RSC Advances
Paper
transferred to a 50 mL ask equipped with a magnetic stirrer
and automatic temperature control system for trans-
esterication reaction (Step 2), then reacted at 60 ꢀC for another
60 min. Aer the vessel was then cooled to room temperature,
the catalysts were distilled from the mixture, and the products
were analyzed by GC.
2011, 4, 42; (j) Z. H. Xiang, D. P. Cao, J. H. Lan,
W. C. Wang and D. P. Broom, Energy Environ. Sci., 2010, 3,
1469.
2 For recent reviews, see: (a) T. Sakakura, J. C. Choi and
H. Yasuda, Chem. Rev., 2007, 107, 2365; (b) Z. Z. Yang,
L. N. He, J. Gao, A. H. Liu and B. Yu, Energy Environ. Sci.,
2012, 5, 6602; (c) M. Mikkelsen, M. Jørgensen and
F. C. Krebs, Energy Environ. Sci., 2010, 3, 43; (d) M. Cokoja,
4. Conclusions
¨
C. Bruckmeier, B. Rieger, W. A. Herrmann and F. E. Kuhn,
We have developed a series of novel base-stable 2-hydrox-
ymethyl-functionalized ILs as catalysts for the synthesis of cyclic
carbonates from CO2 and epoxides without the use of any
co-catalyst or organic solvent. The effects of the types of cation
and anion of 2-hydroxymethyl-functionalized ILs, and other
reaction parameters on the reaction are investigated. In addi-
tion, the catalyst can be easily recovered by a distillation and
reused over six times without obvious loss of its catalytic
activity. The mechanistic details of the xation of CO2 with
epoxide into cyclic carbonate catalyzed by 2-hydroxymethyl-
functionalized ILs are elucidated by density functional theory.
The results demonstrate the xation of CO2 catalyzed by 2-
hydroxymethyl-functionalized ILs with less barrier compared to
process catalyzed by corresponding ILs without hydroxymethyl
group. Moreover, the 2-hydroxymethyl-functionalized ILs
combined with K2CO3 are effective for green synthesis of
dimethyl carbonate from CO2, ethylene oxide and methanol
without catalyst separation. The process reported here repre-
sents a simple, ecologically safer, cost-effective and energy-
saving route to organic carbonates from CO2.
Angew. Chem., Int. Ed., 2011, 50, 8510; (e) M. North,
R. Pasquale and C. Young, Green Chem., 2010, 12, 1514; (f)
D. J. Darensbourg and S. J. Wilson, Green Chem., 2012, 14,
2665; (g) M. O. Sonnati, S. Amigoni, E. P. Taffin de
Givenchy, T. Darmanin, O. Choulet and F. Guittard, Green
Chem., 2013, 15, 283.
3 (a) A. Decortes, A. M. Castilla and A. W. Kleij, Angew Chem.,
Int. Ed., 2010, 49, 9822; (b) T. Sakakura and K. Kohno,
Chem. Commun., 2009, 1312; (c) S. F. Yin and S. Shimada,
Chem. Commun., 2009, 1136.
4 T. Sakakura and K. Kohno, Chem. Commun., 2009, 1312.
5 (a) K. Yamaguchi, K. Ebitani, T. Yoshida, H. Yoshida and
K. Kaneda, J. Am. Chem. Soc., 1999, 121, 4526; (b) T. Yano,
H. Matsui, T. Koike, H. Ishiguro, H. Fujihara, M. Yoshihara
and T. Maeshima, Chem. Commun., 1997, 1129.
6 (a) N. Kihara, N. Hara and T. Endo, J. Org. Chem., 1993, 58,
6198; (b) L. P. Li, C. M. Wang, X. Y. Luo, G. K. Cui and
H. R. Li, Chem. Commun., 2010, 46, 5960.
7 (a) V. Calo, A. Nacci, A. Monopoli and A. Fanizzi, Org. Lett.,
2002, 4, 2561; (b) B. R. Buckley, A. P. Patel and
K. G. Wijayantha, Chem. Commun., 2011, 47, 11888.
8 (a) L. N. Han, S. W. Park and D. W. Park, Energy Environ.
