Chin. J. Org. Chem. ›› 1993, Vol. 13 ›› Issue (2): 139-145. Previous Articles     Next Articles

Original Articles

金属四苯基卟啉-次氯酸钠模拟体系中芳醛氧化反应的研究

李存发;郑维忠;王先元;李广年   

  1. 中国科学院成都有机化学研究所;中国科学院上海有机化学研究所金属开放实验
  • 发布日期:1993-04-25

Oxygenation of aromatic aldehydes by the metallotetraphenylporphyrin-sodium hypochlorite system

LI CUNFA;ZHENG WEIZHONG;WANG XIANYUAN;LI GUANGNIAN   

  • Published:1993-04-25

The catalytic behaviors of Mn(III)-porphyrin in the oxidation of aromatic aldehydes with NaOCl as oxidant under two-phase condition have been investigated. When TPPMn(III)OAc (TPP = tetraphenylporphyrin), TPPFe(III)Cl, TPPCo(II), and TPPNi(II) were used as catalysts, only TPPMn(III)OAc and TPPFeCl exhibit distinct activities. With TPPMn(III)OAc as catalyst, UV - visible spectral changes of the fourth band from 425 nm to 478 nm were observed during the course of the oxygen transfer, suggesting that oxo-manganese(V) porphyrin is the key element for the oxygenation of aldehydes. Electron withdrawing para-substituents of TPPMnOAc lead to an increase in activities and stabilities. Electron withdrawing ortho substituents increase the stabilities of manganese porphyrins, but decrease their activities.

Key words: OXIDATION, CATALYSIS, ACETATE, METAL COMPLEX, CHLORIDE, PORPHYRIN, IRON COMPLEX, SODIUM HYPOCHLORITE, BENZALDEHYDE, MANGANESE COMPLEX

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