化学学报 ›› 1962, Vol. 28 ›› Issue (5): 275-332. 上一篇    下一篇

论文

分子结构与化学活性间的定量关系——Ⅰ.非共轭体系中的诱导效应

蒋明谦, 戴萃辰   

  1. 中国科学院化学研究所
  • 投稿日期:1962-03-28 发布日期:2013-06-03

A QUANTITATIVE RELATIONSHIP BETWEEN MOLECULAR STRUCTURE AND CHEMICAL REACTIVITY Ⅰ. INDUCTIVE EFFECT IN NON-CONJUGATED SYSTEMS

MING-CHIEN CHIANG, TSUI-CHEN TAI   

  1. Institute of Chemistry, Academia Sinica, Peking
  • Received:1962-03-28 Published:2013-06-03

本文中提出由元素的电负性及原子共价半径两种基本常数以系统计算非共轭体系中基团诱导效应的方法,所得出的诱导效应指数与非共轭化合物在各种反应中的能量变化,平衡常数对数与速度常数对数均形成直筱关系。反应中化学变化的百分率,如产率及转化率等,则与诱导效应指数形成S形曲线。在计算方法中,共价键A—B的极性,以两成键原子的电负性分数,xA/xA+xB,及xB/xA+xB之差δ(键极性指数)表示。一键对于邻近各键上的诱导效应,以这键上的极性强度δ/r,为计算基数,其中r为键的长度。

In this paper,a method for the systematic and quantitative evaluation of the inducfive effect exerted over a certain chemical bond in the molecule by a group,from the electronegativities and the atomic radii of its constituent elements,has been presented.The constant for the inductive effect of the group thus obtained is designated as the inductive effect index of the group.It has been found that for a given reaction,the energy changes,the logarithms of the equilibrium constants,and the logarithms of the rate constants can be expressed,respectively,as linear functions of the corresponding inductive effect index involved in the reaction,and that the percentages of chemical changes in the reaction,such as percent yield and conversion,give "sigmoid" curves when plotted versus the latter.These linear functions and sigmoid curves constitute a general quantitative relationship between molecular stmcture and chemical reactivity.