Synthesis of 2-methyl-N-(2,2,2-trichloroethylidene)- and 2-methyl-N-(2,2,2-trichloroethyl)benzenesulfonamides from N,N-dichloro-2- methylbenzenesulfonamide and trichloroethylene

Article abstract of DOI:10.1134/S1070428014030099

The reaction of N,N-dichloro-2-methylbenzenesulfonamide with trichloroethylene gave a new representative of highly electrophilic N-sulfonyl polyhaloaldehyde imines, 2-methyl-N-(2,2,2-trichloroethylidene) benzenesulfonamide. High reactivity of the product

Full text of DOI:10.1134/S1070428014030099

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 3, pp. 355–360. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © Yu.A. Aizina, I.B. Rozentsveig, S.K. Petkevich, V.I. Potkin, G.G. Levkovskaya, 2014, published in Zhurnal Organicheskoi Khimii,
2014, Vol. 50, No. 3, pp. 366–371.
Synthesis of 2-Methyl-N-(2,2,2-trichloroethylidene)-
and 2-Methyl-N-(2,2,2-trichloroethyl)benzenesulfonamides
from N,N-Dichloro-2-methylbenzenesulfonamide
and Trichloroethylene
Yu. A. Aizinaa, I. B. Rozentsveiga, S. K. Petkevichb, V. I. Potkinb, and G. G. Levkovskayaa
a Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: ggl@irioch.irk.ru
b Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus,
ul. Surganova 13, Minsk, 220072 Belarus
Received November 5, 2013
Abstract—The reaction of N,N-dichloro-2-methylbenzenesulfonamide with trichloroethylene gave a new
representative of highly electrophilic N-sulfonyl polyhaloaldehyde imines, 2-methyl-N-(2,2,2-trichloro-
ethylidene)benzenesulfonamide. High reactivity of the product was demonstrated in the addition of water and
2-methylbenzenesulfonamide and reactions with benzene, toluene, anisole, thiophene, and 2-chlorothiophene.
N,N-Dichlorobenzenesulfonamides and N,N-dichlorotrifluoromethanesulfonamide failed to react with
1,1,3,3,4,4-hexachlorobut-1-ene and 1,1,2,3,4-pentachlorobuta-1,3-diene under the conditions ensuring
formation of N-(2,2,2-trichloroethylidene)arenesulfonamides from N,N-dichloroarenesulfonamides and
trichloroethylene.
DOI: 10.1134/S1070428014030099
Sulfonamide derivatives are widely used as medic-
inal agents exhibiting antidiabetic [1, 2], diuretic [1, 3],
analgesic [1, 4], anti-inflammatory [1, 5], and anti-
tumor activity [6]; efficient enzyme inhibitors were
also found among these compounds [7]. Sulfonamides
are also known as herbicides, insecticides, fungicides
[8], and dyes (including those for medical purposes)
[9]. Furthermore, sulfonamides are important reagents
in modern organic synthesis, specifically in the pre-
paration and identification of amines [10] and syn-
thesis of new sulfonamides [11] and Schiff bases [12];
they were also used as enantioselective catalysts [13],
ligands for metal complex catalysts [14], etc.
One of the most efficient methods for the prepara-
tion of highly reactive N-sulfonyl polyhaloaldehyde
imines and a broad series of sulfonamide derivatives
based thereon utilizes the reaction of N,N-dichloro
arene-, phenylmethane-, and perfluoroalkanesulfon-
amides with 1,2-polyhaloethenes [15–20]. However,
the chemical behavior of such an accessible 2-toluene-
sulfonamide derivative as N,N-dichloro-2-methylben-
zenesulfonamide [21] has been studied very poorly.
There are published data only on the reduction of this
compound with DMSO [22] and its electrochemical
(cathodic) reduction to 2-methylbenzenesulfonamide
[23]. Up to now, reactions of N,N-dichloro-2-methyl-
benzenesulfonamide with 1,2-polyhaloethenes have
not been studied.
