Abstract
Data on the effect of the acid-base properties of the medium on the yield and composition of the products of N-dimethoxyphenylation of azoles (pyrazole, triazole, their substituted derivatives, and tetrazole) upon galvanostatic electrolysis of azole—1,4-dimethoxybenzene mixtures in nucleophilic (MeOH) and neutral (MeCN) media were considered and the trends of this process were discussed. The generation of arenium cations (1,4-dimethoxy-1-azolylbenzenium in MeCN and 1,1,4-trimethoxybenzenium in MeOH) as the key intermediates of electrosynthesis of N-(dimethoxyphenyl)azoles, was proved experimentally. A new approach to the synthesis of N-(dimethoxyphenyl)azoles through electrosynthesis of 1,1,4,4-tetramethoxycyclohexa-2,5-diene by electrooxidation of 1,4-dimethoxybenzene in MeOH as the first step and the reaction of this quinone diketal with azoles as the second step was suggested. The efficiency of this route to N-(dimethoxyphenyl)azoles is comparable with the efficiency of the purely electrochemical one-step process.
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2101–2109, November, 2007.
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Petrosyan, V.A., Burasov, A.V. Arenium cation as the key intermediate of the electrosynthesis of N-(2,5-dimethoxyphenyl)azoles. A new approach to the synthesis of N-(dimethoxyphenyl)azoles. Russ Chem Bull 56, 2175–2183 (2007). https://doi.org/10.1007/s11172-007-0342-3
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DOI: https://doi.org/10.1007/s11172-007-0342-3