371-77-7Relevant academic research and scientific papers
Reaction of perfluoro-(2,4-dimethyl-3-oxa-2,4-diazapentane) with substituted ethenes and with cyclohexene
Newsholme, Gordon,Tipping, Anthony E.
, p. 39 - 48 (1994)
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.
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 (2007/10/02)
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.
FLUORINATIONS WITH COMPLEX METAL FLUORIDES. PART 7. FLUORINATIONS OF THE METHYL PYRIDINES WITH CAESIUM TETRAFLUOROCOBALTATE
Plevey, Raymond G.,Rendell, Richard W.,Tatlow, John Colin
, p. 265 - 286 (2007/10/02)
4-Methylpyridine passed over caesium tetrafluorocobaltate at 330-340 deg gave tridecafluoro(1,3-dimethylpyrrolidine) (1) and its 3-difluoromethyl analogue (2), together with a range of polyfluoro-4-picolines (4-10) with -CF3, -CHF2 or -CH2F groups in the 4-position. 3-Methylpyridine similarly gave 1 and its 1,2-isomer (11) together with several polyfluoro-3-picolines (14-18). 2-Methylpyridine at 270 deg gave tridecafluoro(1-ethylpyrrolidine) (13), a trace of 11 and 2-trifluoromethyl- (22), 2-difluoromethyl- (23) and 2-fluoromethyl-tetrafluoropyridine (24); there were also products arising by loss of methyl.Other unidentified fluoroalkylpyridines besides those isolated were present in each case.
FLUORINATIONS WITH COMPLEX METAL FLUORIDES. PART 6. FLUORINATION OF PYRIDINE AND RELATED COMPOUNDS WITH CAESIUM TETRAFLUOROCOBALTATE(III)
Plevey, Raymond G.,Rendell, Richard W.,Tatlow, John Colin
, p. 159 - 170 (2007/10/02)
Pyridine has been fluorinated over caesium tetrafluorocobaltate(III) (CsCo(III)F4) at 300-400 deg C to give a mixture of undecafluoro-N-methyl-pyrrolidine, bis(trifluoromethyl)amine, pentafluoropyridine and several polyfluoropyridines; the product composition depend to some extent on the geometry of the reactor.The fluorinations of pentafluoropyridine, piperidine and undecafluoropiperidine were also investigated.
Reaction of Bistrifluoromethylaminosulphenyl Chloride with Hydrocarbon Olefins and the Synthesis of Bistrifluoromethylaminosulphenylarenes
Service, Colin F.,Tipping, Anthony E.
, p. 91 - 96 (2007/10/02)
Reaction of bistrifluoromethylaminosulphenyl chloride with acyclic and alicyclic hydrocarbon olefins at -78 deg C in the dark affords 1:1 adducts of type in high yield.Treatment of diaryl disulphides with the N-bromo-amine (CF3)2NBr or of benzenesulphenyl chloride with the mercurial 2Hg provide convenient routes to bistrifluoromethylaminosulphenylarenes.
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 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.
Polyfluoroalkyl Derivatives of Nitrogen. Part 48. The Addition of N-Halogenoamines (CF3)2NX to Cyclohexa-1,3- and -1,4-dienes; a New Synthesis of NN-Bistrifluoromethylaniline.
Hart, Terence W.,Haszeldine, Robert N.,Tipping, Anthony E.
, p. 1544 - 1550 (2007/10/02)
Treatment of cyclohexa-1,3-diene with the N-halogenoamines (CF3)2NX (X=Cl or Br) at -78 deg C gives a mixture of the 1:1 adducts, trans- and cis- and trans-; in contrast (CF3)2NI affords the former adduct exclusively.All three amines react with cyclohexa-1,4-diene under analogous conditions to yield the 1:1 adduct trans- only.Dehydrohalogenation of the 1,3-diene adducts (X=Cl or Br) with various bases (KOH powder, PriONa, ButOK) affords a mixture of 1-and 2-(NN-bistrifluoromethylamino)cyclohexa-1,3-diene.The latter diene forms a Diels-Alder adduct with trifluoronitrosomethane and the diene mixture dehydrogenates readily over a Pd-C catalyst at 180-190 deg C to give NN-bistrifluoromethylaniline exclusively in high yield.
