Artículos de revistas
Oxidations By The Reagent O2-h2o2-vanadium Complex - Pyrazine-2-carboxylic Acid. Part 7. Hydroperoxidation Of Higher Alkanes
Registro en:
Tetrahedron. , v. 52, n. 41, p. 13051 - 13062, 1996.
404020
10.1016/0040-4020(96)00769-7
2-s2.0-0030272549
Autor
Shul'pin G.B.
Guerreiro M.C.
Schuchardt U.
Institución
Resumen
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. 52 41 13051 13062 Patai, S., (1983) The Chemistry of Peroxides, , Wiley: Chichester Drauz, K., Waldmann, H., (1995) Enzyme Catalysis in Organic Synthesis, , VCH: New York-Weinheim Jefford, C.W., (1993) Chem. Soc. Rev., p. 59 Shul'pin, G.B., (1988) Organic Reactions Catalyzed by Metal Complexes, , Nauka: Moscow Drago, R.S., (1992) Coord. Chem. Rev., 117, p. 185 Barton, D.H.R., Doller, D., (1992) Acc. Chem. Res., 25, p. 504 Strukul, G., (1992) Catalytic Oxidations with Hydrogen Peroxide as Oxidant, , Kluwer: Dordrecht Barton, D.H.R., Martell, A.E., Sawyer, D.T., (1993) The Activation of Dioxygen and Homogeneous Catalytic Oxidation, , Plenum: New York Schuchardt, U., Carvalho, W.A., Spinacé, E.V., (1993) Synlett, p. 713 Oyama, S.T., Hightower, J.W., (1993) Catalytic Selective Oxidation, , ACS: Washington Crabtree, R.H., (1995) Chem. Rev., 95, p. 987 Shilov, A.E., Shul'pin, G.B., (1995) Activation and Catalytic Reactions of Hydrocarbons, , Nauka: Moscow Shul'pin, G.B., Attanasio, D., Suber, L., (1993) Russ. Chem. Bull., 42, p. 55 Shul'pin, G.B., Druzhinina, A.N., Nizova, G.V., (1993) Russ. Chem. Bull., 42, p. 1326 Nizova, G.V., Shul'pin, G.B., (1994) Russ. Chem. Bull., 43, p. 1146 Shul'pin, G.B., Süss-Fink, G., (1995) J. Chem. Soc., Perkin Trans. 2, 2, p. 1459 Shul'pin, G.B., Drago, R.S., Gonzalez, M., (1996) Russ. Chem. Bull, 45, p. 10 Guerreiro, M.C., Schuchardt, U., Shul'pin, G.B., Russ. Chem. Bull., , submitted for publication Nizova, 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. 1731 Baxendale, J.H., Wilson, J.A., (1957) Trans. Faraday Soc., 53, p. 344 Sawyer, D.T., (1991) Oxygen Chemistry, p. 126. , Oxford University Press: New York, cap. 5, 128 Russel, G.A.J., (1957) J. Am. Chem. Soc., 79, p. 3871 Reid, I.D., Rhodes, C.J., Roduner, E., (1992) Tetrahedron Lett., 33, p. 5617