Sci., 2009, 2, 1286; (b) Y. G. Zhang and J. Y. G. Chan,
Energy Environ. Sci., 2010, 3, 408; (c) J. J. Peng and
Y. Q. Deng, New J. Chem., 2001, 25, 639; (d) H. S. Kim,
J. J. Kim, H. Kim, H. G. H. Kim and H. G. Jang, J. Catal.,
2003, 220, 44; (e) H. Kawanami, A. Sasaki, K. Matsui and
Y. Ikushima, Chem. Commun., 2003, 896; (f) J. M. Sun,
S. I. Fujita, F. Y. Zhao and M. Arai, Green Chem., 2004, 6,
613; (g) H. C. Cho, H. S. Lee, J. Chun, S. M. Lee, H. J. Kim
and S. U. Son, Chem. Commun., 2011, 47, 917; (h)
Y. C. Zhao, C. Q. Yao, G. W. Chen and Q. Yuan, Green
Chem., 2013, 15, 446.
9 (a) M. North and R. Pasquale, Angew. Chem., Int. Ed., 2009,
48, 2946; (b) M. North, B. D. Wang and C. Young, Energy
Environ. Sci., 2009, 4, 4163; (c) J. Melendez and M. North,
Chem. Commun., 2009, 2577; (d) A. Buchard,
M. R. Kember, K. G. Sandeman and C. K. Williams, Chem.
Commun., 2011, 47, 212; (e) A. Decortes, M. M. Belmonte,
J. Benet-Buchholz and A. W. Kleij, Chem. Commun., 2011,
46, 4580.
Acknowledgements
Support of the grant from the National Basic Research Program
of China (2009CB219901) and National Natural Sciences
Foundation of China (no. 21003129, 21036007 and 20936005)
and the Key Laboratory for Green Chemical Technology of
Ministry of Education (Tianjin University) is gratefully
acknowledged.
References
1 (a) M. Aresta, Carbon dioxide as chemical feedstock, Willey-
VCH, Weinheim, 2010; (b) R. W. Dorner, D. R. Hardy,
F. W. Williams and H. D. Willauer, Energy Environ. Sci.,
2010, 3, 884; (c) C. Villiers, J. P. Dognon, R. Pollet,
´
P. Thuery and M. Ephritikhine, Angew. Chem., Int. Ed.,
2012, 51, 187; (d) C. Das Neves Gomes, O. Jacquet,
´
C. Villiers, P. Thuery, M. Ephritikhine and T. Cantat,
Angew. Chem., Int. Ed., 2012, 51, 187; (e) S. Bontemps,
L. Vendier and S. Sabo-Etienne, Angew. Chem., Int. Ed.,
¨
2012, 51, 1674; (f) A. Schafer, W. Saak, D. Haase and 10 (a) Y. Xie, Z. Zhang, T. Jiang, J. He, B. Han, T. Wu and
¨
T. Muller, Angew. Chem., Int. Ed., 2012, 51, 2981; (g)
K. L. Ding, Angew. Chem., Int. Ed., 2007, 46, 7255; (b)
H. S. Kim, J. J. Kim, H. N. Kwon, M. J. Chung, B. G. Lee
and H. G. Jang, J. Catal., 2002, 205, 226; (c) Y. B. Xiong,
H. Wang, R. M. Wang, Y. F. Yan, B. Zheng and Y. P. Wang,
Chem. Commun., 2010, 46, 339; (d) H. Zhou, W. Z. Zhang,
C. H. Liu, J. P. Qu and X. B. Lu, J. Org. Chem., 2008, 73, 8039.
D. J. Darensbourg, Chem. Rev., 2007, 107, 2365; (h)
N. MacDowell, N. Florin, A. Buchard, J. Hallett, A. Galindo,
G. Jackson, C. S. Adjiman, C. K. Williams, N. Shah and
P. Fennell, Energy Environ. Sci., 2010, 3, 1645; (i) Q. Wang,
J. Z. Luo, Z. Y. Zhong and A. Borgna, Energy Environ. Sci.,
2366 | RSC Adv., 2014, 4, 2360–2367
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