75630-17-0Relevant academic research and scientific papers
Polyfluoroalkyl Derivatives of Nitrogen. Part 49. Ene Reactions of Trifluoronitrosomethane: Formation of N-Trifluoromethylhydroxylamines
Barlow, Michael G.,Haszeldine, Robert N.,Murray, Keith W.
, p. 1960 - 1964 (2007/10/02)
Trifluoronitrosomethane is a versatile and reactive enophile, forming N-alkenyl-N-trifluoromethylhydroxylamines, by transfer of allylic hydrogen to oxygen and bonding of olefinic carbon to nitrogen, with the olefins: propene, propene, but-1-ene, (E)-but-2-ene, 2-methylpropene, (Z)-pent-2-ene, 2-methylbut-1-ene, 2-methylbut-2-ene, (Z)-4-methylpent-2-ene, 2,3-dimethylbut-2-ene, cyclopentene, cyclohexene, 1-methylcyclohexene, β-pinene, and allyl bromide, chloride, and cyanide.Cyclo-octa-1,5,diene gives an ene-adduct, while the initial ene-adduct from cyclohexa-1,4-diene undergoes rapid Diels-Alder addition of further trifluoronitrosomethane.Cyclohepta-1,3,5-triene undergoes Diels-Alder addition by way of its bicyclohepta-2,4-diene isomer.Acetylacetone gives the compound CF3*N(OH)*CH(CO*CH3)2.In these ene reactions, nitrogen becomes bonded to the least substituted carbon atom.At -78 deg C, the following relative rates of reaction were observed: The hydroxylamines are easily oxidised to nitroxides, and those from the compound CF3*N(OH)*CMe2*CMe:CH2 and its reduction product, CF3*N(OH)*CMe2*CHMe2, are stable; their 1H n.m.r. spectra have been examined.
