was stirred for 30 min at 50 C and
poured into 50 ml of cold water, and the precipitate
of bis-sulfone XIV was filtered off, dried, and recrys-
tallized.
3-Phenylsulfonylanilines XVIa XVId. A mixture
of 0.015 mol of mononitrosulfone V, VII, XII, or
XIII, 1.2 ml of hydrazine hydrate, 0.04 g of FeCl3
6H2O, 0.5 g of charcoal, and 55 ml of methanol was
heated for 3 h under reflux. It was then filtered, the
filtrate was cooled, and the precipitate was filtered off
and dried.
(from MeOH); 1H NMR spectrum (DMSO-d6),
,
ppm: 7.58 m (14H), 8.07 m (8H), 8.38 m (2H). Found,
%: C 55.32; H 3.91; N 3.04; S 20.06. C36H24N2O8S5.
Calculated, %: C 55.94; H 3.13; N 3.62; S 20.74.
4,4 -Bis(3-nitro-5-phenylsulfonylphenylsulfonyl)-
diphenyl sulfone (XII). A mixture of 1.544 g
(0.002 mol) of tris-sulfide XI, 2 ml (0.024 mol) of
35% hydrogen peroxide, and 40 ml of acetic acid was
heated for 2 h under reflux. The mixture was cooled,
and the precipitate was filtered off and dried. Yield
1
37%. mp 288 290 C. H NMR spectrum (DMSO-d6),
, ppm: 7.65 m (12H), 8.12 m (4H), 8.22 m (4H),
8.40 m (4H), 8.82 m (6H). Found, %: C 49.16;
H 3.17; N 2.60; S 17.88. C36H24N2O14S5. Calculated,
%: C 49.76; H 2.78; N 3.22; S 18.45.
3-Phenoxy-5-phenylsulfonylaniline (XVIa). mp
1
156 157 C. H NMR spectrum (DMSO-d6), , ppm:
4
4
1-Nitro-3,5-bis(phenylsulfonyl)benzene (XIII).
A mixture of 11.13 g (0.03 mol) of sulfone VII,
10.2 ml of 35% hydrogen peroxide, and 70 ml of
acetic acid was heated for 1 h under reflux. The mix-
ture was cooled, and the precipitate was filtered off
and dried. Yield 95%. mp 177 178 C. 1H NMR
spectrum (DMSO-d6), , ppm: 7.70 m (6H), 8.14 d
5.78 s (2H), 6.36 t (1H, J = 2.1 Hz), 6.57 t (1H, J =
4
3
2.1 Hz), 6.85 t (1H, J = 2.1 Hz), 7.04 d (2H, J =
7.8 Hz), 7.20 t (1H, J = 7.8 Hz), 7.41 m (2H),
7.65 m (3H), 7.87 d (2H, J = 8.6 Hz). Found, %:
3
3
C 66.92; H 4.97; N 4.99; S 9.27. C18H15NO3S. Cal-
culated, %: C 66.44; H 4.65; N 4.30; S 9.85.
3-Phenylsulfonyl-5-phenylthioaniline (XVIb).
3
4
1
(4H, J = 8.1 Hz), 8.76 t (1H, J = 2.1 Hz), 8.70 d
(2H, 4J = 2.3 Hz). Found, %: C 53.99; H 3.79;
N 4.01; S 15.21. C18H13NO6S2. Calculated, %:
C 53.59; H 3.25; N 3.47; S 15.90.
mp 134 135 C. H NMR spectrum (DMSO-d6),
,
4
ppm: 5.82 s (2H), 6.64 t (1H, J = 1.9 Hz), 6.81 t
(1H, J = 1.9 Hz), 6.96 t (1H, J = 1.9 Hz), 7.40 m
(5H), 7.65 m (3H), 7.82 d (2H, J = 8.1 Hz). Found,
4
4
3
%: C 63.94; H 4.85; N 4.80; S 18.06. C18H15NO2S2.
Calculated, %: C 63.31; H 4.43; N 4.10; S 18.78.
1-Phenylthio-3,5-bis(phenylsulfonyl)benzene
(XIV). A solution of 4.03 g (0.01 mol) of compound
XIII in 4 ml of NMP was added to a mixture of
1.02 ml (0.01 mol) of benzenethiol, 1.38 g (0.01 mol)
of K2CO3, and 6 ml of NMP. The mixture was heated
for 30 min at 50 C and poured into 50 ml of cold
water, and the precipitate was filtered off, dried, and
recrystallized. Yield 73%. mp 137 138 C (from
MeOH). 1H NMR spectrum (DMSO-d6), , ppm:
7.51 m (5H), 7.62 m (4H), 7.72 m (2H), 7.81 d (2H,
3-Phenylsulfonyl-5-(2-pyridylthio)aniline (XVIc).
1
Reaction time 3.5 h. Yield 64%. mp 126 127 C. H
NMR spectrum (DMSO-d6), , ppm: 5.91 s (2H),
6.94 m (1H), 7.10 m (3H), 7.20 m (1H), 7.66 m (4H),
7.89 m (2H), 8.42 m (1H). Found, %: C 60.15;
H 4.80; N 8.62; S 17.91. C17H14N2O2S2. Calculated,
%: C 59.63; H 4.12; N 8.18; S 18.78.
3,5-Bis(phenylsulfonyl)aniline (XVId). mp 225
3
4J = 2.3 Hz), 7.92 d (4H, J = 8.1 Hz), 8.09 t (1H,
226 C. 1H NMR spectrum (DMSO-d6), , ppm: 6.29 s
4J = 2.1 Hz). Found, %: C 62.16; H 4.12; S 20.04.
C24H18O4S3. Calculated, %: C 61.78; H 3.89; S 20.62.
1,3,5-Tris(phenylsulfonyl)benzene (XV). A mix-
ture of 4.66 g (0.01 mol) of compound XIV, 3.4 ml
4
4
(2H), 7.30 d (2H, J = 2.3 Hz), 7.41 t (1H, J =
2.1 Hz), 7.68 m (6H), 7.91 d (4H, 3J = 8.1 Hz). Found,
%: C 58.27; H 4.51; N 4.05; S 16.91. C18H15NO4S2.
Calculated, %: C 57.89; H 4.05; N 3.75; S 17.17.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 12 2002

SYNTHESIS OF ARYL 3,5-DINITROPHENYL SULFONES AND SULFOXIDES.
1763
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