359-63-7Relevant articles and documents
Some further reactions of bis(trifluoromethyl)amino-oxyl with alkenes
Newsholme, Gordon,Tipping, Anthony E.
, p. 163 - 170 (1994)
The reaction of the oxyl (CF3)2NO. (1) with the alkene (2) at 100 deg C and with the alkenes (CF3)2NCF2CF=CF2 (3), (E)-PhCH=CHPh (4), CH2=CHCOCl (5) and (CF3)2NCF2CF=CFCF2ON(CF3)2 (6) (prepared in 76percent yield by reaction of the oxadiazapentane (CF3)2NON(CF3)2 (7) with the diene CF2=CFCF=CF2) at room temperature gave high yields (92percent - 100percent) of the corresponding 2:1 adducts 8-12; hydrolysis of the acid chloride 11 gave the acid 14 (100percent).A mixture of the oxyl 1 and 3-bromopropene (4:5 molar ratio) on reaction at room temperature afforded at complex mixture of products of which the major compounds were identified by GLC-MS as (CF3)2NCH2CH=CH2 (15), (CH2Br)2CHON(CF3)2 (16), (CF3)2NOCH2CH(CH2Br)ON(CF3)2 (17), (CF3)2NCH2CH(CH2Br)ON(CF3)2 (18) and possibly 2CHBr (19).The following order of reactivity of ethenes towards oxyl 1 attack was obtained; CH2=CCl2 > CHF=CF2 > CHCl=CCl2 > CH2=CHCl > CH2=CH2 > CH2=CHF > CH2=CF2 > CCl2=CCl2. - Keywords: Reactions; Bis(trifluoromethyl)amino-oxyl; Alkenes; NMR spectroscopy; IR spectroscopy; Mass spectrometry
Unsaturated nitrogen compounds containing fluorine. Part 13. Reaction of 2--1,1,1,3,3,3-hexafluoropropan-2-ide with compounds containing N=O or N-O bonds
Bell, David,Tipping, Anthony E.
, p. 279 - 286 (2007/10/02)
Reaction of the title azomethinimine (1) with nitrogen dioxide gives nitric oxide, hexafluoroacetone and 3,3-dimethyl-5,5-bis(trifluoromethyl)-1-pyrazoline (2) in high yield, while with the perfluoronitrosoalkanes RFNO (RF = CF3 and CF2CF2CF3) the products are hexafluoroacetone and the azimines 8a and 8b, respectively.The reactions involve initial cycloaddition involving the N=O bonds, followed by elimination of hexafluoroacetone and niric oxide to give 2 or of hexafluoroacetone to give 8.From reaction of 1 with nitrosyl chloride the major products are nitric oxide, 7-chloro-8,8,8-trifluoro-2-methyl-4,4,7-tris(trifluoromethyl) -5,6-diazaocta-1,5-diene (13) and 5,5-dimethyl-3,3-bis(trifluoromethyl)-1-pyrazolidine (14) formed via decomposition of the 1:1 adduct containing C-chloro and N-nitroso substituents.The oxyl (CF3)2NO. attacks azomethinimine 1 at carbon and the resulting 1:1 adduct decomposes to give hexafluoroacetone, the pyrazoline 2 and (CF3)2N. radicals which are trapped by the oxyl to afford the oxadiazapentane (CF3)2NON(CF3)2 (19).Secondary reaction then takes place involving attack of the oxygen atom of the oxadiazapentane on 1 at carbon to give hexafluoroacetone, N,N-bis(trifluoromethyl)amine and 3-methyl-5,5-bis(trifluoromethyl)-3--1-pyrazoline (21).This is confirmed by treatment of 1 with the oxadiazapentane 19.
The reaction of bis(trifluoromethyl)amino-oxyl with t-butyl bromide, t-butyl chloride, 2,2-dichloropropane, 2-chloro-2-phenylpropane and t-butyl acetate
Connelly, Gregory D.,Tipping, Anthony E.
, p. 83 - 92 (2007/10/02)
Reaction of the oxyl (CF3)2NO(.) (1) with t-butyl bromide (c. 2:1 molar ratio) at room temperature results in initial hydrogen abstraction to give the hydroxylamine (CF3)2NOH (3) and the radical (.)CH2CMe2Br (17) which (i) couples with oxyl 1 to afford the compound (CF3)2NOCH2CMe2Br (6) (33.5percent) and (ii) eliminates a bromine atom to give the alkene CH2=CMe2.Addition of oxyl 1 and bromine to the alkene affords the adducts (CF3)2NOCH2CMe2ON(CF3)2 (4) (10percent) and CH2BrCMe2Br (8) (26.5percent), respectively, while allylic hydrogen abstraction from the alkene leads to the compounds 2CMeON(CF3)2 (5) (10percent) and (CF3)2NOCH2CMeCH2Br (7) (15.5percent).Reaction with t-butyl chloride is more complex and gives a number of unidentified products together with the compounds 4 (37percent), 5 (8percent) and (CF3)2NOCH2CMeCH2Cl (9) (3.5percent) formed by an analogous reaction pathway, although the large amount of hydrogen chloride (61percent) isolated indicates that hydrogen abstraction by chlorine atoms competes with abstraction by oxyl 1.With 2,2-dichloropropane, reaction with the oxyl 1 is slow (even at 70-80 deg C) and gives mainly hydrogen chloride, hydroxylamine 3 (32percent), the substitution product (CF3)2NOCH2CCl2CH3 (10) (42percent) and the 2:1 adduct of oxyl 1 and the alkene CH2=CMeCl, i.e. (CF3)2NOCH2CMeClON(CF3)2 (11) (24percent).In contrast, reaction involving 2-chloro-2-phenylpropane is facile at room temperature and affords hydrogen chloride (97.5percent), hydroxylamine 3 (12.5percent) and the 2:1 adduct (CF3)2NOCH2CMePhON(CF3)2 (12) (78percent) of oxyl 1 and the alkene CH2=CMePh.Treatment of t-butyl acetate with oxyl 1 gives hydroxylamine 3 (49percent), the oxadiazapentane (CF3)2NON(CF3)2 (2) (9percent) and the compounds (CF3)2NOCH2CMe2OAc (14) (36percent), 2CHCMe2OAc (15) (15percent) and (CF3)2NO2CCMe2OAc (16) (40percent) formed via successive oxyl 1 attack on a methyl group.In these reactions, compounds arising via a 1,2-shift of bromine, chlorine or acetate were not detected in the products.
