Collect. Czech. Chem. Commun. 1984, 49, 1627-1634

Electrochemical investigation of radical-anion reactions of 5-nitro-2-furfuryl derivatives

Jiří Klímaa, Josef Prousekb, Jiří Ludvíka and Jiří Volkea

a J. Heyrovský Institute of Physical Chemistry and Electrochemistry, Czechoslovak Academy of Sciences, 118 40 Prague 1
b Department of Environmental Chemistry and Technology, Slovak Institute of Technology, 812 37 Bratislava


In the studies on nucleophilic substitution of 5-nitro-2-furfuryl derivatives the function of nucleophilic agent was substituted by electrolysis. The electrochemical reduction of these substances and the follow-up reactions of the intermediates were studied by cyclic voltammetry, dc-polarography and ESR spectroscopy. The primary reduction step is the uptake of a single electron giving rise to the radical anion R-CH2-X- which spontaneously splits off the anion X- and forms the neutral 5-nitro-2-furfuryl radical R-CH2.. This radical may either dimerize to 1,2-bis(5-nitro-2-furyl)ethane or yield 5-nitro-2-methylfuran (VI) through abstraction of hydrogen from the solvent or from the supporting electrolyte or through the uptake of an electron and the following protonation. The mechanism found here confirms the validity of the formerly suggested radical-anion mechanism in the nucleophilic substitution of some 5-nitro-2-furfuryl derivatives.