95973-55-0Relevant academic research and scientific papers
ELECTROLYTIC REDUCTION OF o-NITROBENZYL THIOCYANATE IN BUFFERED SOLUTIONS ON MERCURY
Hlavaty, Jaromir
, p. 33 - 41 (2007/10/02)
The o-nitrobenzyl thiocyanate (I) behaves differently on the DME and on a large mercury pool electrode.Polarography did not give a sufficiently clear explanation of the reaction mechanism, only the preparative experiments yielded useful results.Whereas polarographic curves in solutions of Britton-Robinson buffer system with 50percent by vol. ethanol exhibit two cathodic waves within the pH region 1-12, corresponding according to their height ratio to an uptake of 4 e and 2 e respectively, the controlled potential preparation electrolysis (CPE) and coulometry results indicate a more complicated reaction path.In the CPE carried out at the concentration of I 1.10-2 mol/l the electroreductive splitting of CH2-SCN occurs as the first step.Nitrobenzyl radicals so formed react in the follow-up dimerization resulting in dibenzyl or toluene structures.Simultaneously or at a later stage the completion of the electrolytic reduction of the nitro group proceeds to the hydroxylamino group.In solution of 9>pH>1 the CPE of nitro compounds I takes place by an ECEC mechanism yielding dibenzodiazocine III, its N-oxide IV and 2,2'-dimethylazoxybenzene (V).In course of preparative electrolysis in strongly acidic medium 2-amino-benzo(1,3)-thiazine-1-oxide (II) is formed by an EC mechanism.
