Imidazol(in)ium-2-carboxylates as Latent, Thermally Activated Organocatalysts for Transesterification Reactions

doi:10.1016/S1872-2067(11)60353-7

Abstract

Abstract: 1,3-Disubstituted imidazol(in)ium-2-carboxylates (ImCO₂) were used as precatalysts for transesterification reactions of unactivated ethyl benzoate with monohydric alcohols, dihydric alcohols, and amino alcohols. Highly active N-heterocyclic carbenes (NHCs) are usually not used directly as catalysts because of their air and moisture sensitivity. Here they were liberated in situ by thermal decarboxylation of ImCO₂ at designated temperatures. The results showed that the yield of the reactions reached up to 95% within 3 h using only 0.5 mol% catalyst. No active enol esters, molecular sieves, or a 20-fold excess of alcohol were used to drive the reaction to completion. It was proved that unsaturated imidazolium-2-carboxylates have a better activity than saturated species in this type of reaction. Different types of substituting groups of ImCO₂exhibited varied transesterification activity.

Key words: N-heterocyclic carbene, organocatalyst, imidazol(in)ium-2-carboxylate, transesterification, unactivated ethyl benzoate

WANG Yan-Qin, LI Zhen-Jiang. Imidazol(in)ium-2-carboxylates as Latent, Thermally Activated Organocatalysts for Transesterification Reactions[J]. Chinese Journal of Catalysis, 2012, 33(3): 502-507.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(11)60353-7

https://www.cjcatal.com/EN/Y2012/V33/I3/502

References

1 Otera J. Chem Rev, 1993, 93: 1449
2 Grasa G A, Singh R, Nolan S P. Synthesis, 2004: 971
3 Crawford E, Lohr T, Leitao E M, Kwok S, Mclndoe J S. Dal-ton Trans, 2009: 9110
4 Buchard A, Platel R H, Auffrant A, Le Goff X F, Le Floch P, Wlliams C K. Organometallics, 2010, 29: 2892
5 Ando Y, Haba Y, Soma K, Hiraoka Y, Takatsu T. Lipids, 2007, 42: 955
6 Bourissou D, Guerret O, Gabbaï F P, Bertrand G. Chem Rev, 2000, 100: 39
7 顾绍金, 倪鹏, 陈万芝. 催化学报 (Gu Sh J, Ni P, Chen W Zh. Chin J Catal), 2010, 31: 875
8 Enders D, Niemeier O, Henseler A. Chem Rev, 2007, 107: 5606
9 Kamber N E, Jeong W, Waymouth R M, Pratt R C, Lohmeijer B G G, Hedrick J L. Chem Rev, 2007, 107: 5813
10 Grasa G A, Kissling R M, Nolan S P. Org Lett, 2002, 4: 3583
11 Nyce G W, Lamboy J A, Connor E F, Waymouth R M, Hedrick J L. Org Lett, 2002, 4: 3587
12 王燕芹, 李振江, 郭畅. 化学进展 (Wang Y Q, Li Zh J, Guo Ch. Progr Chem), 2010, 22: 433
13 Wang X N, Lü H, Huang X L, Ye S. Org Biomol Chem, 2009, 7: 346
14 Kankala S, Edulla R, Modem S, Vadde R, Vasam C S. Tetra-hedron Lett, 2011, 52: 3828
15 Trnka T M, Morgan J P, Sanford M S, Wilhelm T E, Scholl M, Choi T-L, Ding S, Day M W, Grubbs R H. J Am Chem Soc, 2003, 125: 2546
16 Coulembier O, Dove A P, Pratt R C, Sentman A C, Culkin D A, Mesponille L, Dubois P, Waymouth R M, Hedrick J L. Angew Chem, Int Ed, 2005, 44: 4964
17 Nyce G W, Csihony S, Waymouth R M, Hedrick J L. Chem Eur J, 2004, 10: 4073
18 Duong H A, Tekavec T N, Arif A M, Louie J. Chem Commun, 2004: 112
19 Voutchkova A M, Feliz M, Clot E, Eisenstein O, Crabtree R H. J Am Chem Soc, 2007, 129: 12834
20 Bantu B, Manohar P G, Wurst K, Decker U, Schmidt A M, Buchmeiser M R. Eur J Inorg Chem, 2009: 1970
21 Zhou H, Zhang W Z, Liu C H, Qu J P, Lu X B. J Org Chem, 2008, 73: 8039
22 Kayaki Y, Yamamoto M, Ikariya T. Angew Chem, Int Ed, 2009, 48: 4194
23 Pinaud J, Vignolle J, Gnanou Y, Taton D. Macromolecules, 2011, 44: 1900
24 Bantu B, Pawar G M, Decker U, Wurst K, Schmidt A M, Buchmeiser M R. Chem Eur J, 2009, 15: 3103
25 李振江, 王燕芹, 郭畅, 宋萍, 盛世川, 黄和, 应汉杰, 欧阳平凯 (Li Zh J, Wang Y Q, Guo Ch, Song P, Sheng Sh Ch, Huang H, Ying H J, Ouyang P K). CN 200810146619. 8. 2011
26 李振江, 王燕芹, 郭畅, 宋萍, 盛世川, 黄和, 应汉杰, 欧阳平凯 (Li Zh J, Wang Y Q, Guo Ch, Song P, Sheng Sh Ch, Huang H, Ying H J, Ouyang P K). CN 200810146617. 9. 2011
27 Arduengo III A J, Krafczyk R, Schmutzler R, Craig H A, Go-erlich J R, Marshall W J, Unverzagt M. Tetrahedron, 1999, 55: 14523
28 Saba S, Brescia A, Kaloustian M K. Tetrahedron Lett, 1991, 32: 5031
29 Delaude L, Szypa M, Demonceau A, Noels A F. Adv Syn Catal, 2002, 344: 749
30 Kliegman J M, Barnes R K. J Org Chem, 1970, 35: 3140
31 Dzyuba S V. PhD Dissertation, Texas Tech University, Ann Arbor, USA, 2002
32 Wanzlick H W, Kleiner H J. Angew Chem, Int Ed, 1961, 73: 493
33 Magill A M, Cavell K J, Yates B F. J Am Chem Soc, 2004, 126: 8717
34 Huang J K, Stevens E D, Nolan S P, Petersen J L. J Am Chem Soc, 1999, 121: 2674
35 Kim Y-J, Streitwieser A. J Am Chem Soc, 2002, 124: 5757
36 Movassaghi M, Schmidt M A. Org Lett, 2005, 7: 2453

