Methoxide ion promoted efficient synthesis of 1,3-oxathiolane-2-thiones by reaction of oxiranes and carbon disulfide

Article abstract of DOI:10.1055/s-2008-1042927

An efficient one-pot synthesis of functionalized 1,3-oxathiolane-2-thiones is described via reaction of carbon disulfide with oxiranes in the presence of sodium hydride (10 mol%) and methanol. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2008-1042927

LETTER
889
Methoxide Ion Promoted Efficient Synthesis of 1,3-Oxathiolane-2-thiones by
Reaction of Oxiranes and Carbon Disulfide
S
ynthesi
s
s
of 1,3-O
s
xathiolane
a
-2-thione
s
Yavari,* Majid Ghazanfarpour-Darjani, Zinatossadat Hossaini, Maryam Sabbaghan, Nargess Hosseini
Chemistry Department, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran
Fax +98(21)88006544; E-mail: yavarisa@modares.ac.ir
Received 13 December 2007
Table 1 Reaction of MeOH and CS2 with Oxiranes in the Presence
of NaH
Abstract: An efficient one-pot synthesis of functionalized 1,3-
oxathiolane-2-thiones is described via reaction of carbon disulfide
with oxiranes in the presence of sodium hydride (10 mol%) and
methanol.
S
NaH (10 mol%)
MeOH
O
O
S
+
CS2
Key words: oxathiolane, oxiranes, carbon disulfide, methoxide ion
R2
R1
R2
R1
2
1
O,S-Dialkyl dithiocarbonates (xanthates) are a versatile
source of radicals,1–4 intermediates in the synthesis of thi-
ols,5 thiocarbonates,6,7 alkenes,8 alkanes,9 S-activated
carbanions,10 and photosensitizers11 for the polymeriza-
tion of vinyl monomers. They have also been used in
the synthesis of natural products,12 Claisen rearrange-
ments,13–16 and are also important for their biological ac-
tivities.17 There have been many reports on the reaction of
oxiranes with carbon disulfide.18,19 Depending on the cat-
alysts and reaction conditions, five-membered cyclic
dithiocarbonates, trithiocarbonates, and episulfides have
been reported. Alkali-metal halides can effectively cata-
lyze the reaction of carbon dioxide or carbon disulfide
with oxiranes to form five-membered cyclic carbonates.20
The earlier attempts for synthesis of 1,3-oxathiolane-2-
thiones suffered from low yields and formation of byprod-
ucts.
1, 2
a
R
R1
Yield of 2 (%)
Me
Et
H
H
96
94
96
95
94
94
96
88
86
b
c
(CH2)4
d
e
Ph
H
H
H
H
PhOCH2
f
H2C=CHCH2OCH2
g
Me2CHOCH2
h
i
Ph
Ph
Ph (cis)
Ph (trans)
Structures of compounds 2a-i21 were confirmed by IR, 1H
NMR, 13C NMR, and mass spectrometric data. For exam-
Our studies were initiated by treating a solution of carbon
disulfide containing an oxirane derivative in the presence
of sodium hydroxide (10 mol%). The efficiency of this re-
action was low because hydroxide ion is a poor leaving
group (Scheme 1).
1
ple, the H NMR spectrum of 2a exhibited a doublet at
1.56 (3J = 6.7 Hz) for the methyl proton, two doublet dou-
blets at 3.62 (2J = 11.9 Hz, 3J = 7.4 Hz) and 3.98
(2J = 11.9 Hz, 3J = 6.4 Hz) for the CH2 moiety and a mul-
tiplet at d = 4.45-4.51 ppm for the CH group. The 13C
S
2
NaOH (10 mol%)
O
O
S
MeO
+
CS2
CS2
H
PhOCH2
PhOCH2
H
55%
S
Scheme 1
S
MeO
O
S
MeO
S
The nucleophile derived from methanol and carbon disul-
fide in the presence of sodium hydride (10 mol%) was
found to undergo a clean and facile reaction with oxiranes
at room temperature to afford 2 in excellent yields
(Table 1).
3
R
5
S
1
MeO
O
S
R
SYNLETT 2008, No. 6, pp 0889–0891
x
x.
x
x.
2
0
0
8
4
Advanced online publication: 11.03.2008
DOI: 10.1055/s-2008-1042927; Art ID: D39907ST
Scheme 2
© Georg Thieme Verlag Stuttgart · New York

890
I. Yavari et al.
LETTER
5-Ethyl-1,3-oxathiolane-2-thione (2b)
NMR spectrum of 2a shows a signal at d = 228.5 ppm for
the C=S group. The mass spectrum of 2a displayed the
molecular ion peak at m/z = 134.
