Chemistry of Heterocyclic Compounds

, Volume 24, Issue 3, pp 285–289 | Cite as

Pyrroles from ketoximes and acetylene. No. 36. 4,4,6,6-Tetramethyl-4,5,6,7-tetrahydro-5-azaindole, its nitroxyl and vinyl derivatives, and spin-labelled copolymer

  • B. A. Trofimov
  • A. B. Shapiro
  • R. N. Nesterenko
  • A. I. Mikhaleva
  • G. A. Kalabin
  • N. I. Golovanova
  • I. V. Yakovleva
  • S. E. Korostova
Article

Abstract

An oxime containing a nitroxyl functional group site, 2,2,6,6-tetramethyl-1-nitroxyl-4-hydroxyiminopiperidine, has been shown for the first time to engage in productive pyrrole synthesis via reaction with acetylene in KOH-DMSO. The behavior of 2,2,6,6-tetramethyl-4-piperidone oxime and its 1-hydroxy derivative in this reaction has also been investigated. The corresponding 5-azaindole and its 5-nitroxyl and 1-vinyl derivatives have been synthesized in this manner. 1-Hydroxy-4-piperidone oxime reacts at 50–60‡C under the general reaction conditions undergoing oxidative conversion to 5-azaindole, while at 105‡C in the presence of excess acetylene reduction of the hydroxy group also takes place. The formation of a pyrrole ring does not involve radical chains, although vinylation of the resulting pyrroles apparently involves one-electron transfer. 1-Vinyl-4,4,6,6-tetramethyl-4,5,6,7-tetrahydro-5-azaindole has been used for the preparation of a spin-labelled polyvinyl alcohol copolymer.

Keywords

Acetylene Pyrrole Oxime Polyvinyl Alcohol General Reaction 

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Copyright information

© Plenum Publishing Corporation 1988

Authors and Affiliations

  • B. A. Trofimov
    • 1
  • A. B. Shapiro
    • 1
  • R. N. Nesterenko
    • 1
  • A. I. Mikhaleva
    • 1
  • G. A. Kalabin
    • 1
  • N. I. Golovanova
    • 1
  • I. V. Yakovleva
    • 1
  • S. E. Korostova
    • 1
  1. 1.Irkutsk Institute of Organic Chemistry, Siberian BranchAcademy of Sciences of the USSRIrkutsk

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