DOI: 10.1002/cssc.

200700097

A Robust Ionic Liquid as Reaction Medium and Efficient Organocatalyst for

Carbon Dioxide Fixation
Wing-Leung Wong, Pak-Ho Chan, Zhong-Yuan Zhou, Kam-Han Lee, Kwong-Chak Cheung, and
Kwok-Yin Wong*[a]
The increasing production of carbon dioxide from industrial ac- and does not require the use of metals and organic solvents.
tivities has caused a variety of environmental problems such as This green catalytic system is generally thought to be promis-
global warming and acid rain over the past few decades. Such ing in the production of carbonates.[12]
environmental consequences have called for the development Herein, we report the construction of a novel and robust
of an effective approach in recent years to reducing this harm- ionic liquid 1Br3 that can function both as an efficient organo-
ful greenhouse gas. Transformation of carbon dioxide into in- catalyst and a reaction medium in the synthesis of cyclic carbo-
dustrially valued chemicals is generally regarded as an excel- nates with atmospheric carbon dioxide under low temperature
lent route in this respect because of its significant values in and pressure conditions (Scheme 2).
both environmental preservation and resource utilization.[1] To
this end, a variety of synthetic approaches that utilize CO2 as
the feedstock for producing organic carbonates have been de-
veloped.[2, 3] In particular, addition reaction of CO2 with epox-
ides to give cyclic carbonates with 100 % atom efficiency
(Scheme 1) is regarded as an efficient environmentally benign

Scheme 2. Synthetic route to ionic liquid 1Br3 (DPA = 2,2-dipyridylamine;

DIEA = N,N-diisopropylethylamine).

Scheme 1. Addition reaction of CO2 with epoxides with 100 % atom efficien-
cy. Ionic liquid 1Br3 can be easily obtained by a simple two-
step large-scale synthetic process from inexpensive starting
way for fixation of abundant CO2.[4] The resulting cyclic carbo- materials as shown in Scheme 2.[13] This approach was found
nates are valuable fine chemicals which are widely used as sol- to give 1Br3 in excellent yield (90 %) and high purity without
vents, electrolytes, starting materials in polycarbonate produc- purification by column chromatography (see Supporting Infor-
tion, and intermediates in the manufacture of pharmaceuticals mation). The ionic liquid was characterized as its tetrabromo-
and agricultural chemicals.[5] zincate salt by X-ray crystallography (Figure 1). The crystal
The addition reaction of CO2 with epoxides is known to be structure indicates that each of the two pyridine units of the
catalyzed by organic bases,[6] ammonium and phosphonium dipyridylamine is exclusively associated with the pyrrolidinium
salts,[7] metal halides,[8] metal oxides[9] and some transition- moiety through the formation of a covalent propylene bridge,
metal complexes.[10] Recent studies have shown that a number
of imidazolium ionic liquids can serve as an effective medium
for the transformation of CO2 to organic carbonates with cer-
tain metal halides as the catalyst/co-catalyst.[4e,f, 11] Despite this
encouraging observation, this catalytic system is less robust
and requires the use of heavy metals in the synthetic process,
thus reducing its applicability and environmental benignancy.
As such, we are interested in developing an efficient and envi-
ronmentally benign catalytic system that offers the advantages
of high reactivity and selectivity, easy separation and recycling,

[a] Dr. W.-L. Wong, Dr. P.-H. Chan, Prof. Z.-Y. Zhou, K.-H. Lee, Dr. K.-C. Cheung,
Prof. K.-Y. Wong
Department of Applied Biology and Chemical Technology
The Hong Kong Polytechnic University
Hung Hom, Kowloon, Hong Kong (China)
Fax: (+ 852) 2364-9932 Figure 1. ORTEP plot of (1)2ACHTUNGRE(ZnBr4)3 (30 % probability level for the ellipsoids).
E-mail: bckywong@polyu.edu.hk Selected bond lengths [F]: N1C1 1.316(3), N1C14 1.300(3), N2C1 1.375(3),
Supporting information for this article is available on the WWW under N2C5 1.364(3), N2C6 1.484(3), N4C14 1.387(3), N4C18 1.409(3), N4
http://www.chemsuschem.org or from the author. C19 1.455(3).

