Bespal'ko Y. Catalytic acidolysis and phenolysis of epichlorohydrin in the presence of bases

The object of study - the ring opening reaction of epichlorohydrin by nucleophilic reagents in the presence of basic catalysts. The aim of the study - the study of the mechanism of catalytic reaction of epichlorohydrin with carboxylic acids and phenols in the presence of bases and the creation of a kinetic model, which allows to predict the chemical behavior of nucleophilic reagents. Methods of study - pH-potentiometry, NMR, IR spectroscopy, elemental analysis, organic synthesis, quantum chemical calculations, the methods of differential analysis. The thesis focuses on an investigation of reactions between epichlorohydrin and organic acids catalyzed by tertiary bases and quaternary ammonium salts containing free hydroxyl groups. This work also allowed development of a kinetic model suitable for prediction of reactivity of nucleophilic reagents in such reactions. It was found that under these conditions the reaction order with respect to the acids is zero and with respect to the base is one. The reaction rate cross-correlates to the reaction temperature and acid structure. Single isokinetic dependence for both tertiary amines as well as quaternary salts supports the hypothesis of a common reaction mechanism. The geometric parameters of the transition states were calculated at the Density Functional Theory level (B3LYP/6-31+G**) in the gas phase approximating the influence of the solvent by polarizing continuum method (PCM)). It is shown that nucleophilic ring opening of oxiranes is a "soft" (in terms of the HSAB theory) orbital controlled process. It was found that the rate of the reaction is affected more by loose/compressed rather than early/late characteristics of the transition state. The electrophilic assistance is a necessary condition of the process. The developed kinetic model allows to predict the chemical reactivity of nucleophiles for the reaction of oxiranes with carboxylic acids and phenols catalyzed by organic bases.