Yellow oil; yield 0.28 g (94%). IR (KBr): nmax = 1711, 1627,
1507, 1431, 1327, 1273 cm–1. 1H NMR (500.1 MHz,
CDCl3): d = 1.07 (3 H, t, 3J = 7.4 Hz, Me), 1.91–1.97 (2 H,
m, CH2), 3.71 (1 H, dd, 2J = 11.9 Hz, 3J = 7.5 Hz, CH), 3.98
(1 H, dd, 2J = 11.9 Hz, 3J = 5.5 Hz, CH), 4.29-4.33 (1 H, m,
CH). 13C NMR (125.7 MHz, CDCl3): d = 13.1 (Me), 27.2
(CH2), 48.3 (CH2), 62.9 (CH), 228.5 (C=S). MS (EI): m/z
(%) = 148 (10) [M+], 119 (68), 92 (100), 76 (84), 56 (42), 29
(24). Anal. Calcd (%) for C5H8OS2 (148.24): C, 40.51; H,
5.44. Found: C, 40.41; H, 5.49.
A tentative mechanism for this transformation is proposed
in Scheme 2. The first step may involve addition of meth-
oxide ion to CS2 and formations of the 1:1 adduct 3. Sub-
sequent nucleophilic attack of 3 to 1 yields 4, which is
converted to 2 by elimination of sodium methoxide.
In conclusion, the reaction of methanol and carbon disul-
fide with oxiranes in the presence of sodium hydride (10
mol%) leads to 1,3-oxathiolanes in excellent yields.
Hexahydro-1,3-benzoxathiole-2-thione (2c)
Yellow crystals; yield 0.33 g (96%); mp 176-178 °C. IR
(KBr): nmax = 1628, 1431, 1326, 1272, 1094 cm-1. 1H NMR
(500.1 MHz, CDCl3): d = 1.43–1.48 (2 H, m, CH2), 1.68–
1.75 (2 H, m, CH2), 1.93–1.97 (2 H, m, CH2), 2.17–2.22 (2
H, m, CH2), 4.08–4.09 (1 H, m, CH), 4.09–4.11 (1 H, m,
CH). 13C NMR (125.7 MHz, CDCl3): d = 25.5 (2 CH2), 29.5
(2 CH2), 65.0 (2 CH), 227.6 (C=S). MS (EI): m/z (%) = 174
(5) [M+], 118 (78), 92 (100), 82 (64), 76 (48), 56 (45). Anal.
Calcd (%) for C7H10OS2 (174.27): C, 48.24; H, 5.78; found:
C, 48.18; H, 5.79.
References and Notes
(1) Barton, D. H. R.; Chen, M.; Jaszberenyi, J. C.; Rattingan, B.;
Tang, D. Tetrahedron Lett. 1994, 35, 6457.
(2) Barton, D. H. R.; Jang, D. O.; Jaszberenyi, J. C. Tetrahedron
Lett. 1990, 31, 4681.
(3) Barton, D. H. R.; Jang, D. O.; Jaszberenyi, J. C. Tetrahedron
Lett. 1991, 32, 2569.
5-Phenyl-1,3-oxathiolane-2-thione (2d)
(4) Hartwig, W. Tetrahedron 1983, 39, 2609.
(5) Isola, M.; Ciuffarin, E.; Sangromora, L. Synthesis 1976, 326.
(6) Degani, I.; Fochi, R.; Regondi, V. Synthesis 1981, 149.
(7) Baker, R.; Mahony, M.; Swain, C. J. J. Chem. Soc., Perkin
Trans. 1 1987, 1623.
(8) Nace, H. R. Org. React. 1962, 12, 57.
(9) Barton, D. H. R.; Combie, S. W. J. Chem. Soc., Perkin
Trans. 1 1975, 1574.
(10) Degani, I.; Fochi, R.; Regondi, V. Synthesis 1979, 178.
(11) Okatawa, M.; Nakai, T.; Otsuji, Y.; Imoto, E. J. Org. Chem.
1965, 30, 2025.
(12) (a) Curran, D. P. Synthesis 1988, 417. (b) Curran, D. P.
Synthesis 1988, 489.
(13) Ferrier, R. J.; Vethavisar, N. J. Chem. Soc., Chem. Commun.
1970, 1385.
(14) Baldwin, J. E.; Holfe, G. A. J. Am. Chem. Soc. 1971, 93,
Yellow crystals; yield 0.30 g (95%); mp 115–117 °C. IR
(KBr): nmax = 1568, 1470, 1438, 1413, 1357, 1048 cm-1. 1H
NMR (500.1 MHz, CDCl3): d = 4.03 (1 H, dd, 2J = 12.0 Hz,
3J = 5.7 Hz, CH), 4.17 (1 H, dd, 2J = 12.0 Hz, 3J = 11.8 Hz,
CH), 5.65 (1 H, dd, 2J = 10.3 Hz, 3J = 5.7 Hz, CH), 7.37–
7.44 (3 H, m, 3 CH), 7.50 (2 H, d, 3J = 7.2 Hz, 2 CH). 13
NMR (125.7 MHz, CDCl3): d = 49.8 (CH2), 64.2 (CH),
C
127.5 (2 CH), 129.2 (2 CH), 129.3 (CH), 135.3 (C), 227.2
(C=S). MS (EI): m/z 196 (10) [M+], 119 (76), 104 (46), 92
(25), 77 (100). Anal. Calcd (%) for C9H8OS2 (196.28): C,
55.07; H, 4.11. Found: C, 55.03; H, 4.08.
