REACTION OF PERFLUORO-(2,4-DIMETHYL-3-OXA-2,4-DIAZAPENTANE) WITH PROPENE, BUT-2-ENE AND HALOGENO DERIVATIVES

Reaction of the oxadiazapentane (CF3)2NON(CF3)2 (1) with an excess of the propenes CH2 = CXR (X = H or Cl, R = Me or CH2Cl) at room temperature gives high yields (92%-97%) of mixtures of the 1:1 adducts (CF3)2NCH2CXRON(CF3)2 (3) and (CF3)2NCXRCH2ON(CF3)2 (4) in the ratio 87:13 to 90:10 via initial (CF3)2N. radical attack. In contrast, the corresponding reactions of the alkenes CH2 = CClR (R = Me, CH2Cl) with the N-bromoamine (CF3)2NBr (2) under free-radical conditions results in monodirectional (CF3)2N. radical attack to give the 1:1 adducts (CF3)2NCH2CBrClR (14) (95%-98%). With the alkenes CH2 = CHCF3 and CCl2 = CHMe, reaction with 1 affords the adducts (CF3)2NCH2CH(CF3)ON(CF3)2 (3e) (96%) and (CF3)2NCHMeCCl2ON(CF3)2 (10) (86%), respectively, but 3-bromopropene gives a complex mixture of products including the alkene (CF3)2NCH2CH = CH2 (7) (4%), the compound [(CF3)2NCH212CHON(CF3)2 (8) (24%) and the dibromide (BrCH2)2CHON(CF3)2 (9) (48%). Treatment of (E)- or (Z)-but-2-ene with 1 gives in each case a mixture (c. 80%) of the erythro and threo 1:1 adducts (CF3)2NCHMeCHMeON(CF3)2 (11) in the ratio 75:25, while from (E)-1-chlorobut-2-ene the adducts (CF3)2NCH(CH2Cl)CHMeON(CF3)2 (12) (54%) and (CF3)2NCHMeCH(CH2Cl)ON(CF3)2 (13) (42%) are formed each as a mixture of the erythro and threo isomers.