高等学校化学学报

高等学校化学学报 ›› 1995, Vol. 16 ›› Issue (6): 909.

• 论文 • 上一篇    下一篇

模拟细胞色素P-450的仿生氧化反应的研究(Ⅴ)──氯合5,10,15,20-四取代苯基卟吩合铁(Ⅲ)中取代基对催化环己烷单加氧反应的影响

蒋笃孝, 谷晨, 桂明德, 朱申杰   

  1. 南开大学化学系, 天津, 300071
  • 收稿日期:1994-06-24 修回日期:1995-02-09 出版日期:1995-06-24 发布日期:1995-06-24
  • 通讯作者: 桂明德
  • 作者简介:蒋笃孝,男,32岁,硕士,讲师,
  • 基金资助:

    国家自然科学基金

Studies on the Biomimetic Oxidation Catalyzed by the Model Compound of Cytochrome P-450(Ⅴ)──The Influence of Substituent R in T(R-T)PFe(Ⅲ)Cl on the Monooxygenation of Cyclohexane

JIAN Du-Xiao, GU Chen, GUI Ming-De, ZHU Shen-Jie   

  1. Department of Chemistry, Nankai University, Tianjin, 300071
  • Received:1994-06-24 Revised:1995-02-09 Online:1995-06-24 Published:1995-06-24

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摘要： 系统地考察了一系列氯合5,10,15,20-四取代苯基卟吩合铁(Ⅲ)T(R-P)PFe(Ⅲ)Cl(R=o,m,p-Me,MeO,Cl,Br,I,NO2,o-t-Bu,p-t-Bu,o-NH2,Et,i-pr)作模拟酶单加氧催化剂,以亚碘酰苯作供氧体对环己烷进行羟化反应时的取代基效应.环己醇产率随取代基R的拉电子性增强而提高,对位取代基常数σp与环己醇产率间存在Hammett线性相关式:1g(YR/YH)=3.2σp-0.03.邻位取代基的立体效应也增加环己醇的产率.

关键词: T(R-P)PFe(Ⅲ)Cl, 环己烷, 单加氧反应, 取代基效应

Abstract: The influences of monosubstitution at phenyl rings in a series of T(R-P)PFe(Ⅲ)Cl(R=o,m,p-Me,MeO,Cl,Br,I,NO2, o-t-Bu,p-t-Bu,o-NH2,Et,i-Pr)on the biomimetic catalytic monooxygenation of cyclohexane with PhIO were studied.The yields of cyclohexanol were increased by the electron-with drawing substituents Rin these catalysts T(R-I)PFe(Ⅲ)Cl.Afair linear correlation between the yield of cyclohexanol and para substituent constant σpis presented as:lgYR/YH=3. 2σp-0. 03. The steric effect of all ortho substituents in T(R-P)PFe(Ⅲ)Cl increased the yield of cyclohexanol sufficiently.

Key words: T(R-P)PFe(Ⅲ)Cl, Cyclohexane, Monooxygenation, Substituent effect

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