Abstract
Polarography and preparative electrolysis are used to show that the electrochemical behavior of 1-ethyl-4-nitro-3-cyanopyrazole (1) in acidic aqueous-alcoholic solutions resembles the behavior of nitrobenzene. By varying the parameters of the electroreduction (ER) of compound 1, one can obtain either 1-ethyl-4-amino-3-cyanopyrazole (2) or 1-ethyl-4-amino-3-cyano-5-chloropyrazole (3). Compound 2 is formed during the ER of compound 1 in the presence of a mediator (titanium(III)) at temperatures below 10°C. Compound 3 is produced by the direct reduction of compound 1 on a lead electrode (30% ethanol, 10% HCl). The yield of amine chlorohydrates 2 and 3 is 56 and 92%, respectively. The mediated ER of compound 1 at catholite temperatures higher than 10°C yields a mixture of compounds 2 and 3; the proportion of the latter increases with temperature to become the major product at 60°C. Compound 3 is formed due to the rearrangement of the hydroxylamine derivative produced by the ER of compound 1, followed by the substitution of chlorine for the hydroxy group.
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Original Russian Text © L.V. Mikhal’chenko, M.Yu. Leonova, Yu.V. Romanova, B.I. Ugrak, V.P. Gultyai, 2007, published in Elektrokhimiya, 2007, Vol. 43, No. 10, pp. 1247–1250.
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Mikhal’chenko, L.V., Leonova, M.Y., Romanova, Y.V. et al. Amine electrosynthesis from 1-ethyl-4-nitro-3-cyanopyrazole. Russ J Electrochem 43, 1183–1186 (2007). https://doi.org/10.1134/S1023193507100126
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DOI: https://doi.org/10.1134/S1023193507100126