Abstract
Gaseous oxygen, O2, is our most ubiquitous and available oxidizing agent. Through respiration, its reaction with organic molecules sustains life and, through combustion, provides most of our heat and energy. It reacts with many organic molecules at or near room temperature with surprising ease. This process, known as autoxidation, is of great practical importance. On the one hand, it provides the preferred route to a number of important commercial chemicals, for example, terephthalic acid, phenol, acetone, and aliphatic acids. On the other, its prevention is crucial in preserving a host of materials, including plastics, rubber, lubricating oil, and many foodstuffs. Finally, autoxidation is important in biological systems, and there is currently intense interest in its possible role in a number of pathological conditions on the part of medical biochemists.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
Similar content being viewed by others
References
Bäckström, H. L. J. (1934) Der Kettenmechanismus bei der Autoxydation von Aldehyden. Z. Physik Chem., B25, 99–121.
Baeyer, A., and Villiger, V. (1900) Perbenzoic Acid and the Oxidation of Benzaldehyde in the Air. Ber. dtsch. Chem. ges., 33, 1569–1585.
Bartlett, P. D., and Guaraldi, G. (1967) Di-t-butyl Trioxide and Di-t-Butyl Tetroxide. J. Am. Chem. Soc., 89, 4799–4801.
Bartlett, P. D., and Traylor, T. G. (1963) Oxygen-18 Tracer Studies of Alkylperoxy Radicals. I. The Cumylperoxy Radical and Chain Termination in the Autoxidation of Cumene. J. Am. Chem. Soc., 85, 2407–2410.
Benson, S. W., and Nagia, P. S. (1979) Some Unresolved Problems in Oxidation and Combustion. Acc. Chem. Res., 12, 223–228.
Bentrude, W. G. (1982) Phosphoranyl Radicals: Their Structure, Formation, and Reactions. Acc. Chem. Res., 15, 117–125.
Bothe, E., Behrens, G., and Schulte-Frohlinde, D. (1977) Mechanism of the First Order Decay of 2-Hydroxy-propyl-2-peroxy Radicals and of O2- Formation in Aqueous Solution. Z. Naturforsch., 32b, 886–892.
Bromberg, A., and Muszkat, K. A. (1969) Oxidation of 4a–4b-Dihydrophenanthrenes. I. Kinetics of the Thermal Reaction of 9, 10-Cyclopentano-4a–4b-dihydrophenanthrene with Oxygen. J. Am. Chem. Soc., 91, 2860–2866.
Buckler, S. A. (1962) Autoxidation of Trialkyl Phosphines. J. Am. Chem. Soc., 84, 3093–3097.
Burton, G. W., and Ingold, K. U. (1986) Vitamin E: Application of the Principles of Physical Organic Chemistry to the Exploration of Its Structure and Function. Acc Chem. Res., 19, 194–201.
Carlsson, D. J., and Robb, J. C. (1966) Liquid Phase Oxidation of Hydrocarbons, Part 4, Indene and Tetralin. Occurence and Mechanism of the Thermal Initiation Reaction with Oxygen. Trans. Faraday Soc., 62, 3403–3415.
Criegee, R. (1935) Osmic Acid Esters as Intermediates in Oxidations. Liebigs Ann., 522, 75–96.
Dessau, R. M., Sheh, S., and Heiba, E. I. (1970) Oxidation by Metal Salts. A New Chemical Method for Generation of Aromatic Radical Cations. J. Am. Chem. Soc., 92, 412–413.
Flurry, R. L., and Boozer, C. E. (1966) The Mechanism of the Chlorophos-phonation of Hydrocarbons by Phosphorus Trichloride and Oxygen. J. Org. Chem., 31, 2076–2083.
Gardner, H. W. (1989) Oxygen Radical Chemistry of Polyunsaturated Fatty Acids. Free Radical Biol. Med., 7, 65–86.
Graf, R. (1952) The Reaction Mechanism of Sulfoxidation. Leibigs Ann., 578, 50–82.
Hammett, L. P. (1941) Physical Organic Chemistry, McGraw Hill Book Company, New York.
Howard, J. A. (1973) Homogeneous Liquid-Phase Autoxidations, in Free Radicals (J. K. Kochi, Ed.), Vol. 2, Chap. 12, John Wiley & Sons, New York.
Howard, J. A. (1978) Self-Reactions of Alkylperoxy Radicals in Solution, in Organic Free Radicals (W. A. Pryor, Ed.), ACS Symposium Series, 69, American Chemical Society, Washington, DC., pp. 423–432.
