Journal of Organic Chemistry p. 1041 - 1045 (1985)
Update date:2022-08-04
Topics: Decarboxylation Substituent Effects Aromatic Dinitrobenzoate ions SE1 reactions
Segura, Pascual
Bunnett, Joseph F.
Villanova, Laura
Kinetics of decarboxylation, in water solution, of several 4-substituted 2,6-dinitrobenzoic and 2-substituted 4,6-dinitrobenzoic acids were determined, at several temperatures.The reactions are first order at the low concentrations employed, at which the acids are fully dissociated.Decarboxylation is accelerated by electron-attracting substituents; the Hammett ρ for the effects of 4-substituents is about +2.6.All the decarboxylations involve large positive enthalpies and entropies of activation.The solvent kinetic isotope effect (D2O/H2O) is not significantly different from unity.The data support a mechanism where in the substituted benzoate ion loses CO2 in the rate-determining step, forming a substituted aryl anion, which is then rapidly hydronated by the solvent.In the case of 2-methoxy-4,6-dinitrobenzoate ion, reaction occured with strikingly different activation parameters.
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