Proton transfer equilibria between disubstituted benzoic acids and carbinol base of crystal violet in apolar aprotic solvents. Chemometric analysis of disubstituent effects on the strength of benzoic acid in chlorobenzene

Abstract

Proton transfer equilibria in chlorobenzene between a set of di-substituted (2,3-,2,5-,2,6-, 3,5-dichloro and difluoro) benzoic acids including the corresponding mono-substituted acids and the carbinol base of crystal violet have been studied spectrophotometrically. To investigate the effect of disubstitution at ortho- and/or meta- positions on the strength of benzoic acid, the results have been analysed chemometrically on the basis of Fujita Nishioka’s multiparameter approach and the assumption of additivity for substituent effects. The model employed explains 94% of the variance for the disubstituent effects on log K. It is observed that the substituent effect is contributed by ordinary electronic and proximity electronic effects in an almost equal ratio (52:48).