化学学报 ›› 1995, Vol. 53 ›› Issue (10): 1005-1009. 上一篇    下一篇

研究论文

烯烃环丙烷化反应催化研究

万伯顺;陈惠麟;于振远;郭和夫   

  1. 大连大学化工系;中国科学院大连化学物理研究所
  • 发布日期:1995-10-15

Study on catalysis of cyclopropanation of olefins

WAN BOSHUN;CHEN HUILIN;YU ZHENYUAN;GUO HEFU   

  • Published:1995-10-15

本文研究了用Cu(CH3CCHCCH3)2, Ph3PCuX, Cu(O2CCF3)2等催化剂催化四甲基乙烯和重氮乙酸乙酯的环丙烷化反应。结果表明配体吸电子能力越强, 立体位阻越小, 其催化活性也越强。考察了反应物与Cu(O2CCF3)2的配比, 反应温度对Cu(O2CCF3)2催化反应活性的影响。通过对Cu(O2CCF3)2催化活性中心的研究表明,催化活性中心是一价铜配合物, 并推断四甲基乙烯环丙烷化机理是经由金属卡宾机理。

关键词: 反应机理, 烯烃, 催化活性, 环丙烷化, 重氮乙酸乙酯, 四甲基乙烯

Cu(acac)2, Ph3PCuX, Cu(O2CCF3)2 etc copper complexes were used to catalyze the reaction of cyclopropanation of tetramethylethene with ethyldiazoacetate. The stronger the ligand electroaffinity and the lower the sterohandicap of the ligands, the stronger the catalytic activity of their copper complexes. The activity of Cu(O2CCF3)2 and the temperature of the reaction were studied. The active center of the catalysts was crefully researched and it was proved to be a one-valence copper complex. Inducation period is because of the time necessary of the copper (II) to be reduced into copper (I) which is active species for EDA. The mechanism of this reaction was thought by means of metal carbene (A cycle).

Key words: REACTION MECHANISM, ALKENE, CATALYTIC ACTIVITY, TETRAMETHYL-ETHYLENE

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