Russian Journal of Organic Chemistry, Vol. 37, No. 5, 2001, p. 739. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 5, 2001, p. 775.
Original Russian Text Copyright
2001 by Rozentsveig, Kondrashov, Levkovskaya, Mirskova.
SHORT
COMMUNICATIONS
Synthesis of
N-(2,2-Dichloroethylidene)trifluoromethanesulfonamide
I. B. Rozentsveig, E. V. Kondrashov, G. G. Levkovskaya, and A. N. Mirskova
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: i_roz@irioch.irk.ru
Received December 20, 2000
We previously showed [1, 2] that reactions of
N,N-dichloroarenesulfonamides with 1,2-dichloro-
ethylene under conditions of thermal, chemical, or
photochemical initiation lead to formation of mixtures
of N-(2,2-dichloroethylidene)arenesulfonamides,
1,1-bis(arylsulfonylamino)-2,2-dichloroethanes, and
N-(2,2,2-trichloroethylidene)arenesulfonamides; the
yield of the latter products can attain 30%.
We now report for the first time on the reaction of
N,N-dichlorotrifluoromethanesulfonamide with 1,2-di-
chloroethylene, which selectively yields N-(2,2-di-
chloroethylidene)trifluoromethanesulfonamide with no
impurity of trichloroethyl derivative. The reaction
does not require additional thermal initiation; it occurs
in excess 1,2-dichloroethylene and is accompanied by
heat evolution. The reaction time is 5 h in the sunlight
or 1 h under UV irradiation. The chlorine released
from N,N-dichlorotrifluoromethanesulfonamide adds
to 1,2-dichloroethylene, yielding tetrachloroethane.
N-(2,2-Dichloroethylidene)trifluoromethanesul-
fonamide. N,N-Dichlorotrifluoromethanesulfonamide,
2.18 g (0.01 mol) (prepared by the procedure reported
in [3]), was dissolved in 7.7 ml (0.1 mol) of 1,2-di-
chloroethylene, and the solution was purged with
argon for 0.5 h. The mixture was kept in the sunlight
(5 h) or under UV irradiation (ORK-21 lamp, 0.5 h)
until it no longer warmed up, and excess 1,2-dichloro-
ethylene was removed under reduced pressure without
heating. The residue was 3.98 g of a mixture of
N-(2,2-dichloroethylidene)trifluoromethanesulfon-
1
amide and 1,1,2,2-tetrachloroethane. H NMR spec-
trum (Bruker DPX-400, CDCl3, HMDS), , ppm:
8.57 d (CH N), 6.24 d (CHCl2), J = 6.4 Hz; 5.95 s
(Cl2HCCHCl2)1. IR spectrum, (Specord IR75, thin
film), , cm : 1150, 1200, 1240, 1360 (SF3SO2),
1660 (C N), 3095 (C H).
REFERENCES
1. Mirskova, A.N., Drozdova, T.I., Levkovskaya, G.G.,
Kalikhman, I.D., and Voronkov, M.G., Zh. Org.
Khim., 1987, vol. 23, no. 6, pp. 1248 1255.
2. Rozentsveig, I.B., Evstaf’eva, I.T., Levkovskaya, G.G.,
Mirskova, A.H., and Albanov, A.I., Russ. J. Org.
Chem., 2000, vol. 36, no. 6, pp. 813 815.
Thus the reaction of N,N-dichlorotrifluoromethane-
sulfonamide with 1,2-dichloroethylene provides an ef-
ficient route to highly reactive intermediate product
which is used in the synthesis of compounds having
a trifluoromethanesulfonamide group as promising
medicinals, dyes, insectoacaricides, etc.
3. Nazaretyan, V.P., Radchenko, O.A., and Yagupol’-
skii, L.M., Zh. Org. Khim., 1974, vol. 10, no. 11,
p. 2460.
1070-4280/01/3705-0739$25.00 2001 MAIK Nauka/Interperiodica
Rozentsveig