ChemSusChem 2008, 1, 67 70 I 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 67
with an average C N bond length of 1.470 F (N2C6 and N4
C19). Interestingly, the C N bonds of the pyridylamine unit
(Figure 1, N1C1 1.316(3) and N1C14 1.300(3) F) exhibit strong
double-bond character, as revealed by their bonds being short-
er than those in 2,2-dipyridylamine (DPA; NC 1.380 F).[14] In
addition, the crystal data of 13 + indicate a number of torsion
angles within the molecule, implying that the ionic liquid is
conformationally flexible.
The ability of 1Br3 to catalyze the chemical fixation of CO2
was demonstrated with 2-(phenoxymethyl)oxirane as the sub-
strate. Ionic liquid 1Br3 is a hygroscopic solid at room temper-
ature but is readily liquefied in the presence of 2 % (w/w) of
water at 80 8C. With 1Br3 as the catalyst and reaction medium,
the epoxide was converted effectively into 3-phenoxy-1,2-pro-
pylene carbonates within 0.5 h under low CO2 pressures
(0.5 MPa). The product was isolated in 82 % yield and with over
99 % selectivity after extraction with hot ethyl acetate. Both
the catalyst and the solvents were reused after separation. The
effects of varying the reaction time and pressure on the cata-
lytic activity of 1Br3 were then examined. When the reaction
time was further extended to 1 h, the isolated yield was in-
creased to 90 % under similar reaction conditions (Table 1,
Table 1. Addition reaction of CO2 with epoxides in ionic liquid 1Br3.[a]
Entry Epoxide[b] P [MPa][c] t [h] Yield [%][d]
1 0.5 1 90
2 1.5 0.5 98
3 1.5 0.5 98
4 1.5 2 91
5 1.5 2 85
6 3.0 3 92
7 4.0 3 99
8 3.0 3 80
9 3.0 3 58
[a] Reaction conditions: 1Br3 (2.7 g), water (60 mL; 2 % w/w), 80 8C. No
metal salt was used in the experiments. The ionic liquid was reused after
each experiment. [b] 8 mmol of epoxides used in each experiment.
[c] Compressed CO2 was charged directly into the autoclave at room tem-
perature. [d] Yields of isolated product. Selectivity of the cyclic carbonate
was over 99 % in all cases (based on GC-MS).
entry 1). Moreover, an increase in the CO2 pressure was found
to speed up the reaction and further improve the yield. The re-
action was complete within 0.5 h, with 98 % yield of isolated
product and over 99 % selectivity observed as the CO2 pressure
was increased from 0.5 to 1.5 MPa (Table 1, entry 2). These re-
sults indicate that 1Br3 is a very efficient organocatalyst and
reaction medium for synthesizing cyclic carbonates with CO2
as the feedstock under mild reaction conditions.
68 www.chemsuschem.org I 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
The catalytic activity of 1Br3 against other terminal epoxides
was also investigated. With polar epoxides such as epichloro-
hydrin, 1Br3 is capable of producing cyclic carbonates efficient-
ly in a short time (0.5 h) under 1.5 MPa of CO2 (98 % yield of
isolated product; Table 1, entry 3). The transformation of 2-
benzyloxirane, which is a relatively bulky and nonpolar epox-
ide, was also found to be efficient as the reaction proceeded
for 2 h under 1.5 MPa of CO2 ; the yield of the isolated cyclic
carbonates reached 91 % (Table 1, entry 4). With unreactive sty-
rene oxide, a good yield (85 %) was also obtained under mild
conditions (Table 1, entry 5).
Also, the ionic liquid was found to be an efficient catalyst
for synthesizing propylene carbonate, an important industrial
chemical, from propylene oxide under mild conditions. Under
3.0 MPa of CO2, a high yield (92 %) of propylene carbonate was
obtained within 3 h (Table 1, entry 6). The productivity was fur-
ther increased to 99 % when increasing the CO2 pressure from
3.0 to 4.0 MPa (Table 1, entry 7). For other aliphatic terminal
epoxides, the ionic liquid shows moderate catalytic activity
(Table 1, entries 8, 9). The reaction of 2-ethyloxirane with CO2
resulted in 80 % yield of cyclic carbonate under 3.0 MPa of CO2
(Table 1, entry 8). For the long-chain aliphatic epoxide 2-buty-
loxirane, the yield of isolated product was found to be 58 %
under similar conditions (Table 1, entry 9). The reduced produc-
tivity in the addition reaction of CO2 is presumably caused by
the lower solubility of the long-chain aliphatic epoxides in the
highly polar ionic liquid medium.
Taking these interesting results together, ionic liquid 1Br3
can serve as an efficient catalyst and reaction medium in the
transformation of a variety of epoxides to cyclic carbonates
under atmospheric CO2 at low pressures and temperatures.
Moreover, the ionic liquid functions effectively without the aid
of heavy metals and organic solvents, thus increasing its ap-
plicability as a green organocatalyst in the industrial produc-
tion of cyclic carbonates under mild conditions.
To investigate the robustness and recycling ability of 1Br3,
recycling studies were performed. Ionic liquid 1Br3 collected
after the experiments (Table 1) was reused to catalyze the addi-
tion reaction of 2-(phenoxymethyl)oxirane under 1.5 MPa of
CO2 at 80 8C for 0.5 h for another eight cycles, and the yield of
isolated product in each experiment was determined.[15] The
yields were found to be very similar in all cases, with an aver-
age of 94 % (Figure 2). The difference in the yields for the first
and eighth cycle was found to be less than 2 %. This observa-
tion strongly suggests that the ionic liquid is a very robust or-
ganocatalyst and reaction medium, which can be recycled con-
stantly without any significant loss in its catalytic activity.[16]
The reaction mechanism for the addition reaction of CO2
with epoxides using quaternary onium salts as the catalyst has
been investigated in recent studies.[7a,b, 11] Ionic liquid 1Br3,
which contains quaternary ammonium groups, appears to
follow the Lewis acidbase catalytic mechanism in the reaction.
The mechanism involves Lewis acid activation of the epoxide
by the ionic liquid cation and nucleophilic attack by the Lewis
base (Br ) to ring-open the epoxide to form an oxy-anion spe-
cies, which then further reacts with CO2 to give a cyclic carbon-
ate as the product after intramolecular cyclic elimination.
ChemSusChem 2008, 1, 67 70

