359-63-7Relevant academic research and scientific papers
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
PERFLUOROALKYL DERIVATIVES OF NITROGEN. PART LIII. REACTION OF PERFLUORO(2,5-DIMETHYL-4-OXA-3,5-DIAZAHEX-2-ENE) WITH FLUORO-OLEFINS
Fisher, R.,Haszeldine, R. N.,Tipping, A. E.
, p. 155 - 164 (1983)
Thermal decomposition of the title compound at 140 deg C gives mainly nitrogen, hexafluoroacetone and tetrakistrifluoromethylhydrazine while reaction with tetrafluoroethylene and chlorotrifluoroethylene affords equimolar mixtures of the 1:1 adducts (CF3)2C=NCF2CFXON(CF3)2 and (CF3)2C=NOCFXCF2N(CF3)2 (X=F and Cl) in highly yield via four-centre addition or a radical-cage process.
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.
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.
Reaction of bis(trifluoromethyl)amino-oxyl with alkylchlorosilanes and allyldichloro(methyl)silane and of perfluoro-2,5-diazahexane 2,5-dioxyl with vinylsilanes and hydrolysis of the products
Tipping, Anthony E.,Yadav, Rajendraprasad B.
, p. 1 - 10 (2007/10/02)
Treatment of the silanes MeSiHCl2, Me2SiHCl and EtSiMeCl2 with the oxyl (CF3)2NO(.) (1) gives the substitution products (CF3)2NOSiMeCl2 (4) and (CF3)2NOSiMe2Cl (5), and a mixture of (CF3)2NOCHMeSiMeCl2 (8) and (CF3)2NOCH2CH2SiMeCl2 (9) (ratio 20:37), respectively, while the silane EtSiMe2Cl affords mainly the ester (CF3)2NO2CMe (7).Attack of oxyl 1 on the silane CH2=CHCH2SiMeCl2 results in both allylic substitution and addition to give the compounds CH2=CHCH(SiMeCl2)ON(CF3)2 (14) and (CF3)2NOCH2CH(CH2SiMeCl2)ON(CF3)2 (15) (ratio 56:40).Reaction of the dioxyl (.)ON(CF3)CF2CF2N(CF3)O(.) (2) with the vinylsilanes CH2=CHSiX3 (X3 = Me3, Cl3, MeCl2) gives mainly 1:1 copolymers n (17), although the cyclic 1:1 adduct (18) is also formed in low yield.Hydrolysis of the silanes 15, (CF3)2NOCH2CH(SiMeCl2)ON(CF3)2 (19a) and (CF3)2NOCH2CH(SiCl3)ON(CF3)2 (19b) affords the corresponding polysiloxanes 24 and 25, and the polysilsesquioxane 26, respectively; the polymers 25 and 26 undergo rearrangement of the type -CH(Si)ON(CF3)2 --> -CH(OSi)N(CF3)2 on storage.The 1:1 copolymers 17b (X3 = MeCl2) and 17c (X3 = Cl3) are also hydrolysed to the corresponding siloxane and silsesquioxane polymers.In contrast, hydrolysis of the compounds 4,5 and (CF3)2NOCH2CH(OSiX3)N(CF3)2 (20a; X3 = MeCl2) and (20b; X3 = Cl3) results in Si-O bond cleavage.
REACTIONS OF BIS(TRIFLUOROMETHYL)NITROXYL WITH (CF3)2AsX (WHERE X = F, Cl and Br)
ANG, H. G.,SO, K. K.
, p. 433 - 450 (2007/10/02)
(CF3)2AsX (X = F, Cl) give at elevated temperatures substitution reactions with (CF3)2NO to afford (CF3)2NOAs(CF3)X and (CF3)2NOCF3.The formation of addition products at low temperatures to give 2As(CF3)2X, followed by elimination reactions at elevated temperatures to give the final products provide for the first time direct evidence for the mechanisms of the substitution reactions.With (CF3)2AsBr, bromine was initially displaced to afford (CF3)2NOAs(CF3)2, followed by addition reactions to give 3As(CF3)2.
Nitroxide Chemistry. Part 15. Reactions between Bistrifluoromethyl Nitroxide and Benzyl Alcohol, Azide, Chloride, and Cyanide
Banks, Ronald E.,Birchall, J. Michael,Haszeldine, Robert N.,Hughes, Raymond A.,Nona, Shmaiel N.,Stephens, Christopher W.
, p. 455 - 456 (2007/10/02)
Bistrifluoromethyl nitroxide readily attacks benzyl cyanide and benzyl chloride at room temperature to give the α-bistrifluoromethylamino-oxy-derivatives PhCHRCN and PhCHRCl respectively; treatment of the former product with the nitroxide yields benzoyl cyanide and the di-substituted derivative PhCR2CN.Abstraction of a benzylic hydrogen atom by the nitroxide from benzyl alcohol and benzyl azide leads, respectively, to the formation of benzaldehyde (and hence PhCOR) and benzonitrile.
Nitroxide Chemistry. Part 18. Reaction of Bistrifluoromethyl Nitroxide with Some Ethers
Banks, Ronald E.,Brown, Alan K.,Haszeldine, Robert N.,Jefferson, John
, p. 1068 - 1070 (2007/10/02)
Treatment of the methyl ethers MeOX (X = Me, Ph) with a stoicheiometric amount of bistrifluoromethyl nitroxide . = R.> at room temperature converts them efficiently into their bistrifluoromethylamino-oxymethyl counterparts, RCH2OX; the bis-derivative (RCH2)2O is a minor by-product in the case of dimethyl ether (X = Me).Multiple hydrogen-abstraction increases in importance with diethyl ether as substrate, the expected products RCHMeOEt and (RCHMe)2O being accompanied by a bis-derivative (RCH2CHROEt) arguably produced via the αβ-dehydrogenation 2R. + Et2O -> 2RH + CH2=CHOEt.The halogeno-ether MeOCF2CHFCl reacts slowly with the nitroxide at 50 deg C to yield a 7 : 1 mixture of the derivatives RCH2OCF2CHFCl and RCFClCF2OMe, hydrolysis of which gives the esters RCH2OCOCHFCl and RCFClCO2Me, respectively.The latter ester is best obtained via treatment of methyl chlorofluoroacetate with bistrifluoromethyl nitroxide.
Nitroxide Chemistry. Part 13. Reaction of NN-Bis(trifluoromethyl)amino-oxyl with Hexafluoroisopropylideneimine and Related Compounds
Fisher, Raymond,Haszeldine, Robert N.,Tipping, Anthony E.
, p. 406 - 409 (2007/10/02)
The initial product from reaction of the oxyl (CF3)2N-O. with hexafluoroisopropylideneimine is the substituted imine (CF3)2C=N-O-N(CF3)2 (isolated in 81percent yield) which, via further oxyl attack at carbon, gives the compounds (CF3)2CO, (CF3)2N-NO, (CF3)2N-O-N(CF3)2, and (CF3)2N-O-C(CF3)2N+(O-)=N-C(CF3)2-O-N(CF3)2.Oxyl attack on hexafluoroacetone oxime affords as major products (CF3)2CO, (CF3)2NH, and (CF3)2N-O-NO.The oxyl reacts with hexafluoroacetone anil to yield a hexaoxyl adduct, with hexafluoroacetone hydrazone to afford the diazoalkane (CF3)2CN2 (100percent), and with hexafluoroacetone azine to give the bis-1:4-adduct (CF3)2N-O-C(CF3)2-N=N-C(CF3)2-O-N(CF3)2 (100percent).Thus, initial radical attack of the oxyl invariably takes place at carbon in the series of imines studied.