With a view to develop selective procedures for the
synthesis of new important precursors of biologically
active substances and practically valuable products of
the sulfonamide series, including heterocyclic deriva-
tives, in the present work N,N-dichloro-2-methylben-
zenesulfonamide (II) was brought into reaction with
trichloroethylene, as well as with 1,1,3,3,4,4-hexa-
chlorobut-1-ene and 1,1,2,3,4-pentachlorobuta-1,3-di-
ene synthesized from trichloroethylene. Amide II was
prepared in 68% yield by treatment of an alkaline
solution of 2-methylbenzenesulfonamide (I) with
gaseous chlorine, by analogy with the synthesis of
isomeric N,N-dichloro-4-methylbenzenesulfonamide
[24] (Scheme 1).
355

AIZINA et al.
356
Scheme 1.
Me
Me
Me
S
Cl2, NaOH
ClCH=CCl2
Cl
N
–H2O, –NaCl
CCl3
SO2NH2
SO2NCl2
O
O
Cl
I
II
A
Me
N
CCl3
95%
S
O
O
III
We tried to synthesize previously unknown 2-meth-
yl-N-(2,2,2-trichloroethylidene)benzenesulfonamide
(III) by reaction of N,N-dichloro amide II with tri-
chloroethylene under the conditions ensuring quan-
titative formation of N-(2,2,2-trichloroethylidene)-
arenesulfonamides [15, 18, 20]. Compound II reacted
with trichloroethylene in 10–12 h to afford amide III
in a good yield (95%); the reaction was accompanied
by formation of an equimolar amount of pentachloro-
ethane as a result of chlorine addition to trichloro-
ethylene. The reaction followed a radical chain mecha-
nism and involved intermediate formation of unstable
saturated adduct A which readily underwent dechlo-
rination (Scheme 1).
N,N-Dihalo amides derived from arenesulfonic and
trifluoromethanesulfonic acids were reacted with
1,1,3,3,4,4-hexachlorobut-1-ene and 1,1,2,3,4-penta-
chlorobuta-1,3-diene. It was expected that these reac-
tions would give rise to the corresponding highly
reactive polyhaloaldehyde imines (by analogy with the
reaction of N,N-dichloro sulfonamides with 1,2-poly-
haloethenes, which was studied by us in detail [15])
and 1-amido-substituted chlorobutanes as intermediate
products for the synthesis of chloroaziridines [15, 16].
However, under the conditions optimal for the syn-
thesis of N-sulfonyl polyhaloaldehyde imines or
adducts of ethenes and N,N-dichloro amides [15–20],
N,N-dichloro sulfonamides, including the most reac-
tive N,N-dichlorotrifluoromethanesulfonamide [17, 19],
failed to react with the above polychloroalkenes.
tivity. Newly synthesized 2-methyl-N-(2,2,2-trichloro-
ethylidene)benzenesulfonamide (III) was brought into
reactions with water and amide I and amidoalkylation
of benzene, toluene, anisole, thiophene, and 2-chloro-
thiophene, which are typical of chloral imines.
Imine III was quantitatively converted into hy-
droxy derivative IV on exposure to air for 24 h or on
addition of water (Scheme 2), which indicated high
electrophilicity of the CH=N group in III activated by
strong electron-withdrawing substituents. Compound
IV was also synthesized from amide I and trichloro-
acetaldehyde in the presence of a catalytic amount of
concentrated sulfuric acid, but the yield was somewhat
lower. In this case, no imine III was detected in the
reaction mixture by 1H and 13C NMR spectroscopy.
Scheme 2.
