A simple and novel eco-friendly process for the synthesis of cyclic dithiocarbonates from epoxides and carbon disulfide in water

Article abstract of DOI:10.1002/jhet.75

The reaction of oxiranes with carbon disulfide for preparation of cyclic dithiocarbonates was carried out in water under catalytic amount of an organic base such as dimethylaminopyridine or triethylamine. The reaction conditions are simple and give high y

Full text of DOI:10.1002/jhet.75

March 2009
A Simple and Novel Eco-Friendly Process for the Synthesis
of Cyclic Dithiocarbonates from Epoxides and
Carbon Disulfide in Water
347
Azim Ziyaei Halimehjani,a Forogh Ebrahimi,b
Najmedin Azizi,c and Mohammad R. Saidib*
aFaculty of Chemistry, Tarbiat Moallem University, 49 Mofateh St., Tehran, Iran
bDepartment of Chemistry, Sharif University of Technology, P. O. Box 11365-9516, Tehran, Iran
cChemistry and Chemical Engineering Research Center of Iran, P.O. Box 14335-186,
Tehran 11365, Iran
*E-mail: Saidi@sharif.edu
Received April 5, 2008
DOI 10.1002/jhet.75
Published online 13 April 2009 in Wiley InterScience (www.interscience.wiley.com).
The reaction of oxiranes with carbon disulfide for preparation of cyclic dithiocarbonates was carried
out in water under catalytic amount of an organic base such as dimethylaminopyridine or triethylamine.
The reaction conditions are simple and give high yields of desired products.
J. Heterocyclic Chem., 46, 347 (2009).
INTRODUCTION
Harsh reaction conditions have been reported for the
synthesis and purification of five-membered cyclic
dithiocarbonates, its regioisomers, and trithiocarbonates
depending on the catalyst, temperature, and pressure.
Shi and his coworkers studied the reaction between ep-
oxy propane and carbon disulfide in the presence of
DMAP and p-methoxyphenol as a catalyst at high tem-
perature to afford the cyclic dithiocarbonate in 45%
yield [11]. Recently, Maggi et. al reported a very inter-
esting method for the synthesis of cyclic dithiocarbon-
ates in the presence of hydrotalcite catalyst with good
yields [12]. But there is no report for the preparation of
cyclic dithiocarbonates in water therefore availability of
a facile and green procedure to cover these drawbacks is
interesting.
Because it was reported that Diels–Alder reactions
could be greatly accelerated by using water as a solvent
instead of organic solvents [1], considerable attention
has been directed toward the development of organic
reactions in water. Besides Diels–Alder reaction, water
was used in almost all of the useful organic reactions,
even reactions involving water sensitive materials [2]. It
is obvious that water is the most inexpensive and envi-
ronmentally benign solvent. Thus, development of novel
reactivity as well as selectivity that cannot be attained
in conventional organic solvents is one of the challeng-
ing goals of aqueous chemistry [1].
Tertiary amines- and pyridine-based organo catalysts
were introduced to synthetic chemistry as a powerful
nucleophilic group-transfer catalyst since more than 3
decades ago [3], because of their ability to catalyze im-
portant reactions such as acylation [4], esterification [5],
macrolactonization [6], Baylis-Hillman [7], and silyla-
tion reactions [8]. Also, because of high potential of
these compounds for developing of chiral acylating cata-
lyst [9], several research groups are interested in this
field of chemistry. 4-(Dimethylamino) pyridine (DMAP)
is one of the standard catalysts for nucleophilic group-
transfer reactions.
RESULTS AND DISCUSSION
Encouraged by our good experience to open the epox-
ide ring by nucleophiles such as amines [13] and dithio-
carbamate anion [14] in water and in continuation of
our previous work for the synthesis of dithiocarbamates
in water and solvent-free conditions [15], we were inter-
ested to investigate the reaction of epoxides with CS2 in
the presence of Lewis bases in aqueous medium
(Scheme 1). For this purpose, different Lewis bases
such as Et3N, DMAP, DABCO, and DBU were exam-
ined, and we have found that DMAP and Et3N (10 mol
%) gave the best results for the preparation of cyclic
There are many reports on the reaction of epoxide
with carbon disulfide [10]. Usually, high pressure and
elevated temperature as well as long reaction times have
been used for the synthesis of cyclic dithiocarbonates.
