The reactivity of α,β-unsaturated carboxylic acids. Part XVI. The kinetics of the reaction of cycloalkenecarboxylic and cycloalkenylacetic acids with diazodiphenylmethane in various alcohols

• Main Authors: Ušćumlić Gordana S., Nikolić Jasmina B., Krstić Vera V.
• Format: Article
• Language: English
• Published: Serbian Chemical Society 2002-01-01
• Series: Journal of the Serbian Chemical Society
• Subjects: cycloalkenecarboxylic acids; cycloalkenylacetic acids; diazodiphenyl-methane; kinetic measurements; protic solvents
• Online Access: http://www.doiserbia.nb.rs/img/doi/0352-5139/2002/0352-51390202077U.pdf

The rate constants for the reaction of diazodiphenylmethane with 1-cyclopentenecarboxylic, 1-cycloheptenecarboxylic, cyclopent-1-enylacetic and cyclohept-1-enylacetic acids were determined in eight alcohols at 30 ºC using the appropriate UV-spectroscopic method. In order to explain the kinetic results through solvent effects, the second order rate constants of the examined acids were correlated using a total solvatochromic equation, of the form: log k = A0+ s¶*+aα+ bβ, where ¶* is a measure of the solvent polarity, βrepresents the scale of solvent hydrogen bond acceptor basicities and β represents the scale of solvent hydrogen bond donor acidities. The correlations of the kinetic data were carried out by means of multiple linear regression analysis. The opposite sings of the electrophilic and the nucleophilic parameters are in agreement with the well-known reaction mechanism. The results presented in this paper were compared with the kinetic data for 1-cyclohexenecarboxylic and cyclohex-1-enylacetic acids obtained under the same experimental conditions.