TY - JOUR

T1 - Aromatic nucleophilic substitution: A case study of the interaction of a lithiated nitronyl nitroxide with polyfluorinated quinoline-N-oxides

AU - Gurskaya, Larisa

AU - Rybalova, Tatyana

AU - Beregovaya, Irina

AU - Zaytseva, Elena

AU - Kazantsev, Maxim

AU - Tretyakov, Evgeny

N1 - The authors thank the Russian Foundation for Basic Research for funding (project No. 18-33-00203) and the Multi-Access Chemical Research Center of SB RAS for spectral and analytical measurements.

PY - 2020/9/1

Y1 - 2020/9/1

N2 - A 4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl lithium derivative was found to react with 5,6,7,8-tetrafluoro- or 5,7,8-trifluoro-6-(trifluoromethyl)quinoline-N-oxides with the formation of products of aromatic nucleophilic substitution of the H atom at position 2 of the quinoline ring. The reaction regioselectivity is supported by the data of quantum-chemical calculations. Molecular and crystal structures of the obtained nitronyl nitroxides were solved by monocrystal X-ray diffraction analysis, and the nature of the radical was ascertained by electron spin resonance spectroscopy. Heterospin complexes of Cu(hfac)2 with the synthesized quinoline-substituted nitronyl nitroxides were prepared. According to X-ray diffraction analysis, seven-membered metallocycles are formed in the complexes owing to simultaneous coordination of the nitroxyl and N-oxide groups by the Cu atom.

AB - A 4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl lithium derivative was found to react with 5,6,7,8-tetrafluoro- or 5,7,8-trifluoro-6-(trifluoromethyl)quinoline-N-oxides with the formation of products of aromatic nucleophilic substitution of the H atom at position 2 of the quinoline ring. The reaction regioselectivity is supported by the data of quantum-chemical calculations. Molecular and crystal structures of the obtained nitronyl nitroxides were solved by monocrystal X-ray diffraction analysis, and the nature of the radical was ascertained by electron spin resonance spectroscopy. Heterospin complexes of Cu(hfac)2 with the synthesized quinoline-substituted nitronyl nitroxides were prepared. According to X-ray diffraction analysis, seven-membered metallocycles are formed in the complexes owing to simultaneous coordination of the nitroxyl and N-oxide groups by the Cu atom.

KW - Fluorinated hetarenes

KW - Nitronyl nitroxides

KW - Nucleophilic substitution

KW - X-ray diffraction analysis

KW - VAN

KW - MAGNETIC INTERACTION

KW - BENZENE-RING

KW - DIARYLETHENE

KW - FLUORINE

KW - BOND

KW - REGIOSELECTIVITY

KW - PROGRAM

UR - http://www.scopus.com/inward/record.url?scp=85088877011&partnerID=8YFLogxK

U2 - 10.1016/j.jfluchem.2020.109613

DO - 10.1016/j.jfluchem.2020.109613

M3 - Article

AN - SCOPUS:85088877011

VL - 237

JO - Journal of Fluorine Chemistry

JF - Journal of Fluorine Chemistry

SN - 0022-1139

M1 - 109613

ER -