C
V
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348
A. Z. Halimehjani, F. Ebrahimi, N. Azizi, and M. R. Saidi
Vol 46
(IR, 1H NMR, and 13C NMR) by comparison with those
reported in the literature. Reactions were carried out at room
temperature. Carbon disulfide, DMAP, and all epoxides are
commercially available and used without further purification.
General procedure for the synthesis of the cyclic dithio-
carbonates in water. In a round-bottomed flask equipped with
magnet stirrer, epoxide (5 mmol), carbon disulfide (10 mmol)
and water (20 mL) were added. To this mixture, DMAD or
Et3N (0.5 mmol) was added and stirred for 20 h. The progress
of the reaction was checked by TLC. After completion of the
reaction, the product was extracted with ethyl acetate and
washed with water to remove the catalyst. The crude products
were purified with column chromatography using silica gel as
stationary phase and mixture of hexane and ethyl acetate (7:3)
as an eluent to give the pure products with the yields shown in
Table 2. Unreacted epoxides were recovered with column
chromatography. Selected spectroscopic data for compounds
are given in Table 2.
Scheme 1. Synthesis of cyclic dithiocarbonate in water.
dithiocarbonates. We also tried the halide salts such as
LiCl in water as catalyst, but we did not obtain good
results (Table 1, entry 12). Also solvent effect was
examined for the reaction of 2,3-epoxypropyl phenyl
ether and CS2 by using different organic solvents, but
we did not obtain any desired products, except for etha-
nol, which gave only 10% yield (ca. Table 1).
After optimizing the reaction conditions, we tried to
expand our results to other epoxides and the results are
reported in Table 2. As shown in Table 2, 1,2-epoxides
gave moderate to good yields but for cyclic epoxides
such as cyclohexane epoxide, we obtained the product
in low yield. For epichlorohydrin, 91% isolated yield
was obtained. Only for styrene epoxide two regioisom-
ers were obtained in 2:1 ratio and total yields of 52%.
Compound (3a). Yellow crystal; mp 55–57ꢀC. 1H NMR (500
MHz, CDCl3): d 3.78–3.85 (m, 2H, CH2), 4.35 (m, 2H, CH2),
5.48 (m, 1H, CH), 6.96 (d, J ¼ 7.9 Hz, 2H, 2CHar), 7.06 (t, J ¼
7.4, 1H, CHar), 7.36 (m, 2H, 2CHar) ppm. 13C NMR (125.7
MHz, CDCl3): d 36.8, 66.7, 88.2, 114.9, 122.4, 130.2, 158.1,
211.9 ppm; IR (KBr): 1595, 1498, 1199, 1059 cmꢁ1
.
1
Compound (3b). Yellow oil; H NMR (500 MHz, CDCl3):
d 1.15 (d, J ¼ 7.5 Hz, 6H, 2CH3), 3.60–3.65 (m, 3H, CH2 and
CH), 3.70 (m, 2H, CH2), 5.16 (m, 1H, CH) ppm. 13C NMR
(125.7 MHz, CDCl3): d 22.4, 36.6, 67.1, 73.2, 89.7, 211.8
1
The ratio was determined by H NMR with using the
area of the peak of benzylic hydrogen in the two
regioisomers (Entry 7, Table 2).
(C¼¼S) ppm. IR (KBr): 1703, 1452, 1417, 1372, 1332 cmꢁ1
.
A plausible mechanism for this reaction is shown in
Scheme 2. It is possible that the ability of water to give
hydrogen bond with epoxides makes this transformation
very efficient. We supposed that DMAP activates the
CS2 to dithiocarbamate anion 1, which attacks to the
water-activated epoxide to give compound 2. In the next
step, the epoxide’s oxygen attacks the thiocarbonyl to
remove DMAP and to form the cyclic dithiocarbonate 3.
