105488-71-9Relevant academic research and scientific papers
Trapping of the cyano radical: Does it ever happen?
Eberson, Lennart,Persson, Ola
, p. 608 - 621 (2007/10/03)
The possible trapping of the cyano radical by α-phenyl-N-tert-butylnitrone (PBN) has been probed by a new method for the generation of CN, photolysis of N-cyanosuccinimide with PBN. Only in 1,1,1,3,3,3-hexaflueropropan-2-ol was EPR spectral evidence obtained for the formation of a true spin adduct, namely the isocyano adduct of PBN. In other solvents, like dichloromethane or acetonitrile, the photolysis reaction took an entirely different course and gave the N-cyano-3-succinimidyl adduct of PBN and a second aminoxyl of unknown structure. The same pair of adducts could be obtained by photolysis of N-cyanomaleimide and PBN in a reductive coupling reaction. Maleimide gave a similar but clearly different pair of spectra. The possibility that the cyano or isocyano PBN adduct might undergo spontaneous hydrolysis to give the aminoformyl or formylamino adduct, respectively, was explored. It was shown that the authentic cyano adduct does not give the aminoformyl adduct under hydrolytic conditions. Since there is no method to prepare the isocyano adduct for such experiments, the problem of its hydrolytic reactivity is still open. The aminoformyl adduct of PBN was prepared by addition of the formamide anion to PBN, followed by oxidation by nickel peroxide, and characterized by its EPR spectrum. Acta Chemica Scandinavica 1998.
Spin adduct formation from the spontaneous reaction between spin traps and weak electron acceptors, as exemplified by trichloroacetonitrile. An acid promoted version of the Forrester-Hepburn addition-oxidation mechanism
Eberson, Lennart,MacCullough, John J.,Persson, Ola
, p. 133 - 134 (2007/10/03)
The thermal reaction between N-tert-butyl-α-phenylnitrone (PBN) and trichloroacetonitrile is promoted by acids HA, giving spin adducts A-PBN. and CCl2=C=N-PBN., presumably via addition of HA to the nitrone with formation of a hydroxylamine and oxidation of the latter by trichloroacetonitrile (the Forrester-Hepburn mechanism).
Cyano-O-silylhydroxylamines as Nitrone Blocking Groups
Padwa, Albert,Koehler, Konrad F.
, p. 789 - 790 (2007/10/02)
Addition of trimethylsilyl cyanide to N-alkyl-C-phenylnitrones affords cyano-O-silylhydroxylamines; reaction of these species with silver fluoride regenerates the nitrone in quantitative yield thereby providing a useful nitrone blocking group.
