Oxidation of N(1-hydroxypolychloroethyl)sulfonamides

Article abstract of DOI:10.1023/A:1013179504546

N-(2,2,2-Trichloro-1-hydroxyethyl)- and N-(2,2-dichloro-1-hydroxy-2-phenylethyl)arenesulfonamides are oxidized with chromium(VI) oxide to give, respectively, N-(arylsulfonyl)trichloroacetamides and N-(arylsulfbnyl)dichloro(phenyl)acetamidcs. Under analogo

Full text of DOI:10.1023/A:1013179504546

Russian Journal of Organic Chemistry, Vol. 37, No. 9, 2001, pp. 1284 1286. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 9, 2001,
pp. 1351 1353.
Original Russian Text Copyright
2001 by I. Rozentsveig, G. Rozentsveig, Levkovskaya, Mirskova.
Oxidation of N-(1-Hydroxypolychloroethyl)sulfonamides
I. B. Rozentsveig, G. N. Rozentsveig, G. G. Levkovskaya, and A. N. Mirskova
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
fax: (3952)396046
Received December 20, 2000
Abstract N-(2,2,2-Trichloro-1-hydroxyethyl)- and N-(2,2-dichloro-1-hydroxy-2-phenylethyl)arenesulfon-
amides are oxidized with chromium(VI) oxide to give, respectively, N-(arylsulfonyl)trichloroacetamides and
N-(arylsulfonyl)dichloro(phenyl)acetamides. Under analogous conditions N-(2,2,2-trichloro-1-hydroxyethyl)-
trifluoromethanesulfonamide is converted into 1,1,1-trichloro-2,2-bis(trifluoromethylsulfonylamino)ethane.
N-(1-hydroxy-2-polyhaloethyl)amides are important
intermediate products in the synthesis of Schiff bases
from polyhalogenated aldehydes and also of polyhalo-
ethylamides which possess biological activity and are
useful from the synthetic viewpoint [1 4].
We previously performed a systematic study of the
reactivity of N-(1-hydroxy-2-polychloroethyl)arenesul-
fonamides [5] and found that these compounds are
unstable toward aqueous solutions of acids and bases:
their decomposition leads to formation of arenesulfon-
amides. We also showed [2, 3] that N-(1-hydroxy-2-
polychloroethyl)arenesulfonamides do not undergo
decomposition in concentrated sulfuric acid but react
with aromatic and heteroaromatic compounds.
The present communication reports for the first
time on the behavior of a series of N-(1-hydroxy-
2-polychloroethyl)sulfonamides in reactions with
oxidants. N-(2,2,2-Trichloro-1-hydroxyethyl)arenesul-
fonamides Ia Id and N-(2,2-dichloro-1-hydroxy-2-
phenylethyl)-p-chlorobenzenesulfonamide (II) are
readily oxidized with potassium dichromate in con-
centrated sulfuric acid to give, respectively, N-(aryl-
sulfonyl)trichloroacetamides III and N-(p-chloro-
phenylsulfonyl)dichloro(phenyl)acetamide (IV). The
reaction is exothermic, and the yields of the oxidation
products attain 70 95% in 3 5 h (Scheme 1). Raising
the temperature or increasing the reaction time did
not result in increased yield of target products. Over-
heating of the reaction mixture was accompanied by
vigorous evolution of NO2.
We failed to obtain mixed amides III and IV
by the action of other oxidants, such as hydrogen
peroxide in acetic acid and potassium permanganate
in the presence of alkali. In these cases, only the
corresponding arenesulfonamides were isolated as
a result of decomposition of initial N-(1-hydroxy-2-
polychloroethyl)arenesulfonamides Ia Id and II.
The structure of products IIIa IIId and IV was
proved by IR and NMR spectroscopy and analytical
data. The structure of amide IIIa was additionally
proved by independent synthesis via condensation of
trichloroacetyl chloride with benzenesulfonamide in
the presence of triethylamine (Scheme 2).
Scheme 1.
Scheme 2.
The spectral parameters and melting points of
samples of IIIa obtained by the two methods were
identical, but the yield of IIIa according to Scheme 2
did not exceed 20%; moreover, the product required
a laborious multistep purification procedure.
I, III, X = Cl; Ia, IIIa, Ar = Ph; Ib, IIIb, Ar = 4-ClC6H4;
Ic, IIIc, Ar = 4-MeC6H4; Id, IIId, Ar = 3-NO2C6H4; II, IV,
X = Ph, Ar = 4-ClC6H4.
1070-4280/01/3709-1284$25.00 2001 MAIK Nauka/Interperiodica