5-(Phenoxymethyl)-1,3-oxathiolane-2-thione (2e)
Yellow crystals; yield 0.42 g (94%); mp 55–57 °C. IR
(KBr): nmax = 1584, 1481, 1448, 1238, 1165, 1063 cm-1. 1H
NMR (500.1 MHz, CDCl3): d = 4.06 (1 H, dd, 2J = 12.3 Hz,
3J = 4.0 Hz, CH), 4.18–4.23 (2 H, m, CH2), 4.36 (1 H, dd,
2J = 12.2 Hz, 3J = 4.5 Hz, CH), 4.61–4.66 (1 H, m, CH), 6.93
(2 H, d, 3J = 7.9 Hz, 2 CH), 7.02 (1 H, t, 3J = 7.3 Hz, CH),
7.33 (2 H, t, 3J = 7.5 Hz, 2 CH). 13C NMR (125.7 MHz,
CDCl3): d = 45.0 (CH2), 57.4 (CH), 66.7 (CH), 114.7 (2 CH),
121.9 (CH), 129.7 (2 CH), 157.8 (C), 227.5 (C=S). MS (EI):
m/z 226 (5) [M+], 149 (78), 134 (64), 107 (94), 92 (46), 77
(100). Anal. Calcd (%) for C10H10O2S2 (226.31): C, 53.07;
H, 4.45. Found: C, 53.05; H, 4.40.
5-(Vinyloxymethyl)-1,3-oxathiolane-2-thione (2f)
Yellow oil; yield: 0.36 g (94%). IR (KBr): nmax = 1702, 1630,
1451, 1414, 1348 cm–1. 1H NMR (500.1 MHz, CDCl3): d =
3.64 (1 H, dd, 2J = 9.8 Hz, 3J = 5.8 Hz, CH), 3.79–3.81 (1 H,
m, CH), 3.94 (1 H, dd, 2J = 12.1 Hz, 3J = 4.7 Hz, CH), 4.04
(2 H, d, 3J = 5.6 Hz, 2 CH), 4.07 (1 H, dd, 2J = 12.1 Hz,
3J = 5.7 Hz, CH), 4.44–4.49 (1 H, m, CH), 5.20–5.30 (2 H,
m, 2 CH), 5.83–5.91 (1 H, m, CH). 13C NMR (125.7 MHz,
CDCl3): d = 45.4 (CH2), 58.7 (CH), 69.4 (CH2), 72.8 (CH2),
118.4 (CH2), 134.3 (CH), 227.9 (C=S). MS (EI): 190 (15)
[M+], 133 (74), 114 (58), 92 (46), 57 (100). Anal. Calcd (%)
for C7H10O2S2 (190.27): C, 44.19; H, 5.30. Found: C, 44.15;
H, 5.36.
6307.
(15) Nakai, T.; Ari-Izumi, A. Tetrahedron Lett. 1976, 27, 2335.
(16) Alexander, B. H.; Gertler, S. I.; Oda, T. A.; Bown, R. T.;
Ihndris, R. W.; Beroza, M. J. Org. Chem. 1960, 25, 626.
(17) Taguchi, Y.; Yasumoto, M.; Shibuya, I.; Suhara, Y. Bull.
Chem. Soc. Jpn. 1989, 62, 474.
(18) Jesudason, M. V.; Owen, L. N. J. Chem. Soc., Perkin Trans.
1 1974, 1443.
(19) Durden, J. A. Jr.; Stambury, H. A. Jr.; Catlette, W. H. J. Am.
Chem. Soc. 1960, 82, 3082.
(20) Nobuhiro, K.; Yuichi, N.; Takeshi, E. J. Org. Chem. 1996,
60, 473.
(21) General Procedure for the Preparation of Compounds 2
To a stirred solution of CS2 (0.35 g, 5 mmol) in MeOH
(0.064 g, 2 mmol) containing NaH (10 mol%), was added, at
r.t., the oxirane derivative 1 (2 mmol). The mixture was
stirred for 12 h, and filtered to remove the white precipitates
(presumably, NaOMe). The residue was purified by
extraction with Et2O to afford pure 2.
