有机化学 ›› 1993, Vol. 13 ›› Issue (5): 482-485. 上一篇    下一篇

研究论文

双核铜酶模型的合成及对安息香的催化氧化

鄢家明;谢如刚;赵华明   

  1. 四川大学化学系.成都(610064)
  • 发布日期:1993-10-25

Synthesis of binuclear copper enzyme models and their catalytic behaviour in oxidation of benzoin

Yan Jiaming;Xie Rugang;Zhao Huaming   

  1. Sichuan Univ, Dept Chem.Chengdu(610064)
  • Published:1993-10-25

为寻求更有效的仿酶模型,本文设计合成了含四个咪唑配基、两个咪唑基与铜配位的新型双核铜酶模型,并实现了在氧气存在下模型对安息香的催化氧化作用。以邻-氯苯酚为原料,经直接咪唑甲基化,醚化偶联,继与[Cu(CH~3CN)~4]CLO~4反应合成目标酶模型6-8。类似地,由对-氯苯酚合成酶模型9。以机械7为例,研究了在氧气下它们催化氧化安息香为二苯乙二酮的反应,高产率地合成目标产物,并求得催化氧化反应动力学参数。考查不同催化剂对反应的影响,发现它们的活性次序如下:7>4+[Cu(CH~3CN)~4]ClO~4>[Cu(CH~3(CN)~4]ClO~4>2+[Cu(CH~3CN)~4]ClO~4。

关键词: 安息香, 二苯乙二酮, 氯苯酚, 双核铜酶模型, 咪唑, 甲基化, 催化剂, 催化氧化

Four new binuclear copper enzyme models (6-9) are efficiently synthesized and structurally confirmed. o-chloro phenol is treated with paraformaldehyde and imidazole to give the bis-imidazolylmethyl derivative 2. Treatment of 2 with α, ω-dibromoalkanes gives the corresponding coupling derivatives 3-5. Three models 6-8 are obtained from the reaction of [Cu(CH~3CN)~4]ClO~4 with 3-5. Another model(9) was Likewise synthesized under otherwise identical condition except employing p-chloro phenol in place of the o-counterpart. Oxidation reactions of benzoin to benzil catalyzed by 6-9 with oxygen have also been investigated. The catalytic ability in the following order: 7>4+[Cu(CH~3CN)~4]ClO~4>[Cu(CH~3(CN)~4]ClO~4>2+[Cu(CH~3CN)~4]ClO~4 is observed. In the presence of 7, the oxidation reaction follows Michaelis-Menten Saturation behaviour and the kinetic parameters are obtained.

Key words: GUM BENZOIN, METHYLATION, CATALYST, IMIDAZOLE, CATALYTIC OXIDATION

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