应用化学 ›› 1992, Vol. 0 ›› Issue (3): 102-105.

• 研究简报 • 上一篇    下一篇

四甲基乙烯环丙烷化反应的催化研究

李争宁, 陈惠麟, 于振远, 郭和夫   

  1. 中国科学院大连化学物理研究所, 大连 116023
  • 收稿日期:1991-08-06 修回日期:1991-11-26 出版日期:1992-06-10 发布日期:1992-06-10

CATALYTIC CYCLOPROPANATION OF TETRAMETHYL ETHYLENE

Li Zhengning, Chen Huilin, Yu Zhenyuan, Guo Hefu   

  1. Dalian Institute of Chemical Physics, Academia Sinica, Dalian 116023
  • Received:1991-08-06 Revised:1991-11-26 Published:1992-06-10 Online:1992-06-10

摘要: 烯烃和重氮乙酸酯(RDA)在光照、加热或催化剂作用下反应生成的环丙烷羧酸酯是合成拟除虫菊酯的重要中间体[1]。铜、铑等金属的化合物作为催化剂在这类反应中得到了广泛应用[2]。对RDA和四甲基乙烯TME的环丙烷化反应,曾以CuSO4[3]、Cu(acac)2[4]、Cu(OTf)2[5]等作催化剂,但产率低,而且均有诱导期。

关键词: 铜, 重氮乙酸乙酯, 四甲基烯, 环丙烷化

Abstract: Cu(Salad)2, Cu(gly)2H2O, Cu(o-NH2C6H4CO2)2, Cu(ClO4)26H2O, Cu(CH3CN)4ClO4 were use first time for catalyzing cyclopropanation of ethyl diazoaeetate (EDA) with tetramethyl ethylene (TME). Cu(Ⅱ) amino acid salts showed no catalytic activity, when they were used directly. High catalytic activity appeared only cohen they were pre-reduccd to Cu(Ⅰ) High TME/EDA ratio, high EDA/Cat ratio, longer addition period of EDA-TME mixture, and high reaction temperature benefited the product yield. Cu(salad)2 and Cu(gly)2H2O showed higher catalytic efficiency for the reaction under suitable conditions.

Key words: copper catalyst, tetramethyene, ethyl diazoacetate, cyclopropanation