1
Compound (3c). Yellow oil; H NMR (500 MHz, CDCl3): d
3.73–3.78(m, 2H, CH2), 3.9 (m, 2H, CH2), 5.3 (m, 1H, CH) ppm.
13C NMR (125.7 MHz, CDCl3): d 31.2, 37.3, 42.9, 88.4, 209.9
(C¼¼S) ppm. IR (KBr): 1706, 1430, 1425, 1377, 1141, 1072 cmꢁ1
.
1
Compound (3d). Yellow oil; H NMR (500 MHz, CDCl3):
d 3.60–3.70 (m, 2H, CH2), 3.73–3.83 (m, 2H, CH2), 4.07 (d, J
¼ 5.7 Hz, 2H, CH2), 5.2–5.3 (m, 3H, CH and CH2), 5.88 (m,
1H, CH) ppm. 13C NMR (125.7 MHz, CDCl3): d 36.5, 68.9,
72.9, 89.5, 118.3, 134.2, 211.2 (C¼¼S) ppm. IR (KBr): 1702,
1638, 1423, 1419, 1354 cmꢁ1
.
CONCLUSIONS
Table 1
In conclusion, we showed a very mild, facile, eco-
nomical, and friendly method for the synthesis of cyclic
dithiocarbonates in the presence of catalytic amount of
DMAP. Also in large scale synthesis, extraction of prod-
ucts does not need to any organic solvent and only sepa-
ration of organic phase from aqueous phase gives the
crude products. Trying to do this reaction under asym-
metrical conditions with chiral Lewis bases is under-
taken in our laboratory.
Solvent and catalyst effects on the syntheis of cyclic dithiocarbonates.
Entry
Solvent
Catalyst (mol %)
Yield (%)
1
2
H2O
H2O
DMAP (50%)
DMAP (10%)
Et3N (10%)
84
76
72
10
0
3
H2O
4
5
C2H5OH
CH2Cl2
ClCH2CH2Cl
CH3CN
THF
Toluene
Acetone
Solvent free
H2O
DMAP (10%)
DMAP (10%)
DMAP (10%)
DMAP (10%)
DMAP (10%)
DMAP (10%)
DMAP (10%)
DMAP (10%)
LiCl (10%)
EXPERIMENTAL
6
7
0
0
General. All chemicals were purchased and used without
any further purification. NMR spectra were recorded at 500
MHz for proton and at 125 MHz for carbon nuclei in CDCl3.
The products were purified by column chromatography carried
out on silica gel using ethyl acetate/petroleum ether mixtures.
All compounds were characterized by their spectroscopic data
8
9
0
0
10
11
12
0
50
0
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

March 2009 A Simple and Novel Eco-Friendly Process for the Synthesis of Cyclic Dithiocarbonates
from Epoxides and Carbon Disulfide in Water
349
1
Scheme 2. Proposed mechanism for the synthesis of cyclic
dithiocarbonate.
Compound (3e). Yellow oil H NMR (500 MHz, CDCl3): d
1.08 (t, J ¼ 7.5 Hz, 3H, CH3), 1.85 (m, 1H, one proton of
CH2), 2.00 (m, 1H, one proton of CH2), 3.39 (dd, J ¼ 11.7,
Table 2
Synthesis of cyclic dithiocarbonates by reaction
of epoxide and carbon sisulfide in water.
Entry
1
Epoxide
Product
Yield (%)a
76[16]
7.2 Hz, 1H, one proton of CH2), 3.61 (dd, J ¼ 11.7, 5.4 Hz,
1H, one proton of CH2), 5.05 (m, 1H, CH) ppm. 13C NMR
(125.7 MHz, CDCl3): d 10.2, 27.2, 39.4, 93.2, 212.1 (C¼¼S)
2
79 [16]
ppm. IR (KBr): 1714, 1619, 1511, 1426, 1332, 1268 cmꢁ1
.
