Perepichka I. Phenolysis of epichlorhydrine catalised by organic bases

The dissertation research is devoted to determination of quantitative relationships of catalytic phenolysis of a-oxide cycle of epychlorohydrine and identification of the mechanism of catalysis by amines and ammonium salts. It has been shown that a catalytic phenolysis of epychlorohydrine with phenols of various acidity proceeds in two steps: the fast formation of phenol chloropropylenehydrine ether and its conversion to glycidylic ether in the slower step. The rate of the second step becomes significant only in the presence of catalysts. The relationship between the kinetic order of the reaction and the phenol acidity has been discovered. The phenols reactivity increases with decrease of their acidity, but the sensitivity of the reaction rate to the phenol' structure is low. It was shown that tertiary amines, pyridine, methylpyridines, tetraalkylammonium halides, who's differs by more then 10 orders of magnitude, posses virtually the same catalytic activity in the reaction of phenols with epychlorohydrine while the last acts as a reagent and a solvent. The first kinetic order towards each of these catalysts has been determined. The isotope kinetic effect for catalytic and noncatalytic reactions of phenols with epychlorohydrine and the energy's parameters of the reaction were also calcu-lated. The mechanism of catalysis with amines and ammonium salts, which selfconsistently explains the changeable kinetic order of the reaction (depending on the phenol's acidity) and low sensitivity of the reaction to the phenol's structure has been proposed