Matviyenko A. Liquid-phase cooxidation of alkylarеnes, reactivity of their molecules and peroxyradicals.

Reactions of oxidation and cooxidation of benzene, biphenyl, naphtalene, pyridine, pyridine-N-oxide, thiophene alkylderivatives. Reactivity of molecules and peroxyradicals in hydrogen atom abstration reaction, peroxyradicals in recombination reaction. Volumetric, gas-liquid chromatography ("Chromatograf - 504", ЛХМ - 8МД), EPR - spectroscopy (RADIOPAN SE/X - 2544) methods; kinetic methods of cooxidation, chemiluminescence; quantum chemical method PM3. There have been established general kinetic regularities of alkylarenes binary mixtures oxidation depending on molecules chemical structure; the parameters of cooxidation being determined and the rate constants for reaction of peroxyradicals with molecules calculated. It was shown that in respect with the structure of molecules the responsible for their reactivity factors are thermodynamic, polar, steric, entropy ones or their combination. As it was stated the reactivity of O-centered radicals in hydrogen atom abstration reaction is determined by the rad ical lower free molecular orbital energy which is characteristic of its electrone accepting ability and reactivity in recombination reaction depends on the value of charge at the end oxygen atom. As it follows from quantum chemical calculations transition states of peroxyradicals reactions with alkylarene molecules are structures with charge separation and negative charge transition from the molecule to the radical is greater for molecules with less ionization potential and for radical with greater electron affinity. Results of the work can be used in alkylarenes liquid-phase oxidation technological process development as well as in radical-chain reaction kinetics and organic compounds reactivity studies.