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RSC Advances
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DOI: 10.1039/C6RA13008A
ARTICLE
Journal Name
CO2 and higher temperature 120 °
C.24 This is, therefore, mainly filtration, the DMF in the filtrate was removed under reduced
because of
a
large steric hindrance to generate pressure. The residue was purified by silica gel column
less reactive chromatography (hexane/EtOAc = 1:1 v/v (2a 2d 2f) or 2:1 v/v
2g), thus affording the corresponding cyclic carbonate.
monoalkylcarbonate anions, and 1f is
a
,
,
chlorohydrin. In contrast, the yield of 2g further improved to
(2b, 2e,
78% by increasing the CO2 pressure to 5 atm. Unfortunately,
the reaction of
a 1,3-halohydrin failed to afford the
Acknowledgements
corresponding cyclic carbonate in this system (entry 8). This
result is in contrast with those reported by Zhang et al.20 They
achieved a high yield of six-membered carbonate from 3-
chloropropanol using Cs2CO3, as confirmed in the present
study (Table S2, entry 2). This is probably because of the so-
called “cesium effect” for nucleophilic reactions.25
The authors thank Mr. Makoto Tokunaga of Comprehensive
Analysis Center for Science, Saitama University, for his strong
support for the measurements and analysis of SEM and XRD.
References
1
For example: (a) M. Aresta and R. van Eldik, Eds., CO2
Chemistry, Volume 66 in Advances in Inorganic Chemistry,
Academic Press, San Diego, 2014; (b) B. M. Bhanage, and M.
Araki, Eds., Transformation and Utilization of Carbon Dioxide,
in Green Chemistry and Sustainable Technology, Springer,
Heidelberg, 2014.
Conclusions
In summary, a simple, economical, and selective synthesis of
five-membered carbonates was developed from 1,2-
halohydrins and CO2 using K2CO3, an inexpensive base, in good-
to-high yields under very mild reaction conditions (30 °C, 1 atm
2
(a) M. He, Y. Sun and B. Han, Angew. Chem. Int. Ed., 2013, 52,
9620-9633; (b) T. Sakakura, J.-C. Choi and H. Yasuda, Chem.
Rev. 2007, 107, 2365−2387; (c) T. Sakakura and K. Kohno,
Chem. Commun., 2009, 1312−1330.
M. A. Pacheco and C. L. Marshall, Energy & Fuels, 1997, 11,
2−29.
S. Fukuoka, M. Kawamura, K. Komiya, M. Tojo, H. Hachiya, K.
Hasegawa, M. Aminaka, H. Okamoto, I. Fukawa and S.
Konno, Green Chem. 2003, 5, 497−507.
(a) J. Tharun, G. Mathai, A. C. Kathalikkattil, R. Roshan, J.-Y.
Kwak and D.-W. Park, Green Chem., 2013, 15, 1673−1677; (b)
Z. Wu, H. Xie, X. Yu and E. Liu, ChemCatChem, 2013, 5,
1328−1333; (c) S. Liang, H. Liu, T. Jiang, J. Song, G Yang and
B. Han, Chem. Commun., 2011, 47, 2131−2133.
(a) D. S. Bai, S. H. Duan, L. Hai and H. W. Jing, ChemCatChem,
2012, 4, 1752-1758; (b) T. Ema, Y. Miyazaki, T. Taniguchi and
J. Takada, Green Chem., 2013, 15, 2485-2492.
(a) J. Melendez, M. North and P. Villuendas, Chem.
Commun., 2009, 2577-2579; (b) A. Decortes, A. M. Castilla
and A. W. Kleij, Angew. Chem. Int. Ed., 2010, 49, 9822-9837.
(a) K. Motokura, S. Itagaki, Y. Iwasawa, A. Miyaji and T. Baba,
Green Chem., 2009, 11, 1876−1880; (b) W.-L. Wong, P.-H.
Chan, Z.-Y. Zhou, K.-H. Lee, K.-C. Cheung and K.-Y. Wong,
ChemSusChem, 2008, 1, 67-70.
