醛和二苯基N-无取代硫亚胺反应生成睛的机理Mechanism of the Formation of Nitriles by the Reaction of Aldehyde with Diphenyl N- unsubstituted Sulfilimine
张景榴;
摘要(Abstract)：
研究了醛和二苯基N-无取代硫亚胺(Ⅰ)反应生成腈的机理。(Ⅰ)跟对位取代苯甲醛的反应速度按Hammett方程作图,得到正的ρ值(ρ=+2.4)。测得活化焓和活化熵分别为△H≠=23.1 kcal/mole和△S≠=23.1 kcal/mole和△S≠=-5.1 e.u。(苯甲醛)。用氘代苯甲醛PhCDO观测到同位素效应(k_H/k_D=2.0)。以上观察结果表明,反应起初是经过氮原子亲核加成到羰基中的碳原子上,接着脱出氢氧阴离子和决定反应速度的质子。
关键词(KeyWords)：
基金项目(Foundation):
作者(Authors): 张景榴;
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