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化学学报
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化学学报 ›› 1964, Vol. 30 ›› Issue (2): 176-182. 上一篇    下一篇

论文

分子结构与化学活性间的定量关系Ⅱ.烯类与丙二酸二乙酯的加成反应

蒋明谦, 李森   

  1. 中国科学院化学研究所
  • 投稿日期:1963-06-14 发布日期:2013-06-03

A QUANTITATIVE RELATIONSHIP BETWEEN MOLECULAR STRUCTURE AND CHEMICAL REACTIVITY Ⅱ. THE ADDITION REACTION OF ALKENES AND DIETHYL MALONATE

CHIANG MING-CHIEN, LI SEN   

  1. Institute of Chemistry, Academia Sinica
  • Received:1963-06-14 Published:2013-06-03

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被引次数

1

在相同反应条件下,进行一系列烯烃与丙二酸二乙酯的加成反应,求得产率与烯烃结构间的定量关系,即反S型曲线.根据此结构关系可以推定此加成反应是由丙二酸二乙酯形成的自由基[·CH(CO2C2H5)2]对烯烃的亲电子性自由基加成反应.从产率曲线可以确定在一定的反应条件下I50点的位置.根据I50值讨论各类烯烃同系物在反应中的产率变化,及可得高产率的结构范围.例如,可以推定所有脂肪α-烯的产率均高,在氯烷基代烯中,氯原子与双键至少应隔两碳原子,而在羧代烷基烯中,羧基应隔三碳原子,始能得高产率.

The free-radical addition reaction of malonic ester with a series of alkenes under the uniform conditions has been studied.The relationship between the yields and the structure of the alkenes,as expressed in teems of the inductive indices for the substituent groups on the ethylenic bond,has been found to be a reversed sigmoid ("S-") curve.It indicates that this addition reaction is an electrophilic free-radical addition of the malonic ester radical,·CH(COOC2H5)2,to the alkene molecules.