Reaction of bis(prop-2-yn-1-yl) sulfide with sulfur dichloride. First example of cyclization of bis(prop-2-yn-1-yl) chalcogenides by the action of chalcogen halides

Full text of DOI:10.1134/S1070428011120207

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 12, pp. 1894–1895. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.V. Martynov, S.V. Amosova, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 12, pp. 1857–1858.
SHORT
COMMUNICATIONS
Dedicated to Full Member of the Russian Academy of Sciences
M.G. Voronkov on his 90th anniversary
Reaction of Bis(prop-2-yn-1-yl) Sulfide with Sulfur Dichloride.
First Example of Cyclization of Bis(prop-2-yn-1-yl)
Chalcogenides by the Action of Chalcogen Halides
A. V. Martynov and S. V. Amosova
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: amosova@irioch.irk.ru
Received August 19, 2011
DOI: 10.1134/S1070428011120207
Electrophilic reactions of sulfur dichloride with
various allyl and diallyl systems were reported [1–6];
however, among propargyl derivatives, data on reac-
tions of sulfur dichloride only with propargyl alcohols
are available [7–9]. These reactions lead to the forma-
tion of diallenic sulfones rather than addition products.
We have found no published data on reactions of sulfur
dihalides with compounds containing two propargyl
fragments.
The E configuration of the exocyclic double bonds in
molecule II follows from the coupling constant for
3
the CH
carbon nuclei (t.d, JCH = 6.7 Hz [11]) in the
2
1
3
C NMR spectrum and from the absence of cross
peaks for the vinylic and methylene protons in the 2D
NOESY spectrum. The structure of compound II was
also confirmed by elemental analysis and mass spec-
trum which contained a strong peak from the molec-
3
5
ular ion, m/z 212 ( Cl).
The observed regio- and stereoselectivity in the
reaction of sulfur dichloride with bis(prop-2-yn-1-yl)
sulfide (I) is consistent with the known preference of
anti-Markovnikov anti addition over Markovnikov ad-
dition in electrophilic reactions of sulfenyl halides with
terminal acetylenes [12]. However, it is interesting that
reactions of propargyl alcohols with selenium di-
chloride lead to the formation of (Z,Z)-bis(2-chloro-1-
hydroxymethylvinyl) selenides as a result of anoma-
lous anti-Markovnikov syn addition [13].
We have found that bis(prop-2-yn-1-yl) sulfide (I)
reacts with sulfur dichloride in chloroform at –30°C in
stereo- and regioselective fashion. The reaction fol-
lows anti-Markovnikov anti addition scheme at both
triple bonds of compound I and yields previously un-
known (E,E)-2,6-bis(chloromethylidene)-1,4-dithiane
(
II). The structure of heterocyclic compound II
1
13
was confirmed by the H and C NMR spectra.
The =CHCl group gave rise to a doublet of triplets at
1
3
1
δC 115.56 ppm in the C NMR spectrum ( J
=
CH
2
00 Hz), indicating that the chlorine atom is attached
The described reaction is the first example of cy-
clization of dipropargyl systems containing a bridging
chalcogen atom by the action of chalcogen halides.
2
1
to an sp -hybridized carbon atom [10]. The H NMR
spectrum of II contained a singlet at δ 6.29 ppm with
satellites characterized by the same coupling constant.
(
E,E)-2,6-Bis(chloromethylidene)-1,4-dithiane
(
II). A solution of 0.550 g (5 mmol) of bis(prop-2-yn-
HC
CH
+
SCl2
S
1-yl) sulfide (I) in 15 ml of anhydrous chloroform was
cooled to –30 to –45°C, a solution of 0.514 g (5 mmol)
of sulfur dichloride in 10 ml of chloroform was added
over a period of 25 min under stirring in an argon
atmosphere, and the mixture was allowed to warm up
to room temperature and stirred for 5.5 h. The solvent
was removed under reduced pressure, the residue was
I
S
CHCl , –30°C
3
Cl
Cl
S
II
1
894

