NEW SYNTHETIC APPROACH TO PHENYLMETHANESULFONAMIDE DERIVATIVES
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were measured on a Bruker DPX-400 instrument at
400.61 and 100.13 MHz, respectively, using tetra-
methylsilane as internal reference. Phenylmethanesul-
fonamide (I) was synthesized as described in [10].
(1H, NCH, J = 10.5 Hz), 7.38 m (5H, C6H5), 8.39 d
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(1H, NH, J = 10.5 Hz). 13C NMR spectrum
(DMSO-d6), δC, ppm: 59.8 (CH2); 85.7 (NCH); 102.0
(CCl3); 128.2, 128.4, 129.5, 130.9 (C6H5). Found, %:
C 33.75; H 3.21; Cl 33.59; N 4.58; S 10.37.
C9H10Cl3NO3S. Calculated, %: C 33.93; H 3.16;
Cl 33.38; N 4.40; S 10.06.
N,N-Dichlorophenylmethanesulfonamide (II).
Phenylmethanesulfonamide (I), 1.71 g (10 mmol), was
added under stirring to a solution of 0.80 g (20 mmol)
of sodium hydroxide in 20 ml of water, gaseous
chlorine was passed through the resulting solution until
its absorption ceased, and the mixture was kept for 2 h
at room temperature. The precipitate was filtered off,
washed with cold water until the absence of chloride
ions in the washings, dried, and recrystallized from
chloroform. Yield 1.63 g (68%), mp 75–76°C. IR spec-
trum, ν, cm–1: 3086–3010 (C–Harom), 2957–2851
Phenyl-N-[2,2,2-trichloro-1-(4-methylphenyl)-
ethyl]methanesulfonamide (Va). A mixture of imine
III [prepared from 2.40 g (10 mmol) of II], 1 ml of
96% H2SO4, and 0.5 g of P4O10 in 10 ml of toluene
was stirred for 3 h. The mixture was evaporated, and
the residue was washed with water until neutral
washings, 20% aqueous ammonia (30 ml), and water
again, dried, and recrystallized from acetone–CCl4
(1:10 by volume). Yield 3.18 g (81%), mp 181–183°C.
IR spectrum, ν, cm–1: 3254 (NH), 1338, 1153 (SO2).
1H NMR spectrum (CDCl3), δ, ppm: 2.38 s (3H, CH3),
4.12 m (2H, CH2, AB pattern), 5.30 s (1H, CH), 7.08,
7.20 m (4H, C6H4, AA′BB′); 7.18 m, 7.27 m, and
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(C–Haliph), 1376, 1172 (SO2). H NMR spectrum
(CDCl3), δ, ppm: 4.86 s (2H, CH2), 7.48–7.54 m (5H,
C6H5). 13C NMR spectrum (CDCl3), δC, ppm: 52.4
(CH2); 125.2, 129.3, 129.9, 132.3 (C6H5). 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.
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7.63 m (5H, C6H5). C NMR spectrum (CDCl3), δC,
ppm: 20.9 (CH3), 60.4 (CH2), 72.5 (CH), 102.7 (CCl3);
126.8, 128.4, 128.7, 128.9, 129.4, 130.41, 133.0, 139.8
(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.
Phenyl-N-(2,2,2-trichloroethylidene)methanesul-
fonamide (III). A mixture of 2.40 g (10 mmol) of
dichloro amide II and 10.50 g (80 mmol) of trichloro-
ethylene was heated for 10–12 h under reflux in
an argon atmosphere until chlorine no longer evolved
(iodine–starch test), and the solvent was distilled off
under reduced pressure. Yield 2.85 g (95%), mp 128–
Phenyl-N-[2,2,2-trichloro-1-(4-methoxyphenyl)-
ethyl]methanesulfonamide (Vb). A mixture of imine
III [prepared from 2.40 g (10 mmol) of II], 1 ml of
96% H2SO4, 0.5 g of P4O10, and 3 ml of anisole in
10 ml of CCl4 was stirred for 3 h and was then treated
as described above for Va. Yield 3.38 g (83%),
mp 154–157°C. IR spectrum, ν, cm–1: 3257 (NH),
1337, 1168 (SO2). 1H NMR spectrum (CDCl3), δ, ppm:
3.89 s (3H, CH3), 4.15 m (2H, CH2, AB), 5.25 d (1H,
CH, J = 9.8 Hz), 5.74 d (1H, NH, J = 9.8 Hz), 6.90,
7.41 m (4H, C6H4, AA′BB′); 7.14 m, 7.30 m, and
7.57 m (5H, C6H5). C NMR spectrum (CDCl3), δC,
ppm: 54.6 (CH3), 59.9 (CH2), 70.8 (CH), 101.0 (CCl3);
113.1, 130.1, 133.2, 159.9 (C6H4); 126.4, 127.6, 128.3,
130.6 (C6H5). 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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130°C. H NMR spectrum (CDCl3), δ, ppm: 4.47 s
(2H, CH2), 7.25–7.38 m (5H, C6H5), 8.11 s (1H,
N=CH). 13C NMR spectrum (CDCl3), δC, ppm: 58.1
(CH2); 90.8 (CCl3); 125.9, 126.2, 128.5, 130.6 (C6H5),
166.5 (C=N). Found, %: C 35.83; H 2.62; Cl 35.48;
N 4.53; S 10.43. C9H8Cl3NO2S. Calculated, %:
C 35.96; H 2.68; Cl 35.38; N 4.66; S 10.67.
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Phenyl-N-(2,2,2-trichloro-1-hydroxyethyl)-
methanesulfonamide (IV). a. Compound III, 1.50 g
(5 mmol) was kept for 24 h on exposure to air. Yield
1.59 g (100%).
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b. A solution of 1.71 g (10 mmol) of phenylmeth-
anesulfonamide (I), 2.21 g (15 mmol) of trichloro-
acetaldehyde, and 0.3 ml of concentrated sulfuric acid
in 30 ml of anhydrous CCl4 was vigorously stirred for
30 min. The precipitate was filtered off, washed with
water, and dried in air. Yield 2.93 g (92%), mp 93–
95°C. IR spectrum, ν, cm–1: 3512 (OH), 3205 (NH),
3089–3033 (C–Harom), 2973–2886 (C–Haliph), 1314,
Compounds Vc and Vd were synthesized in a sim-
ilar way.
Phenyl-N-[2,2,2-trichloro-1-(thiophen-2-yl)ethyl]-
methanesulfonamide (Vc) was synthesized from
2.40 g (10 mmol) of II and 3 ml of thiophene using
1 ml of 96% H2SO4 and 0.5 g of P4O10. Yield 2.37g
(62%), mp 125–127°C. IR spectrum, ν, cm–1: 3250
1
1157 (SO2). H NMR spectrum (DMSO-d6), δ, ppm:
3.64 s (1H, OH), 4.42 m (2H, CH2, AB pattern), 5.22 d
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012