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Chemistry of Heterocyclic Compounds

, Volume 55, Issue 10, pp 968–977 | Cite as

Reinvestigation of the reaction of 3-substituted 1,2,4-triazines with nitronate anions: unexpected behavior of 3-(2-ethoxyphenyl)-1,2,4-triazine in the reaction with anions of nitroalkanes

  • Mariusz MojzychEmail author
  • Zofia Bernat
  • Zbigniew Karczmarzyk
Article
  • 27 Downloads

3-Substituted 1,2,4-triazines easily react with nitronate anions to replace hydrogen atom in the position C-5 according to nucleophilic substitution mechanism and form appropriate oximes of 5-formyl- or 5-acyl-1,2,4-triazines. Present study has shown that the course of the reaction strongly depends on the structure of the substituent in the position C-3 of 1,2,4-triazine ring. Thus, 2-ethoxyphenyl substituent in 1,2,4-triazine allowed to form, besides appropriate oximes, also new nitronic acid derivatives stabilized by intramolecular hydrogen bonds. The synthesis pathway and molecular structures of oximes were confirmed by X-ray analysis performed for model compound 1-[3-(2-ethoxyphenyl)-1,2,4-triazin-5-yl]ethanone oxime. The presence of the new nitronic acid derivatives in the reaction mixture and the theoretical calculations at DFT/B3LYP/6-311++G(d,p) level strongly suggest that intermediate stabilized by bifurcated intramolecular hydrogen bond is a common intermediate for the construction of appropriate oximes.

Keywords

nitroalkanes nitronate anions oximes 1,2,4-triazine nucleophilic substitution reaction 

Supplementary material

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  • Mariusz Mojzych
    • 1
    Email author
  • Zofia Bernat
    • 1
  • Zbigniew Karczmarzyk
    • 1
  1. 1.Department of ChemistrySiedlce University of Natural Sciences and HumanitiesSiedlcePoland

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