Fluorocarbon derivatives of nitrogen. Part 6. Reactions of some perfluorinated nitroso-compounds with hydrogen sulphite ion: conversion of fluorocarbon olefins into perfluoro-ketone oximes

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_FCFCFR_F→(with KF–CF₃CO₂Ag) R¹_FCFAgCF₂R_F→(with NOCl) R¹_FCF(NO)CF₂R_F(R¹_F= CF₃, R_F= F; R¹_FR_F= CF₂CF₂)(R_FCF₂= R²_F), the reductive defluorination with aqueous hydrogen sulphite anion completes a fluorocarbon olefin → fluorocarbon ketone oxime conversion.