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化学学报
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化学学报 ›› 1964, Vol. 30 ›› Issue (3): 312-316323. 上一篇    下一篇

论文

分子结构与化学活性间的定量关系——Ⅲ.脂肪腈与甲醇的加成反应

蒋明谦, 戴萃辰   

  1. 中国科学院化学研究所
  • 投稿日期:1963-08-15 发布日期:2013-06-03

A QUANTITATIVE RELATIONSHIP BETWEEN MOLECULAR STRUCTURE AND CHEMICAL REACTIVITY——Ⅲ.ADDITION REACTION OF ALIPHATIC NITRILES AND METHANOL

CHIANG MING-CHIEN, TAI TSUI-CHEN   

  1. Institute of Chemistry, Academia Sinica
  • Received:1963-08-15 Published:2013-06-03

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562

被引次数

14

在甲醇钠的作用下,进行了脂肪腈类与甲醇的加成反应.实验结果表明:加成反应百分率与腈分子中烷基的诱导效应指数形成一正S型曲线,而反应的平衡常数及速度常数的对数则分别与烷基的诱导效应指数形成直线关系.根据转化率S型曲线上I50点的位置(103I50=10),可以肯定所有烷基腈在这个反应中的转化率都很低,而且反应速度很慢;在卤素、羧基及氰基取代烷基腈中,α-取代物反应迅速且转化率高,但取代基在γ-位置以外,则情况与简单烷腈相近.蒋化率曲线的正S走向及速度常数与平衡常数对数的直线的正倾斜度,均表明这个反应是甲醇对腈的亲核子加成反应.

The addition reaction of methyl alcohol to aliphatic nitrites with sodium methoxide as catalyst has been studied.The results reveal that the percentage of conversion of the nitrites when plotted versus the inductive index 1 for the alkyl groups in their molecules constitutes a "sigmoid" curve, while the logarithms of the rate and equilibrium constants for the addition reaction give straight lines when plotted respectively against the corresponding inductive index.