Crown ether catalysis of decarboxylation: a general survey of reactivity and detailed analysis of the triphenylacetate anion

Abstract

The effect of 18-crown-6 ether 3 on the decarboxylation rate in THF of sodium salts of carboxylic acids formally derived from hydrocarbons has been investigated and these acids include 9-phenylfluorene-9-carboxylic acid, fluorene-9-carboxylic acid, phenylacetylene carboxylic acid, triphenylacetic acid, and diphenylacetic acid. Addition of equimolar 3 resulted in an increase in decarboxylation rate of 13- to 500-fold and there was a correlation between the decarboxylation rate and the pKa value of the product hydrocarbon.The decarboxylation of triphenylacetate was investigated in detail. The effect on reaction rate of cation (Li+, Na+, K+), crown ether concentration, water concentration, and solvent polarity has provided information as to optimum reaction conditions and has helped to clarify the reaction mechanism.