Solvent and structural effects on the kinetics of the reactions of 2‐substituted cyclohex‐1‐enylcarboxylic and 2‐substituted benzoic acids with diazodiphenylmethane |
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| Authors: | J B Nikoli? G S U??umli? I O Jurani? |
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| Institution: | 1. Department of Organic Chemistry, Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, P.O. Box. 3505, 11120 Belgrade, SerbiaDepartment of Organic Chemistry, Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, P.O. Box. 3505, 11120 Belgrade, Serbia;2. Department of Organic Chemistry, Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, P.O. Box. 3505, 11120 Belgrade, Serbia;3. Faculty of Chemistry, University of Belgrade, Studentski trg 12‐16, P.O. Box. 158, 11001 Belgrade, Serbia |
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| Abstract: | The rate constants for the reaction of 2‐methyl‐cyclohex‐1‐enylcarboxylic, 2‐phenylcyclohex‐1‐enylcarboxylic, and 2‐methylbenzoic and 2‐phenylbenzoic acids with diazodiphenyl‐methane were determined in 14 various solvents at 30°C. To explain the kinetic results through solvent effects, the second‐order rate constants 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 initial and transition state contributions. The quantitative relationship between the molecular structure and the chemical reactivity has been discussed, as well as the effect of geometry on the reactivity of the examined molecules. The geometric data of all the examined compounds corresponding to the energy minima in solvent, simulated as dielectric continuum, obtained using semiempirical MNDO‐PM3 energy calculations. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 664–671, 2007 |
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