OXIDATION OF N-(1-HYDROXYPOLYCHLOROETHYL)SULFONAMIDES
1285
Yields, melting points, IR spectra, and elemental analyses of compounds IIIa IIId, IV, and VI
1
IR spectrum, , cm
Compound
Yield, %
mp,
C
no.
C O
NH
SO2
IIIa
IIIba
IIIc
IIId
IV
95
86
77
56
69
9
163 165
187 189
215 218b
172 175
123 124
151 152
1200, 1380
1170, 1380
1200, 1380
1190, 1340
1180, 1350
3220
3200
3210
3220
3260
3250
1700, 1780
1720
1730
1710
1730
VIc
Found, %
Calculated, %
Compound
no.
Formula
C
H
N
S
C
H
N
S
IIIa
IIIba
IIIc
IIId
IV
31.02
28.13
30.80
28.01
43.12
11.18
2.13
1.75
2.02
1.83
3.15
0.93
10.58
0.02
10.45
9.79
9.99
6.73
4.49
4.19
4.45
8.61
4.62
15.07
C8H6Cl3NO3S
C8H5Cl4NO3S
C9H8Cl3NO3S
C8H5Cl3N2O5S
C14H10Cl3NO3S
C4H3Cl3F6N2O4S2
31.76
28.51
34.15
27.65
44.41
11.24
2.00
1.50
2.55
1.45
2.66
0.71
10.60
9.51
10.13
9.22
8.47
6.55
4.63
4.16
4.42
8.06
3.70
15.00
VIc
a
1H NMR spectrum, , ppm: 7.89, 7.60 (AA BB ); 13C NMR spectrum, C, ppm: 100.00 (CCl3), 129.34 (o- and m-C2, C3), 137.28
(CCl2), 140.92 (CSO2), 163.03 (C O).
Melts with decomposition.
1H NMR spectrum, , ppm (the signals are broadened): 5.54 (CH), 11.51 (NH); IR spectrum, (CF3SO2), cm : 1380, 1230,
b
c
1
1200, 1130.
Amides III and IV showed in the IR spectra
ferent pathway. Instead of the expected N-(trifluoro-
methylsulfonyl)trichloroacetamide we isolated 1,1,1-
trichloro-2,2-bis(trifluoromethylsulfonylamino)ethane
(VI) in a small yield (Scheme 3). The structure of
absorption bands belonging to stretching vibrations
1
of the carbonyl group (1710 1720 cm ), N H bond
1
1
(3230 3250 cm ), and SO2 group (1150, 1370 cm );
hydroxy group absorption typical of initial hydroxy-
1
compound VI was established by IR and H NMR
ethylamides (3500 cm ) was absent. The 13C NMR
1
spectroscopy and was confirmed by elemental analysis
(see table). The IR spectrum of VI contained absorp-
tion bands due to NH group and CF3SO2 fragment.
spectrum of sulfonamide IIIb contained a signal at
163.03 ppm, belonging to the carbonyl carbon
C
1
1
In the H NMR spectrum, the intensity of the NH
atom. In the H NMR spectra of oxidation products
III and IV only signals of aromatic protons were
observed. The NH proton did not appear in the spec-
trum, presumably because of fast H D exchange. By
signal was twice as large as that of the CH signal.
Compound VI was also synthesized by reaction of
N-(2,2,2-trichloroethylidene)trifluoromethanesulfon-
amide with trifluoromethanesulfonamide as shown
in Scheme 4. Samples of VI obtained by the two
methods had identical melting points and spectral
parameters.
1
contrast, the H NMR spectra of initial N-(1-hydroxy-
polychloroethyl)amides I and II contain two doublets
with a coupling constant of 10 11 Hz due to the
NH CH fragment [2, 3].
The oxidation of N-(2,2,2-trichloro-1-hydroxy-
ethyl)trifluoromethanesulfonamide (V) takes a dif-
Scheme 4.
Scheme 3.
N-(arylsulfonyl)amides III and IV are crystalline
substances, soluble in polar organic solvents, aromatic
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 9 2001

