Reaction of perfluoro-(2,4-dimethyl-3-oxa-2,4-diazapentane) with substituted ethenes and with cyclohexene

Article abstract of DOI:10.1016/0022-1139(93)02978-N

The reaction of the oxadiazapentane (CF3)2NON(CF3)2 (1) with the alkenes CH2=CHX (X = Br, Cl, Ph, CN), CH2=CX2 (X = Cl, F), CHCl=CCl2 and CF2=CCl2 at c. 20 deg C gives in each case a single 1:1 adduct formed via initial (CF3)2N(.) radical attack.With the alkene CH2=CHF, bidirectional radical attack occurs to afford the 1:1 adducts (CF3)2NCH2CHFON(CF3)2 and (CF3)2NCHFCH2ON(CF3)2 in the ratio 94:6, while with (E)-CHCl=CHCl a mixture of the erythro and threo 1:1 adducts is formed (ratio 70:30).Reaction of 1 with the alkene CCl2=CCl2 at 50 deg C gives the hydrazine (CF3)2NN(CF3)2 (39percent), the 1:1 adduct (CF3)2NCCl2CCl2ON(CF3)2 (21percent) and the 2:1 adduct of the oxyl (CF3)2NO(.) and the alkene, i.e. (CF3)2NOCCl2CCl2ON(CF3)2 (39percent), while with cyclohexene allylic hydrogen abstraction competes with addition to afford the compounds (CF3)2NH (4percent), (27percent), (23percent) and the 1:1 adduct (44percent).From competition experiments, the order of reactivity of alkenes, CH2=CCl2 > CHF=CF2 > CH2=CHCl > CH2=CH2 > CH2=CHF > CH2=CF2 > CHCl=CCl2 > CCl2=CCl2, towards (CF3)2N(.) radical attack is obtained.