The effect of tertiary amine structure and solvent polarity on 2-(chloromethyl)oxirane acetolysis

Abstract

The kinetic regularities of the ring opening of the 2-(chloromethyl)oxirane by acetic acid in the presence of tertiary amines with a variable volume of substituents at the nitrogen atom in the binary solvent epichlorohydrin : nitrobenzene in the ratio of solvent components 1 : 1 were studied. The zeroth order of the reaction for the acid and the first one for the catalyst was established. The regioselectivity and kinetic regularities of the reaction depending on the catalyst structure and the solvent polarity were studied. It was shown that the catalytic activity of the tertiary amines is determined by their nucleophilicity. The row of tertiary amines on catalytic activity in the reaction of 2- (chloromethyl)oxirane with acetic acid were determined. The activation parameters of the reaction were calculated. The first order of reaction for acid at increase of its concentration is established. The presence of kinetic enthalpy-entropy compensation effect was shown. The correlations between the rate of acetolysis of epichlorohydrin and structural and electronic parameters of tertiary amines were established.