Me
H
N
Cl3CCHO
H2O
CCl3
I
III
S
O
O
OH
IV
Imine III reacted with amide I in trichloroethylene
at 90–92°C in the absence of a catalyst to produce bis-
amide V in quantitative yield (Scheme 3). The ability
of imine III to react with aromatic and heteroaromatic
compounds under acid catalysis was demonstrated
using benzene, toluene, anisole, thiophene, and
2-chlorothiophene as substrates. As a result, the corre-
sponding N-[1-aryl(hetaryl)-2,2,2-trichloroethyl]-
In continuation of our systematic studies on the
reactivity of N-(polychloroethylidene)arenesulfon-
amides we examined some reactions of amide III with
a view to develop synthetic approaches to new
N-(haloalkyl)sulfonamides containing additional het-
eroatom, aromatic, and heterocyclic fragments. These
compounds attract interest from the viewpoints of their
further transformations and potential biological ac-
Scheme 3.
Me
Me
H
N
H
N
ClCH=CCl2, Δ
I
+ III
S
S
O
O
O
O
CCl3
V
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 3 2014

SYNTHESIS OF 2-METHYL-N-(2,2,2-TRICHLOROETHYLIDENE)- ...
357
Yields of amide VIa in the reaction of benzene with sulfon-
amide IIIa
2-methylbenzenesulfonamides VIa–VIe were obtained
in good yields (Scheme 4). When fuming sulfuric acid
(10–20% SO3) was used as catalyst [25], the reaction
was accompanied by tarring and side sulfonation of the
aromatic substrate, while no compounds VIa–VIe
were formed in the presence of concentrated sulfuric
acid alone. Efficient C-amidoalkylation was achieved
when imine III was added to excess aromatic substrate
and a mixture of 90–94% sulfuric acid and phosphoric
anhydride (0.4–0.5 g of H2SO4 and 0.25–0.3 g of P4O10
per 0.01 mol of III; see table).
Catalyst (amount)
Time, h Yield, %
AlCl3 (1.33 g, 10 mmol)
BF3·Et2O (1.42 g, 10 mmol)
P4O10 (2.84 g, 10 mmol)
100% H2SO4 (0.98 g, 10 mmol)
Oleum, 10% SO3 (1.0 g)
Oleum, 20% SO3 (1.0 g)
94% H2SO4 (1.0 g), P4O10 (1.0 g)
94% H2SO4 (1.0 g), P4O10 (0.5 g)
94% H2SO4 (0.5 g), P4O10 (0.5 g)
50
50
50
07
07
07
05
05
03
00
00
00
25b
45c
40c
78
80
81
Scheme 4.
Me
ArH or HtH
a
H
N
H2SO4, P4O10
The reactions were carried out according to the procedure de-
scribed in Experimental for the synthesis of amide VIa.
Sulfonamide I and bis-amide V were also formed.
Ar (Ht)
III
S
62–85%
b
c
O
O
CCl3
VIa–VIe
Toluene- and benzenesulfonic acids were also formed.
Ar = Ph (a), 4-MeC6H4 (b), 4-MeOC6H4 (c); Ht =
2-thienyl (d), 5-chlorothiophen-2-yl (e).
and the spectrum of hemiaminal IV also contained OH
vibration band.
1
The H NMR spectra of II–VI contained signals
The reactions were carried out at room temperature
under vigorous stirring using the substrate (in the syn-
thesis of VIa–VIc) or halogenated hydrocarbon as
solvent (in the synthesis of thiophene derivatives VId
and Ve). The substitution in arenes and hetarenes was
regioselective with formation of 4-substitued benzenes
VIb and VIc and 2-substituted thiophenes VId and Ve;
the optimal reaction time was 3–5 h. No bis-amide V
was detected in the reaction mixtures under these
conditions.
The proposed approach to the synthesis of 2-meth-
ylbenzenesulfonamide derivatives via transformations
of 2-methyl-N-(2,2,2-trichloroethylidene)benzenesul-
fonamide features high chemo- and regioselectivity.