REACTION OF BIS(PROP-2-YN-1-YL) SULFIDE WITH SULFUR DICHLORIDE.
1895
dissolved in methanol, and slow crystallization gave
.690 g (65%) of compound II as white plates with
2. Lautenschlaeger, F. and Schwartz, N.V., J. Org. Chem.,
1
969, vol. 34, p. 3991.
0
1
mp 88°C. H NMR spectrum, δ, ppm: 3.73 s (2H, CH ,
3. Anisimov, A.V., Grishkyan, A.A., Gaisina, Kh.A., and
Viktorova, E.A., Khim. Geterotsikl. Soedin., 1992,
p. 1276.
2
1
1
JCH = 142.0 Hz), 6.29 s (1H, =CHCl, J
=
CH
1
3
2
00.2 Hz). C NMR spectrum, δ , ppm: 29.76 t.d
CH , J = 143, J = 6.7 Hz), 115.56 d.t (=CHCl,
JCH = 200, J = 5 Hz), 131.78 s (C , C ). Mass spec-
trum, m/z ( Cl, I , %): 212 (46) [M] , 177 (22) [M –
C
1
3
(
4. Grishkyan, A.A., Koldobskii, A.B., and Anisimov, A.V.,
2
CH
CH
1
3
2
6
Khim. Geterotsikl. Soedin., 1994, p. 767.
CH
3
5
+
5. Anisimov, A.V., Ramazanov, P.A., Vagabov, M.V.,
Sosonyuk, S.E., Tarakanova, A.V., and Zyk, N.V., Vestn.
Mosk. Gos. Univ., 2002, vol. 43, p. 317.
rel
Cl], 141 (13), 138 (10), 106 (19), 103 (23), 92 (21), 71
(
64), 45 (100), 39 (59). Found, %: C 33.42; H 2.75;
Cl 33.10; S 29.62. C H Cl S . Calculated, %: C 33.81;
H 2.84; Cl 33.27; S 30.09.
6. Abramov, A.A., Anisimov, A.V., and Bobyleva, A.A.,
6
6
2 2
Khim. Geterotsikl. Soedin., 2002, p. 291.
7
8
9
. Braverman, S. and Segev, D., J. Am. Chem. Soc., 1974,
vol. 96, p. 1245.
Bis(prop-2-yn-1-yl) sulfide (I) was synthesized
from 3-bromopropyne and Na S in alcohol [14]. The
2
1
13
. Braverman, S., Zafrani, Y., and Gottlieb, H.E., Tetra-
hedron Lett., 2000, vol. 41, p. 2675.
H and C NMR spectra were recorded on a Bruker
DPX-400 spectrometer at 400.13 and 100.61 MHz,
. Braverman, S., Zafrani, Y., and Gottlieb, H.E., Tetra-
hedron, 2001, vol. 57, p. 9177.
respectively, from 5–10% solutions in CDCl . The
3
mass spectrum (electron impact, 70 eV) was obtained
on a Shimadzu QP5050A GC–MS system (SPB-5 ms
capillary column, 60 m; injector temperature 260°C,
oven temperature 50–220°C).
1
0. Stothers, J.B., Carbon-13 Nuclear Magnetic Resonance
Spectroscopy, New York: Academic, 1972.
11. Breitmaier, E., Structure Elucidation by NMR in
Organic Chemistry: A Practical Guide, Chichester:
Wiley, 2002, p. 26.
This study was performed under financial support
by the Presidium of the Russian Academy of Sciences
project no. 7.19) and by the Russian Foundation for
1
2. Schmid, G.H., The Chemistry of the Carbon–Carbon
Triple Bond, Patai, S., Ed., Chichester: Wiley, 1978,
pp. 1, 275.
(
Basic Research (project no. 11-03-00810).
1
3. Braverman, S., Jana, R., Cherkinsky, M., Gottlieb, H.E.,
REFERENCES
and Sprecher, M., Synlett, 2007, p. 2663.
1
. Lautenschlaeger, F., J. Org. Chem., 1968, vol. 33,
14. Gal, Y.-S. and Choi, S.-K., J. Polymer Sci., Part C,
p. 2620.
1988, vol. 26, p. 115.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 12 2011