Research output: Contribution to journal › Article › peer-review
Substitution of a Fluorine Atom in Perfluorobenzonitrile by a Lithiated Nitronyl Nitroxide. / Tretyakov, Evgeny V.; Fedyushin, Pavel A.; Panteleeva, Elena V. et al.
In: Journal of Organic Chemistry, Vol. 82, No. 8, 21.04.2017, p. 4179-4185.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Substitution of a Fluorine Atom in Perfluorobenzonitrile by a Lithiated Nitronyl Nitroxide
AU - Tretyakov, Evgeny V.
AU - Fedyushin, Pavel A.
AU - Panteleeva, Elena V.
AU - Stass, Dmitri V.
AU - Bagryanskaya, Irina Yu
AU - Beregovaya, Irina V.
AU - Bogomyakov, Artem S.
PY - 2017/4/21
Y1 - 2017/4/21
N2 - 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.
AB - 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.
KW - NUCLEOPHILIC AROMATIC-SUBSTITUTION
KW - BETA-AMINOCINNAMONITRILES
KW - DERIVATIVES
KW - INHIBITORS
KW - RADICALS
KW - SYSTEMS
KW - AGENTS
UR - http://www.scopus.com/inward/record.url?scp=85018509951&partnerID=8YFLogxK
U2 - 10.1021/acs.joc.7b00144
DO - 10.1021/acs.joc.7b00144
M3 - Article
C2 - 28358985
AN - SCOPUS:85018509951
VL - 82
SP - 4179
EP - 4185
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 8
ER -
ID: 9032709