Undoubtedly, the products attract interest from the
viewpoint of preparation of various 2-methylbenzene-
sulfonamide derivatives, including N-protected aryl-
and hetarylglycines [26] and polyfunctional [15, 27]
and heterocyclic compounds [15, 28], by analogy with
the transformations of other N-arylsulfonyl imines
derived from polyhalogenated aldehydes.
from protons in the methyl group, and the NH–CH
fragment of amides IV–VI was represented in the
spectra by two doublets with a coupling constant of
9.5–10.5 Hz. Signals from the aromatic protons in VIb
and VIc appeared as an AA′BB′ pattern, indicating
para substitution of the aromatic ring. The signal
1
intensities in the H NMR spectra of II–VI and the
13
position of signals in the C NMR spectra of III–VI
were fully consistent with the assumed structures.
EXPERIMENTAL
1
The H and 13C NMR spectra were measured on
a Bruker DPX-400 instrument at 400.61 and
100.13 MHz, respectively, using tetramethylsilane as
internal reference. The IR spectra were recorded in
KBr on a Bruker IFS-25 spectrometer. 2-Methylben-
zenesulfonamide and N,N-dichloroarenesulfonamides
were commercial products. 1,1,3,3,4,4-Hexachlorobut-
1-ene and 1,1,2,3,4-pentachlorobuta-1,3-diene were
synthesized according to the procedures reported in
[29, 30]. N,N-Dichlorotrifluoromethanesulfonamide
was prepared as described in [31].
Compounds III–VI are colorless crystalline sub-
stances, which are readily soluble in polar organic
solvents and insoluble in water. The structure of II–VI
was proved by spectral data and elemental analyses.
All compounds II–VI displayed in the IR spectra
absorption bands typical of SO2 group. In the spectra
of substituted amides III–VI we observed absorption
bands due to stretching vibrations of the NH group,
N,N-Dichloro-2-methylbenzenesulfonamide (II).
Amide I, 1.71g (10 mmol), was added under stirring to
a solution of 1.60 g (40 mmol) of sodium hydroxide in
20 mL of water, gaseous chlorine was passed through
the solution until saturation, and the mixture was kept
for 2 h at room temperature. The tarry precipitate was
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 3 2014

AIZINA et al.
358
separated, washed with water, and dried. Yield 1.63 g
(OH), 3259 (NH), 3098 (C–Harom), 1314 (SO2), 1152.
1H NMR spectrum (DMSO-d6), δ, ppm: 2.57 s (3H,
CH3), 5.07 d (1H, NHCH, 3J = 9.2 Hz); 7.33 t, 7.46 d,
(68%); mp 33°C (CHCl3) [21]. IR spectrum, ν, cm–1:
1
3064 (C–Harom); 1331, 1164 (SO2). H NMR spectrum
3
(CDCl3), δ, ppm: 2.71 s (3H, CH3); 7.42 t, 7.64 t,
8.14 d (4H, C6H4). 13C NMR spectrum (CDCl3), δC,
ppm: 21.1 (CH3); 123.8, 126.6, 133.3, 133.7, 135.8,
141.5 (C6H4). Found, %: C 34.87; H 2.81; Cl 30.09;
N 5.58; S 12.87. C7H7Cl2NO2S. Calculated, %:
C 35.02; H 2.94; Cl 29.53; N 5.83; S 13.35.
7.90 d (4H, C6H4); 9.04 d (1H, NH, J = 9.2 Hz).
13C NMR spectrum (DMSO-d6), δC, ppm: 20.8 (CH3),
85.7 (NCH), 102.0 (CCl3); 128.2, 128.4, 129.5, 130.9
(Carom). Found, %: C 35.02; H 3.12; Cl 33.75; N 4.53;
S 10.02. C9H10Cl3NO3S. Calculated, %: C 34.93;
H 3.16; Cl 33.38; N 4.40; S 10.06.
