Abstract
The electrochemical behavior of cinnamic acid (CA) on the cathodes with a high hydrogen overpotential (Hg, glassy carbon, and carbositall) in the aprotic solvent (DMF) and in DMF with additions of H2O or Et4NOH is studied by the methods of polarography, preparative electrolysis, cyclic voltammetry (CVA), coulometry, and chronoammetry. It is found that the mechanism of CA electroreduction is in conflict with the classical notion of the mechanism of electroreduction of α,β-unsaturated carboxyl compounds. It is shown that in the aprotic solution, in contrast to similar carbonyl compounds or ethers, which are the derivatives of organic acids, the products of double-bond hydrogenation, rather than the dimeric compounds, are the only products of CA electroreduction, i.e the presence of carboxyl group changes essentially the direction of electrochemical process. From the data of CVA, it is concluded that stable dimeric associates are present in the DMF solutions in the equilibrium with nondissociated CA.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Organic electrochemistry, Lund, H. and Hammerich, O., Eds., New York, Basel: Marcel Dekker, 2001.
Tomilov, A.P., Mairanovskii, S.G., Fioshin, M.Ya., and Smirnov, V.A., Elektrokhimiya organicheskikh soedinenii (The Electrochemistry of Organic Compounds), Leningrad: Khimiya, 1968.
Tomilov, A.P., Fioshin, M.Ya., and Smirnov, V.A., Elektrokhimicheskii sintez organicheskikh veshchestv (Electrochemical Synthesis of Organic Compounds), Leningrad: Khimiya, 1976.
Organic Electrochemistry, Baizer, M.M. and Lund, H., Eds., New York: Marcel Dekker, 1983.
Nekrasov, L.N. and Korotkov, A.P., Elektrokhimiya, 1980, vol. 16, p. 168.
Wilson, Ch.L. and Wilson, K.B., Trans. Electrochem. Soc., 1943, vol. 84, p. 153.
Kanetsuna, H. and Nonaka, T., Denki Kagaku, 1981, vol. 49, p. 526.
Smirnov, V.A., Vosstanovlenie amal’gamami (Reduction by Amalgams), Leningrad: Khimiya, 1970.
Brand, M.J.D. and Fleet, B., J. Electroanal. Chem., 1968, vol. 16, p. 341.
Korotaeva, L.M., Rubinskaya, T.Ya., Rybakova, I.A., and Gul’tyai, V.P., Russ. Chem. Bull., 2011, p. 63.
Macias-Ruvalcaba, N.A. and Evans, D.H., J. Phys. Chem. B, 2005, vol. 109, p. 14642.
Organikum. Praktikum po organicheskoi khimii Organikum. (Workshop on Organic Chemistry), Moscow: Mir, 1979, vol. 2.
Heyrovsky, J. and Kuta, J., Zaklady Polarografie, Prague: Nakl. Cheskoslovenske Akad. Ved., 1965.
Mishustin, A.I. and Kessler, Yu.M., Zh. Strukturn. Khimii, 1974, vol. 15, p. 205.
Amatore, C., Carabianco, G., Farnia, G., Sandona, G., Saveant J.-M., Severin, M.G., and Vianello, E., J. Am. Chem. Soc., 1985, vol. 107, p. 1815.
Bard, A.J. and Faulkner, L.R., Electrochemical Methods. Fundamentals and Applications, New York: Wiley, 2001.
Cohen, M.D., Schmidt, G.M., and Sonntag, F.I., J. Chem. Soc., 1964, p. 2000.
Il’chibaeva, I.B., Kagan, E.Sh., and Tomilov, A.P., Elektrokhimiya, 2002, vol. 38, p. 1159 [Russ. J. Electrochem., 2002, vol. 38, p. 1045].
Fietkau, N., Paddon, C.A., Bhatti, F.L., Donohoe, T.J., and Compton, R.G., J. Electroanal. Chem., 2006, vol. 593, p. 131.
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © L.M. Korotaeva, T.Ya. Rubinskaya, L.V. Mikhal’chenko, I.A. Rybakova, V.P. Gul’tyai, 2011, published in Elektrokhimiya, 2011, Vol. 47, No. 10, pp. 1220–1227.
Rights and permissions
About this article
Cite this article
Korotaeva, L.M., Rubinskaya, T.Y., Mikhal’chenko, L.V. et al. Peculiarities of the mechanism of electroreduction of cinnamic acid in DMF and DMF-H2O mixture. Russ J Electrochem 47, 1139–1145 (2011). https://doi.org/10.1134/S1023193511100065
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S1023193511100065