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Polynitroalkanes, Nitroazoles and Oximes in Electroorganic Synthesis

Published online by Cambridge University Press:  10 February 2011

Murat Niyazymbetov
Murat Niyazymbetov*
Affiliation:
Zelinsky Institute of Organic Chemistry, Moscow and University of Delaware, Department of Chemistry and Biochemistry, Newark, DE 19716, murat@brahms.udel.edu
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Abstract

Electrochemical oxidation of anions of polynitroalkanes (PNA) proceeds via one-electron transfer and results in the formation of unstable radicals. The radicals undergo fragmentation, abstraction of a hydrogen atom from the solvent, and reaction with aromatic compounds to form aryl-PNA. The yield of aryl-PNA depends on the structure of the radicals and on the electron donating properties of the aromatic substrates. Due to their electrophilic properties, PNA-radicals also react with compounds containing heteroatoms with unshared electron pairs resulting in formation of dinitromethylides. Under anodic electrolysis conditions dinitromethylides which have a carbanionic structure can effectively transfer the dinitromethyl group to other organic substrates. Electrochemical oxidation of anions of nitroazoles also proceeds via one-electron transfer to generate nitroazolyl radicals. Their principal reaction is abstraction of hydrogen from the solvent. However, electrolysis of nitroazoles in the presence of aromatic compounds results in formation of N-aryl derivatives in good yield. It has been shown that electrooxidation of mono oximes leads to formation of unstable nitroso dimers, while electrooxidation of vicinal dioximes results in formation of furoxans in high yield.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 418: Symposium GG – Decomposition, Combustion, and Detonation Chemistry of Energetic Materials , 1995 , 25
Copyright
Copyright © Materials Research Society 1996

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