Amide II was extracted from the reaction mixture
into chloroform (2×30 mL), the extracts were com-
bined and dried over calcium chloride, and the result-
ing solution was used to prepare imine III.
b. Imine III, 1.50 g (5 mmol), was kept for 24 h on
exposure to air. Yield of IV 1.59 g (100%).
N,N′-(2,2,2-Trichloroethane-1,1-diyl)bis-
(2-methylbenzenesulfonamide) (V). A mixture of
imine III [prepared from 2.40 g (10 mmol) of amide II
and 10.50 g (80 mmol) of trichloroethylene] and 1.71 g
(10 mmol) of amide I was stirred for 3 h on heating to
90–92°C. The mixture was cooled to room tempera-
ture, the solvent was distilled under reduced pressure,
and the residue was washed with water and dried.
Yield 4.51g (96%), mp 158–161°C. IR spectrum, ν,
cm–1: 3302, 3253 (NH); 2988 (C–Haliph); 1329, 1161
(SO2). 1H NMR spectrum (CDCl3), δ, ppm: 2.65 s (6H,
Reaction of N,N-dichloro sulfonamides with
polychloroalkenes (general procedure). A mixture of
0.01 mol of N,N-dichloro sulfonamide and 0.01–
0.02 mol of 1,1,3,3,4,4-hexachlorobut-1-ene or
1,1,2,3,4-pentachlorobuta-1,3-diene was heated for
10–12 h in anhydrous carbon tetrachloride under reflux
or in chlorobenzene at 110–120°C. The reactions were
also carried out under analogous conditions with
addition of 4–10% of benzoyl peroxide. Evaporation of
the mixture under reduced pressure gave the initial
N,N-dichloro sulfonamide.
2-Methyl-N-(2,2,2-trichloroethylidene)benzene-
sulfonamide (III). A mixture of 2.40 g (10 mmol) of
amide II and 10.50 g (80 mmol) of trichloroethylene
was heated for 10–12 h under reflux in an argon
atmosphere until chlorine no longer evolved (starch–
iodine test) and was then evaporated under reduced
pressure. Yield 2.85 g (95%), mp 128–130°C. 1H NMR
spectrum (CDCl3), δ, ppm: 2.67 s (3H, CH3); 7.33 t,
7.53 t, 8.03 d (4H, C6H4); 8.50 s (1H, N=CH).
13C NMR spectrum (CDCl3), δC, ppm: 21.0 (CH3),
81.3 (CCl3); 123.8, 126.6, 129.0, 133.2, 133.7, 135.8
(C6H4); 141.5 (C=N). Found, %: C 35.87; H 2.81;
Cl 35.09; N 4.58; S 10.87. C9H8Cl3NO2S. Calculated,
%: C 35.96; H 2.68; Cl 35.38; N 4.66; S 10.67.
3
CH3), 5.38 t (1H, NHCH, J = 8.8 Hz), 7.28–7.41 m
3
13
(8H, C6H4); 7.99 d (2H, NH, J = 8.8 Hz). C NMR
spectrum (CDCl3), δC, ppm: 19.9 (CH3), 74.6 (CH),
100.7 (CCl3); 125.5, 128.6, 131.8, 131.9, 136.5, 138.4
(C6H4). Found, %: C 40.21; H 3.52; Cl 22.98; N 5.71;
S 12.91. C16H17Cl3N2O4S2. Calculated, %: C 40.73;
H 3.63; Cl 22.54; N 5.94; S 13.59.
2-Methyl-N-(2,2,2-trichloro-1-phenylethyl)ben-
zenesulfonamide (VIa). A mixture of imine III [pre-
pared from 2.40 g (10 mmol) of N,N-dichloro amide II
and 10.50 g (7.2 mL, 80 mmol) or 8.0 g (5.4 mL,
60 mmol) of trichloroethylene], 0.5–0.6 mL of 96%
H2SO4, and 0.4–0.5 g of P4O10 in 10 mL of benzene
was stirred for 3 h. The mixture was evaporated under
reduced pressure, and the residue was washed with
water, 30 mL of 20% aqueous ammonia, and water
again (until neutral washings) and dried in air at room
temperature. Yield 3.18 g (81%), mp 125–127°C. IR
spectrum, ν, cm–1: 3259 (NH); 3061 (C–Harom); 1330,
Imine III was brought into further transformations
without isolation.
