The electrochemical transformation of ααα-trifluoroacetophenone into acetophenone; an unusually ready hydrogenolysis of the C–F bond

Electrochemical and spectroscopic behavior of trifluoromethylacetophenone in aqueous and micellar medium

“…Moreover, under our electrolysis conditions at very negative potential, one may consider a possible C-F. bond cleavage concomitant to the ketone reduction (22). In aqueous solution, it has been reported that the successive reductive removal of the three fluorine atoms of trifluoromethyl compounds can be carried out at a single potential (-1.7 V in the case of TFMA) (8,9,13). For such a cleavage the presence of an activating group in the molecule is clearly necessary as demonstrated by the fact that trifluoromethylbenzene itself is non-reducible even at more cathodic potentials than -2.0 V vs. SCE (13), while for aromatic compounds bearing a sulfamyl function, a trifluoromethyl substituent is reduced to the methyl group at -1.76 V in aqueous solution (8).…”

“…However, in aqueous solutions, numerous carbonyl compounds are known to be subject to complex equilibria involving hydration-dehydration of the carbonyl group and keto-enol and acid-base equilibria; these result in the formation of both geminal-diols and enols or carbanion enolates according to the pH (5-7). Moreover, the reduction of trifluoromethyl compounds in aqueous and nonaqueous solutions may also involve C-F bond fission (8)(9)(10)(11)(12)(13). In this work, both the electrochemical and spectroscopic behavior of TFMA have been investigated in various protic solvents such as aqueous, micellar, and ethanolic solutions.…”

Organic polarography

“…1,4-Dichloro-l ,3butadiene was identified as the product in the reduction of hexachlorobutadiene (153). Reduction data were reported for a',a',a '-trifluoroacetonephenone (472) and for octachloroand hexachlorocyclopentadiene (152). The polarographic behavior of benzoyl chloride (67) and of iodobenzene, bromobenzene, and p-chlorobenzaldehyde (50) in nonaqueous and mixed solvents was described.…”

Electroreductive Defluorination of Trifluoromethyl Ketones and Trifluoroacetic Acid Derivatives

“…Recently, we have found the reaction of ( N -aryl)trifluoromethylimines with diethylzinc provides N -aryl- N- ethyl-β,β-difluoroenamines, which arise presumably via an electron transfer from the zinc reagent to the imine , and the subsequent trapping of the anionic intermediate with electrophiles on the π-system would provide 3 . The strategy of an electroreductive defluorination is illustrated in Figure .…”