Radical and Nitrenoid Reactivity of 3-Halo-3-phenyldiazirines
Rafael Navrátil1, Ján Tarábek2, Igor Linhart1
1Department of Organic Chemistry, University of Chemistry and Technology , Technická 5, 166 28 Prague, Czech Republic.
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.
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