5-Methyl-1,3-oxathiolane-2-thione (2a)
Yellow oil; yield 0.26 g (96%). IR (KBr): nmax = 1700, 1439,
1414, 1370, 1143, 1073 cm–1. 1H NMR (500.1 MHz,
CDCl3): d 1.56 (3 H, d, 3J = 6.7 Hz, Me), 3.62 (1 H, dd,
2J = 11.9 Hz, 3J = 7.4 Hz, CH), 3.98 (1 H, dd, 2J = 11.9 Hz,
3J = 6.4 Hz, CH), 4.45–4.51 (1 H, m, CH). 13C NMR (125.7
MHz, CDCl3): d = 19.1 (Me), 50.3 (CH2), 55.5 (CH), 228.5
(C=S). MS (EI): m/z (%) = 134 (15) [M+], 119 (78), 92 (100),
76 (64), 58 (48), 42 (56). Anal. Calcd (%) for C4H6OS2
(134.21): C, 35.80; H, 4.51. Found: C, 35.90; H, 4.55.
5-(Isopropoxymethyl)-1,3-oxathiolane-2-thione (2g)
Pale yellow oil; yield 0.37 g (96%). IR (KBr): nmax = 1703,
1643, 1452, 1417, 1372, 1332 cm–1. 1H NMR (500.1 MHz,
CDCl3): d = 1.12 (6 H, d, 3J = 6.1 Hz, 2 Me), 3.53–3.62 (2
H, m, CH2), 3.73 (1 H, m, CH), 3.89 (1 H, dd, 2J = 12.0 Hz,
3J = 4.9 Hz, CH), 4.01 (1 H, dd, 2J = 12.0 Hz, 3J = 5.7 Hz,
CH), 4.36–44.40 (1 H, m, CH). 13C NMR (125.7 MHz,
Synlett 2008, No. 6, 889–891 © Thieme Stuttgart · New York

LETTER
CDCl3): d = 21.7 (Me), 21.8 (Me), 44.7 (CH2), 58.6 (CH2),
Synthesis of 1,3-Oxathiolane-2-thiones
891
4.44. Found: C, 66.08; H, 4.39.
(4R,5R)-4,5-Diphenyl-1,3-oxathiolane-2-thione (2i)
67.0 (CH), 72.3 (CH), 227.3 (C=S). MS (EI): m/z 192 (5)
[M+], 149 (84), 119 (25), 116 (52), 92 (32), 43 (42), 73 (100).
Anal. Calcd (%) for C7H12O2S2 (192.29): C, 43.72; H, 6.29.
Found: C, 43.85; H, 6.26.
Yellow crystals; yield 0.47g (86%); mp 127-129 °C. IR
(KBr): nmax = 1479, 1439, 1142, 1056 cm-1. 1H NMR (500.1
MHz, CDCl3): d = 4.08 (1 H, s, CH), 5.76 (1 H, s, CH), 7.00
(2 H, d, 3J = 7.4 Hz, 2 CH), 7.18 (2 H, t, 3J = 7.8 Hz, 2 CH),
7.27-7.30 (3 H, m, 3 CH), 7.38 (2 H, t, 3J = 7.5 Hz, 2 CH),
7.54 (1 H, d, 3J = 7.4 Hz, CH). 13C NMR (125.7 MHz,
CDCl3): d = 45.9 (CH), 68.4 (CH), 126.9 (2 CH), 128.0
(CH), 128.8 (2 CH), 129.1 (2 CH), 129.2 (2 CH), 129.3
(CH), 133.5 (C), 137.7 (C), 227.9 (C=S). MS (EI): m/z
(%) = 272 (15) [M+], 196 (76), 180 (62), 92 (62), 77 (100).
Anal. Calcd (%) for C15H12OS2 (272.38): C, 66.15; H, 4.44.
Found: C, 66.08; H, 4.46.
(4S,5R)-4,5-Diphenyl-1,3-oxathiolane-2-thione (2h)
Yellow crystals; yield 0.48 g (88%); mp 123-125 °C. IR
(KBr): n = 1475, 1435, 1140, 1050 cm-1. 1H NMR (500.1
MHz, CDCl3): d = 4.41 (1 H, s, CH), 5.74 (1 H, s, CH), 7.13-
7.17 (5 H, m, 5 CH), 7.31-7.33 (5 H, m, 5 CH). 13C NMR
(125.7 MHz, CDCl3): d = 44.5 (CH), 70.6 (CH), 127.6 (CH),
128.1 (2 CH), 128.5 (2 CH), 129.5 (2 CH), 129.6 (CH),
129.8 (2 CH), 133.6 (C), 135.5 (C), 225.3 (C=S). MS (EI):
m/z (%) = 272 (15) [M+], 196 (78), 180 (64), 92 (58), 77
(100). Anal. Calcd (%) for C15H12OS2 (272.38): C, 66.15; H,
Synlett 2008, No. 6, 889–891 © Thieme Stuttgart · New York