Synthesis of Cyclic Organic Carbonates from C3-C16 Epoxides

Article abstract of DOI:10.1023/A:1026054529816

Cyclic organic carbonates were prepared from epoxides (derivatives of C₃-C₁₆ olefins, C₄ and C₈ dienes, styrene; epichlorohydrin) in the presence of a catalytic system consisting of CoCl₂ · 6H₂O and dimethylformamide.

Full text of DOI:10.1023/A:1026054529816

Russian Journal of Applied Chemistry, Vol. 76, No. 5, 2003, pp. 842 843. Translated from Zhurnal Prikladnoi Khimii, Vol. 76, No. 5,
2003, pp. 870 871.
Original Russian Text Copyright
2003 by Rybina, Srednev, Bobyleva.
BRIEF
COMMUNICATIONS
Synthesis of Cyclic Organic Carbonates from C3 C16 Epoxides
G. V. Rybina, S. S. Srednev, and L. I. Bobyleva
Yaroslavl State Technical University, Yaroslavl, Russia
Received October 28, 2002; in final form, March 2003
Abstract Cyclic organic carbonates were prepared from epoxides (derivatives of C3 C16 olefins, C4 and C8
dienes, styrene; epichlorohydrin) in the presence of a catalytic system consisting of CoCl2 6H2O and di-
methylformamide.
Cyclic organic carbonates are used in oil refining
as extractants of aromatic hydrocarbons, and also in
synthesis of drugs and plant protection agents. Of par-
ticular interest for industrial organic synthesis is prep-
aration of nitrogen-containing polymers from cyclic
carbonates [1].
fractionation; their purity was no less than 98.5%.
The purity, composition, and structure of the target
products were confirmed by chromatography, chemi-
13
cal analysis, and C NMR spectroscopy.
EXPERIMENTAL
Cyclic organic carbonates are prepared in industry
The starting epoxides were prepared by hydroper-
oxide oxidation of appropriate olefins and isolated by
distillation. The main substance content was no less
than 98.5%. The solvent, catalyst, and auxiliary sub-
stances met the requirements of the corresponding
State Standards. Carboxylation of epoxides was per-
formed in a temperature-controlled stirred metallic
vessel.
by reactions of epoxides with CO in the presence of
2
alkali metal halides:
R
CH CH2
.
R CH CH2 + CO2
O
O
O
C
O
This process, however, requires high pressures (3
10 MPa) and temperatures (180 220 C) [2].
The reaction products were analyzed by gas liquid
chromatography on an LKhM-8 MD device (3000
3-mm steel column, stationary phase 15% diisooctyl
sebacate + 1.5% sebacic acid on Chromaton N AW-
DMCS). 1-Propanol was used as internal reference.
Chemical analysis was performed according to [5].
It was suggested previously [3] to perform this
reaction in the presence of a Co(II) or Ni(II) halide
and dimethylformamide (or dimethylacetamide). With
this catalytic system, it appeared possible to decrease
the reaction temperature (to 120 130 C) and pressure
(to 1.0 1.5 MPa), and also to prepare vinylethylene
carbonate by carboxylation of divinyl oxide at a high
rate and with a high selectivity with respect to the
target product [4].
13
The C NMR spectra were recorded on a Tesla BS-
576A spectrometer (25.142 MHz, internal reference
HMDS).
CONCLUSION
Our goal was to test the suggested catalytic system
for synthesis of cyclic carbonates from epoxides of
various structures, containing aliphatic (saturated and
unsaturated), aromatic, and other substituents.
A catalytic system consisting of CoCl 6H O and
2
2
dimethylformamide is effective in synthesis of cyclic
carbonates from various saturated and unsaturated
epoxides.
Carboxylation was performed at 130 C and CO
2
pressure of 1.5 MPa; the starting mixture contained
25.0 wt % epoxide and 2.50 wt % CoCl 6H O. The
ACKNOWLEDGMENTS
2
2
reaction time was 120 min. The results are listed in
the table.
The study was financially supported by the pro-
gram Research at Higher Schools in Priority Fields
of Science and Engineering, 2001.
The cyclic carbonates were isolated by vacuum
1070-4272/03/7605-0842$25.00 2003 MAIK Nauka/Interperiodica

SYNTHESIS OF CYCLIC ORGANIC CARBONATES
843
Synthesis of cyclic carbonates from epoxides in the presence of CoCl2 6H2O and dimethylformamide
Conver-
sion,
%
Cyclic carbonate
selectivity, % state of aggregation Tb,
Epoxide
C
P, kPa content, wt % [5]
Propylene oxide
1-Pentene oxide
1-Heptene oxide
1-Octene oxide
1-Nonene oxide
1-Undecene oxide
1-Dodecene oxide
1-Tetradecene oxide
1-Hexadecene oxide
1,3-Butadiene oxide
1,7-Octadiene oxide
3-Methyl-1-butene oxide
Epichlorohydrin
97.4
95.0
92.7
88.9
84.8
81.0
78.1
67.2
51.8
92.4
96.9
86.1
96.6
85.2
95.7
91.1
89.8
89.1
84.5
81.4
80.4
85.1
72.5
91.4
94.2
91.1
94.9
80.0
Liquid*
127.0 127.5
125.5 126.0
131.0 131.5
148.0 149.0
163.0 163.5
176.0 178.0
181.5 182.0
199.0 199.5
121.0 121.5
156.0 156.6
96.0 96.5
0.93
0.27
0.27
0.27
0.40
0.27
0.27
0.40
1.33
1.33
0.27
0.27
98.81 0.16
99.1 0.13
98.5 0.14
98.68 0.27
99.01 0.11
99.23 0.08
98.96 0.22
99.17 0.09
99.41 0.03
98.78 0.19
99.06 0.12
98.56 0.22
Amorphous
Liquid
128.5 129.0
Styrene oxide
Liquid*
* Not isolated from the reaction mixture.
3. RF Patent 2128658.
REFERENCES
4. Bobyleva, L.I., Rybina, G.V., and Srednev, S.S., Khim.
Prom st., 2002, no. 7, pp. 1 5.
5. Bobyleva, L.I., Kozlova, O.S., Rybina, G.V., and Mos-
kvichev, Yu.A., Zh. Anal. Khim., 2000, vol. 55, no. 10,
pp. 1102 1104.
1. Koren’kova, O.P. and Kvasha, V.V., Khim. Prom st.,
1961, no. 9, pp. 33 38.
2. Ufimtsev, A.V. and Kuzora, I.E., Khim. Prom st.,
1993, no. 11, pp. 555 557.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 76 No. 5 2003