A quantum-chemical study of the oxidation of ethylene by peroxyacetic acid derivatives

Density functional theory (B3LYP/6-31G(d, p)) and the Möller-Plesset perturbation theory (MP2/6-31G(d, p)) were used to study the electronic and geometric structure and relative stability of possible peroxyacetic acid and its trifluorinated derivative tautomers (including conformers), R-C(=O)(-OOH), R = CH3, CF3. Four types of stable tautomers of both compounds were found, and the energy characteristics of transitions between them were determined. The results of quantum-chemical modeling were used to study some special features of the oxidation of ethylene with the participation of all the tautomeric forms of both peroxy acids. For the acyclic form (ground state) of both peroxy acids and its conformers, two reactions are possible, namely, epoxidation with the formation of ethylene oxide (plus acid) and hydroxylation with the formation of ethanediol acetate ester and/or its isomer acetaldehyde semiacetal. At the same time, the oxidation of ethylene with the participation of all the other tautomeric forms (dioxirane and tautomers of the type of carbonyl and water oxides) only results in ethylene epoxidation. © Pleiades Publishing, Ltd., 2010.