6141-72-6Relevant articles and documents
On the reaction of perfluoro-aza-propene with oxygen difluoride and fluorination of bis(trifluoromethyl)-hydroxylamine
Minkwitz, Rolf,Reinemann, Stefan,Ludwig, Ralf
, p. 145 - 149 (2007/10/03)
The reactions of perfluoro-aza-propene CF3NCF2 with an excess of oxygen difluoride OF2 and the fluorination of bis(trifluoromethyl)-hydroxylamine (CF3)2NOH are discussed. Additionally, we present density functional calculations (B3LYP/6-31G*) on bis(trifluoromethyl)-hypofluorite (CF3)2NOF, which clearly show that this molecule is a model substance for the discussion of negative hyperconjugation.
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.
NITROXIDE CHEMISTRY XXI. REACTIONS OF BIS(BISTRIFLUOROMETHYLAMINO-OXY)-MERCURY(II) AND NN-BIS(TRIFLUOROMETHYL)NITROXIDE WITH THIOCARBONYL COMPOUNDS
Booth, B. L.,Browne, R. F.,Haszeldine, R. N.,Varley, J. S.
, p. 485 - 502 (2007/10/02)
Thiobenzophenone, 9-thiocarbonylfluorene and carbonyl sulphide react with the mercurial, Hg2, to form HgS and the compounds Ph2C2, (C6H4)2C2 and 2CO respectively.The last compound is also formed as the major product on mixing the mercurial with carbon disulphide.With thiophosgene, reaction occurs to form HgCl2 and a mixture of the compounds (CF3)2NSCOCl and (CF3)2NSCOON(CF3)2, which are thought to arise by rearrangement of the intermediates (CF3)2NOC(S)Cl and 2CS.A similar rearrangement may also occur during the reactions of thiobenzoyl chloride and aryl chlorothionoformates with the mercurial but the product mixtures from these reactions are more complex and pure compounds have not been isolated.Reaction between thiophosgene dimer and the mercurial results in a simple chlorine exchange to afford the 1,3-dithietane 2cyclo2S>.The low temperature reaction of thiophosgene with (CF3)2NO gives a thermally unstable product believed to be (CF3)2NOCCl2S(O)ON(CF3)2, while the similar reaction with thiobenzophenone appears to give (CF3)2NOCPh2SON(CF3)2, which decomposes above 0 deg C.
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 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.
