The influence of the solvent on organic reactivity. Part II. Hydroxylic solvent effects on the reaction rates of diazodiphenylmethane with 2-(2-substituted cyclohex-1-enyl)acetic and 2-(2-substituted phenyl)acetic acids

Abstract

The rate constants for the reaction of diazodiphenylmethane with 2-(2-substituted cyclohex-1-enyl)acetic acids and 2-(2-substituted phenyl)acetic acids, previously determined in seven hydroxylic solvents, were correlated using the total solvatochromic equation, of the form: log k = log k0 + sp* + aa + bb, the two-parameter model, log log k = log k0 + sp* + aa, and a single parameter model k = log k0 + sp* + bb, where p* is a measure of the solvent polarity, b represents the scale of solvent hydrogen bond acceptor basicities and a represents the scale of solvent hydrogen bond donor acidities. The correlations of the kinetic data were carried out by means of multiple linear regression analysis and the solvent effects on the reaction rates were analysed in terms of initial state and transition state contributions.

Keywords

• 2-(2-substitued cyclohex-1-enyl)acetic acids
• 2-(2-substituted phenyl)acetic acids
• diazodiphenylmethane
• kinetic measurements
• protic solvents