Substitution of a Fluorine Atom in Perfluorobenzonitrile by a Lithiated Nitronyl Nitroxide

Evgeny V. Tretyakov, Pavel A. Fedyushin, Elena V. Panteleeva, Dmitri V. Stass, Irina Yu Bagryanskaya, Irina V. Beregovaya, Artem S. Bogomyakov

Research output: Contribution to journalArticlepeer-review

18 Citations (Scopus)

Abstract

A 4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (1) lithium derivative was found to react with perfluorobenzonitrile (2) substituting its para-fluorine atom to form 2-(4-cyanotetrafluorophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-3-oxide-1-oxyl (3), a new nitronyl nitroxide containing a multifunctional framework of strong electron-withdrawing nature. This result shows the possibility of obtaining multifunctional nitronyl nitroxides via the interaction of paramagnetic lithium derivatives as C-nucleophiles with polyfluoroarenes activated for nucleophilic substitution. The reaction regioselectivity is supported by the data of quantum-chemical calculations, which also show that the reaction follows a concerted pathway without formation of an intermediate. Reduction of nitronyl nitroxide 3 in system NaNO2-AcOH yielded corresponding iminonitroxide 4. Characterization of persistent radicals 3 and 4 obtained by the SNF synthetic strategy includes X-ray crystal structures, electron spin resonance data, and static magnetic-susceptibility measurements. X-ray diffraction analysis of both nitronyl nitroxide and iminonitroxide revealed a complete match of the parameters of their crystal lattices.

Original languageEnglish
Pages (from-to)4179-4185
Number of pages7
JournalJournal of Organic Chemistry
Volume82
Issue number8
DOIs
Publication statusPublished - 21 Apr 2017

Keywords

  • NUCLEOPHILIC AROMATIC-SUBSTITUTION
  • BETA-AMINOCINNAMONITRILES
  • DERIVATIVES
  • INHIBITORS
  • RADICALS
  • SYSTEMS
  • AGENTS

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