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有机化学
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有机化学 ›› 1993, Vol. 13 ›› Issue (2): 139-145. 上一篇    下一篇

研究论文

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

被引次数

4

研究了以次氯酸钠为氧化剂在两相条件下芳香醛氧化反应中锰(III)-卟啉的催化性质, 在TPPMn(III)醋酸盐, TPPFe(III)氯化物, TPPCo(II)和TPPNi(II)催化剂中(四苯基卟啉, TPP), 前二个化合物呈现催化活性, 研究表明, OXO-金属卟啉的形成是反应的关键步骤。

关键词: 锰络合物, 催化, 金属络合物, 氧化, 乙酸盐, 氯化物, 铁络合物, 次氯酸钠, 苯甲醛, 卟啉

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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