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Open AccessArticle

Aromatic SNF-Approach to Fluorinated Phenyl tert-Butyl Nitroxides

1
N. N. Vorozhtsov Institute of Organic Chemistry, 9 Ac. Lavrentiev Avenue, 630090 Novosibirsk, Russia
2
Novosibirsk State University, 2 Pirogova Str., 630090 Novosibirsk, Russia
3
International Tomography Center, 3a Institutskaya Str., 630090 Novosibirsk, Russia
*
Authors to whom correspondence should be addressed.
Academic Editor: Fawaz Aldabbagh
Molecules 2019, 24(24), 4493; https://doi.org/10.3390/molecules24244493
Received: 17 November 2019 / Revised: 3 December 2019 / Accepted: 5 December 2019 / Published: 8 December 2019
(This article belongs to the Special Issue Stable Organic Radicals)
The interaction of octafluorotoluene (1a), as well as pentafluorobenzonitrile (1b) with tert-butylamine, followed by the oxidation of thus formed tert-butylanilines (2a,b) with meta-chloroperoxybenzoic acid led to functionalized perfluorinated phenyl tert-butyl nitroxides [namely, 4-(N-tert-butyl(oxyl)amino)heptafluorotoluene (3a) and 4-(N-tert-butyl(oxyl)amino)tetrafluorobenzonitrile (3b)] with nearly quantitative total yields. The molecular and crystal structures of nitroxide 3a were proved by single crystal X-ray diffraction analysis. The radical nature of both nitroxides was confirmed by ESR data. The interaction of Cu(hfac)2 with the obtained nitroxides 3a,b gave corresponding trans-bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato-κ2O,O′)bis{4-(N-tert-butyl(oxyl)amino)perfluoroarene-κO}copper (II) complexes ([Cu(hfac)2(3a)2] and [Cu(hfac)2(3b)2]). X-ray crystal structure analysis showed square bipyramid coordination of a centrally symmetric Cu polyhedron with the axial positions occupied by oxygen atoms of the nitroxide groups. Magnetic measurements revealed intramolecular ferromagnetic exchange interactions between unpaired electrons of Cu(II) ions and paramagnetic ligands, with exchange interaction parameters JCu–R reaching 53 cm−1. View Full-Text
Keywords: fluoroarenes; aromatic nucleophilic substitution; tert-butylanilines; nitroxides; copper-nitroxide complexes; magneto-structural correlations fluoroarenes; aromatic nucleophilic substitution; tert-butylanilines; nitroxides; copper-nitroxide complexes; magneto-structural correlations
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MDPI and ACS Style

Tretyakov, E.; Fedyushin, P.; Panteleeva, E.; Gurskaya, L.; Rybalova, T.; Bogomyakov, A.; Zaytseva, E.; Kazantsev, M.; Shundrina, I.; Ovcharenko, V. Aromatic SNF-Approach to Fluorinated Phenyl tert-Butyl Nitroxides. Molecules 2019, 24, 4493.

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