In:
Journal of The Electrochemical Society, The Electrochemical Society, Vol. 167, No. 15 ( 2020-01-12), p. 155517-
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 D 2 O 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.
Type of Medium:
Online Resource
ISSN:
0013-4651
,
1945-7111
DOI:
10.1149/1945-7111/abb8f9
Language:
Unknown
Publisher:
The Electrochemical Society
Publication Date:
2020
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