Kinetics of the reactions of biphenyl-4-carboxylic acids and 1-naphthoic acids with diazodiphenylmethane in various alcohols

Abstract

Rate constants have been determined for the reactions at 30, 35, and 40 °C of diazodiphenylmethane with 4′-substituted biphenyl-4-carboxylic acids and 4-substituted 1-naphthoic acids in 14 alcohols. Hammett ρ values have been evaluated for the reactions in 11 of the alcohols. The log k values for reactions of biphenyl-4-carboxylic acid and 1-naphthoic acid in the 14 alcohols are linearly related to the corresponding values for benzoic acid. Multiple correlations of log k with groups of suitable solvent parameters are very successful. The dielectric effect has a negative influence on ρ values which decrease with temperature. The transmission of electronic effects through the biphenyl ring system is compared with that in benzene.