Free Energy Profile of the Reaction between the Hydroxide Ion and Ethyl Acetate in Aqueous and Dimethyl Sulfoxide Solutions: A Theoretical Analysis of the Changes Induced by the Solvent on the Different Reaction Pathways

摘要: An extensive analysis of the free energy profile for reaction hydroxide ion with ethyl acetate in both aqueous and dimethyl sulfoxide (DMSO) solutions has been carried out using ab initio calculations including solvent effect by polarizable continuum model. Different pathways were investigated, such as usual BAC2 mechanism, carbanion elimination SN2 mechanism. Our calculation agrees view that DMSO solution basic hydrolysis occurs In water, predicted activation value is 17.6 kcal mol-1, which very good agreement experimental 18.8 mol-1. Using a new parametrization model adequate to describe anions neutral species DMSO, present study predicts rate enhancement factor 435 when going from water (protic solvent) (dipolar aprotic solvent). this solvent, ...