title: An unusual radical Smiles rearrangement.
abstract: Radicals derived from N-(alpha-xanthyl)acetanilides or N-(alpha-xanthyl)acetylaminopyridines possessing a substituent next to the nitrogen undergo a hitherto undocumented Smiles rearrangement proceeding through a four-membered ring. It was also found that under certain conditions the amidyl radical produced by cleavage of the four-membered ring intermediate can undergo fragmentation to give an isocyanate. Such fragmentations are unprecedented at temperatures corresponding to refluxing benzene or chlorobenzene. [reaction: see text]
authors.affiliation: Laboratoire de Synthèse Organique associé au CNRS, Ecole Polytechnique, 91128 Palaiseau, France.
authors.forename: Eric
authors.initials: E
authors.lastname: Bacqué
authors.forename: Myriem
authors.initials: M
authors.lastname: El Qacemi
authors.forename: Samir Z
authors.initials: SZ
authors.lastname: Zard