Abstract
The sequence of events R1 FR2 FCFNO + HSO3 aq. → R1 FR2 FCFN(OH)SO3 → R1 FR2 FCFNHOH → R1 FR2 FCNOH is proposed to account for the production of N-trifluoromethylhydroxylamine, perfluoropropanohydroximoyl fluoride, perfluoroacetone oxime, and perfluorocyclobutanone oxime when the nitroso-compounds CF3NO, n-C3F7NO, (CF3)2CFNO, and [graphic omitted]FNO, respectively, are treated with aqueous potassium hydrogen sulphite; understandably, perfluoro-1-nitrosopropane reacts with the same reagent in the presence of lead(IV) oxide to give the purple water-soluble oxyl n-C3F7N(O˙)SO3 K+ Since perfluoro-2-nitrosopropane and perfluoronitrosocyclobutane are easily obtained via the route R1 FCFCFRF→(with KF–CF3CO2Ag) R1 FCFAgCF2RF→(with NOCl) R1 FCF(NO)CF2RF(R1 F= CF3, RF= F; R1 FRF= CF2CF2)(RFCF2= R2 F), the reductive defluorination with aqueous hydrogen sulphite anion completes a fluorocarbon olefin → fluorocarbon ketone oxime conversion.

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