Reactivity of 2-substituted cyclohex-1-enylacetic acids with diazodiphenylmethane in various alcohols

Abstract

The reactivities of 2-substituted cyclohex-1-enylacetic acids with diazodiphenylmethane in eleven alcohols has been investigated. The solvent effect is interpreted in terms of the influence of the relative permittivity on the rate constants. The multiple linear correlation of log k with the Kirkwood function of relative permittivity, Taft σ* value for the alkyl group of the alcohol and the number of γ-hydrogen atoms in the alcohol n_γH was highly successful (R= 0.9927). The log k values for the various acids were correlated by using the appropriate form of the extended Hammett equation involving inductive, resonance and steric parameters.

The reaction of cyclohex-1-enylacetic acid with diazodiphenylmethane in eleven alcohols shows a good linear free energy relationship with the corresponding reaction of phenylacetic acid (R= 0.9793). The results obtained for 2-substituted cyclohex-1-enylacetic acids were compared with the results for ortho-substituted phenylacetic acids under the same experimental conditions.