Difluoromethyl group oxidation

The difluoromethyl group in chlorofluoroalkanes can be oxidized into a carboxylic group by a mixture of chlorine and dinitrogen tetroxide at high temperatures [2] (equation 1)... 

The monofluoromethylene group and difluoromethyl group m 1H perfluoro-alkanes and -cycloalkanes are oxidized at the C-H bond to perfluoroalkyl and perfluorocycloalkyl fluorosulfates by anodic oxidation m fluorosulfonic acid [J, 4] Two modifications of the method are used ox idation by fluorosulfonyl peroxide generated pnor to the reaction [J] (equation 2A) and direct electrolysis m the acid [i, 4] (equabons 2B and 3)... 

The enzyme is irreversibly inhibited by the difluoromethyl analog of androstendione. The mechanism postulated for the inhibition involves oxidation of the difluoromethyl group and subsequent elimination of hydrofluoric acid. The resulting carbonyl fluoride binds covalently to a nucleophilic group of the enzyme, disabling it permanently [80]. 

Toluene derivatives bearing electronegative substituents are fluorinated on the methyl group when reacted with lead(IV) oxide, nickcl(IV) oxide, cobalt(IIl) fluoride, cobalt(lll) acetate. silver(II) fluoride, or silver(ll) oxide in liquid hydrogen fluoride. The product obtained is dependent on the substrate and the metal oxidant employed, with benzyl fluorides I or (difluoromethyl)benzenes 2 as the major products. 

From a further observation that the 3-methylene analogues (35) and (36) of 10) -difluoromethyl- and 10/S-(2-propynyl)estr-4-ene-3,17-dione, both known to be irreversible inhibitors of AR [168, 169], were inactive, it was concluded that the 3-keto function was required to assist in the primary oxidation of the 10-methyl group of these inhibitors. This conclusion indicates a possible enzyme guided movement of the primary oxidation products to realign for the 2-oxidation leading to eventual aromatization, assuming this pathway is being evoked. This is consistent with the observation that the... 

---