title: Radical and Nitrenoid Reactivity of 3-Halo-3-phenyldiazirines.
abstract: 3-Halo-3-phenyl-3H-diazirines (halogen = Br or Cl) undergo a dissociative single-electron transfer from alkyllithiums (RLi) in THF-based solvent mixtures. The resulting 3-phenyldiazirinyl radical, observed by EPR spectroscopy, is eventually transformed to benzonitrile. In Et2O, 2 equiv of RLi add to both nitrogens of halodiazirine N═N bond, affording N,N'-dialkylbenzamidines. The nitrenoid reactivity of some N-alkyl-1H-diazirine intermediates is manifested by their insertion into the α-C-H bond of THF or Et2O.
authors.affiliation: Department of Organic Chemistry, University of Chemistry and Technology , Technická 5, 166 28 Prague, Czech Republic.
authors.forename: Rafael
authors.initials: R
authors.lastname: Navrátil
authors.affiliation: Institute of Organic Chemistry and Biochemistry CAS, v.v.i., Flemingovo náměstí 542/2, 166 10 Prague, Czech Republic.
authors.forename: Ján
authors.initials: J
authors.lastname: Tarábek
authors.affiliation: Department of Organic Chemistry, University of Chemistry and Technology , Technická 5, 166 28 Prague, Czech Republic.
authors.forename: Igor
authors.initials: I
authors.lastname: Linhart
authors.affiliation: Department of Organic Chemistry, University of Chemistry and Technology , Technická 5, 166 28 Prague, Czech Republic.
authors.forename: Tomáš
authors.initials: T
authors.lastname: Martinů