高等学校化学学报

高等学校化学学报 ›› 1997, Vol. 18 ›› Issue (4): 567.

• 论文 • 上一篇    下一篇

非对称Schiff碱过渡金属配合物模拟酶催化烯烃环氧化(Ⅰ)

杜向东, 俞贤达   

  1. 羰基合成与选择氧化国家重点实验室中国科学院兰州化学物理研究所, 兰州, 730000
  • 收稿日期:1996-04-28 出版日期:1997-05-24 发布日期:1997-05-24
  • 通讯作者: 俞贤达.
  • 作者简介:杜向东, 男, 28岁, 博士.
  • 基金资助:

    羰基合成与选择氧化国家重点实验室基金

Epoxidation of Unfunctionalized Olefins Catalyzed by Unsymmetric Schiff-base-Mn(Ⅲ) Complexes

DU Xiang-Dong, YU Xian-Da   

  1. State Key Laboratory of Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000
  • Received:1996-04-28 Online:1997-05-24 Published:1997-05-24

PDF (PC)

被引次数

97

摘要： 研究了温和条件下以亚碘酰苯为氧源,非对称性的和对称性的Mn(Ⅲ)Schiff碱配合物[Mn(Ⅲ)(CBP－phen－Xsal)Cl,X=H,Cl,Br,NO2,CH3,OCH3]和[Mn(Ⅲ)(CBP－R－CBP)Y,R=CH2CH2－,－CH(CH3)CH2－,－C6H4－;Y=Cl,OCH3]催化非官能性烯烃苯乙烯、环己烯和α-甲基苯乙烯的环氧化反应.结果表明,非对称配合物Mn(Ⅲ)(CBP－phen－Xsal)Cl是一个良好的催化非官能性烯烃环氧化反应的催化剂体系;中心金属离子Mn(Ⅲ)的电子结合能越小,催化环氧化效果越好;对上述3种烯烃环氧化物最好收率分别达到73％、100％和92％.

关键词: Schiff碱, 非对称Schiff碱, 非对称Mn(Ⅲ)Schiff碱配合物, 环氧化, 催化环氧化

Abstract: The selective epoxidation of unfunctionalized olefins (styrene, cyclohexene,a-methylstyrene) catalyzed by synthesized unsymmetric Schiff-base-Mn (Ⅲ) complexesMn(CBP-phen-XSal)Cl [X = H, Cl, Br, NO2, CH3, OCH3] and the symmetric analogsMn(CBP-R-CBP)Y[R =CH2CH2, CH (CH3)CH2, C6H4; Y=Cl, OAc] was investigated un-der mild conditions with iodosylbenzene as the terminal oxidant.The results show that theunsymmetric complexes Mn(Ⅲ) (CBP-phen-XSal)Cl is an effective system in catalytically se-lective olefin-epoxidation; the smaller the binding energy of Mn(Ⅲ), the more effective inepoxidation; the highest epoxidation yields of the mentioned three olefins are 73%, 100%and 92% respectively.

Key words: Schiff base, Unsymmetric Schiff-base, Unsymmetric Mn(Ⅲ)-Schiff-base complexes, Epoxidation, Catalytical epoxidation

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