[1]	Gong Zhang, Wei-Song Zhang, Xiao-Yu Wang, Yang Yang, Ding-Wei Ji, Boshun Wan, Qing-An Chen. Ni-catalyzed unnatural prenylation and cyclic monoterpenation of heteroarenes with isoprene [J]. Chinese Journal of Catalysis, 2023, 49(6): 123-131.
[2]	Lizhu Chen, Xiaojun Su, Jonah W. Jurss. Electrocatalytic hydrogen evolution from water at low overpotentials with cobalt complexes supported by redox-active bipyridyl-NHC donors [J]. Chinese Journal of Catalysis, 2022, 43(12): 3187-3194.
[3]	Yuanyuan Jiang, Ruru Zhou, Huaiyuan Zhao, Boyong Ye, Yihua Long, Zhengbao Wang, Zhaoyin Hou. A highly active and stable organic-inorganic combined solid acid for the transesterification of glycerol under mild conditions [J]. Chinese Journal of Catalysis, 2021, 42(10): 1772-1781.
[4]	Justina Gaidukevič, Jurgis Barkauskas, Anna Malaika, Paulina Rechnia-Gorący, Aleksandra Możdżyńska, Vitalija Jasulaitienė, Mieczysław Kozłowski. Modified graphene-based materials as effective catalysts for transesterification of rapeseed oil to biodiesel fuel [J]. Chinese Journal of Catalysis, 2018, 39(10): 1633-1645.
[5]	Yunhui Liao, Feng Li, Xin Dai, Ning Zhao, Fukui Xiao. Solid base catalysts derived from Ca-M-Al (M=Mg, La, Ce, Y) layered double hydroxides for dimethyl carbonate synthesis by transesterification of methanol with propylene carbonate [J]. Chinese Journal of Catalysis, 2017, 38(11): 1860-1869.
[6]	Wei Wang, Zhenxin Xu, Zhanglong Guo, Chengfa Jiang, Wei Chu. Layered double hydroxide and related catalysts for hydrogen production and a biorefinery [J]. Chinese Journal of Catalysis, 2015, 36(2): 139-147.
[7]	Liping Zheng, Shuixin Xia, Xiuyang Lu, Zhaoyin Hou. Transesterification of glycerol with dimethyl carbonate over calcined Ca-Al hydrocalumite [J]. Chinese Journal of Catalysis, 2015, 36(10): 1759-1765.
[8]	Fubao Zhang, Xiaopeng Yu, Fei Ma, Xiangui Yang, Jing Hu, Zhiyong Deng, Gongying Wang. Transesterification of dimethyl oxalate with phenol over a MoO₃/SiO₂ catalyst prepared by thermal spreading [J]. Chinese Journal of Catalysis, 2014, 35(7): 1043-1053.
[9]	Petr Kutálek, Libor Čapek, Lucie Smoláková, David Kubička, Martin Hájek. Aspects of stability of K/Al₂O₃ catalysts for the transesterification of rapeseed oil in batch and fixed-bed reactors [J]. Chinese Journal of Catalysis, 2014, 35(7): 1084-1090.
[10]	YuxuanYi, Yue Shen, Jiankui Sun, Bo Wang, Feng Xu, Runcang Sun. Basic ionic liquids promoted the synthesis of glycerol 1,2-carbonate from glycerol [J]. Chinese Journal of Catalysis, 2014, 35(5): 757-762.
[11]	Xianfeng Fu, Jianyong Zheng, Xiangxian Ying, Hongde Yan, Zhao Wang. Investigation of Lipozyme TL IM-catalyzed transesterification using ultraviolet spectrophotometric assay [J]. Chinese Journal of Catalysis, 2014, 35(4): 553-559.
[12]	Rongzhi Tang, Tong Chen, Yong Chen, Yuanzhuo Zhang, Gongying Wang. Core-shell TiO₂@SiO₂ catalyst for transesterification of dimethyl carbonate and phenol to diphenyl carbonate [J]. Chinese Journal of Catalysis, 2014, 35(4): 457-461.
[13]	Xi Zhou, Xin Ge, Rongzhi Tang, Tong Chen, Gongying Wang. Preparation and catalytic property of modified multi-walled carbon nanotube-supported TiO₂ for the transesterification of dimethyl carbonate with phenol [J]. Chinese Journal of Catalysis, 2014, 35(4): 481-489.
[14]	Liping Zheng, Shuixin Xia, Zhaotong Hou, Mengyuan Zhang, Zhaoyin Hou. Transesterification of glycerol with dimethyl carbonate over Mg-Al hydrotalcites [J]. Chinese Journal of Catalysis, 2014, 35(3): 310-318.
[15]	DU Ze-Xue, TANG Zhong, WANG Hai-Jing, ZENG Jian-Li, CHEN Yan-Feng, MIN En-Ze. Research and development of a sub-critical methanol alcoholysis process for producing biodiesel using waste oils and fats [J]. Chinese Journal of Catalysis, 2013, 34(1): 101-115.