咪唑 (啉)-2-羧酸盐作为潜在的/可热活化的有机小分子催化剂催化转酯反应

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

催化学报 ›› 2012, Vol. 33 ›› Issue (3): 502-507.DOI: 10.1016/S1872-2067(11)60353-7

咪唑 (啉)-2-羧酸盐作为潜在的/可热活化的有机小分子催化剂催化转酯反应

王燕芹1,2, 李振江1,*

1 南京工业大学生物与制药工程学院, 材料化学工程国家重点实验室, 江苏南京 210009; 2 南京林业大学理学院, 江苏南京 210037

收稿日期:2011-09-10 修回日期:2011-12-10 出版日期:2012-03-15 发布日期:2015-07-27

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

WANG Yanqin1,2, LI Zhenjiang1,*

1State Key Laboratory of Materials-Oriented Chemical Engineering, College of Biotechnology and Pharmaceutical Engineering, Nanjing University of Technology, Nanjing 210009, Jiangsu, China; 2College of Science, Nanjing Forestry University, Nanjing 210037, Jiangsu, China

Received:2011-09-10 Revised:2011-12-10 Online:2012-03-15 Published:2015-07-27

摘要/Abstract

摘要： 采用咪唑 (啉)-2-羧酸盐 (ImCO₂) 作为催化剂前驱体, 通过温度控制脱除 ImCO₂ 的 2-位羧酸根, 再原位释放出高活性的 N-杂环卡宾 (NHCs), 进而催化转酯反应. 研究了 NHCs 在苯甲酸乙酯与一元醇、二元醇及氨基醇反应体系中的催化活性. 结果表明, 在该体系中不需要选用活化酯为原料, 无需加入分子筛或加大醇酯比提高产率, 仅用少量催化剂 (0.5 mol%), 在较短时间内 (3 h), 即可使反应转化率达到 95%.

关键词: N-杂环卡宾, 有机小分子催化剂, 咪唑 (啉)-2-羧酸盐, 转酯反应, 非活性酯

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

王燕芹, 李振江. 咪唑 (啉)-2-羧酸盐作为潜在的/可热活化的有机小分子催化剂催化转酯反应[J]. 催化学报, 2012, 33(3): 502-507.

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.

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咪唑 (啉)-2-羧酸盐作为潜在的/可热活化的有机小分子催化剂催化转酯反应

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

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