DOI: https://doi.org/10.15421/081418
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The quantum-chemical investigation of N-cyclization reaction mechanism for epichlorohydrin aminolysis products

Andrey V. Tokar

Abstract


The mechanism of intramolecular cyclization for products of epichlorohydrin aminolysis by secondary amines has been investigated at ab initio level of theory. By comparative analysis of energetic characteristics, which obtained in vacuo 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 EACT 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.


Keywords


azetidinium chloride; nonspecific solvation; ab initio calculations

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References


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