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ROZENTSVEIG et al.
1
air. According to the H NMR data, the product was
a mixture of amide IVb, 6.11 g (70%), and 3-nitro-
benzenesulfonamide.
b. A mixture of 3.5 g of amide IVb, 7 ml of
toluene, and 3 5 ml of concentrated sulfuric acid was
vigorously stirred for 5 h. Water, 15 ml, was added,
and the mixture was stirred for 10 min. The precip-
itate was filtered off, washed on a filter with 5%
aqueous ammonia until slightly alkaline washings
(15 20 ml), dried in air, and purified by recrystalliza-
tion from benzene.
N-[2,2,2-Trichloro-1-(4-methoxyphenyl)ethyl]-4-
nitrobenzenesulfonamide (VIII). Anhydrous methyl
phenyl ether, 2 ml, and 5 drops of freshly distilled
boron trifluoride ether complex were added to the
solution of amide IIIc, obtained from 2.71 g of Ic
and 10 ml of trichloroethylene. The mixture was
heated for 8 h at 40 50 C, evaporated by half under
reduced pressure, and kept for 12 h in the cold
( 10 C). The precipitate was filtered off, dried under
reduced pressure, and recrystallized from ethanol.
2-Nitro- and 4-nitrobenzenesulfonamides failed to
react with trichloroacetaldehyde under the same con-
ditions and were recovered from the reaction mixtures.
N-(2,2,2-Trichloro-1-methoxyethyl)-2-nitroben-
zenesulfonamide (V). Anhydrous methanol, 4 ml,
was added to amide IIa prepared from 2.71 g of Ia
and 8 10 ml of trichloroethylene. The mixture spon-
taneously warmed up. It was kept for 12 h and
evaporated, and the solid residue was recrystallized
from methanol chloroform (1:3).
N-(2,2,2-Trichloro-1-phenylethyl)-2-nitroben-
zenesulfonamide (VIa). A mixture of amide IIa,
prepared from 2.71 g of Ia and 8 10 ml of trichloro-
ethylene, 3 5 ml of dry benzene, and 0.5 1 ml of
oleum (10 30% SO3) was vigorously stirred for 5 h
under argon. The organic phase was separated by
decanting and evaporated. The solid residue was
washed with 3 5% aqueous ammonia (10 ml) and
dried. The remaining oleum was diluted with 10 ml
of ice water, the mixture was stirred for 5 min, and
the precipitate was filtered off, washed with aqueous
ammonia, and dried in air. The products obtained
from the organic and oleum phases were combined
and recrystallized from benzene.
REFERENCES
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3. Xu, B. and Shu, S., Heteroatom Chem., 1997, vol. 8,
N-[2,2,2-Trichloro-1-(4-chlorophenyl)ethyl]-2-
nitrobenzenesulfonamide (VIb) was synthesized in
a similar way from 2.71 g of dichloro amide Ia and
excess chlorobenzene. Yield 3.15 g (71%).
no. 4, p. 309.
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N-[2,2,2-Trichloro-1-(4-methylphenyl)ethyl]-3-
nitrobenzenesulfonamide (VIIa). a. A mixture of
amide IIb, prepared from 2.71 g of Ib and 8 10 ml
of trichloroethylene, 3 5 ml of dry toluene, and
0.5 1 ml of oleum (10 30% SO3) was vigorously
stirred for 4 5 h. Ice water, 20 ml, was added, the
mixture was stirred for 10 min, and the precipitate was
filtered off, washed on a filter with 3 5% aqueous
ammonia until slightly alkaline washings ( 30 ml),
dried in air, and recrystallized from benzene.
N-[2,2,2-Trichloro-1-(4-fluorophenyl)ethyl]-3-
nitrobenzenesulfonamide (VIIb) was synthesized in
a similar way from 2.71 g of Ib and excess fluoro-
benzene.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 1 2001