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.
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For Communication No. 35, see [1].
Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 24, No. 3, pp. 350–355, March, 1988.
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Trofimov, B.A., Shapiro, A.B., Nesterenko, R.N. et al. 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. Chem Heterocycl Compd 24, 285–289 (1988). https://doi.org/10.1007/BF00475325
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DOI: https://doi.org/10.1007/BF00475325