ORGANIC
LETTERS
Cyclic Carbonate Formation from
Carbon Dioxide and Oxiranes in
Tetrabutylammonium Halides as
Solvents and Catalysts
Vincenzo Caló,* Angelo Nacci, Antonio Monopoli, and Antonello Fanizzi
Department of Chemistry, Istituto di Chimica dei Composti Organometallici
(Sezione di Bari), Via Amendola 173, UniVersity of Bari, 70126-Bari, Italy
calo@chimica.uniba.it
Received May 15, 2002
ABSTRACT
Epoxides dissolved in molten tetralkylammonium salts bearing halides as counterions are converted into cyclic carbonates under atmospheric
pressure of carbon dioxide. The reaction rate depends on the nucleophilicity of the halide ion as well as the structure of the cation.
The chemical fixation of CO2 onto organic compounds such
as epoxides, which affords cyclic carbonates, is an important
process (Scheme 1), as it allows the transformation of
Scheme 1
harmful waste such as CO2 into useful raw materials for
engineering plastics, cosmetics, and polar solvents.1,2
Many inorganic and organic compounds including amines,3
phosphanes,3 organotin halides,4 alkali metal salts,5 transition
(1) Behr, A. Carbon Dioxide ActiVation by Metal Complexes; VCH: New
York, 1988.
(2) Darensbourg, D. J.; Holtcamp, M. W. Coord. Chem. ReV. 1996, 153,
155-174.
(3) Brindöpke, G. German Pat. DE 3529263, 1987.
(4) Baba, A.; Nozaki, T.; Matsuda, H. Bull. Chem. Soc. Jpn. 1987, 60,
1552-1554.
(5) Kihara, N.; Hara, N.; Endo, T. J. Org. Chem. 1993, 58, 6198-6202.
10.1021/ol026189w CCC: $22.00 © 2002 American Chemical Society
Published on Web 06/29/2002
2002
Vol. 4, No. 15
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metal complexes,6-8 magnesium oxide,9 calcinated hydro-
talcites,10 and phthalocyaninatoaluminum in supercritical
carbon dioxide11 are known to catalyze activation of the CO2
molecule. More recently, propylene carbonate was synthe-
sized in imidazolium tetrafluoroborate as solvent under
electrochemical conditions.12,13 For these processes, high
temperatures, high pressures of CO2, and toxic polar solvents
such as DMF or CH2Cl2 have been thought to be necessary.
However, under these reaction conditions, some inactive or
polymerization-sensitive oxiranes can be hardly converted
to the corresponding cyclic carbonates.
We report a straightforward method for chemical fixation
of CO2 onto epoxides by simply dissolving these compounds
(6) Kruper, W. J.; Dellar, D. V. J. Org. Chem. 1995, 60, 725-727.
(7) Magdesieva, T. V.; Milovanov, S. V.; Lokshin, B. V.; Klemenkova,
Z. S.; Tomilova, L. G. Russ. Chem. Bull. 1998, 47, 2137-2145.
(8) Kim, H. S.; Kim, J. J.; Lee, B. G.; Jung, O. S.; Jang, H. G.; Kang,
S. O. Angew. Chem., Int. Ed. 2000, 39, 4096-4098.
(9) Yano, T.; Matsui, H.; Koike, T.; Ishiguro, H.; Fujihara, H.; Yoshihara,
M.; Maeshima, T. Chem. Commun. 1997, 1129-1130.
(10) Yamaguchi, K.; Ebitani, K.; Yoshida, T.; Yoshida, H.; Kaneda, K.
J. Am. Chem. Soc. 1999, 121, 4526-4527.
(11) Lu, X. B.; Pan, Y. Z.; Ji, D. F.; He, R. Chin. Chem. Lett. 2000, 11,
589.
(12) Deng, Y.; Peng, J. New J. Chem., 2001, 25, 639.
(13) Yang, H.; Gu, Y.; Deng, Y.; Shi, F. Chem. Commun. 2002, 274.
Table 1. Synthesis of Cyclic Carbonates in
Tetralkylammonium Salts
a Isolated yields are average of at least two runs; >95% pure as judged
by 1H NMR and GC. b As method A but with TBAB as solvent. c Catalyst
1. d Catalyst 2. e Catalyst 3.
in molten tetrabutylammonium bromide (TBAB) as solvent,
in the presence of CO2 at atmospheric pressure. Once the
reaction was complete, pure cyclic carbonates were isolated
by vacuum distillation or extraction with ethyl acetate, in
which the ionic liquid is insoluble. This procedure allowed
the recycling of the ammonium salt.14 Polymerization-
sensitive epoxides also reacted very well. For example, the
glycidyl methacrylate was converted into the corresponding
carbonate in 4 h without polymerization (Table 1, run 1).
