A new method for the synthesis of 1,3-oxathiolan-2-ones by the reaction of epoxides with sulfur and carbon monoxide

Article abstract of DOI:10.1016/j.tetlet.2004.09.105

The convenient method for the synthesis of 1,3-oxathiolan-2-ones by the reaction of epoxides with elemental sulfur and carbon monoxide in the presence of catalytic amount of sodium hydride has been developed.

Full text of DOI:10.1016/j.tetlet.2004.09.105

Tetrahedron
Letters
Tetrahedron Letters 45 (2004) 8539–8540
A new method for the synthesis of 1,3-oxathiolan-2-ones
by the reaction of epoxides with sulfur and carbon monoxide
*
Yutaka Nishiyama, Chisato Katahira and Noboru Sonoda
*
Department of Applied Chemistry, Faculty of Engineering, Kansai University, Suita, Osaka 564-8680, Japan
Received 20 July 2004; revised 6 September 2004; accepted 10 September 2004
Available online 30 September 2004
Abstract—The convenient method for the synthesis of 1,3-oxathiolan-2-ones by the reaction of epoxides with elemental sulfur and
carbon monoxide in the presence of catalytic amount of sodium hydride has been developed.
Ó 2004 Elsevier Ltd. All rights reserved.
Since 1,3-oxathiolan-2-one is an important synthetic
1
When 1,2-epoxydodecane (2mmol) was allowed to react
with sulfur (10mmol) in the presence of a catalytic
amount of sodium hydride (0.5mmol) under the pressu-
rized carbon monoxide (10atm) in THF solvent at 60°C
for 3h, the thiocarbonylation of epoxide proceeded reg-
ioselectively to give 5-decyl-1,3-oxathiolan-2-one in 95%
intermediate in polymer science, considerable attention
has been devoted to the development of a convenient
2
method for the synthesis of 1,3-oxathiolan-2-one. For
instance, the carbonylation route of b-hydroxy thiol
with phosgene is a simple method for the synthesis of
6
1
,3-oxathiolan-2-one, but the use of poisonous phosgene
yield (entry 1). Although the reaction of 1,2-epoxydo-
and untolerable odorous thiol are required for the
method. As another one, the treatment of epoxides with
carbonyl sulfide in the presence of triethylamine gave
decane with elemental sulfur and carbon monoxide
was undertaken in the presence of a catalytic amount
of potassium hydride instead of sodium hydride used
as a base, no formation of 5-dodecyl-1,3-oxathiolan-2-
one was confirmed. However, the reaction was
accelerated by the addition of dibenzo-18-crown-6, and
5-decyl-1,3-oxathiolan-2-one was obtained in 82% yield.
The results of the reaction of various epoxides with ele-
mental sulfur and carbon monoxide in the presence of a
catalytic amount of sodium hydride were shown in
Table 1. 5-Alkyl substituted 1,3-oxathiolan-2-ones were
obtained in good to excellent yields by the reaction of
mono substituted epoxides (entries 1 and 2). In the case
of 1,1-dialkyl substituted epoxide such as isobutylene
oxide, the same reaction occurred efficiently to give 5,5-
dialkyl-1,3-oxathiolan-2-one in excellent yield, however,
for trialkyl substituted epoxide, the yield was very low
(entry 4). When epoxides possessing aromatic ring were
allowed to react with sulfur and carbon monoxide, the
yields of 1,3-oxathiolan-2-ones were slightly decreased
owing to the preparation of olefins and 5-phenylthiiranes
as by-products (entry 5).
1
,3-oxathiolan-2-ones in moderate yields, however, the
use of poisonous carbonyl sulfide as a starting material
is also required. Furthermore, the decarboxylation of
1
reaction conditions, and thiirane was formed as a
,3-oxathiolan-2-one sometimes occurred under these
3
by-product.
We found a new method for the synthesis of 1,3-oxa-
thiolan-2-ones (1) by the reaction of epoxides with ele-
mental sulfur and carbon monoxide in the presence of
4
,5
a catalytic amount of sodium hydride (Scheme 1).
R2
R3
R2
R3
cat.
R1
NaH
THF
+
S
+
CO
O
S
R1
O
O
1
Scheme 1.
We have already shown that the carbonyl sulfide was
easily prepared by a facile exchange reaction of elemen-
tal sulfur with carbonyl selenide, generated in situ by the
reaction of elemental selenium with carbon monoxide in
*
Corresponding authors. Tel.: +81 6 6368 1121; fax: +81 6 6369
026; e-mail: nishiya@ipcku.kansai-u.ac.jp
4
0
040-4039/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2004.09.105

