Abstract
Cyclic voltammetry and controlled-potential (bulk) electrolysis have been employed to investigate the direct electrochemical reduction of acetochlor (1) at carbon and silver cathodes in dimethylformamide. Voltammograms of 1 exhibit a single irreversible cathodic peak at both cathode materials. Catalytic properties of silver towards carbon–halogen bond cleavage are evidenced by a positive shift in the reduction of acetochlor as compared to the more inert glassy carbon electrode. Voltammograms in the presence of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), and comparisons of calculated relative interaction energies between acetochlor, possible intermediates, and deschloroacetochlor in the presence of different proton donors, suggest strong hydrogen-bonding interactions between HFIP and a carbanion intermediate. Addition of HFIP to electrolysis conditions promotes complete reduction at both cathode materials, with formation of deschloroacetochlor in high yields. In deuterium labelling studies, the use of DMF-d
7 led to no evidence for deuterium atom incorporation. However, when HFIP-OD or D2O were employed as a proton source, substantial amounts of deuterated deschloroacetochlor were observed. A mechanism for the reduction of acetochlor is proposed, in which radical intermediates do not play a significant role in reduction, rather a carbanion intermediate pathway is followed.
Funder
National Science Foundation
Publisher
The Electrochemical Society
Subject
Materials Chemistry,Electrochemistry,Surfaces, Coatings and Films,Condensed Matter Physics,Renewable Energy, Sustainability and the Environment,Electronic, Optical and Magnetic Materials
Cited by
6 articles.
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