Oxidations By The Reagent O2-h2o2-vanadium Complex - Pyrazine-2-carboxylic Acid. Part 7. Hydroperoxidation Of Higher Alkanes

Alkanes (n-heptane, 2- and 3-methylhexane, cis- and trans-decalin) are readily oxidized under air in acetonitrile by the O2-H2O2-PCA-VO3 - reagent at room temperature to produce alkyl hydroperoxides as main products as well as minor amounts of the corresponding alcohols and carbonyl compounds. The site selectivities of the reactions are very similar to those observed with hydroxylation of the alkanes with hydrogen peroxide under UV irradiation. The proposed mechanism involves the catalytic formation of hydroxyl radicals from hydrogen peroxide which abstract hydrogen atoms from the alkanes. The alkyl radicals react rapidly with molecular oxygen to produce peroxyl radicals which are transformed mainly into the hydroperoxides.52411305113062Patai, S., (1983) The Chemistry of Peroxides, , Wiley: ChichesterDrauz, K., Waldmann, H., (1995) Enzyme Catalysis in Organic Synthesis, , VCH: New York-WeinheimJefford, C.W., (1993) Chem. Soc. Rev., p. 59Shul'pin, G.B., (1988) Organic Reactions Catalyzed by Metal Complexes, , Nauka: MoscowDrago, R.S., (1992) Coord. Chem. Rev., 117, p. 185Barton, D.H.R., Doller, D., (1992) Acc. Chem. Res., 25, p. 504Strukul, G., (1992) Catalytic Oxidations with Hydrogen Peroxide as Oxidant, , Kluwer: DordrechtBarton, D.H.R., Martell, A.E., Sawyer, D.T., (1993) The Activation of Dioxygen and Homogeneous Catalytic Oxidation, , Plenum: New YorkSchuchardt, U., Carvalho, W.A., Spinacé, E.V., (1993) Synlett, p. 713Oyama, S.T., Hightower, J.W., (1993) Catalytic Selective Oxidation, , ACS: WashingtonCrabtree, R.H., (1995) Chem. Rev., 95, p. 987Shilov, A.E., Shul'pin, G.B., (1995) Activation and Catalytic Reactions of Hydrocarbons, , Nauka: MoscowShul'pin, G.B., Attanasio, D., Suber, L., (1993) Russ. Chem. Bull., 42, p. 55Shul'pin, G.B., Druzhinina, A.N., Nizova, G.V., (1993) Russ. Chem. Bull., 42, p. 1326Nizova, G.V., Shul'pin, G.B., (1994) Russ. Chem. Bull., 43, p. 1146Shul'pin, G.B., Süss-Fink, G., (1995) J. Chem. Soc., Perkin Trans. 2, 2, p. 1459Shul'pin, G.B., Drago, R.S., Gonzalez, M., (1996) Russ. Chem. Bull, 45, p. 10Guerreiro, M.C., Schuchardt, U., Shul'pin, G.B., Russ. Chem. Bull., , submitted for publicationNizova, G.V., Süss-Fink, G., Shul'pin, G.B., unpublished resultsGalimova, L.G., Maslennikov, S.I., Nikolaev, A.I., (1980) Bull. Acad. Sci. USSR, Div. Chem. Sci., 29, p. 1731Baxendale, J.H., Wilson, J.A., (1957) Trans. Faraday Soc., 53, p. 344Sawyer, D.T., (1991) Oxygen Chemistry, p. 126. , Oxford University Press: New York, cap. 5, 128Russel, G.A.J., (1957) J. Am. Chem. Soc., 79, p. 3871Reid, I.D., Rhodes, C.J., Roduner, E., (1992) Tetrahedron Lett., 33, p. 561