Howard, J. A., and Ingold, K. U. (1968) The Self-Reaction of sec-Butylperoxy Radicals, Confirmation of the Russell Mechanism. J. Am. Chem. Soc., 90, 1056–1058.
Howard, J. A., and Ingold, K. U. (1967a) Absolute Rate Constants for Hydrocarbon Autoxidation. V. The Hydroperoxy Radical in Chain Propagation and Termination. Can. J. Chem., 45, 785–792.
Howard, J A., and Ingold, K. U. (1967b) Absolute Rate Constants for Hydrocarbon Autoxidation. VI. Alkylaromatic and Oleflnic Hydrocarbons. Can J. Chem. 45, 793–803.
Howard, J. A., and Ingold, K. U. (1970) Absolute Rate Constants for Hydrocarbon Autoxidation. XVIII. Oxidation of some Acyclic Ethers. Can. J. Chem., 48, 873–880.
Howard, J. A., and Korcek, S. (1970) Absolute Rate Constants for Hydrocarbon Autoxidation. XIX. Oxidation of Some α-Substituted Toluenes. Can. J. Chem., 48, 2165–1272.
Howard, J. A., and Scaiano, J. C. (1984) Oxyl, Peroxyl, and Related Radicals, in Landolt Börnstein Numerical Data and Functional Relations in Science and Technology (H. Fischer, Ed.), New Series, Vol. 13, Subvolume d Springer-Verlag, New York.
Ingold, K. U. (1969) Peroxy Radicals. Acc. Chem. Res., 2, 1–9.
Ingold, K. U., Bowry, V. W., Stocker, R., and Walling, C. (1993) Autoxidation of Lipids and Antioxidation by α-Tocopherol and Ubiquinol in Homogeneous Solution and in Aqueous Dispersions of Lipids: Unrecognized Consequences of Lipid Particle Size as Exemplified by Oxidation of Human Low Density Lipoprotein. Proc. Natl. Acad. Sci. USA 90, 45–49.
Ingold, K. U., and Roberts, B. P. (1971) Free Radical Substitution Reactions, Wiley-Interscience, New York.
Janzen, E. G., Johnston, F. J., and Ayers, C. A. (1967) The Reversible Thermal Decomposition of Triphenylmethylperoxy Radical to Triphenylmethyl Radical and Oxygen. J. Am. Chem. Soc., 89, 1176–1183.
Kellogg, R. E. (1969) The Mechanism of Chemiluminescence from Peroxy Radicals. J. Am. Chem. Soc., 91, 5433–5439.
Kharasch, M. S., Nudenberg, W., and Mantell, G. J. (1951) Reactions of Atoms and Free Radicals in Solution, XXV. The Reactions of Olefins with Mercaptans in the Presence of Oxygen. J. Org. Chem., 16, 524–532.
Korcek, S., Chenier, J. H. B., Howard, J. A., and Ingold, K. U. (1972) Absolute Rate Constants for Hydrocarbon Autoxidation. XXI. Activation Energies for Propagation and Correlation of Propagation Rate Constants with Carbon-Hydrogen Bond Strengths. Can. J. Chem., 50, 2285–2297.
Mahoney, L. R., and DaRooge, M. A. (1970) The Equilibrium Reaction of 2,4,6-Tri-t-butylphenol and Organic Peroxy Radicals. J. Am. Chem. Soc., 92, 4063–4067.
Morimoto, T., and Ogata, Y. (1967) Kinetics of the Oxidation of Toluene Catalyzed by Cobaltic Acetate, Part II. Effect of Benzaldehyde, Cobalt, and Substituent. J. Chem. Soc. B62, 1353–1357.
Mayo, F. R. (1968) Free-Radical Autoxidations of Hydrocarbons. Acc. Chem. Res., 1, 193–201.
Mayo, F. R., Durham, L. Y., and Griggs, K. S. (1963) The Reaction of Alkanes with Phosphorus Trichloride and Oxygen. J. Am. Chem. Soc., 85, 3156–3164.
Niu, Q. J., and Mendenhall, G. D. (1992) Singlet Molecular Oxygen from Peroxyl Radical Termination. Possible Violation of Wigner Spin Conservation in a Concerted Reaction. J. Am. Chem. Soc., 114, 165–172.
Nugteren, D. H., Vonkeman, H., and van Dorp, D. A. (1967) Non-enzymatic Conversion of All-cis-8,11,14-eicosatrienoic Acid into Prostaglandin E1. Rec. Trav. Chim., 86, 1237–1245.
