Research output: Contribution to journal › Article › peer-review
Interaction of a lithiated nitronyl nitroxide with polyfluorinated 1,4-naphthoquinones. / Zhivetyeva, S. I.; Zayakin, I. A.; Bagryanskaya, I. Yu et al.
In: Tetrahedron, Vol. 74, No. 28, 12.07.2018, p. 3924-3930.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Interaction of a lithiated nitronyl nitroxide with polyfluorinated 1,4-naphthoquinones
AU - Zhivetyeva, S. I.
AU - Zayakin, I. A.
AU - Bagryanskaya, I. Yu
AU - Zaytseva, E. V.
AU - Bagryanskaya, E. G.
AU - Tretyakov, E. V.
N1 - Funding Information: This work was financially supported by the Russian Science Foundation (project No. 17-73-10238 ). The authors would like to acknowledge the Multi-Access Chemical Service Center SB RAS for spectral and analytical measurements. Publisher Copyright: © 2018 Elsevier Ltd
PY - 2018/7/12
Y1 - 2018/7/12
N2 - A 4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl lithium derivative was found to react with 2-methoxypentafluoro-1,4-naphthoquinone to form a product of addition at the carbonyl function: radical 2-(3,5,6,7,8-pentafluoro-1-hydroxy-2-methoxy-4-oxo-1,4-dihydronaphthalen-1-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl. The yield of the addition product increased with temperature and reached 84% at 0 °C. The reaction of the lithium derivative with hexafluoro-1,4-naphthoquinone gave rise to a product of addition at both carbonyl groups, namely, nitronyl nitroxide diradical 2,3,5,6,7,8-hexafluoro-1,4-bis(4,4,5,5-tetramethyl-3-oxide-1-oxyl-4,5-dihydro-1H-imidazole-2-yl)-1,4-dihydronaphthalene-1,4-diol in a 16% yield. The structures of both mono- and diradical were solved by X-ray diffraction analysis, which revealed formation of an intramolecular H-bond between the OH group and nitroxide oxygen. According to electron paramagnetic resonance (EPR) spectroscopy, the obtained mono- and dinitroxide are prone to spontaneous deoxygenation in a toluene solution to give corresponding iminonitroxides. In water, they are much more stable.
AB - A 4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl lithium derivative was found to react with 2-methoxypentafluoro-1,4-naphthoquinone to form a product of addition at the carbonyl function: radical 2-(3,5,6,7,8-pentafluoro-1-hydroxy-2-methoxy-4-oxo-1,4-dihydronaphthalen-1-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl. The yield of the addition product increased with temperature and reached 84% at 0 °C. The reaction of the lithium derivative with hexafluoro-1,4-naphthoquinone gave rise to a product of addition at both carbonyl groups, namely, nitronyl nitroxide diradical 2,3,5,6,7,8-hexafluoro-1,4-bis(4,4,5,5-tetramethyl-3-oxide-1-oxyl-4,5-dihydro-1H-imidazole-2-yl)-1,4-dihydronaphthalene-1,4-diol in a 16% yield. The structures of both mono- and diradical were solved by X-ray diffraction analysis, which revealed formation of an intramolecular H-bond between the OH group and nitroxide oxygen. According to electron paramagnetic resonance (EPR) spectroscopy, the obtained mono- and dinitroxide are prone to spontaneous deoxygenation in a toluene solution to give corresponding iminonitroxides. In water, they are much more stable.
KW - 1,4-Naphthoquinones
KW - ESR spectra
KW - Iminonitroxides
KW - Nitronyl nitroxides
KW - Organic diradicals
KW - X-ray diffraction study
KW - SUBSTITUTION
KW - DESIGN
KW - HYDROGEN-BONDS
KW - ORGANIC MOLECULAR-SOLIDS
KW - BIRADICALS
KW - FERROMAGNETIC INTERACTIONS
KW - RADICALS
KW - DERIVATIVES
KW - CYTOTOXICITY
UR - http://www.scopus.com/inward/record.url?scp=85048315684&partnerID=8YFLogxK
U2 - 10.1016/j.tet.2018.05.075
DO - 10.1016/j.tet.2018.05.075
M3 - Article
AN - SCOPUS:85048315684
VL - 74
SP - 3924
EP - 3930
JO - Tetrahedron
JF - Tetrahedron
SN - 0040-4020
IS - 28
ER -
ID: 13923996