Abstract
Two variants of the reaction of radicals with the carboxyl group of carboxylic acids, namely, RO •2 + R i COOH → ROOH + R i CO •2 and RO • i + R j COOH → ROOH + R • i + CO2 are theoretically analyzed. It is demonstrated by the intersecting-parabolas method that if the reaction proceeded via the formation of an intermediate carboxyl radical, it would be much slower than is actually observed. Quantum-chemical calculations carried out by the density functional method using the nonempirical functional PBE have shown that the reactions of the methyl radical with the carboxyl group of acetic, butyric and vinylacetic acids include concerted H atom abstraction and C-C bond breaking. In the framework of the intersecting-parabolas model, an algorithm has been developed to calculate the activation energy and rate constant for X• + R i COOH → XH + CO2 + R • i reactions, where X = R•, RO•, HO•, ArO•, Ar2N• or H•
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Berezin, I.V., Berezkina, L.T., and Nosova, T.L., in Okislenie uglevodorodov v zhidkoi faze (Liquid-Phase Oxidation of Hydrocarbons), Emanuel’, N.M., Ed., Moscow: Akad. Nauk SSSR, 1958, p. 101.
Berezin, I.V. and Ragimova, A.M., Zh. Fiz. Khim., 1962, vol. 36, no. 3, p. 581.
Mitskevich, N.I., Extended Abstract of Doctoral (Chem.) Dissertation, Minsk: Institute of Physical Organic Chemistry, 1963.
Agabekov, V.E., Extended Abstract of Cand. Sci. (Chem.) Dissertation, Minsk: Institute of Physical Organic Chemistry, 1969.
Mitskevich, N.I. and Erofeev, B.V., Sopryazhennoe s okisleniem dekarboksilirovanie karbonovykh kislot (Carboxylic Acid Decarboxylation Coupled with Oxidation), Minsk: Nauka i Tekhnika, 1970.
Denisov, E.T., Mitskevich, N.I., and Agabekov, V.E., Liquid-Phase Oxidation of Oxygen-Containing Compounds, New York: Consultants Bureau, 1977.
Denisov, E.T. and Afanas’ev, I.B., Oxidation and Antioxidants in Organic Chemistry and Biology, Boca Raton: CRC, Taylor & Francis Group, 2005.
Agabekov, V.E., Mitskevich, N.I., Denisov, E.T., Azarko, V.A., and Budeiko, N.A., Dokl. Akad. Nauk BSSR, 1974, vol. 18, no. 1, p. 38.
Denisov, E.T. and Shestakov, A.F., Russ. Chem. Bull., 2012, vol. 61, no. 1, p. 17.
Denisov, E.T. and Tumanov, V.E., Russ. Chem. Rev., 2005, vol. 74, p. 825.
Lide, D.R., Handbook of Chemistry and Physics, Boca Raton, Fla.: CRC, 2004.
Denisov, E.T., Russ. Chem. Rev., 1997, vol. 66, p. 859.
Denisov, E., in General Aspects of Chemistry of Radicals, Alfassi, Z.B, Ed., Chichester: Wiley, 1999, p. 79.
Denisov, E.T. and Denisova, T.G., Handbook of Antioxidants: Bond Dissociation Energies, Rate Constants, Activation Energies and Enthalpies of Reactions. Boca Raton: CRC, 2000.
Denisov, E.T., Khim. Fiz., 2009, vol. 29, no. 12, p. 15.
Aleksandrov, I.V., Teor. Eksp. Khim., 1976, vol. 12, p. 299.
Perdew, J.P., Burke, K., and Ernzerhof, M., Phys. Rev. Lett., 1996, vol. 77, p. 3865.
Laikov, D.N. and Ustynyuk, Yu.A., Russ. Chem. Bull., 2005, no. 3, p. 820.
Abel, B., Assmann, J., Botschwina, P., Buback, M., Kling, M., Oswald, R., Schmatz, S., Schroeder, J., and Witte, T., J. Phys. Chem. A, 2003, vol. 107, p. 5157.
Kling, M. and Schmatz, S., Phys. Chem. Chem. Phys., 2003, vol. 5, no. 18, p. 3891.
Pritzkow, W. and Voerckel, V., Oxid. Commun., 1983, vol. 4, nos. 1–4, p. 223.
Pritzkow, W. and Voerckel, V., J. Prakt. Chem., 1984, vol. 326, no. 4, p. 572.
Pimentel, G.C. and McClellan, A.L., The Hydrogen Bond, Pauling, L., Ed., San Francisco: Freeman, 1960.
Nemes, I., Heberger, K., Keszler, A., Vasvari, G., Gal, D., Cotarca, L., and Devodu, P., Ber. Bunsen-Ges. Phys. Chem., 1994, vol. 98, no. 1, p. 75.
Heberger, K., Keszler, A., Vasvari, G., and Gal, D., Ber. Bunsen-Ges. Phys. Chem., 1994, vol. 98, no. 1, p. 1303.
Denisova, T.G. and Denisov, E.T., Pet. Chem., 2004, vol. 44, no. 4, p. 250.
Denisov, E.T. and Pokidova, T.S., Khim. Fiz., 2010, vol. 29, no. 8, p. 29.
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Original Russian Text © E.T. Denisov, A.F. Shestakov, 2013, published in Kinetika i Kataliz, 2013, Vol. 54, No. 1, pp. 24–34.
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Denisov, E.T., Shestakov, A.F. Free-radical decarboxylation of carboxylic acids as a concerted abstraction and fragmentation reaction. Kinet Catal 54, 22–33 (2013). https://doi.org/10.1134/S0023158413010059
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DOI: https://doi.org/10.1134/S0023158413010059