化学学报 ›› 1991, Vol. 49 ›› Issue (5): 477-482. 上一篇    下一篇

研究论文

水溶性金属卟啉存在下硫醇氧化反应的研究

王先元;王有治;李广年   

  1. 中国科学院成都有机化学研究所
  • 发布日期:1991-05-15

Autoxidation of thiols in the presence of water-soluble metalloporphyrins

WANG XIANYUAN;WANG YOUZHI;LI GUANGNIAN   

  • Published:1991-05-15

本文研究了水溶性金属卟啉存在下丁硫醇的氧化过程, 考察了金属卟啉的中心金属离子、周围基团及轴向配体与其催化活性之间的关系。发现只有钴卟啉对硫醇的氧化反应有明显的催化作用。卟啉环的周围基团对钴卟啉的催化性能有显著影响, 其活性顺序为: CoTPyP>Co(p-SO3Na)TPP>Co(p-OH)TPP>Co(p-NH2)TPP>CoTPP。研究了各种动力学因素(底物浓度、催化剂浓度、碱浓度和吡啶添加物浓度)与硫醇转化速度之间的关系并借助设想的催化循环解释了反应的动力学规律。

关键词: 硫醇, 催化剂, 水溶性, 金属络合物, 卟啉, 催化活性, 动力学研究, 氧化反应

In the presence of water-sol. metalloporphyrins, the autoxidn. of Bu mercaptan was studied. When different metallotetrapyridyl-porphyrins (CoTPyP, MnTPyPCl, FeTPyPCl, NiTPyP, CuTPyP, ZnTPyP) were used as catalysts, only CoTPyP exhibited distinct activity. With different cobalt porphyrins as catalysts, the activity decreased in the order of CoTPyP>Co(p-SO3Na)TPP>Co(p-OH)TPP>Co(p-NH2)TPP>CoTPP. The relationship between the reaction rate and the thiol concentration was measured. At high concns. a saturation effect was observed Michaelis-Menten kinetics appear to be obeyed. The effect of some kinetic factors (the concentration of catalyst, the concentration of alkali, and the concentration of pyridine additive) on the oxidation reaction was also investigated.

Key words: MERCAPTAN, CATALYST, WATER SOLUBILITY, METAL COMPLEX, PORPHYRIN, CATALYTIC ACTIVITY, KINETIC STUDY, OXIDATION REACTION

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