21894-29-1Relevant articles and documents
Generation and Identification of the Amidyl Radical Resulting from Homolytic N-O Cleavage in Carcinogenic N-Acetyl-N-(acyloxy)-2-aminofluorene
Michon, Josette,Jeunet, Andre,Pelloux, Nadia,Defrancq, Eric,Lhomme, Marie-France,Lhomme, Jean
, p. 6143 - 6145 (1993)
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Fluoro spin adducts and their modes of formation
Eberson, Lennart,Persson, Ola
, p. 893 - 898 (2007/10/03)
The reactions of two fluorinating reagents, XeF2 and N-fluorodibenzenesulfonamide [(PhSO2)2N-F], with several spin traps have been investigated. In dichloromethane, the strong oxidant XeF2 cleanly gives fluoro spin adducts with N-tert-butyl-α-phenylnitrone (PBN) or 5,5-dimethyl-1-pyrroline 1-oxide (DMPO) according to a mechanism mediated by the radical cation of the spin trap. In both cases, further fluorination takes place with replacement of the a hydrogen by fluorine. The much weaker oxidant (PhSO2)2N-F reacts with PBN or DMPO in dichloromethane giving both the fluoro adduct and an adduct formally derived from an N-centred radical, assigned the structure of PhSO2N(F)-PBN? or (PhSO2)2N-DMPO?, respectively. This type of reaction proceeds by a version of the Forrester-Hepburn mechanism, in which an acid HA, in this case HF, initially adds to the nitrone function to give a hydroxylamine derivative which is oxidized by (PhSO2)N-F giving the fluoro spin adduct, a proton and the highly labile radical anion (PhSO2)2N-F?-. By decomposition of the latter to PhSO2(F)N- and PhSO2?, conditions are set up for propagation of the reaction by a new molecule of HA [now PhSO2(F)NH] and thus formation of the PhSO2(F)N spin adduct.
