Sadova I. Combined effects of structures and temperatures in the reactions of aryloxiranes with organic acids

The thesis contains the results of cross correlation analysis of the combined effects of structural factors and temperatures on the kinetics and mechanisms of oxirane ring opening reactions between aryloxiranes and organic acids of different nature. General conclusions favour the development of the quantitative theory of oxirane reactions. The polilinear regression models of the reactivity of aryloxirane - acid systems were obtained. Previously unknown isoparametrical reaction series were found, where combined effects of cross-varied factors are nonadditive (structure - structure and structure - temperature). In the reactions of aryloxiranes with benzoic acids and NH-acids joint effects of structures and temperatures are additive, because these reactions belong to the isoenthalpic type. On the strength of cross-correlation analysis the mechanisms of oxirane ring opening reactions were postulated and transition state structures were discussed in details. It has been established by investigation of catalytic effects of tetraethylammonium halides and benzoates in reaction of phenyloxirane with benzoic acids, that in a reactive system tetraethylammonium halides are converted rapidly into benzoates, which are the nucleophilic catalysts of oxirane ring opening.