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Solvent and Structural Effects on the Activation Parameters of the Reaction of Carboxylic Acids with Diazodiphenylmethane


  • Contract grant sponsor: Ministry of Science and Environmental Protection of the Republic of Serbia.

  • Contract grant number: 172013.

Correspondence to: J. B. Nikolić; e-mail:


The kinetics of the reaction of benzoic, 2-methylbenzoic, phenylacetic, cyclohex-1-enecarboxylic, 2-methylcyclohex-1-enecarboxylic, and cyclohex-1-eneacetic acids with diazodiphenylmethane was studied at 30, 33, 37, 40, and 45°C in a set of 12 protic and aprotic solvents. The reactions were found to follow the second-order kinetics. The activation energy as well as the activation parameters, such as the standard entropy, the standard enthalpy, and the standard Gibbs energy of the activation, was calculated from the second-order rate constants. The solvent and structural effects on the activation energy and the standard Gibbs energy of activation, for each examined compound, were analyzed. The results of Kamlet–Taft multiple correlation analysis show that the specific solvent–solute interactions play a dominant role in the governing of the reaction. The signs of the equation coefficients support the proposed reaction mechanism.