Figure 2. Recycling study of 1Br3 in the addition reaction CO2 with 2-(phe-
noxymethyl)oxirane.
Cation 13 + is presumably a very good Lewis acid that renders
this ionic liquid an efficient catalyst for the activation of epox-
ides in the addition reaction with CO2.
In conclusion, we have successfully prepared a new ionic
liquid that can function both as an organocatalyst and a reac-
tion medium. This ionic liquid efficiently catalyzes the green
synthesis of cyclic carbonates with CO2 as the feedstock under
mild conditions, without requiring metal salts. Moreover, the
ionic liquid is very robust and can be recycled and reused con-
stantly without showing any significant loss in its catalytic ac-
tivity. These advantageous properties render the ionic liquid a
promising organocatalyst in the chemical fixation of carbon di-
oxide.
Experimental Section
Experimental details for the synthesis of the ionic liquid, X-ray char-
acterization, and the catalytic studies are provided in the Support-
ing Information.
General Procedure for the Catalytic Addition of Epoxides
with CO2 in 1Br3
The epoxide (8 mmol), ionic liquid 1Br3 (2.7 g, 4 mmol), and deion-
ized water (60 mL, 2 % w/w of 1Br3) were thoroughly mixed in an
autoclave. The compressed CO2 was directly charged into the auto-
clave at room temperature and atmosphere. The mixture was al-
lowed to react at 80 8C for 0.53 h in the autoclave with stirring.
After completion of the reaction, the autoclave was cooled using
cold water and the pressure was released slowly. The reaction mix-
ture was extracted with hot ethyl acetate (15 mL), and the solution
was then decanted from the autoclave. The extraction process was
repeated five times to ensure complete removal of the products.
The cyclic carbonates were characterized by GC-MS and 1H and
13
C NMR spectroscopy. The residue in the autoclave was recycled
and reused for the next run after removal of the ethyl acetate
under vacuum. The ethyl acetate solvent was collected and reused
for extraction.
Crystal data for (1)2ACHTUNGRE(ZnBr4)3 : C54H90Br12N10O1Zn3, Mr = 2050.39, triclin-
ic, space group P-1, a = 9.7917(15) F, b = 15.325(2) F, c =
25.513(4) F, a = 81.245(3)8, b = 81.001(3)8, g = 79.258(3)8, V =
3685.0(10) F3, T = 294(2) K, Z = 2, 1 = 1.849 Mg m 3, m = 7.516 mm 1;
25 023 reflections collected, 16 721 independent reflections (R(int) =
ChemSusChem 2008, 1, 67 70 I 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
0.1373), final R values [I > 2s(I)]: R1 = 0.0834, wR2 = 0.1615; R indices
(all data): R1 = 0.3173, wR2 = 0.2279. CCDC-653539 contains the sup-
plementary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgements
We acknowledge support from The Hong Kong Polytechnic Uni-
