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Chemistry of Heterocyclic Compounds

, Volume 42, Issue 11, pp 1427–1434 | Cite as

Radical-anions in the vicarious C-amination reactions of N-substituted nitrotriazoles

  • T. I. Vakul’skaya
  • I. A. Titova
  • L. I. Larina
  • O. N. Verkhozina
  • G. V. Dolgushin
  • V. A. Lopyrev
Article

Abstract

The vicarious nucleophilic substitution of hydrogen in symmetrical and vicinal nitrotriazoles by 1,1,1-trimethylhydrazinium iodide in t-BuOK/DMSO was studied by ESR. In the ESR monitoring of the reactions the primary radical-anions of 4-nitro-2-phenyl-1,2,3-triazole and 1-methyl-3-nitro-1,2,4-triazole were detected and characterized. It was shown by NMR that the amination of 4-nitro-2-phenyl-1,2,3-triazole takes place exclusively in the triazole ring with the formation of 5-amino-4-nitro-2-phenyl-1,2,3-triazole. 1-Methyl-3-nitro-1,2,4-triazole, like 3-nitro-1,2,4-triazole, does not form amination products. A possible mechanism for the vicarious C-amination of nitrotriazoles and the formation of the radical-anions of the substrates is discussed.

Keywords

radical-anions nitrotriazoles amination vicarious nucleophilic substitution of hydrogen ESR NMR 

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Copyright information

© Springer Science+Business Media, Inc. 2006

Authors and Affiliations

  • T. I. Vakul’skaya
    • 1
  • I. A. Titova
    • 1
  • L. I. Larina
    • 1
  • O. N. Verkhozina
    • 1
  • G. V. Dolgushin
    • 1
  • V. A. Lopyrev
    • 1
  1. 1.A. E. Favorsky Irkutsk Institute of ChemistrySiberian Branch of the Russian Academy of SciencesIrkutsk

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