中文摘要：

以苯乙烯、环己烯和反式二苯乙烯为烯烃底物,以双氧水、叔丁基过氧化氢和异丙苯过氧化氢为氧化剂,以苯环上对位和邻位氯取代的四苯基金属卟啉为仿生催化剂,对烯烃的催化环氧化反应进行了对比研究.讨论了不同氯取代位的四苯基金属卟啉对烯烃环氧化性能的影响.实验结果表明,在没有助催化剂存在下,邻位氯代的四（2,6-二氯苯基）铁（锰）卟啉对烯烃的环氧化具有优异的催化性能,烯烃底物的转化率和环氧选择性都比对位氯代的四苯基铁（锰）卟啉高,且反应条件温和.其中FeⅢ（TDCPP）Cl的催化性能最好,环氧化选择性最高,催化氧化苯乙烯时,环氧苯乙烷的选择性达到了90.4%.相同金属离子不同配体的金属卟啉传递氧原子的能力为TDCPP〉T（p-Cl）PP〉TPP.氧化剂的结构对环氧化物的选择性有较大影响.过氧键连有吸电子基团的异丙苯过氧化氢对环氧化物的选择性最高.根据实验结果,对金属卟啉催化环氧化机理进行了分析.

英文摘要：

The reaction of hydrogen peroxide, tert-butyl hydrogen peroxide or cumene hydrogen peroxide with styrene, cyclohexene and trans-stilbene, catalyzed by phenyl ortho or para CI substituent position of tetraphenylmetalloporphyrins, have been studied in this paper. Effect of different C1 substituent position on the catalytic per- formance for olefins epoxidation of tetraphenylmetalloporphyrins has been investigated. The results show that 5,10, 15,20-tetrakis- （ 2,6-dichlorophenyl ） porphyrin iron （ or manganese） chloride （ Fem （ TDCPP ） C1 or Mn Ⅲ （ TDCPP ） C1） on the epoxidation of olefin exhibits excellent catalytic properties, which the olefins conversion and epoxide selectivity is better than the tetra- （p-chorophenyl） -porphyrin iron （ or manganese） chloride （ Fe ^Ⅲ T （p-C1） PPC1 or Mn^Ⅲ T（p-C1）PPC1）, and the reaction conditions is mild. FeZ（TDCPP） C1 exhibits the best catalytic performance and epoxide selectivity. When it applied to catalyze oxidation of styrene, the styrene oxide selectivity reached 90.4%. The catalytic performance of different metalloporphyrin ligands with same metal ions are in the following order： TDCPP〉T（p-Cl）PP〉TPP. Oxidant structure affects the selectivity of epoxides. Cumene hydrogen perox- ide, which peroxy bond links with electron drawing groups, gets the highest epoxide selectivity. According to the experimental results, the metalloporphyrins＇ epoxidation mechanism is also analyzed.