The dimerization of radical anions of aromatic carboxylic acids competing with the self-protonation reaction |
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Authors: | T. Ya. Rubinskaya A. S. Mendkovich N. K. Lisitsina I. P. Yakovlev V. P. Gultyai |
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Affiliation: | (1) N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 117913 Moscow, Russian Federation |
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Abstract: | Quantum-chemical calculations (CNDO/2) of the theoretical relationship between the rate constants for the dimerization and self-protonation of radical anions show that dimer formation in the one-electron electroreduction of aromatic carboxylic acids (benzoic (1), 1-naphthoic (2), and 9-anthroic (3) is most probable for1. It is established that during the constant potential electrolysis (CPE) of1 a mixture of “head-to-tail” dimers is formed in the presence of 0.1M Bu4NClO4 (DMF). Their ratio depends on the amount of electricity passed through the solution. The CPE of 2 in the presence of 20 % H2O affords 1,4-dihydro-1-naphthoic acid in up to 70 % yield. The high yield (∼70 %) of 9,10-dihydro-9-anthroic acid during the CPE of 3 can be accounted for by the decomposition of the dimeric product followed by protonation of the anionic species. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1735–1738, October, 1993. |
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Keywords: | dimerization self-protonation aromatic carboxylic acids electroreduction radical anions |
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