title: Substitution of a Fluorine Atom in Perfluorobenzonitrile by a Lithiated Nitronyl Nitroxide.
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 SNFsynthetic 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.
authors.affiliation: N. N. Vorozhtsov Institute of Organic Chemistry , 9 Ac. Lavrentiev Avenue, Novosibirsk 630090, Russia.|Novosibirsk State University , 2 Pirogova Str., Novosibirsk 630090, Russia.
authors.forename: Evgeny V
authors.identifier: 0000-0003-1540-7033
authors.initials: EV
authors.lastname: Tretyakov
authors.affiliation: N. N. Vorozhtsov Institute of Organic Chemistry , 9 Ac. Lavrentiev Avenue, Novosibirsk 630090, Russia.
authors.forename: Pavel A
authors.initials: PA
authors.lastname: Fedyushin
authors.affiliation: N. N. Vorozhtsov Institute of Organic Chemistry , 9 Ac. Lavrentiev Avenue, Novosibirsk 630090, Russia.|Novosibirsk State University , 2 Pirogova Str., Novosibirsk 630090, Russia.
authors.forename: Elena V
authors.initials: EV
authors.lastname: Panteleeva
authors.affiliation: Novosibirsk State University , 2 Pirogova Str., Novosibirsk 630090, Russia.|Institute of Chemical Kinetics and Combustion , 3 Institutskaya Str., Novosibirsk 630090, Russia.
authors.forename: Dmitri V
authors.initials: DV
authors.lastname: Stass
authors.affiliation: N. N. Vorozhtsov Institute of Organic Chemistry , 9 Ac. Lavrentiev Avenue, Novosibirsk 630090, Russia.|Novosibirsk State University , 2 Pirogova Str., Novosibirsk 630090, Russia.
authors.forename: Irina Yu
authors.initials: IY
authors.lastname: Bagryanskaya
authors.affiliation: N. N. Vorozhtsov Institute of Organic Chemistry , 9 Ac. Lavrentiev Avenue, Novosibirsk 630090, Russia.
authors.forename: Irina V
authors.initials: IV
authors.lastname: Beregovaya
authors.affiliation: International Tomography Center , 3a Institutskaya Str., Novosibirsk 630090, Russia.
authors.forename: Artem S
authors.identifier: 0000-0002-6918-5459
authors.initials: AS
authors.lastname: Bogomyakov