8540
Y. Nishiyama et al. / Tetrahedron Letters 45 (2004) 8539–8540
a,b
Table 1. Synthesis of 1,3-oxathiolan-2-ones
Although the reaction pathway was not completely clari-
c
fied at the present stage, a plausible reaction path was
proposed on the reaction. Initially, carbonyl sulfide
was generated in situ by the reaction of elemental sulfur
with carbon monoxide in the presence sodium hydride.
Carbonyl sulfide attacked to epoxide from the sterically
less-hindered side in the presence of NaH and subse-
quent intramolecular cyclized to give 1,3-oxathiolan-2-
one.
Entry
1
Epoxide
Product
Yield (%)
95
9
9
O
O
O
S
S
O
O
O
2
3
87
98
From the viewpoint of simple operation, mild reaction
conditions, and good yields, the present reaction pro-
vides a useful method for synthesis of 1,3-oxathiolan-
2-ones. Furthermore, application of the reaction and
elucidation of the reaction pathway as well as selenium
catalyst effect are now in progress.
O
S
O
O
O
d
4
O
S
4
O
Acknowledgement
Ph
Ph
5
6
7
O
S
39 (79)
53 (97)
24 (66)
This research was supported by a Grant-in-aid for
Science Research (No. 155550096) and Research and
Development Organization of Industry-University
Cooperation from the Ministry of Education, Culture,
Sports, Science and Technology of Japan.
O
O
O
Ph
Ph
S
O
O
PhO
References and notes
PhO
O
S
O
1
2
. Wang, P. C. Heterocycles 1986, 24, 329.
O
. (a) Ethylene-Plastique, S. A. BP 1,135,799, 1968. Chem.
Abstr. 1976, 70, 46877; (b) Razuvaev, G. A.; Etlis, V. S.;
Grobov, L. N. Zh. Obshch. Khim. 1962, 32, 994; (c) Thiokol
Chemical Corp. U.S. Chem. Abstr. 1972, 66, 28781; (d)
Etlis, H. V. S.; Grobov, L. N.; Razuvaev, G. A. Zh. Obshch.
Khim. 1962, 32, 2940; (e) Johnson, D. L.; Fields, D. L.
Chem. Abstr. 1963, 58, 12426.
a
b
c
Reaction conditions: Epoxide (2mmol), S (10mmol), CO (10atm),
NaH (0.5mmol), and THF (2mL) at 60°C for 3h.
Reaction conditions: Epoxide (2mmol), S (10mmol), CO (10atm),
NaH (0.5mmol), Se (0.05mmol), and THF (2mL) at 60°C for 3h.
GC yield. The numbers in parentheses show the yield of product in
the presence of selenium catalyst.
d
At 150°C for 8h.
3. (a) Reynolds, D. D. J. Am. Chem. Soc. 1957, 79, 4951; (b)
Reynolds, D. D. U.S. Patent 2,828,318, 1958. Chem. Abstr.
7
1
958, 52, 14651.
the presence of triethylamine under mild conditions.
Furthermore, this exchange reaction has been widely
applicable to a synthesis of various organosulfur com-
pounds such as S-alkyl thiocarbamates and S-alkyl car-
4
. W. R. Roush et al. have recently reported the new method
for the synthesis of 1,3-oxathiolan-2-one via the cyclization
of imidazolide. See: Roush, W. R.; Gustin, D. Tetrahedron
Lett. 1994, 35, 4931.
8
bonothiolates. Then, the catalytic use of selenium in the
5
. We have recently shown that the reaction of 2-alkyn-1-ols
with sulfur and carbon monoxide, followed by copper(I)-
catalyzed cyclization gave 4-alkylidene-2-oxo-1,3-oxathiol-
anes in moderate to good yields. See: Mizuno, T.; Nakam-
ura, F.; Ishino, Y.; Nishiguchi, I.; Hirashima, T.; Ogawa,
A.; Kambe, N.; Sonoda, N. Synthesis 1989, 770.
synthesis of 1,3-oxothiolan-2-ones by the reaction of
epoxide with sulfur and carbon monoxide was next
investigated in order to improve the yields of 1,3-oxa-
thiolan-2-one having aromatic ring. In fact, when styr-
ene oxide was allowed to react with sulfur in the
presence of a catalytic amount of selenium (2.5mol%)
under the pressurized carbon monoxide at 60°C for
6
7
. When the reaction solution was oxidized by air, grew
selenium precipitate was recovered by filtration.
. Sonoda, N.; Mizuno, T.; Murakami, S.; Kondo, K.;
Ogawa, A.; Ryu, I. Angew. Chem., Int. Ed. Engl. 1989,
3
1
5
h, the yield of 1,3-oxathiolan-2-one was improved.
,3-Oxathionlan-2-one having aromatic ring such as
-benzyl-[1,3]oxathiolan-2-one and 5-phenoxymethyl-
28, 452.
. (a) Mizuno, T.; Nishiguchi, I.; Hirashima, T.; Ogawa, A.;
Kambe, N.; Sonoda, N. Tetrahedron Lett. 1990, 30, 4773;
8
[
1,3]oxathiolan-2-one were also obtained in moderate
to good yields by the use of selenium catalyst (entries
–7).
(b) Mizuno, T.; Nishiguchi, I.; Sonoda, N. Tetrahedron
1994, 50, 5669.
5