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

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

Journal

Journal of Organic Chemistry
ISSN: 0022-3263

Output data

Year: 2017, Volume: 82, Number: 8, Pages: 4179-4185 Pages count : 7 DOI: 10.1021/acs.joc.7b00144

Authors

Tretyakov Evgeny V. ^1,2 , Fedyushin Pavel A. ¹ , Panteleeva Elena V. ^1,2 , Stass Dmitri V. ^2,3 , Bagryanskaya Irina Yu. ^1,2 , Beregovaya Irina V. ¹ , Bogomyakov Artem S. ⁴

Affiliations

1	(Данные Web of science) NN Vorozhtsov Inst Organ Chem, 9 Ac Lavrentiev Ave, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, 2 Pirogova Str, Novosibirsk 630090, Russia
3	(Данные Web of science) Inst Chem Kinet & Combust, 3 Inst Skaya Str, Novosibirsk 630090, Russia
4	(Данные Web of science) Int Tomog Ctr, 3a Inst Skaya Str, Novosibirsk 630090, Russia

A 4,4,5,5-tetramethy1-4,5-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-cyanotetrafluoropheny1)4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-3-okide-l-okyl (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 paramagnetia-litbium derivatives as C-nucleophiles with polyfluoroarenes activated for nucleophilic substitution. The reaction regioselectivity is supported by the data of quanturn-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 SNP, 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.

Tretyakov E.V. , Fedyushin P.A. , Panteleeva E.V. , Stass D.V. , Bagryanskaya I.Y. , Beregovaya I.V. , Bogomyakov A.S.
Substitution of a Fluorine Atom in Perfluorobenzonitrile by a Lithiated Nitronyl Nitroxide
Journal of Organic Chemistry. 2017. V.82. N8. P.4179-4185. DOI: 10.1021/acs.joc.7b00144 WOS Scopus РИНЦ

Published online:	Apr 6, 2017
Published print:	Apr 21, 2017

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