Hydroxylic solvent effects on the reaction rates of diazodiphenylmethane with 2-substituted cyclohex-1-enylcarboxylic and 2-substituted benzoic acids: Part II

Abstract

The rate constants for the reaction of diazodiphenylmethane with 2-substituted cyclohex-1-enylcarboxylic acids, determined in butan-1-ol, 2-methylpropan-1-ol and ethylene glycol, together with the rate constants determined previously in methanol, ethanol, propan-1-ol and propan-2-ol, are correlated using the total solvatochromic equation, of the form log <i>k </i>= A_o + s<img src='/image/spc_char/pi.gif' border=0>^* + a<img src='/image/spc_char/alpha.gif' border=0> + b<img src='/image/spc_char/beta.gif' border=0>, the two parameter model log <i>k </i>= A_o+ s<img src='/image/spc_char/pi.gif' border=0>* + a<img src='/image/spc_char/alpha.gif' border=0> and the single parameter model log <i>k </i>= A_o + b<img src='/image/spc_char/beta.gif' border=0>, where <img src='/image/spc_char/pi.gif' border=0>^*, <img src='/image/spc_char/beta.gif' border=0> and <img src='/image/spc_char/alpha.gif' border=0> represent the solvent dipolarity/polarizability, solvent hydrogen bond acceptor basicity and hydrogen bond donor acidity, respectively. The correlation of the kinetic data are carried out by means of multiple linear regression analysis and solvent effects on the reaction rates have been analysed in terms of initial state and transition state contributions. The results obtained for 2-substituted cyclohex-1-enylcarboxylic acids are compared with the results for 2-subsituted benzoic acids under the same experimental conditions.