Exchange of substituents in the reaction of alkylene oxides with beta-hydroxyalkyl sulfides

摘要

The mechanism of an unusual exchange of substituents in the previously unknown reaction of alkylene oxides with beta-hydroxyalkyl sulfides is considered. Such an exchange-type reaction is demonstrated for numerous systems, as examples. The reaction order for each component is determined. Kinetic and spectroscopic methods are used to establish the initial composition of the reaction mixture, including the H-complex formed from the starting components. The reaction mechanism involves the unimolecular intracomplex rearrangement of the H-complex leading to the formation of a cyclic bipolar ion with an intramolecular hydrogen bond, the decomposition of which determines the composition and nature of the final reaction products. To confirm the proposed mechanism and to elucidate its details, quantum-chemical calculations of the characteristics of the alkylene oxide-beta-hydroxyalkyl sulfide system are used. The kinetic and thermodynamic characteristics of the reaction are obtained.