Direct Electrochemical Reduction of Acetochlor at Carbon and Silver Cathodes in Dimethylformamide Academic Article uri icon


  • 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 carbonhalogen 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.

published proceedings


altmetric score

  • 14.25

author list (cited authors)

  • Petro, A., Thapa, B., Karty, J. A., Raghavachari, K., Baker, L. A., & Peters, D. G.

citation count

  • 5

complete list of authors

  • Petro, Ana G Couto||Thapa, Bishnu||Karty, Jonathan A||Raghavachari, Krishnan||Baker, Lane A||Peters, Dennis G

publication date

  • January 2020