REACTIONS OF 2-(α-HALOALKYL)THIIRANES WITH NUCLEOPHILIC REAGENTS: IV.
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N-Phenyl-2-nitrobenzenesulfonamide (IVa).
H 2.99; N 8.84. C12H9ClN2O4S. Calculated, %: C 46.09;
Yield 95%, light yellow crystals, mp 118–120°C (from
ethanol–water, 4:1). H NMR spectrum (CDCl3), δ,
H 2.90; N 8.96.
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N-(1-Naphthyl)-2-nitrobenzenesulfonamide
(IVe). The crude product was purified by heating in
boiling ethanol, followed by recrystallization from
CHCl3–hexane (3:1). Yield 72%, pale violet crystals,
ppm: 7.13–7.37 m (6H, Ph, SO2NH), 7.54–7.63 t.d
(1H, J = 7.7, 1.5 Hz), 7.66–7.75 t.d (1H, J = 7.7,
1.5 Hz), 7.79–7.90 m (2H). 13C NMR spectrum
(CDCl3), δC, ppm: 123.7 (+, 2C), 125.7 (+), 127.0 (+),
129.9 (+, 2C), 132.2 (+), 132.6 (q), 133.0 (+), 134.4 (+),
135.9 (q), 148.6 (q). Mass spectrum, m/z (Irel, %): 278
[M]+ (10), 92 (78), 76 (21), 65 (100), 50 (53), 39 (83).
Found, %: C 51.78; H 3.67; N 10.14. C12H10N2O4S.
Calculated, %: C 51.79; H 3.62; N 10.07.
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mp 165–167°C. H NMR spectrum (CDCl3), δ, ppm:
7.34–7.96 m (11H, Ar, SO2NH), 8.05–8.15 m (1H).
13C NMR spectrum (CDCl3), δ, ppm: 122.3 (+), 124.6
(+), 125.6 (+), 125.7 (+), 126.9 (+), 127.4 (+), 128.7
(+), 128.8 (+), 130.2 (q), 131.3 (q), 131.8 (+), 133.0
(+), 133.4 (q), 134.2 (+), 134.7 (q), 148.5 (q). Mass
spectrum, m/z (Irel, %): 328 [M]+ (12), 142 (83), 115
(100), 89 (10), 76 (12), 63 (17), 50 (27), 39 (17).
Found, %: C 58.73; H 3.77; N 8.41. C16H12N2O4S. Cal-
culated, %: C 58.53; H 3.68; N 8.53.
N-(4-Methoxyphenyl)-2-nitrobenzenesulfon-
amide (IVb). Yield 90%, yellow crystals, mp 106–
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108°C (from ethanol–water, 4:1). H NMR spectrum
(CDCl3), δ, ppm: 3.76 s (3H, CH3O), 6.79 d (2H, J =
9.2 Hz), 7.09 d (2H, J = 9.2 Hz), 7.16 br.s (1H,
SO2NH), 7.57 t.d (1H, J = 7.7, 1.5 Hz), 7.65–7.79 m
(2H), 7.86 d (1H, J = 7.7 Hz). 13C NMR spectrum
(CDCl3), δC, ppm: 55.8 (+), 115.0 (+, 2C), 125.6 (+),
126.6 (+, 2C), 128.3 (q), 132.3 (+), 132.5 (q), 132.9
(+), 134.4 (+), 148.6 (q), 159.0 (q). Mass spectrum,
m/z (Irel, %): 308 [M]+ (6), 122 (100), 95 (19), 64 (10),
54 (19), 41 (16). Found, %: C 50.87; H 3.95; N 9.06.
C13H12N2O5S. Calculated, %: C 50.64; H 3.92; N 9.09.
b. A mixture of 144 mmol of the corresponding
aromatic amine and 72 mmol of 2-nitrobenzenesul-
fonyl chloride in 100 ml of dioxane (preliminarily
dried over KOH) was heated for 30–50 h under reflux.
The yield of the product increased on prolonged
heating. The resulting dark brown mixture was poured
into a solution of 25 g of sodium hydroxide in 700 ml
of water, stirred for 20 min, and filtered from undis-
solved material. The filtrate was acidified with con-
centrated hydrochloric acid and was left to stand for
crystallization. The precipitate (sulfonamide IVf or
IVg) was recrystallized from aqueous ethanol.