versity and the Research Grants Council (grant no. PolyU 5015/
05P). W.-L.W. acknowledges the award of a postdoctoral fellow-
ship administered by the Research Committee of The Hong Kong
Polytechnic University.
Keywords: carbon dioxide fixation carbonates
green chemistry ionic liquids organocatalysis
[1] a) CO2 Conversion and Utilization (Eds: C.-S. Song, A. M. Gaffney, K. Fuji-
moto), ACS, Washington, DC, 2002; b) S.-I. Fujita, B. M. Bhanage, M.
Arai, in Progress in Catalysis Research (Ed: L. P. Bevy), Nova Science Pub-
lishers, New York, 2005, chapter 3, pp. 5779; c) C.-S. Song, Cat. Today
2006, 115, 232; d) T. Sakakura, J.-C. Choi, H. Yasuda, Chem. Rev. 2007,
107, 23652387.
[2] a) A. Behr, Angew. Chem. 1988, 100, 681698; Angew. Chem. Int. Ed. Engl.
1988, 27, 661678; b) D. H. Gibson, Chem. Rev. 1996, 96, 20632095;
c) W. Leitner, Coord. Chem. Rev. 1996, 153, 257284; d) X. L. Yin, J. R.
Moss, Coord. Chem. Rev. 1999, 181, 2759; e) D. Walther, M. Ruben, S.
Rau, Coord. Chem. Rev. 1999, 182, 67100; f) H. Arakawa, M. Aresta, J. N.
Armor, M. A. Barteau, E. J. Beckman, A. T. Bell, J. E. Bercaw, C. Creutz, E.
Dinjus, D. A. Dixon, K. Domen, D. L. DuBois, J. Eckert, E. Fujita, D. H.
Gibson, W. A. Goddard, D. W. Goodman, J. Keller, G. J. Kubas, H. H.
Kung, J. E. Lyons, L. E. Manzer, T. J. Marks, K. Morokuma, K. M. Nicholas,
R. Periana, L. Que, J. Rostrup-Nielson, W. M. H. Sachtler, L. D. Schmidt, A.
Sen, G. A. Somorjai, P. C. Stair, B. R. Stults, W. Tumas, Chem. Rev. 2001,
101, 953996.
[3] a) Carbon Dioxide Recovery and Utilization (Ed: M. Aresta), Kluwer Aca-
demic Publishers, Dordrecht, 2003; b) C. M. Rayner, Org. Process Res.
Dev. 2007, 11, 121132; c) S. K. Ritter, Chem. Eng. News 2007, 85, 1117.
[4] a) D. J. Darensbourg, M. W. Holtcamp, Coord. Chem. Rev. 1996, 153, 155
174; b) A.-A. G. Shaikh, S. Sivaram, Chem. Rev. 1996, 96, 951976; c) M.
Yoshida, M. Ihara, Chem. Eur. J. 2004, 10, 28862893; d) G. W. Coates,
D. R. Moore, Angew. Chem. 2004, 116, 67846806; Angew. Chem. Int. Ed.
2004, 43, 66186639; e) J.-M. Sun, S.-I. Fujita, M. Arai, J. Organomet.
Chem. 2005, 690, 34903497; f) S.-J. Zhang, Y.-H. Chen, F.-W. Li, X.-M. Lu,
W.-B. Dai, R. Mori, Cat. Today 2006, 115, 6169.
[5] a) X.-D. Xu, J. A. Moulijn, Energy Fuels 1996, 10, 305325; b) J. P. Parrish,
R. N. Salvatore, K. W. Jung, Tetrahedron 2000, 56, 82078237; c) J. H.
Clements, Ind. Eng. Chem. Res. 2003, 42, 663674.
[6] a) H. Kawanami, Y. Ikushima, Chem. Commun. 2000, 20892090; b) Y. M.
Shen, W. L. Duah, M. Shi, Adv. Synth. Catal. 2003, 345, 337340; c) A. Bar-
barini, R. Maggi, A. Mazzacani, G. Mori, G. Sartori, R. Sartrio, Tetrahedron
Lett. 2003, 44, 29312934.
[7] a) V. CalS , A. Nacci, A. Monopoli, A. Fanizzi, Org. Lett. 2002, 4, 2561
