Salen金属配合物水解动力学拆分环氧氯丙烷研究进展

doi:10.12422/j.issn.1006-396X.2023.04.008

石油化工高等学校学报 ›› 2023, Vol. 36 ›› Issue (4): 53-62.DOI: 10.12422/j.issn.1006-396X.2023.04.008

Salen金属配合物水解动力学拆分环氧氯丙烷研究进展

刘娜¹(), 梁光敏¹, 季久玉²(), 周坤¹, 罗根祥¹, 李微³

^1.辽宁石油化工大学石油化工学院, 辽宁抚顺 113001
^2.辽宁石油化工大学人工智能与软件学院, 辽宁抚顺 113001
^3.黔南民族师范学院化学化工学院, 贵州都匀 558001

收稿日期:2022-10-04 修回日期:2023-03-07 出版日期:2023-08-25 发布日期:2023-09-05
通讯作者: 季久玉
作者简介:刘娜（1997⁃），女，硕士研究生，从事功能配合物化学方面的研究；E⁃mail：ln19841354295@163.com。
基金资助:
辽宁省教育厅面上项目(LJKZ0397);贵州省普通高等学校磷石膏综合利用工程研究中心资助项目(黔教合KY字[2018]010)

Research Progress of Hydrolytic Kinetic Resolution of Epichlorohydrin Catalyzed by Salen Metal Complexes

Na Liu¹(), Guangmin Liang¹, Jiuyu Ji²(), Kun Zhou¹, Genxiang Luo¹, Wei Li³

^1.School of Petrochemical Engineering，Liaoning Petrochemical University，Fushun Liaoning 113001，China
^2.School of Artificial Intelligence and Software，Liaoning Petrochemical University，Fushun Liaoning 113001，China
^3.School of Chemistry and Chemical Engineering，Qiannan Noraml University for Nationalites，Duyun Guizhou 558001，China

Received:2022-10-04 Revised:2023-03-07 Published:2023-08-25 Online:2023-09-05
Contact: Jiuyu Ji

摘要/Abstract

摘要：

环氧氯丙烷通过水解动力学拆分可得到手性环氧氯丙烷。手性环氧氯丙烷是具有很高价值的中间体，被广泛应用于医药、材料等领域。Salen是指两个相同的醛分子和一个二胺分子缩合生成的碱，其与金属化合形成的配合物被称为Salen金属配合物，常用于手性环氧氯丙烷的合成。综述了近年来Salen金属配合物催化剂的发展历程及其用于手性环氧氯丙烷合成的研究进展，探究了水解动力学拆分过程中催化剂的失活机理，对以Salen金属配合物为催化剂合成的手性环氧氯丙烷的应用进行了展望。

关键词: 手性环氧氯丙烷, Salen金属配合物, 水解动力学拆分, 对映体

Abstract:

Chiral epichlorohydrin is obtained by kinetic resolution of racemic epichlorohydrin through hydrolysis. Chiral epichlorohydrin is a valuable intermediate which is widely used in the synthesis of medicine and material. Salen refers to a base formed by the condensation of two identical aldehyde molecules and a diamine molecule, and the complex formed by its combination with metals is called Salen metal complex, which is often used in the synthesis of chiral epichlorohydrin. In this paper, the development of Salen metal complex catalysts and their application in chiral epichlorohydrin synthesis are reviewed. At the same time, the deactivation mechanism of catalyst in the process of hydrolytic kinetic resolution was investigated and the application prospect of synthesis of chiral epichlorohydrin using Salen metal complex catalysts was prospected.

Key words: Chiral epichlorohydrin, Salen metal complex, Hydrolytic kinetic resolution, Enantiomer

中图分类号:

TQ013.2

刘娜, 梁光敏, 季久玉, 周坤, 罗根祥, 李微. Salen金属配合物水解动力学拆分环氧氯丙烷研究进展[J]. 石油化工高等学校学报, 2023, 36(4): 53-62.

Na Liu, Guangmin Liang, Jiuyu Ji, Kun Zhou, Genxiang Luo, Wei Li. Research Progress of Hydrolytic Kinetic Resolution of Epichlorohydrin Catalyzed by Salen Metal Complexes[J]. Journal of Petrochemical Universities, 2023, 36(4): 53-62.

图/表 21

图1 催化剂1的结构

Fig.1 Structure of catalyst 1

图2 催化剂2的结构

Fig.2 Structure of catalyst 2

图3 催化剂3的结构及其催化环氧氯丙烷的水解动力学拆分

Fig.3 Structure of catalyst 3 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

图4 催化剂4的结构及其催化环氧氯丙烷的水解动力学拆分

Fig.4 Structure of catalyst 4 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

图5 催化剂5的结构

Fig.5 Structure of catalyst 5

图6 催化剂6的结构及其催化环氧氯丙烷的水解动力学拆分

Fig.6 Structure of catalyst 6 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

图7 催化剂7的合成路线

Fig.7 Synthesis route of catalyst 7

图8 催化剂8的结构及其催化环氧氯丙烷的水解动力学拆分

Fig.8 Structure of catalyst 8 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

图9 催化剂9的结构及其催化环氧氯丙烷水解动力学拆分

Fig.9 Structure of catalyst 9 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

图10 催化剂10的结构及其催化环氧氯丙烷水解动力学拆分

Fig.10 Structure of catalyst 10 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

图11 催化剂11的结构及其催化环氧氯丙烷水解动力学拆分

Fig.11 Structure of catalyst 11 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

图12 催化剂12的结构及其催化环氧氯丙烷水解动力学拆分

Fig.12 Structure of catalyst 12 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

图13 催化剂13的结构及其催化环氧氯丙烷水解动力学拆分

Fig.13 Structure of catalyst 13 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

图14 催化剂14的结构及其催化环氧氯丙烷水解动力学拆分

Fig.14 Structure of catalyst 14 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

图15 催化剂15催化环氧氯丙烷水解动力学拆分

Fig.15 Hydrolytic kinetic resolution of epichlorohydrin by catalyst 15

图16 催化剂16的结构及其催化环氧氯丙烷水解动力学拆分

Fig.16 Structure of catalyst 16 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

图17 催化剂17的结构及其催化环氧氯丙烷水解动力学拆分

Fig.17 Structure of catalyst 17 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

图18 催化剂18的结构及其催化环氧氯丙烷的水解动力学拆分

Fig.18 Structure of catalyst 18 and its catalytic hydrolysis kinetic resolution of epichlorohydrin

图19 Co(Ⅲ)?Salen双金属配合物催化末端环氧化合物水解动力学拆分

Fig.19 HKR of terminal epoxides catalyzed by Co(Ⅲ)?Salen bimetallic complex

图20 Co—X(X≠OH）主导催化末端环氧化合物HKR反应

Fig.20 Catalyst Co-X(X≠OH) dominant HKR reactions of terminal epoxide

图21 反离子对Co?Salen催化剂的活性作用机制

Fig.21 Mechanism of counterion activity on Co?Salen catalyst

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Salen金属配合物水解动力学拆分环氧氯丙烷研究进展

Research Progress of Hydrolytic Kinetic Resolution of Epichlorohydrin Catalyzed by Salen Metal Complexes

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