Abstract: Perfluorodiacyl peroxides, (RFCO₂)₂[R₂= n-C₃F₇, n-C₇F₁₅ and H(CF₂)₄], oxidize secondary aliphatic amines into bis-alkyl nitroxides, RN (O^·)R, which are stable in F113 (CClF₂-CCl₂F) solutions at roon temperatureIn one-electron oxidation reactions of the primary amines, RNH₂(R = primary, secondary, as well as tertiary, such as t-butyl) with (RFCO₂)₂ under the similar conditions, alkyl perfluoroacyloxyl nitroxides RN(O^·)OCOR_F, are always formed and detected by EPRIn the case of t-butyl amine, four more nitroxides of quite different life times, RN(O^·)R, RN(O^·)H, RN(O^·)RFand RN(O^·)R_F′(R_F′=R_F-CF₂), are observedOur EPRand product studies have revealed the dependence of the reaction patterns on the nature of the Rgroups, of the one-electron oxidation of the primary amines.

Key words: Perfluorodiacyl peroxides, Aliphatic amines, Single electron transfer (SET), EPR, Alkyl perfluoroacyloxyl nitroxides