1388
NAIDAN, SMALIUS
The crystals that formed were separated and recrystal-
lized from ethanol water, 2:1.
4-Chloro-1-(p-nitrophenylsulfonyl)-2-methyl-2-
butene (Ih) were prepared similarly to sulfone Ic using
6.4 ml of isoprene instead of 1,3-butadiene and puri-
fied by recrystallization from ethanol water, 1:1.
1-(p-Chlorophenylsulfonyl)- and 1-(p-Bromo-
phenylsulfonyl)-4-chloro-2-butenes (Ia, Ib) were
prepared similarly to sulfone Ic using a solution of
4.8 g of NaCl in 24 ml of water instead of HCl and
7.4 g of 1-(p-chlorophenyl)-3,3-dimethyl-1-triazene
and 9.2 g of 1-(p-bromophenyl)-3,3-dimethyl-1-tri-
azene, respectively, instead of 3,3-dimethyl-1-(p-nitro-
phenyl)-1-triazene. Compound Ia was purified by
crystallization from ethanol water, 1:1, and com-
pound Ib, from acetic acid water, 1:1.
REFERENCES
1. Naidan, V.M. and Fesak, A.Yu., Zh. Obshch. Khim.,
2003, vol. 73, no. 9, p. 1501.
2. Naidan, V.M., Naidan, G.D., Drozdova, S.G., and
Musienko, V.M., Zh. Obshch. Khim., 1985, vol. 55,
no. 2, p. 391.
3. Pochinok, V.Ya., Triazeny (Triazenes), Kiev: Kiev.
4-Chloro-2-methyl-1-(phenylsulfonyl)-2-butene
(Id). a. Acetone, 24 ml, was mixed with 24 ml of
glacial acetic acid, 24 ml of water, and 0.68 g of cop-
per(I) chloride. The resulting solution was saturated
with sulfur(IV) oxide as described for sulfone Ic.
After the saturation had been complete, 4.8 g of
powdered NaCl and 8 ml of isoprene. The temperature
of the reaction mixture was raised to 10 C, and 6 g of
3,3-dimethyl-1-phenyl-1-triazene was added to it.
Uniform gas evolution was observed at 10 15 C. After
the reaction had been complete, the reaction mixture
was poured into 300 ml of water. The crystals that
formed were separated and recrystallized from
ethanol water, 1:1.
Gos. Univ., 1968, pp. 16, 62, 155.
4. Porai-Koshits, B.A., Azokrasiteli (Azo Dyes), Lenin-
grad: Khimiya, 1972, p. 42.
5. Zollinger, H., Chemie der Azofarbstoffe, Basel:
Berghauser, 1958. Traslated under the title Khimiya
azokrasitelei, Leningrad: GNTIHL, 1960, p. 120.
6. Dombrovskii, A.V., Usp. Khim., 1957, vol. 26, no. 6,
p. 695.
7. Dombrovskii, A.V., Reakts. Metody Issled. Org.
Soedin., 1962, vol. 11, p. 285.
8. Rondestvedt, H.S., Organicheskie reaktsii (Organic
Reactions), Moscow: Mir, 1965, vol. 2, pp. 199 266.
b. 1,3-Diphenyltriazene, 7 g, was added in small
portions to the same reaction mixture as that described
in procedure a. Gas evolution was observed at 5 10 C.
Compound Id, 2.5 g (35%), was obtained and purified
as in procedure a.
9. Rondestvedt, C.S., Jr., Org. React., 1976, vol. 24,
pp. 225 258.
10. Dombrovskii, A.V., Usp. Khim., 1984, vol. 53, no. 10,
p. 1625.
11. Grishchuk, B.D., Gorbovoi, P.M., Ganushchak, N.I.,
and Dombrovskii, A.V., Usp. Khim., 1994, vol. 63,
no. 3, p. 269.
4-Chloro-1-(phenylsulfonyl)-2-methyl-2-butene
was also obtained independently by the reaction of
3.6 g of phenylsulfonyl chloride, 2.5 ml of isoprene,
2 g of triethylamine hydrochloride, and 2 g of cop-
per(I) chloride in 10 ml of acetonitrile (yield 1 g), as
well as by isoprene chlorophenylsulfonylation [2].
Mixed samples of sulfone Id with compounds ob-
tained by independent synthesis showed no melting
point depression.
12. Naidan, V.M., Naidan, G.D., and Litvin, G.V., Zh.
Org. Khim., 1978, vol. 14, no. 12, p. 2622.
13. Naidan, V.M., Naidan, G.D., and Dombrovskii, A.V.,
Zh. Obshch. Khim., 1979, vol. 49, no. 8, p. 1829.
14. Naidan, V.M. and Naidan, G.D., Zh. Obshch. Khim.,
1980, vol. 50, no. 11, p. 2611.
1-(Arylsulfonyl)-4-chloro-2-methyl-2-butenes Ie
Ig were prepared similarly to sulfone Id using, instead
of 3,3-dimethyl-1-phenyl-1-triazene, 6.6 g of 3,3-di-
methyl-1-p-tolyl-1-triazene, 7.4 g of 1-(p-chloro-
phenyl)-3,3-dimethyl-1-triazene, and 9.2 g of 1-(p-
bromophenyl)-3,3-dimethyl-1-triazene, respectively.
The products were purified by recrystallization from
acetic acid water, 1:1.
15. Weygand Hilgetag
organisch-chemische
Experi-
mentierkunst, Hilgetag, G. and Martini, A., Eds.,
Leipzig: Barth, 1964, 3rd ed. Translated under the
title Metody eksperimenta v organicheskoi khimii,
Moscow: Khimiya, 1969, p. 601.
16. Asscher, M. and Vofsi, D., J. Chem. Soc., 1964,
no. 12, p. 4962.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 9 2004