Oxidation and Antioxidants in Organic Chemistry and Biology

Book Preface

Oxidation of organic compounds by dioxygen is a phenomenon of exceptional importance in nature, technology, and life. The liquid-phase oxidation of hydrocarbons forms the basis of several efficient technological synthetic processes such as the production of phenol via cumene oxidation, cyclohexanone from cyclohexane, styrene oxide from ethylbenzene, etc. The intensive development of oxidative petrochemical processes was observed in 1950–1970. Free radicals participate in the oxidation of organic compounds. Oxidation occurs very often as a chain reaction. Hydroperoxides are formed as intermediates and accelerate oxidation. The chemistry of the liquid-phase oxidation of organic compounds is closely interwoven with free radical chemistry, chemistry of peroxides, kinetics of chain reactions, and polymer chemistry.

The science of oxidation processes developed intensively during the 20th century. In the very beginning of this century, A.N. Bach and C. Engler formulated the peroxide conception of oxidation by dioxygen. H. Backstrom proved the chain mechanism of slow liquid-phase oxidation (1927). N.N. Semenov formulated the theory of chain oxidation with degenerate branching of chains applied to hydrocarbon oxidation (1934). A line of brilliant kinetic experiments were performed in the period 1960–1980 concerning elementary steps of liquidphase oxidation of hydrocarbons. The results of these studies were collected in two volumes edited by W.O. Lundberg, Autoxidation and Antioxidants (1961) and monograph Liquid- Phase Oxidation of Hydrocarbons written by N.M. Emanuel, E.T. Denisov, and Z.K. Maizus (1967). The results of the study of oxidation of oxygen-containing compounds were systematized in the monograph Liquid-Phase Oxidation of Oxygen-Containing Compounds (E.T. Denisov, N.I. Mitskevich, V.E. Agabekov, 1977). Several new excellent experimental methods were developed in the second half of the 20th century for the study of free radical reactions. A great body of kinetic data on reactions of alkyl, peroxyl, alkoxyl, and others radicals was obtained in many publications from 1960 to 1990 (see Database applied to the book).