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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.
In this work, eleven kinds of tetraphenylporphinium manganese compounds (TXPPMn (?) Cl) with different substituents were synthesized and investigated their catalytic yield, rate of cyclohexane hydroxylation under mild conditions And the relationship between the product selectivity and the nature of the substituents on the porphyrin ring.The results show that the substituents on the porphyrin ring can improve the reaction yield and product selectivity of cyclohexane hydroxylation.For the relative position substitution The reaction of cyclohexane hydroxylation catalyzed by manganese porphyrin conforms to the Hammett relationship between the reaction rate constant and the substituent constant, while the ortho-substituted manganese porphyrin can obviously improve the reaction yield compared with other substituted porphyrins. The rate And product selectivity.