Abstract
Data obtained while studying the kinetics of quaternization of tertiary phosphines with the unsaturated carboxylic acids in the series of aprotic solvents indicate the participation of a second molecule of acid playing the part of the external proton donor in this process. Quantitative analysis of the effect of solvent within the frames of the Koppel-Palm equation showed that the main contribution in the reaction rate belongs to the nucleophilicity of medium while the effects of polarity and electrophilicity are smaller. The results obtained suggest the step-by-step mechanism of interaction including the formation of the zwitterionic intermediate on the reaction pathway common for the solvents with different proton activity.
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Galkin, V.I., Salin, A.V., Bakhtiyarova, Yu.V., and Sabanov, A.A., Zh. Obshch. Khim., 2009, vol. 79, no. 5, p. 747.
Salin, A.V., Sobanov, A.A., Bakhtiyarova, Yu.V., Khabibullin, A.A., and Galkin, V.I., Zh. Obshch. Khim., 2010, vol. 80, no. 9, p. 1418.
Prostranstvennye effekty v organicheskoi khimii (Spatial Effects in Organic Chemistry), Newman, M.S., Ed., Moscow: Inostrannaya Literatura, 1960.
Palm, V.A., Osnovy kolichestvennoi teorii organicheskikh reaktsii (Basis of the Quantitative Theory of Organic Reactions), Leningrad: Khimiya, 1977.
Rayhardt, K., Rastvoriteli i effekty sredy v organicheskoi khimii (Solvents and the Effects of Medium in Organic Chemistry), Moscow: Mir, 1991.
Makitra, R.G. and Pirig, Ya.N., Zh. Obshch. Khim., 1998, vol. 68, no. 3, p. 425.
Liang, Y., Liu, S., Xia, Y., Li, Y., and Yu, Z,-X., Chem. Eur. J., 2008, no. 14, p. 4361.
Zhu, X.-F., Henry, C.E., and Kwon, O., J. Am. Chem. Soc., 2007, no. 129, p. 4361.
Galkin, V.I., Salin, A.V., and Bakhtiyarova, Yu.V., Uchenye Zapiski Kazanskogo Universiteta. Estestvennye Nauki, 2008, vol. 150, no. 3, p. 54.
Galkin, V.I., Bakhtiyarova, Yu.V., Polezhaeva, N.A., Galkina, I.V., Cherkasov, R.A., Krivolapov, D.B., Gubaidullin, A.T., and Litvinov, I.A., Zh. Obshch. Khim., 2002, vol. 72, no. 3, p. 404.
Methot, J.L. and Roush, W.R., Adv. Synth. Catal., 2004, no. 346, p. 1035.
Blomberg, M.R.A. and Siegbahn, P.E.M., Biochim. Biophys. Acta, 2006, no. 1757, p. 969.
Riddick, J.A., Bunger, W.B., and Sakano, T.K., Organic Solvents, New York: Wiley, 1986, vol. 2, 1325 p.
Gordon, A.J. and Ford, R.A., The Chemist’s Companion. A Handbook of Practical Data, Techniques and References, New York: Wiley, 1972.
Obshchii praktikum po organicheskoi khimii (General Laboratory Course of Organic Chemistry), Kost, A.N., Ed., Moscow: Mir, 1965.
Kormachev, V.V. and Fedoseeva, M.S., Preparativnaya khimiya fosfora (Preparative Phosphorus Chemistry), Perm’: Ural. Otd. Ross. Akad. Nauk, 1992.
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Original Russian Text © A.V. Salin, A.A. Sobanov, Yu.V. Bakhtiyarova, A.A. Khabibullin, V.I. Galkin, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 5, pp. 737–743.
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Salin, A.V., Sobanov, A.A., Bakhtiyarova, Y.V. et al. Kinetics and mechanism of quaternization of tertiary phosphines with unsaturated carboxylic acids. Kinetic studies of the reactions in aprotic solvents. Russ J Gen Chem 81, 824–830 (2011). https://doi.org/10.1134/S1070363211050057
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DOI: https://doi.org/10.1134/S1070363211050057