2-Methyl-N-(2,2,2-trichloro-1-hydroxyethyl)ben-
zenesulfonamide (IV). a. A mixture of 1.71 g
(10 mmol) of 2-methylbenzenesulfonamide (I), 3.26 g
(20 mmol) of trichloroacetaldehyde, and 1 mL of
concentrated sulfuric acid was vigorously stirred for
15 min at 60–65°C. The mixture was then kept for
15 min at room temperature, and the precipitate was
filtered off, washed with water until neutral washings,
and dried. Yield 3.16 g (95%), mp 128–130°C; pub-
lished data [32]: mp 148°C. IR spectrum, ν, cm–1: 3380
1
1168 (SO2). H NMR spectrum (CDCl3), δ, ppm:
3
2.41 s (3H, CH3), 5.04 d (1H, NHCH, J = 10.4 Hz);
7.08 d, 7.18 m, 7.31 t, 7.48 d, 7.76 d (9H, Harom);
3
9.27 (1H, NH, J = 10.4 Hz). 13C NMR spectrum
(CDCl3), δC, ppm: 19.8 (CH3), 71.6 (CH), 100.9
(CCl3); 125.1, 127.8, 128.4, 128.7, 131.1, 131.5, 131.8,
136.6, 137.9 (Carom). Found, %: C 47.87; H 4.08;
Cl 27.21; N 3.42; S 8.24. C15H14Cl3NO2S. Calculated,
%: C 47.57; H 3.73; Cl 28.08; N 3.70; S 8.47.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 3 2014

SYNTHESIS OF 2-METHYL-N-(2,2,2-TRICHLOROETHYLIDENE)- ...
359
2-Methyl-N-[2,2,2-trichloro-1-(4-methylphenyl)-
ethyl]benzenesulfonamide (VIb) was synthesized in
a similar way from 2.40 g (10 mmol) of N,N-dichloro
amide II, 8.0 g (5.4 mL, 60 mmol) of trichloroethylene,
and 10 mL of toluene using 0.5 mL of 96% H2SO4 and
0.5 g of P4O10. Yield 3.18 g (81%), mp 80–83°C.
IR spectrum, ν, cm–1: 3254 (NH); 1338, 1153 (SO2).
1H NMR spectrum (CDCl3), δ, ppm: 2.24 s (3H, CH3),
2-Methyl-N-[2,2,2-trichloro-1-(5-chlorothiophen-
2-yl)ethyl]benzenesulfonamide (VIe) was synthe-
sized in a similar way from 3 mL of 2-chlorothiophene
using 0.6 mL of 96% H2SO4 and 0.5 g of P4O10. Yield
3.14 g (75%), mp 108–110°C. IR spectrum, ν, cm–1:
1
3254 (NH), 1330 (SO2), 1166. H NMR spectrum
(DMSO-d6), δ, ppm: 2.40 s (3H, CH3), 5.28 d (1H,
CH, 3J = 10.2 Hz), 6.87 d and 7.02 d (2H, 3′-H, 4′-H);
7.21 d, 7.28 t, 7.43 t, 7.82 d (4H, C6H4), 9.36 d (1H,
NH, 3J = 10.2 Hz). 13C NMR spectrum (DMSO-d6), δC,
ppm: 19.9 (CH3), 67.6 (CH), 100.6 (CCl3); 125.8,
126.1, 129.0, 129.8, 132.2, 132.8, 135.2, 136.8, 138.2
(Carom). Found, %: C 38.22; H 2.85; Cl 33.33; N 3.45;
S 15.89. C13H11Cl4NO2S2. Calculated, %: C 37.25;
H 2.65; Cl 33.83; N 3.34; S 15.30.