Plesnicar, B. (1983) Organic Polyoxides, in The Chemistry of Peroxides (S. Patai, Ed.), John Wiley & Sons, New York, pp. 521–584.
Porter, C. W., and Steele, C. (1920) Oxidation of the Grignard Reagent. J. Am. Chem. Soc., 42, 2650–2654.
Porter, N. A. (1986) Mechanisms for the Autoxidation of Polyunsaturated Lipids. Acc Chem. Res., 19, 262–268.
Porter, N. A., and Zuraw, P. J. (1985) The Allylic Rearrangement of Hydroperoxides: Oxygen Entrapment of the Propsed Carbon Radical Intermediate. Chem. Soc., Chem. Commun., 1472–1473.
Roelofs, M. G., Wasserman, E., and Jensen, J. H. (1987) Oscillations and Complex Mechanisms: O2 Oxidation of Benzaldehyde. J. Am. Chem. Soc., 109, 4207–4217.
Russell, G. A. (1956) The Rate of Oxidation of Aralkyl Hydrocarbons. Polar Effects in Free Radical Reactions. J. Am. Chem. Soc., 78, 1047–1054.
Russell, G. A. (1957) Deuterium-isotope Effects on the Autoxidation of Aralkyl Hydrocarbons. Mechanism of the Interaction of Peroxy Radicals. J. Am. Chem. Soc., 79, 3871–3877.
Russell, G. A., Janzen, E. C., Bemis, A. G., Geels, E. J., Moye, A. J., Mak, S., and Strom, E. T. (1965) Oxidation of Hydrocarbons in Basic Solution, Adv. Chem., 51, 112–171.
Russell, G. A., Bemis, A. G., Geels, E. J., Janzen, E. C., and Moye, A. J. (1968) Oxidation of Carbanions: Oxidation of Diarylmethanes and Diarylcarbinols in Basic Solution, Adv. Chem., 75, 174–202.
Russell, G. A., and Williamson, R. C., Jr. (1964) Nature of the Polar Effect in Reactions of Atoms and Radicals. II. Reactions of Chlorine Atoms and Peroxy Radicals. J. Am. Chem. Soc., 86, 2357–2364.
Vassil’ev, R. F. (1967) Chemiluminescence in Liquid Phase Reactions. Prog. Reaction Kinetics, 4, 305–352.
Walling, C. (1957) Free Radicals in Solution, John Wiley & Sons, New York.
Walling, C. (1969) Limiting Rates of Hydrocarbon Autoxidations. J. Am. Chem. Soc., 91, 7590–7594.
Walling, C., and Buckler, S. A. (1955) The Reaction of Oxygen with Organo-metallic Compounds. A New Synthesis of Hydroperoxide. J. Am. Chem. Soc., 77, 1632–6038.
Walling, C., and Cioffari, A. (1970) Radical Cyclization During Autoxidation of 5-Hexenylmagnesium Bromide. J. Am. Chem. Soc., 92, 6609–6611.
Walling, C., and McElhill, E. A. (1951) The Reactivities of Benzaldehydes with Perbenzoate Radicals. J. Am. Chem. Soc., 73, 2927–2931.
Walling, C., Stacey, F. R., Jamison, S. E., and Huyser, E. S. (1958) The Reaction of Olefins with Oxygen and Phosphorus. J. Am. Chem. Soc., 80, 4543–4546.
Wöhler, F., and Liebig, J. (1832) Research Concerning the Radical of Benzoic Acid. Liebigs Ann., 3, 249–288.
Woodward, A. E., and Mesrobian, R. B. (1953) Low Temperature Oxidation of Hydrocarbons: The Kinetics of Tetralin Oxidation. J. Am. Chem. Soc., 75, 6189–1695.
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1995 Chapman & Hall
About this chapter
Cite this chapter
Walling, C. (1995). Autoxidation. In: Foote, C.S., Valentine, J.S., Greenberg, A., Liebman, J.F. (eds) Active Oxygen in Chemistry. Structure Energetics and Reactivity in Chemistry Series (SEARCH Series), vol 2. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-0874-7_2
Download citation
DOI: https://doi.org/10.1007/978-94-007-0874-7_2
Publisher Name: Springer, Dordrecht
Print ISBN: 978-0-7514-0371-8
Online ISBN: 978-94-007-0874-7
eBook Packages: Springer Book Archive