2563; b) T. Chang, H.-W. Jing, L.-L. Jin, W.-Y. Qiu, J. Mol. Catal. A 2007,
264, 241247; c) W.-N. Sit, S.-M. Ng, K.-Y. Kwong, C.-P. Lau, J. Org. Chem.
2005, 70, 85838586; d) T. Takahashi, T. Watahiki, S. Kitazume, H.
Yasuda, T. Sakakura, Chem. Commun. 2006, 16641666; e) L.-N. He, H.
Yasuda, T. Sakakura, Green Chem. 2003, 5, 9294.
[8] a) M. Ratzenhofer, H. Kisch, Angew. Chem. 1980, 92, 303; Angew. Chem.
Int. Ed. Engl. 1980, 19, 317318; b) N. Kihara, N. Hara, T. Endo, J. Org.
Chem. 1993, 58, 61986202.
[9] a) T. Yano, H. Matsui, T. Koike, H. Ishiguro, H. Fujihara, M. Yoshihara, T.
Maeshima, Chem. Commun. 1997, 11291130; b) K. Yamaguchi, K. Ebita-
ni, T. Yoshida, H. Yoshida, K. Kaneda, J. Am. Chem. Soc. 1999, 121, 4526
4527; c) B. M. Bhanage, S.-I. Fujita, Y. Ikushima, M. Arai, Appl. Catal. A
2001, 219, 259266; d) H. Yasuda, L.-N. He, T. Sakakura, J. Catal. 2002,
www.chemsuschem.org 69
 209, 547550; e) J. Beckmann, D. Dakternieks, A. Duthie, N. A. Lewcen-
ko, C. Mitchell, Angew. Chem. 2004, 116, 68516853; Angew. Chem. Int.
Ed. 2004, 43, 66836685.
[10] a) W. J. Kruper, D. V. Dellar, J. Org. Chem. 1995, 60, 725727; b) F.-W. Li,
C.-G. Xia, L.-W. Xu, W. Sun, G.-X. Chen, Chem. Commun. 2003, 2042
2043; c) Y.-M. Shen, W.-L. Duan, M. Shi, J. Org. Chem. 2003, 68, 1559
1562; d) M.-L. Man, K.-C. Lam, W.-N. Sit, S.-M. Ng, Z.-Y. Zhou, Z.-Y Lin, C.-
P. Lau, Chem. Eur. J. 2006, 12, 10041015; e) W.-L. Wong, K.-C. Cheung,
P.-H. Chan, Z.-Y. Zhou, K.-H. Lee, K.-Y. Wong, Chem. Commun. 2007,
21752177.
[11] a) J.-J. Peng, Y.-Q. Deng, New J. Chem. 2001, 25, 639941; b) H. S. Kim,
J. J. Kim, H. Kim, H. G. Jang, J. Catal. 2003, 220, 4446; c) H. Kawanami,
A. Sasaki, K. Matsuia, Y. Ikushima, Chem. Commun. 2003, 896897; d) F.-
W. Li, L.-F. Xiao, C.-G. Xia, B. Hu, Tetrahedron Lett. 2004, 45, 83078310;
e) Y. J. Kim, R. S. Varma, J. Org. Chem. 2005, 70, 78827891.
70 www.chemsuschem.org I 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
[12] a) F. Cozzi, Adv. Synth. Catal. 2006, 348, 13671390; b) M. Avalos, R. Ba-
biano, P. Cintas, J. L. JimTnez, J. C. Palacios, Angew. Chem. 2006, 118,
40084012; Angew. Chem. Int. Ed. 2006, 45, 39043908.
[13] A. P. Gray, D. C. Schlieper, E. E. Spinner, C. J. Cavallito, J. Am. Chem. Soc.
1955, 77, 36483649.
[14] J. E. Johnson, R. A. Jacobson, Acta Crystallogr. 1973, B29, 16691674.
[15] After eight cycles, the yield of isolated product was 94 %.
[16] All the reactions described herein were performed with the same
sample of ionic liquid, so that the ionic liquid catalyst was reused over
20 times for the experiments.
Received: August 27, 2007
Revised: September 21, 2007
Published online on December 4, 2007
ChemSusChem 2008, 1, 67 70