The mechanism of electrochemical oxidation of 1,2,3,4-tetrahydropyridines in acetonitrile has been studied. A single reversible one-electron oxidation is registered in the accessible voltage range. The reversibility of the process is sensitive to the traces of oxygen in solution. The electrochemically generated radical cation of tetrahydropyridine may act as a mediator in an indirect oxidation of dihydropyridines if the difference in oxidation potentials between two compounds is less than 200 mV. During the indirect oxidation of 2,4,6-trimethyl-1,4-dihydropyridine-3,5-dicarboxylic acid diethyl ester to 3,5-bis(ethoxycarbonyl)-2,4,6-trimethylpyridinium perchlorate, some of the starting tetrahydropyridine is protonated, thus making it anodically inactive.
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Notes
Independently the electrode was tested with the well-known 1e reversible redox reaction benzo-quinone/semiquinone in MeCN. It gave the same value N = 0.35.
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The work was financially supported by the Latvian Council of Science (grant 09-1558) and by the European Regional Development Fund (ERDF) project No. 2DP/2.1.1.1.0/10/APIA/VIAA/065.
The authors thank Dr. Chem. E. Liepinsh for NMR analysis of epimers on the Bruker DMX-600 spectrometer and Dr. Chem. S. Grinberga for GC-MS analysis.
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Deceased (I. Turovskis).
Publushed in Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1770-1782, November, 2013.
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Turovska, B., Goba, I., Lielpetere, A. et al. Electron Transfer Reactions in the Chemistry of Di- and Tetrahydropyridines. Chem Heterocycl Comp 49, 1640–1652 (2014). https://doi.org/10.1007/s10593-014-1415-5
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DOI: https://doi.org/10.1007/s10593-014-1415-5