CO2) in DMF. Diverse monosubstituted carbonates were
prepared from the corresponding 1,2-halohydrins. This system
was also applicable for commercial “anhydrous” DMF, as
received without further purification or drying operations. The
SEM and XRD analysis of the precipitate showed the formation
of KHCO3 and KBr as the by-products, supporting the proposed
reaction mechanism for the coupling reaction. Other aprotic
polar solvents (CH3CN, DMSO) and even a DMF/H2O (1:1 v/v)
mixture were shown to be effective in this system. The
proposed protocol provides an alternative method for a simple
and commercially viable chemical fixation of CO2 into five-
membered cyclic carbonates, not six-membered cyclic
carbonates. A difference between K and Cs was observed by
comparing previous studies with this study.
3
4
5
6
7
8
Experimental section
All the starting materials and solvents were commercially
available. The highest quality products were purchased from
Sigma-Aldrich, Wako and Kanto and used as received except
dry DMF. Dry DMF was used after fractional distillation from
CaCl2 under high vacuum and stored over 4 Å molecular sieves.
The chemical yields refer to the yields of pure isolated
9
(a) Y. J. Kim and R. S. Varma, J. Org. Chem., 2005, 70,
7882−7891; b) H. Kawanami, A. Sasaki, K. Matsui and Y.
Ikushima, Chem. Commun., 2003, 896−897.
10 (a) A. Decortes, M. Martinez Belmonte, J. Benet-Buchholz
and A. W. Kleij, Chem. Commun., 2010, 46, 4580−4582; (b)
M. North and R. Pasquale, Angew. Chem. Int. Ed., 2009, 48,
2946-2946; (c) X.-B. Lu, B. Liang, Y.-J. Zhang, Y.-Z. Tian, Y.-M.
Wang, C.-X. Bai, H. Wang and R. Zhang, J. Am. Chem. Soc.,
2004, 126, 3732-3733.
11 (a) C.-X. Miao, J.-Q. Wang, Y. Wu, Y. Du and L.-N. He,
ChemSusChem, 2008, 1, 236−241; (b) L.-N. He, H. Yasuda and
T. Sakakura, Green Chem., 2003, 5, 92−94.
1
substances. All the H and 13C NMR data of the products were
consistent with previously reported data except 2f 14
.
(See
Supporting Information for the NMR data of 2d+2d′ and 2f).
The SEM images were recorded using a Hitachi S-3400N
instrument equipped with an EDX analytical system, Bruker
XFlash 5010, operated at 10 kV. The XRD patterns were
collected using a Bruker D2 Phaser operated at 30 kV and 10
mA equipped with monochromatized CuKα radiation.
12 Y. Kayaki, M. Yamamoto and T. Ikariya, Angew. Chem. Int.
Ed., 2009, 48, 4194−4197.
13 (a) J. Sun, L. J. Han, W.-G. Cheng, J.-Q. Wang, X.-P. Zhang and
S.-J. Zhang, ChemSusChem, 2011, 4, 502−507; (b) K. R.
Roshan, G. Mathai, J. Kim, J. Tharun, G.-A. Park and D.-W.
Park, Green Chem., 2012, 14, 2933−2940; (c) Y. Zhang, S. Yin,
S. Luo and C. T. Au, Ind. Eng. Chem. Res., 2012, 51,
3951−3957; (d) J. Sun, J. Wang, W. Cheng, J. Zhang, X. Li, S.
Zhang and Y. She, Green Chem., 2012, 14, 654−660.
General Experimental Procedure
In a 30 mL two-neck flask, K2CO3 (5.5 mmol) and DMF (5 mL)
were stirred at 30 °C for 4 h under an atmosphere of CO2
(99.999%, balloon). Then, the halohydrin (5 mmol) was added,
and the reaction mixture was stirred for 20 h at the same
temperature. After removing the precipitated solid by
4 | J. Name., 2012, 00, 1-3
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