催化学报

催化学报 ›› 2012, Vol. 33 ›› Issue (5): 891-897.DOI: 10.3724/SP.J.1088.2012.11213

• 研究论文 • 上一篇    下一篇

多壁碳纳米管固载金鸡纳生物碱季铵盐类手性相转移催化剂的制备及其催化烷基化反应性能

刘健1, 刘2,a, 石鑫1,b, 杨启华2,c   

  1. 1辽宁师范大学化学化工学院功能材料化学研究所, 辽宁大连 116029; 2中国科学院大连化学物理研究所催化基础国家重点实验室, 辽宁大连 116023
  • 收稿日期:2011-12-10 修回日期:2012-03-02 出版日期:2012-05-09 发布日期:2012-05-09

Immobilization of Cinchona Quaternary Ammonium Salts as the Chiral Phase Transfer Catalysts on Multi-walled Carbon Nanotubes and Their Application in Enantioselective Alkylation

LIU Jian1, LIU Yan2,a, SHI Xin1,b, YANG Qihua2,c   

  1. 1Institute of Chemistry for Functionalized Materials, School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, Liaoning, China; 2State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
  • Received:2011-12-10 Revised:2012-03-02 Online:2012-05-09 Published:2012-05-09

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摘要： 制备了多壁碳纳米管 (MWCNTs) 固载的金鸡纳生物碱季铵盐类手性相转移催化剂 PTC-1/MWCNTs, 并用于催化 N-二苯亚甲基-甘氨酸叔丁酯的不对称烷基化反应中. 采用紫外-可见光谱系统研究了五种有机溶剂对 PTC-1 在 MWCNTs 上吸附和脱附的影响. 结果表明, 在甲苯中, MWCNTs 对 PTC-1 的吸附率最高 (53%), 而在三氯甲烷中 PTC-1 的脱附率最低 (仅为 0.75%). PTC-1/MWCNTs 催化剂在催化 N-二苯亚甲基-甘氨酸叔丁酯和不同卤代烃的不对称烷基化反应中, 所得产物的收率和对映体选择性都较高, 而且该催化剂可回收循环使用, 说明 PTC-1 经 MWCNTs 固载后, 仍能够有效地催化多种卤代烃的不对称烷基化反应.

关键词: 多壁碳纳米管, 手性相转移催化剂, 金鸡纳生物碱, 吸附, 不对称烷基化反应

Abstract: The pyrene-tagged cinchona quaternary ammonium salt, the chiral phase transfer catalysts (PTC-1), was synthesized and immobilized on multi-walled carbon nanotubes (MWCNTs). The new catalysts (PTC-1/MWCNTs) were employed in enantioselective alkylation of N-(diphenylmethyene)glycine tert-butyl ester. UV-Vis absorption spectra show the effect of different organic solvents on the adsorption and desorption of PTC-1 onto and from MWCNTs, respectively. The results show that 5.3 mg PTC-1 can be loaded on 10 mg MWCNTs in toluene, and 0.02025 mg PTC-1 was desorbed from 12.7 mg PTC-1/MWCNTs when washed by CHCl3. In the enantioselective alkylation of different halohydrocarbons with N-(diphenylmethyene)glycine tert-butyl ester using PTC-1/MWCNTs as a catalyst, the alkylating products were obtained with high yield and ee value. Furthermore, PTC-1/MWCNTs catalyst can be recovered and used repeatedly. PTC-1/MWCNTs as a new catalyst is effective in enantioselective alkylation of multiple halohydrocarbon.

Key words: multi-walled carbon nanotube, chiral phase transfer catalyst, cinchona alkaloid, adsorption, enantioselective alkylation