Abstract
The rate of the keto-enol tautomerization of acetylacetone was studied in water-acetonitrile (AN) and water-dimethyl sulfoxide (DMSO) mixtures. The apparent partition coefficients of acetylacetone between n-heptane and these mixed solvents were measured to estimate the free energies of transfer of each tautomer from water to the mixed solvents. The rate constants of enolization and ketonization depended remarkably on the composition of the mixed solvents, and a maximum in the enolization reaction was observed at about 20 mol% DMSO in water-DMSO mixtures. These kinetic solvent effects were analyzed with “rate-partition relationship” (RPR) derived on the basis of the transfer free energy concept, and the unusual kinetic solvent effect observed in water-DMSO mixtures was interpreted in terms of the destabilization of the keto form in the mixed solvents. An applicability of the RPR to other reactions was suggested.
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