期刊论文

Structure and reactivity of aliphatic saturated hydrocarbon dicarboxylic acids

中文

电力科学与技术学报

1673-9140

2006

21

4

107-112

10.3969/j.issn.1673-9140.2006.04.027

湖南省教育科学“十五”规划资助项目（XJK03CG026）；

本校为第一机构

通过对脂肪族二元酸的空间构象和电子结构分析,结果表明:(1)乙二酸的两C=O键处于反式为能量最优势构象,单键自由运动的最大与最小能差12.313 kcal/mol;丙二酸的羧基O-C=O键平面与C-C-C键平面的二面角分别呈59.6°和69.5°为能量最优势构象,单键自由运动的最大与最小能差14.282 kcal/mol;丁二酸的羧基O-C=O键平面与C-C-C键平面的二面角在0°为能量最优势构象,单键自由运动的最大与最小能差2.3 745 kcal/mol;(2)羧基的拉电子作用增加了O-H键极性,羧基氢有发生一级离解趋势,二元酸中一旦一个H+离解,形成氧负离子,该羧酸根对另一羧基的吸电子能力下降,二级离解小于一级离解;(3)羧基的拉电子作用使丙...

In this paper, the relationship between structure and reactivity is discussed via the stereo effect and electronic structure analysis of aliphatie diearboxylie acids, respectively. （1） A potential energy plot for rotation about the C--C bond is shown that the eclipsed conformation in oxalic acid is 12.313 kcal/ mol higher in energy than the more stable staggered conformation. In malonie acid the barrier to rotation about the C--C bond for R - COOH is 14.282 kcal/mol,the stable conformation is that the dihedral angle between the two O--C =0 pl...