The spectral and analytical studies were carried out
using the facilities of the Baikal Joint Analytical
Center. This work was financially supported by the
Siberian Branch, Russian Academy of Sciences (project
no. 21) and by the Belarusian Republican Foundation
for Basic Research (project no. Kh12SO-012).
3
2.77 s (3H, CH3), 4.67 d (1H, NHCH, J = 10.2 Hz),
6.73 d and 7.00 d (4H, AA′BB′, C6H4); 6.77 t, 6.89 t,
3
7.53 d (4H, C6H4); 8.21 (1H, NH, J = 10.2 Hz).
13C NMR spectrum (CDCl3), δC, ppm: 19.7 (CH3),
20.5 (CH3), 71.6 (CH), 100.9 (CCl3); 125.1, 127.8,
128.4, 128.7, 131.1, 131.5, 131.8, 136.6, 137.9 (Carom).
Found, %: C 48.87; H 4.08; Cl 27.21; N 3.42; S 8.24.
C16H16Cl3NO2S. Calculated, %: C 48.93; H 4.11;
Cl 27.08; N 3.57; S 8.16.
2-Methyl-N-[2,2,2-trichloro-1-(4-methoxyphenyl)-
ethyl]benzenesulfonamide (VIc) was synthesized in
a similar way from 2.40 g (10 mmol) of N,N-dichloro
amide II, 7.2 mL (80 mmol) of trichloroethylene, and
3 mL of anisole in 10 ml of carbon tetrachloride con-
taining 0.5 mL of 96% H2SO4 and 0.5 g of P4O10. Yield
3.55 g (87%), mp 134–136°C. IR spectrum, ν, cm–1:
3293 (NH); 3062 (C–Harom); 2964 (C–Haliph); 1336,
REFERENCES
1. Mashkovskii, M.D., Lekarstvennye sredstva (Medicines),
1
Moscow: Novaya Volna, 2010, 16th ed.
1164 (SO2). H NMR spectrum (DMSO-d6), δ, ppm:
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Sammes, P.G., and Taylor, J.B., Eds., Oxford: Pergamon,
1990, vol. 2, chap. 7.1.
2.44 s (3H, CH3), 3.71 s (3H, OCH3), 4.99 d (1H, CH,
3J = 10.5 Hz); 6.76 d and 7.42 d (4H, AA′BB′,
CH3OC6H4); 7.12 d, 7.22 t, 7.36 t, 7.76 d (4H,
3. Connor, E.E., Primary Care Update OB/GYNS, 1998,
3
13
CH3C6H4); 9.17 d (1H, NH, J = 10.4 Hz). C NMR
spectrum (DMSO-d6), δC, ppm: 20.4 (CH3), 55.7
(OCH3), 71.6 (CH), 102.6 (CCl3); 126.4, 127.03,
129.3, 131.4, 132.6, 133.0, 137.1, 139.1, 159.9 (Carom).
Found, %: C 47.23; H 3.88; Cl 26.17; N 3.55; S 7.93.
C16H16Cl3NO3S. Calculated, %: C 47.02; H 3.95;
Cl 26.02; N 3.43; S 7.85.
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2-Methyl-N-[2,2,2-trichloro-1-(2-thienyl)ethyl]-
benzenesulfonamide (VId) was synthesized in a simi-
lar way from 3 mL of thiophene using 0.7 g of H2SO4
and 0.7 g of P4O10. Yield 2.37g (62%), mp 125–127°C.
IR spectrum, ν, cm–1: 3250 (NH); 1335, 1168 (SO2).
1H NMR spectrum (DMSO-d6), δ, ppm: 2.40 s (3H,
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3
(3H, thiophene); 7.52 d (1H, NH, J = 9.5 Hz),
7.35 m and 7.47 m (4H, C6H4). 13C NMR spectrum
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