A plausible mechanism for this reaction is the ring opening
of the epoxide by means of a nucleophilic attack by the
bromide ion, which leads to an oxy anion species affording
the corresponding cyclic carbonate after reaction with CO2
(Scheme 2).
This is conceivable15 since the anions may have greatly
enhanced nucleophilicity in the absence of other organic
(14) General Procedure. Method A: 20 g of epoxide and 50 g of a
mixture of TBAB and TBAI (1:1 w/w) were added to a Schlenk flask,
stirred, and heated at 120 °C under CO2. The reaction pressure (1 bar CO2)
was held constant by means of a CO2 reservoir connected to the flask. After
the proper reaction time, the flask was cooled and the carbonate was distilled
under reduced pressure or extracted with ethyl acetate, leaving the
ammonium salts, which were further recycled. Method B: 3 g of TBAI
dissolved in 30 g of epoxide were heated at 60 °C under CO2 as described
above. The carbonate was distilled or extracted with ethyl acetate.
(15) As a proof for this mechanism, we isolated, in some cases, a small
quantity of bromohydrines.
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Scheme 2
solvents due to low solvation.16 If so, the substitution in the
ammonium salt of a bromide ion by a more nucleophilic
iodide ion would yield better results such as an increase of
reaction rate.17-20 Indeed, by using a mixture of TBAB and
tetrabutylammonium iodide (TBAI), the conversion rate
increased as glycidyl methacrylate reacted fully in only 1 h
(Table 1, run 2, method A). As a clean chemical process
should require the lowest possible energy input and solvent
quantity, we tested the CO2 fixation method by dissolving
only 10% (w/w) of TBAI into liquid epoxides at 60 °C.
Though the rates were lower, all of the epoxides reacted well
to afford pure carbonates (method B).
In addition to the anion effect, we tested a possible role
exerted by the cation on this reaction. This was explored by
using the salts 1 and 2 and the poly(N-methyl-4-vinylpyri-
dinium) salt 3 as catalysts (10% w/w), which were found
inefficient at 60 °C (Figure 1). Furthermore 1 and 3
decomposed by increasing the temperature (Table 1, entries
14-16).
Figure 1.
We believe that the better performance of tetralkylammo-
nium salts as catalysts could be ascribed to the structural
differences among [NBu4]+ and [bmim]+ (1-butyl-3-meth-
(16) Reichardt, C. SolVents and SolVent Effects in Organic Chemistry,
2nd ed.; VCH: New York, 1988.
(17) Caló, V.; Nacci, A.; Lopez, L.; Mannarini, N. Tetrahedron Lett.
2000, 41, 8973-8976.
(18) Caló, V.; Nacci, A.; Lopez, L.; Napola, A. Tetrahedron Lett. 2001,
42, 4701-4703.
(19) Caló, V.; Nacci, A.;. Monopoli, A.; Lopez, L.; di Cosmo, A.
Tetrahedron 2001, 57, 6071-6077.
(20) Caló, V.; Nacci, A. Z. Naturforsch. 2001, 56a, 702-706.
(21) Gannon, T. J.; Law, G.; Watson, P. R.; Carmichael, A. J.; Seddon,
K. R. Langmuir 1999, 15, 8429-8434.
Org. Lett., Vol. 4, No. 15, 2002
ylimidazolium) or pyridinium cations, which could influence
the behavior of anions. Indeed, the bulkiness of the tetra-
hedral ammonium ion forces the bromide or iodide ion away
from the cation, and this less electrostatic interaction would
render these anions more nucleophilic. On the contrary, the
planar cations 1-3, by binding the anion tightly,21 would
decrease its availability for reaction with epoxides.
Org. Lett., Vol. 4, No. 15, 2002
Acknowledgment. This work has been supported, in part,
by Ministero dell’Università e della Ricerca Scientifica e
Tecnologica, Rome, and the University of Bari (National
Project: “Stereoselezione in Sintesi Organica: Metodologie
ed Applicazioni”).
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