【摘要】 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。更多还原

【Abstract】 In the presence of a three-component catalyst(tri-n-butylamine,tetramethyl-ethylene-diamine,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 com-parison of the reactivities of these silanes revealed that the percentages of yields for theaddition give a “sigmoid”curve when plotted versus the corresponding inductive indicesfor the substituted atoms or groups in the silane molecules.A study on the influence of the structure of the nitriles(ethyl α-cyanoacrylate,acry-lonitrile,α-methylacrylonitrile,α-ethylacrylonitrile,and allyl cyanide)has also been made.Similarly,a “sigmoid”curve for the percentages of yields has been obtained.The structures of the addition products have been determined by alkylation withGrignard reagents and by alkaline hydrolysis.The results show that the silyl group isadded to the β-position of the olefinic nitriles(“β-addition”).On the basis of the structure versus reactivity relationships as embodied in the sig-moid curves,the mechanism of the addition reaction has been discussed.更多还原