A Quantum-Chemical Study of the Oxidation of Ethyleneby Peroxyacetic Acid Derivatives

摘要

Density functional theory (B3LYP/6-31G(d, p)) and the Moller—Plesset perturbation theory(MP2/6-31G(d, p)) were used to study the electronic and geometric structure and relative stability of possibleperoxyacetic 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 characteristicsof transitions between them were determined. The results of quantum-chemical modeling were used to studysome special features of the oxidation of ethylene with the participation of all the tautomeric forms of bothperoxy acids. For the acyclic form (ground state) of both peroxy acids and its conformers, two reactions arepossible, namely, epoxidation with the formation of ethylene oxide (plus acid) and hydroxylation with theformation of ethanediol acetate ester and/or its isomer acetaldehyde semiacetal. At the same time, the oxi-dation of ethylene with the participation of all the other tautomeric forms (dioxirane and tautomers of thetype of carbonyl and water oxides) only results in ethylene epoxidation.