A linear solvation energy relationship study for the reactivity of 2-substituted cyclohex-1-enecarboxylic and 2-substituted benzoic acids with diazodiphenylmethane in aprotic and protic solvents

• Main Authors: Nikolić Jasmina B., Ušćumlić Gordana S.
• Format: Article
• Language: English
• Published: Serbian Chemical Society 2007-01-01
• Series: Journal of the Serbian Chemical Society
• Subjects: carboxylic acids; linear solvation energy relationship; diazodiphenylmethane; aprotic solvents; protic solvents
• Online Access: http://www.doiserbia.nb.rs/img/doi/0352-5139/2007/0352-51390712217N.pdf

The rate constants for the reaction of 2-substituted cyclohex-1-enecarboxylic acids and the corresponding 2-substituted benzoic acids with diazodiphenylmethane were determined in various aprotic solvents at 30 ºC. In order to explain the kinetic results through solvent effects, the second order rate constants of the reaction of the examined acids were correlated using the Kamlet-Taft solvatochromic equation. The correlations of the kinetic data were carried out by means of multiple linear regression analysis and the solvent effects on the reaction rates were analyzed in terms of the contributions of the initial and transition state. The signs of the equation coefficients support the proposed reaction mechanism. The quantitative relationship between the molecular structure and the chemical reactivity is discussed, as well as the effect of geometry on the reactivity of the examined molecules.