化学学报 ›› 1964, Vol. 30 ›› Issue (3): 316-324. 上一篇    下一篇

论文

Ⅳ.硅烷与烯腈结构对硅氢加成反应的影响

蒋明谦, 曹怡, 汪文石   

  1. 中国科学院化学研究所
  • 投稿日期:1963-08-03 发布日期:2013-06-03

Ⅳ.THE INFLUENCE OF THE STRUCTURES OF HYDROSILANES AND OLEFINIC NITRILES ON THE ADDITION REACTION BETWEEN THEM

CHIANG MING-CHIEN, TSAO I, WANG WEN-SHI   

  1. Institute oF Chemistry, Academia Sinica
  • Received:1963-08-03 Published:2013-06-03

在三组分催化剂——三正丁胺、四甲基乙二胺、氯化亚铜作用下,进行不同硅烷(三氯硅烷、苯基二氯硅烷、甲基二氯硅烷、二苯基氯硅烷、甲基苯基氯硅烷、二乙基氯硅烷、三乙基硅烷)与丙烯腈的加成反应.在相同的反应条件下,对于七种硅烷的活性作定量的比较,发现加成产率百分数与相应的硅烷基团的诱导效应指数间形成一正S型曲线.改变烯腈结构(α-氰基丙烯酸乙酯、丙烯腈、α-甲基丙烯腈、α-乙基丙烯腈、丁烯腈),研究其在三氯硅烷加成反应中的影响,同样也得到产率百分数的正S型曲线.基于与Grignard试剂的反应和碱性水解作用,确定加成产物的结构.实验表明,硅原子系加在烯腈的β-碳上(β-加成).根据结构活性关系的S型曲线讨论加成反应的机理.

In the presence of a three-component catalyst (tri-n-butylamine, tetramethyl-ethylenediamine, and cuprous chloride), the addition reaction of a series of silanes (trichlorosilane, phenyldichlorosilane, methyldichlorosilane, diphenylchlorosilane, methylphenylchlorosilane, diphenylchlorosilane, methylphenylchlorosilane, diethylchlorosilane and, triethylsilane) with acrylonitrile has been studied.Under the same reaction conditions, a quantitative tomparison of the reactivities of these silanes revealed that the percentages of yields for the addition give a "sigmoid" curve when plotted versus the corresponding inductive indices for the substituted atoms or groups in the silane molecules.