1286
ROZENTSVEIG et al.
hydrocarbons, and aqueous alkalies and insoluble
in water.
(0.01 mol) of N-(2,2,2-trichloro-1-hydroxyethyl)-m-
nitrobenzenesulfonamide (Id). Yield 1.77 g (56%).
N-[Dichloro(phenyl)acetyl]-p-chlorobenzenesul-
fonamide (IV) was synthesized in a similar way from
3.81 g (0.01 mol) of N-(2,2-dichloro-1-hydroxy-2-
phenylethyl)-p-chlorobenzenesulfonamide (II). Yield
2.6 g (69%).
1,1,1-Trichloro-2,2-bis(trifluoromethylsulfonyl-
amino)ethane (VI). a. Following the above proce-
dure, from 2.97 g (0.01 mol) of N-(2,2,2-trichloro-1-
hydroxyethyl)trifluoromethanesulfonamide (V) 0.18 g
(9%) of compound VI was obtained.
Thus, the oxidation of accessible [1 3] N-(2,2,2-tri-
chloro-1-hydroxyethyl)- and N-(2,2-dichloro-1-hy-
droxy-2-phenylethyl)arenesulfonamides with potas-
sium dichromate in concentrated sulfuric acid can be
recommended as a convenient method for preparation
of N-arylsulfonylpolychloroacetamides which are
promising intermediate products in the synthesis of
oxygen- and nitrogen-containing heterocycles.
EXPERIMENTAL
b. A strong stream of argon was passed over
a period of 20 30 min through a solution of 2.18 g
(0.01 mol) of N,N-dichlorotrifluoromethanesulfon-
amide [6] in 6 7 ml (0.08 0.1 mol) of trichloroethene
which was preliminarily distilled over P2O5. The
mixture was exposed to sunlight for 20 25 h, and
1.49 g (0.01 mol) of trifluoromethanesulfonamide was
added to the resulting colorless solution. The mixture
was heated for 60 h at 60 70 C and was then kept
for 20 h at room temperature. The large transparent
crystals of compound VI were separated and dried.
Yield 1.08 g (37%).
The 1H NMR spectra were obtained on Bruker
DPX-400 (400 MHz) and Jeol FX-90Q spectrometers
(90 MHz); samples were prepared as 5 10% solutions
in appropriate solvents; HMDS was used as internal
reference. The IR spectra were recorded on a Specord
75IR instrument from samples pelleted with KBr.
N-(Trichloroacetyl)benzenesulfonamide (IIIa).
N-(2,2,2-Trichloro-1-hydroxyethyl)benzenesulfon-
amide (Ia), 6.09 g (0.02 mol), was added in small
portions under stirring to a mixture of 20 ml of con-
centrated sulfuric acid, 5 ml of acetic acid, and 12 g
(0.04 mol) of potassium dichromate in such a way
that the temperature did not exceed 25 C (above that
temperature vigorous evolution of NO2 occurs, and the
mixture can overflow the reaction flask). The mixture
was stirred for 5 h and poured into 50 ml of water,
and the precipitate of N-(trichloroacetyl)benzenesul-
fonamide (IIIa) was filtered off, washed on a filter
with water until it became colorless, and dried. Yield
5.61 g (93%). An additional amount of product IIIa,
0.11 g (2%), precipitated from the filtrate on storage.
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N-(Trichloroacetyl)-p-chlorobenzenesulfonamide
(IIIb) was synthesized in a similar way from 3.4 g
(0.01 mol) of N-(2,2,2-trichloro-1-hydroxyethyl)-p-
chlorobenzenesulfonamide (Ib). Yield 2.91 g (86%).
4. Rozentsveig, I.B., Levkovskaya, G.G., and Mirsko-
va, A.N., Russ. J. Org. Chem., 1999, vol. 35, no. 9,
pp. 1398 1399.
N-(Trichloroacetyl)-p-toluenesulfonamide (IIIc)
was synthesized in a similar way from 3.19 g
(0.01 mol) of N-(2,2,2-trichloroethyl)-p-toluenesulfon-
amide (Ic). Yield 3.44 g (77%).
N-(Trichloroacetyl)-m-nitrobenzenesulfonamide
(IIId) was synthesized in a similar way from 3.18 g
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and Kashik, T.V., Russ. J. Org. Chem., 2000, vol. 36,
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 9 2001