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 synthesis of -substituted dialkyldichlorosilanes and their conversion into polysiloxanes
Ducker, Graham E.,Tipping, Anthony E.
, p. 253 - 262 (2007/10/02)
Attack of the oxyl (CF3)2NO. (1) on an ethyl group of the silane Et2SiCl2 occurs at both the α- and β-positions relative to silicon (ratio 31:45), whereas with the silane PrnSiMeCl2 attack takes place at the β-position of the propyl group.With the disilane Me3SiCH2SiMe3, the mojor silicon-containing products formed from treatment with oxyl 1 are Me3SiF, (CF3)2NOSiMe3 and Me3SiSiMe3.Speier-catalysed (H2PtCl6) addition of the silane HSiCl2X (X = Me and Cl) to the alkene (CF3)2NOCH2CH=CH2 gives the adducts (CF3)2NOCH2CH2CH2SiCl2X (29, X = Me) and (28, X = Cl)in high yield.The substituted dichlorosilanes (CF3)2NOCH2CH2SiEtCl2 (9), (CF3)2NOCHMeCH2SiMeCl2 (14) and (CF3)2NOCH2CH2CH2SiMeCl2 (29) are converted into corresponding polysiloxanes ("prepolymers" of low molecular weight) by reaction with reagents including water, acid, base and metal oxides; equilibration of the polysiloxane "prepolymer" 38, derived from dichlorosilane 29 by heating with powdered KOH, affords a solid rubbery polysiloxane.
