CONTROLLED-POTENTIAL ELECTROLYTIC REDUCTION: 1,1-BIS(BROMOMETHYL)CYCLOPROPANE

1972 ◽  
Vol 52 ◽  
pp. 22 ◽  
Keyword(s):  
Electrolytic Reduction ◽  
Controlled Potential

Electrolytic reduction of o-nitrobenzyl thiocyanate in buffered solutions on mercury

1985 ◽  
Vol 50 (1) ◽  
pp. 33-41 ◽  
Author(s):  
Jaromír Hlavatý
Keyword(s):  
Acidic Medium ◽  
Reaction Path ◽  
Electrolytic Reduction ◽  
Buffer System ◽  
Height Ratio ◽  
Preparative Electrolysis ◽  
Clear Explanation ◽  
Ec Mechanism ◽  
Controlled Potential

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 50% 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 compound 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(l,3)-thiazine-l-oxide (II) is formed by an EC mechanism.

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