Compound (3f). Yellow oil; 1H NMR (500 MHz, CDCl3):
d 1.66 (d, J ¼ 6.3 Hz, 3H, CH3), 3.39 (dd, J ¼ 11.7, 7.2 Hz,
1H, one proton of CH2), 3.66 (dd, J ¼ 11.7, 4.5 Hz, 1H, one
proton of CH2), 5.27 (m, 1H, CH) ppm. 13C NMR (125.7
MHz, CDCl3): d 19.8, 41.2, 88.0, 211.6 (C¼¼S) ppm. IR
Compound (3g). Yellow crystal; mp 115–117ꢀC. 1H NMR
(500.1 MHz, CDCl3): d 4.03 (1 H, dd, J ¼ 12.0 Hz, J ¼ 5.7
Hz, CH), 4.17 (1 H, dd, J ¼ 12.0 Hz, J ¼ 11.8 Hz, CH), 5.65
(1 H, dd, J ¼ 10.3 Hz, J ¼ 5.7 Hz, CH), 7.37–7.50 (5HAr).
13C NMR (125.7 MHz, CDCl3): d 49.8 (CH2), 64.2 (CH),
127.5 (2 CH), 129.2 (2 CH), 129.3 (CH), 135.3 (C), 227.2
3
4
5
6
91
(KBr): 1703, 1439, 1417, 1370, 1141, 1079 cmꢁ1
.
77(56)b [16]
50 [16]
(C¼¼S). IR (KBr): 1568, 1470, 1438, 1413, 1357, 1048 cmꢁ1
.
1
Compound (3h). H NMR (500.1 MHz, CDCl3): d 3.70–
3.88 (2 H, CH2), 5.35 (1 H, dd, J ¼ 10.3 Hz, J ¼ 5.7 Hz,
CH), 7.37–7.44 7.50 (5 HAr). IR (KBr): 1560, 1461, 1445,
30(45)b [16]
1410, 1351, 1049 cmꢁ1
.
Compound (3i). Yellow oil; 1H NMR (500 MHz, CDCl3):
d 3.63–3.73(m, 2H, CH2), 3.8 (m, 2H, CH2), 5.25 (m, 1H,
CH) ppm. 13C NMR (125.7 MHz, CDCl3): d 30.3, 36.3, 41.9,
87.4, 206.9 (C¼¼S) ppm. IR (KBr): 1700, 1425, 1370, 1143,
7
52 [10j]
1071 cmꢁ1
.
Compound (3j). Yellow oil; 1H NMR (500.1 MHz,
CDCl3): d 0.79–1.68 (15 H), 1.80 (1 H, m, CH2), 1.98 (1H, m,
CH2), 3.44–3.79 (2H, CH2), 5.12 (1H, CH). IR (KBr): 1701,
8
9
26
24
1455, 1417, 1374, 1338 cmꢁ1
.
Compound (3k). Yellow crystal; mp 176–178ꢀC. 1H NMR
(500 MHz, CDCl3): d 0.6–2.4 (m, 8H, 4CH2), 3.47–4.70 (m,
2H, 2CH) ppm. 13C NMR (125.7 MHz, CDCl3): d 23.6, 24.9,
28.1, 29.7, 56.3, 94.6, 212.4(C¼¼S) ppm; IR (KBr): 1628,
1431, 1326, 1272, 1094 cmꢁ1
.
10
18 [16]
Acknowledgment. We are grateful to the research council of
Sharif University of Technology for financial support. We also
have thanks to Faculty of Chemistry of Tarbiat Moallem Univer-
sity for supporting this work. We also thank Professor J. Ipaktschi
for his friendly discussion and critically reading the manuscript.
a Isolated yield.
b Triethyl amine as catalyst.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

350
A. Z. Halimehjani, F. Ebrahimi, N. Azizi, and M. R. Saidi
Vol 46
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