Russian Journal of Organic Chemistry, Vol. 38, No. 10, 2002, pp. 1445 1448. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 10, 2002,
pp. 1498 1501.
Original Russian Text Copyright
2002 by Russavskaya, Korchevin, Alekminskaya, Sukhomazova, Levanova, Deryagina.
New Preparative Procedure
for the Synthesis of Chloroalkyl Sulfides*
N. V. Russavskaya, N. A. Korchevin, O. V. Alekminskaya, E. N. Sukhomazova,
E. P. Levanova, and E. N. Deryagina
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
fax: (3952)356046; e-mail: admin@irioch.irk.ru
Received January 8, 2002
Abstract Reaction of thiols with dihaloalkanes in the system hydrazine hydrate base leads to alkyl(chloro-
alkyl) sulfides with different positions of the chlorine atom with respect to sulfur. The developed one-step
procedure for the synthesis of such unsymmetrical sulfides is most suitable for arenethiols and alkanethiols
having a long polymethylene chain. The reaction mechanism is discussed.
Chloroalkyl sulfides are used as pesticides [1] and
intermediate products in organic synthesis [2, 3].
-Chloroalkyl sulfides available by the Bohme reac-
tion or its modifications were studied to the greatest
extent [4]. -Chloroalkyl sulfides were also studied
in sufficient detail; they are usually prepared from
sulfur dichloride or sulfenyl chlorides and unsaturated
compounds [5, 6]. Chloroalkyl sulfides with a longer
alkyl chain are synthesized in two steps from thiols
and chlorohydrins with subsequent replacement of
the OH group by chlorine by the action of sulfuryl
chloride [7].
We recently studied the reaction of dihaloalkanes
with thiolate ions RS generated by reductive splitting
of organic disulfides in the system hydrazine hydrate
alkali, which resulted in formation of bis(alkylthio)-
alkanes [8]. In most cases, intermediate unsymmetrical
sulfides having one chlorine atom were not detected.
These were obtained only from diaryl disulfides. In
continuation of our studies on reactions of thiolate
ions with polyelectrophiles, we examined the behavior
of various thiols I toward dihaloalkanes II in the
system hydrazine hydrate alkali. This system prevents
oxidation to disulfides of thiolate ions generated from
thiols. It was surprising that, unlike disulfides, thiols I
reacted with dihalogen derivatives II to give unsym-
metrical chlorine-containing sulfides III even when
____________
the amount of dihaloalkane II was less than stoichio-
metric. In some cases, sulfides III were the major
products (Scheme 1). Simultaneously, bis-sulfide
derivatives IV were formed. The reaction conditions
and yields of the products are given in Table 1.
Scheme 1.
(1)
(2)
(3)
I, R = Et (a), Pr (b), Bu (c), Ph (d), 2-thienyl (e); II, n = 2,
X = Y = Cl (a), Br (b); n = 3, X = Br, Y = Cl (c); n = 5,
X = Y = Cl (d), Br (e); III (Y = Cl), IV, n = 2, R = Et (a),
Pr (b), Bu (c), Ph (d), 2-thienyl (e); n = 3, R = Pr (g);
n = 5, R = Pr (h).
It is seen that the yield of chloro sulfides III from
the same dihaloalkane increases as the alkyl chain in
the alkanethiol becomes longer: Ia < Ib < Ic. This
may be due to decrease of the solubility of the corre-
sponding sulfide III in hydrazine hydrate, which
changes in the same order. In a similar way (cf. [8]),
we can explain the behavior of arenethiols Id and Ie
in reactions (1) (3). Reaction (3) is hampered by
withdrawal of sulfides III to the organic phase.
*
This study was financially supported by the Russian Founda-
tion for Basic Research (project nos. 00-03-32810a and
01-03-06136).
1070-4280/02/3810-1445$27.00 2002 MAIK Nauka/Interperiodica
Russavskaya
