卟啉化合物的合成及其对细胞色素P—450的模拟 11.…

SYNTHESIS OF PORPHYRIN COMPOUNDS AND BIOMINESIS FOR CYTOCHROME P-450 Ⅸ.Substituent Effect of Cyclohexane Hydroxylation Catalyzed By Manganese(Ⅲ)Porphyrins

本工作合成了11种具有不同取代基的氯化四苯基卟吩合锰化合物(TXPPMn(?)Cl)、并考察了它们在温和条件下催化环己烷羟基化反应的反应产率、速率及产物选择性与卟啉环上取代基性质的关系.研究结果表明,卟啉环上的取代基都能提高环己烷羟基化反应的反应产率和产物选择性.对于问位相对位取代锰卟啉催化下的环己烷羟基化反应,其反应速率常数与取代基常数之间符合Hammett关系,而邻位取代的锰卟啉比其它取代卟啉更能明显地提高反应产率、速率和产物选择性.

Eleven kinds of substituent manganeseporphyrins(TXPPMn~Ⅲ Cl)aresynthesized.and effect of the substituents on porphyrin ring on the reaction yields.rates andproductive selectivities of cyclohexane hydroxylation catalyzed by these porphyrins at roomtemperature and atmosphere are researched.The results show that all substituents onporphyrin ring can improve the yields and productive selectivies of the hydroxylations.Thereare Hammett relationships between the rates of the hydroxylation and the substituentconstants for meso-and para-substituent porphyrins.The reaction yields.rates andselectivities of cyclohexane hydroxylation catalyzed by ortho-substituent porphyrins can beenincreased more than those of other substituent porphyrins.