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RUDYAKOVA et al.
by us previously [6] by reaction of N-(2,2,2-trichloro-
and the residue was washed with dry petroleum ether
ethylidene)-4-chlorobenzenesulfonamide with methyl and dried. Yield 2.78 g (97%) [7, 8].
phenoxyacetates [6].
N-(2,2,2-Trichloroethylidene)-4-methylbenzene-
sulfonamide (Ib) was obtained in a similar way from
2.4 g (0.01 mol) of N,N-dichloro-4-methylbenzene-
sulfonamide and 15 ml of trichloroethylene. Yield
2.85 g (95%) [7, 8].
N-(2,2,2-Trichloroethylidene)-4-chlorobenzene-
sulfonamide (Ic) was synthesized in a similar way
from 2.56 g (0.01 mol) of N,N,4-trichlorobenzene-
sulfonamide and 15 ml of trichloroethylene. Yield
3.12 g (97%) [7, 8].
N-(2,2,2-Trichloro-1-phenoxyethyl)-4-chloro-
benzenesulfonamide (IIb). To a solution of Schiff
base Ic in trichloroethylene, prepared from 2.56 g
(0.01 mol) of N,N,4-trichlorobenzenesulfonamide by
the procedure described above, we added with stirring
0.94 g (0.01 mol) of phenol. The mixture sponta-
neously warmed up to 32 C and was stirred for
1.5 2 h at room temperature. Excess trichloroethylene
was removed under reduced pressure, and the precip-
itate was separated, washed with hexane diethyl ether,
and dried in air. Yield 3.64 g.
N-[2,2,2-Trichloro-1-(2-methylphenoxy)ethyl]-4-
chlorobenzenesulfonamide (IIc) was synthesized in
a similar way from 1.08 g (0.01 mol) of 2-methyl-
phenol and a solution of Schiff base Ic in trichloro-
ethylene, which was prepared from 2.56 g (0.01 mol)
of N,N,4-trichlorobenzenesulfonamide. Yield 3.86 g.
4-(2,2,2-Trichloro-1-phenylsulfonylaminoethyl)-
phenol (III). Method A. To a solution of 2.86 g
(0.01 mol) of N-(2,2,2-trichloroethylidene)benzene-
sulfonamide (Ia) in 10 ml of dry benzene we added
dropwise 1 ml of oleum while stirring under argon.
After 5 min, 1.88 g (0.02 mol) of phenol was added
on cooling with water to 15 20 C. The mixture
spontaneously warmed up and turned brown (the
original mixture was light brown). After 15 min, the
mixture was allowed to warm up to room temperature
and was stirred for 3 h. The product was filtered off,
washed with water (3 20 ml) and diethyl ether
(3 10 ml), and dried in air. Yield 2.63 g.
The IR spectra of compounds IIa IIc contain
bands belonging to stretching vibrations of the SO2
and NH groups and aromatic C C and C H bonds
(Table 2). Substituted phenols III V showed in the
IR spectra absorption band of the hydroxy group, and
the NH band was observed at higher frequencies. In
1
the H NMR spectra of 2,2,2-trichloro-1-aroxyethyl-
amides IIb and IIc and N-(2,2,2-trichloro-1-phenoxy-
ethyl)benzenesulfonamide (IIa) (which were not given
in [5]) we observed signals from aromatic protons and
doublet signals from the NH and CH protons with
1
a coupling constant J of 9.2 Hz (Table 2). The H
NMR spectra of substituted phenols III V contained
analogous signals (Table 2) with the difference that
the NH and CH doublets had a coupling constant of
10.5 Hz and were displaced upfield by 0.6 1 ppm
relative to the corresponding signals of IIa IIc.
We can conclude that, depending on the conditions,
reactions of N-(2,2,2-trichloroethylidene)arenesulfon-
amides with phenols yield either 1-arylsulfonylamino-
2,2,2-trichloro-1-phenoxyethanes or 4-(1-arylsulfonyl-
amino-2,2,2-trichloroethyl)phenols. The addition of
phenol and 2-methylphenol to N-(2,2,2-trichloro-
ethylidene)arenesulfonamides occurs in the absence
of a catalyst and is accompanied by heat evolution.
By contrast, reactions of N-(2,2,2-trichloroethylidene)-
arenesulfonamides with phenol, 2-chlorophenol, and
2-methylphenol in the presence of oleum yield only
the corresponding 4-(2,2,2-trichloro-1-arylsulfonyl-
aminoethyl)phenols. Similar products are formed by
reaction of phenols with N-[2,2,2-trichloro-1-hydroxy-
(methoxy or 4-chlorophenylsulfonylamino)ethyl]-
arenesulfonamides in the presence of sulfuric acid.
EXPERIMENTAL
The IR spectra were recorded on a Specord IR-75
spectrometer in KBr. The 1H NMR spectra were
obtained on a Jeol FX-90Q instrument (90 MHz) in
DMSO-d6 using TMS as internal reference.
4-[2,2,2-Trichloro-1-(4-methylphenylsulfonyl-
amino)ethyl]phenol (IV) was synthesized in a similar
way from 3.0 g (0.01 mol) of N-(2,2,2-trichloro-
ethylidene)-4-methylbenzenesulfonamide (Ib) and
1.88 g (0.02 mol) of phenol. Yield 2.70 g.
4-[2,2,2-Trichloro-1-(4-chlorophenylsulfonyl-
amino)ethyl]phenol (Va) was synthesized in a similar
way from 3.21 g (0.01 mol) of N-(2,2,2-trichloro-
ethylidene)-4-chlorobenzenesulfonamide (Ic) and
1.88 g (0.02 mol) of phenol. Yield 3.02 g.
N-(2,2,2-Trichloro-1-phenoxyethyl)benzenesul-
fonamide (IIa) was synthesized by the procedure
reported in [5].
N-(2,2,2-Trichloroethylidene)benzenesulfon-
amide (Ia). A mixture of 2.26 g (0.01 mol) of N,N-di-
chlorobenzenesulfonamide and 15 ml of trichloro-
ethylene was heated for 8 h at 87 89 C under dry
argon until vigorous evolution of chlorine ceased
(starch iodine test). Excess trichloroethylene was
removed under reduced pressure (5 6 mm, 18 20 C),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 1 2001
Rudyakova
