Synthesis of thietane from sulfur and 1-bromo-3-chloropropane in hydrazine hydrate-alkali system

Full text of DOI:10.1134/S1070363206010300

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ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 1, pp. 156 157.
Pleiades Publishing, Inc., 2006.
Original Russian Text
N.V. Russavskaya, E.P. Levanova, L.V. Klyba, E.R. Zhanchipova, V.A. Grabel’nykh, E.N. Sukhomazova, A.I. Albanov,
N.A. Kochervin, E.N. Deryagina, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76, No. 1, pp. 159 160.
LETTERS
TO THE EDITOR
Synthesis of Thietane from
Sulfur and 1-Bromo-3-Chloropropane
in Hydrazine Hydrate Alkali System
N. V. Russavskaya, E. P. Levanova, L. V. Klyba, E. R. Zhanchipova,
V. A. Grabel’nykh, E. N. Sukhomazova, A. I. Albanov,
N. A. Kochervin, and E. N. Deryagina
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: venk@irioch.irk.ru
Received August 4, 2005
DOI: 10.1134/S1070363206010300
1-Bromo-3-chloropropane (I) reacts with solutions
of sulfur in the water hydrazine hydrate alkali system
to form polymeric products [1]. Our detailed gas
ferent solvation of the sulfide and disulfide anions in
water and hydrazine hydrate. Recently [4] we sug-
gested formation in the hydrazine hydrate alkali
chromatography mass spectrometry analysis of chloro- system of complex VI, which alters the reactivities of
form extracts of the raw polymer and extracts of the
aqueous layer after separation of the polymer showed
that, together with the polymer, thietane (II) and
1,2-dithiolane (III) are formed in small amounts.
both polysulfide anions and hydrazine.
K+----S2x
H
N
N
Unexpectedly, it was found that the reaction of di-
halide I with sulfur in the hydrazine hydrate KOH
system without water takes another pathway, yielding
heterocyclic compounds II and III as major pro-
ducts. Their yield depends on the KOH:sulfur ratio.
When this ratio was 1:2, thietane II was isolated in
26% yield, and 1,2-dithiolane III is formed in 4%
yield. Polymer IV is formed in 65% yield. At equi-
molar KOH:sulfur ratio, the yield of polymer IV is
50%, thietane II was obtained in 13% yield, and di-
thiolane III, in 23% yield. Besides, 1,3-propanethiol
V is formed in 7% yield.
H
H H
VI
x = 1 4.
Evidently, in the hydrazine hydrate alkali system
with an excess of hydrazine, the S2x anions react with
dielectrophile I mainly in the form of complex VI,
which favors formation of kinetically controlled pro-
ducts II and III.
To a solution of 22.4 g of KOH in 60 ml of hydra-
zine hydrate, 6.4 g of powdered elemental sulfur was
added in portions with vigorous stirring over the
course of 1 h at 70 80 C. The reaction mixture was
kept for 2 h at 80 85 C, cooled to 50 C, and addition
of 1-bromo-3-chloropropane (I) was initiated at that
temperature. The temperature of the exothermic reac-
tion was maintained at 65 70 C. The organic layer
that formed was removed, dried over calcium chloride,
and distilled. The fraction with bp 96 100 C was
S/N2H4 H2O/KOH
+
Br(CH2)3Cl
S
S
II
S
I
III
+ ( SCH2CH2CH2S )n + HSCH2CH2CH2SH.
IV
V
The increased yield of the highly strained cyclic
systems of thietane and 1,2-dithiolane [2, 3] in reac-
tion (1) in the absence of water is caused by the dif-
1
almost pure thietane II, yield 3.5 g (26%). H NMR
156

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SYNTHESIS OF THIETANE FROM SULFUR AND 1-BROMO-3-CHLOROPROPANE
157
spectrum (CDCl3), , ppm: 3.23 t (4H), 2.94 quintet
(2H). Mass spectrum (m/z, Irel, %): M+, 74, 50,
(CH2S)+, 46, 100; (CHS)+, 41, 10; (C3H3)+, 39, 12
[5]. The yields of 1,2-dithiolane (III) and 1,3-propa-
nedithiol (V) were evaluated by means of GLC and
1H NMR spectroscopy.
REFERENCES
1. Alekminskaya, O.V., Russavskaya, N.V., Korche-
vin, N.A., Deryagina, E.N., and Trofimov, B.A.,
Zh. Obshch. Khim., 2000, vol. 70, no. 5, p. 784.
2. Sander, M., Chem. Rev., 1966, vol. 66, no. 3, p. 341.
3. Harpp, D.N. and Gleason, J.G., J. Org. Ghem., 1979,
vol. 35, no. 10, p. 3259.
The NMR spectra were recorded on a Bruker DPX-
400 spectrometer (400.1 MHz) against internal HMDS.
The mass spectra were measured on a QP5050A
GC MS system, column 60 m 0.25 mm, program-
med temperature increase (15 deg min ), carrier gas
helium, electron energy 70 eV.
4. Russavskaya, N.V., Grabel’nykh, V.A., Levanova, E.P.,
Sukhomazova, E.N., and Deryagina, E.N., Zh. Org.
Khim., 2002, vol. 38, no. 10, p. 1551.
5. Zaikin, V.G., Mikaya, A.I., and Vdovin, V.M., Mass-
spektrometriya malykh tsiklov (Mass Spectrometry
of Small Rings), Moscow: Nauka, 1983.
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