GAS-PHASE BASICITIES OF AMIDES AND IMIDATES - ESTIMATION OF PROTOMERIC EQUILIBRIUM-CONSTANTS BY THE BASICITY METHOD IN THE GAS-PHASE

被引：48

作者：

AUE, DH ^{[1
]}

BETOWSKI, LD ^{[1
]}

DAVIDSON, WR ^{[1
]}

BOWERS, MT ^{[1
]}

BEAK, P ^{[1
]}

LEE, J ^{[1
]}

机构：

[1] UNIV ILLINOIS,ROGER ADAMS LAB,URBANA,IL 61801

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1979年 / 101卷 / 06期

关键词：

D O I：

10.1021/ja00500a001

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The gas-phase basicities of 2-methoxypyridine (3), 1-methyl-2-pyridone (4), 1-methyl-2-pyrrolidone (8), 2-methoxy-1-pyrrolidene (9), 1-methyl-2-piperidone (10), 2-methoxy-1-piperidene (11), 6-chloro-2-methoxypyridine (12), and 6-chloro-1-methyl-2-pyridone (13) are reported. The importance of considering the relative energies of isomeric bases in assessing structural effects on gas-phase and solution basicities is illustrated by a comparison of 3-4, 9-10, and 12-13. The relative basicities of 3-4 and 12-13 are used to provide estimates of the protomeric equilibrium between 2-hydroxypyridine (1)-2-pyridone (2) and 6-chloro-2-hydroxypyridine (18)-6-chloro-2-pyridone (19) which are in approximate agreement with the independently measured values. The gas-phase basicities of 8-9 and 10-11 are used to estimate the amide-imidic acid equilibrium of pyrrolidone and piperidone in the vapor. The compensations in energies which are required for successful application of the basicity method for estimation of protomeric equilibria in the vapor and solution are discussed. © 1979, American Chemical Society. All rights reserved.

引用

页码：1361 / 1368

页数：8