The quantum-chemical investigation of N-cyclization reaction mechanism for epichlorohydrin aminolysis products

<p>The mechanism of intramolecular cyclization for products of epichlorohydrin aminolysis by secondary amines has been investigated at <em>ab initio</em> level of theory. By comparative analysis of energetic characteristics, which obtained <em>in vacuo</em> as well as in acetonitrile solution with the trace quantities of water as an «active» solvation partner of reaction, it has been shown a decisive role of solvent, which occurs mainly at the expense of the polarizable effects for nonspecific solvation. Indeed, the addition to the substrate of one water molecule have decreased corresponding E_ACT values only 24.1 kJ/mol, while the appearance of acetonitrile surroundings have the same influence ~42.0 kJ/mol. The results of calculations are in good agreement with that data, which have been obtained for such type modeling previously.