N-(2-Isopropylphenyl)-2-nitrobenzenesulfon-
amide (IVc). Yield 90%, colorless crystals, mp 117–
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119°C (from ethanol). H NMR spectrum (CDCl3), δ,
ppm: 1.08 d (6H, CH3, J = 6.9 Hz), 3.27 septet (1H,
CH, J = 6.9 Hz), 7.05–7.35 m (5H, C6H4, SO2NH),
7.63 t (1H, J = 7.7 Hz), 7.70–7.84 m (2H), 7.87–7.95 d
(1H, J = 7.7 Hz). 13C NMR spectrum (CDCl3), δC,
ppm: 23.8 (+, 2C), 27.8 (+), 125.7 (+), 126.8 (+), 127.0
(+), 127.3 (+), 128.5 (+), 131.8 (+), 132.4 (q), 133.0 (+),
133.8 (q), 134.3 (+), 145.5 (q), 148.4 (q). Mass spec-
trum, m/z (Irel, %): 320 [M]+ (12), 132 (95), 118 (65),
106 (61), 91 (94), 77 (64), 65 (67), 50 (100), 39 (95).
Found, %: C 56.10; H 4.99; N 8.75. C15H16N2O4S. Cal-
culated, %: C 56.24; H 5.03; N 8.74.
N-(3-Nitrophenyl)-2-nitrobenzenesulfonamide
(IVf). Yield 91%, light brown crystals, mp 165–166°C.
1H NMR spectrum (DMSO-d6–CCl4), δ, ppm: 7.45–
7.63 m (2H), 7.73–7.93 m (4H), 7.98–8.11 m
(2H), 11.14 br.s (1H, SO2NH). 13C NMR spectrum
(DMSO-d6–CCl4), δC, ppm: 114.9 (1C, +), 119.3 (1C,
+), 125.5 (1C, +), 126.2 (1C, +), 131.0 (1C, +), 131.1
(1C, +), 132.3 (q), 133.1 (1C, +), 135.4 (1C, +), 139.2
(q), 148.7 (q), 149.1 (q). Mass spectrum, m/z (Irel, %):
323 [M]+ (37), 186 (100), 91 (9), 63 (15). Found, %:
C 44.51; H 2.74; N 13.19. C12H9N3O6S. Calculated, %:
C 44.58; H 2.81; N 13.00.
N-(4-Chlorophenyl)-2-nitrobenzenesulfonamide
(IVd). Yield 96%, greenish–yellow crystals, mp 123–
N-(4-Nitrophenyl)-2-nitrobenzenesulfonamide
(IVg). Yield 75%, light brown (from aqueous ethanol)
or golden brown crystals (from CHCl3), mp 173–
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124°C (from ethanol). H NMR spectrum (CDCl3), δ,
ppm: 7.16 d (2H, J = 8.7 Hz), 7.22–7.35 d and br.s
(2H, Ar, SO2NH, J = 8.7 Hz), 7.63 t.d (1H, J = 7.7,
1.5 Hz), 7.74 t.d (1H, J = 7.7, 1.5 Hz), 7.80–7.92 m
(2H). 13C NMR spectrum (CDCl3), δC, ppm: 125.0 (+,
2C), 125.8 (+), 130.0 (+, 2C), 132.2 (+), 132.7 (q),
133.2 (+), 134.5 (q), 134.7 (+), 148.5 (q). Mass spec-
trum, m/z (Irel, %): 312 [M]+ (36), 186 (19), 126 (100),
99 (33), 90 (10), 53 (11), 50 (10). Found, %: C 46.10;
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175°C. H NMR spectrum (CDCl3), δ, ppm: 7.42 d
(2H, J = 9 Hz), 7.60–7.84 m (3H, Ar, SO2NH), 7.92 d
(1H, J = 7.7 Hz), 8.02 d (1H, J = 7.7 Hz), 8.20 d (2H,
J = 9 Hz). 13C NMR spectrum (DMSO-d6–CCl4), δC,
ppm: 119.1 (+, 2C), 125.6 (+), 125.7 (+, 2C), 131.3
(+), 132.2 (q), 133.2 (+), 135.5 (+), 143.8 (q), 144.1
(q), 148.7 (q). Mass spectrum, m/z (Irel, %): 323 [M]+
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 7 2005