An approach to fluorinated phthalonitriles containing a nitronyl nitroxide or iminonitroxide moiety

An approach to fluorinated phthalonitriles containing a nitronyl nitroxide or iminonitroxide moiety Научная публикация

Журнал

Journal of Fluorine Chemistry
ISSN: 0022-1139

Вых. Данные

Год: 2019, Том: 217, Страницы: 1-7 Страниц : 7 DOI: 10.1016/j.jfluchem.2018.10.016

Ключевые слова

Fluorinated phthalonitriles; Nucleophilic substitution; Nitronyl nitroxides; Iminonitroxides; X-ray diffraction analysis

Авторы

Fedyushin Pavel ¹ , Panteleeva Elena ^1,2 , Bagryanskaya Irina ^1,2 , Maryunina Kseniya ^3,4 , Inoue Katsuya ^3,4 , Stass Dmitri ^2,5 , Tretyakov Evgeny ^1,2

Организации

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) Hiroshima Univ, Grad Sch Sci, Dept Chem, Chiral Res Ctr CResCent, 1-3-1 Kagamiyama, Higashihiroshima 7398526, Japan
4	(Данные Web of science) Hiroshima Univ, Inst Adv Mat Res, 1-3-1 Kagamiyama, Higashihiroshima 7398526, Japan
5	(Данные Web of science) VV Voevodsky Inst Chem Kinet & Combust, 3 Inst Skaya Str, Novosibirsk 630090, Russia

A 4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl lithium derivative was found to react with perfluorophthalonitrile with formation of 2-(3,4-dicyano-2,5,6-trifluorophenyl)- (1) and 2-(2-amino-4,5-dicyano-3,6-difluorophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-3-oxide-1-oxyl (2). The yields of 1 were near 15% independently of reaction time (from 2 to 6 h), whereas the yields of 2 considerably increased from a trace amount to 20%. Both nitronyl nitroxides were reduced to the corresponding iminonitroxides in the presence of NaNO2/AcOH with yields 80-95%. Molecular and crystal structures of the obtained nitroxides were solved by monocrystal X-ray diffraction analysis, and the nature of the radical was ascertained by electron spin spectroscopy (ESR) and SQUID magnetometry. Static magnetochemical measurements of 1 revealed domination of the ferromagnetic exchange interactions between the odd electrons of the paramagnetic centres. The exchange interactions probably proceed via short intermolecular contacts (3.021(3) and 3.05(2) angstrom) between the nitroxide O atoms and cyanide C atoms. Structural characteristics of the prepared nitroxides make them valuable precursors for the synthesis of paramagnetic macrocycles, which may serve as building blocks in the field of molecular magnetism.

Fedyushin P. , Panteleeva E. , Bagryanskaya I. , Maryunina K. , Inoue K. , Stass D. , Tretyakov E.
An approach to fluorinated phthalonitriles containing a nitronyl nitroxide or iminonitroxide moiety
Journal of Fluorine Chemistry. 2019. V.217. P.1-7. DOI: 10.1016/j.jfluchem.2018.10.016 WOS Scopus РИНЦ

Опубликована в печати:

1 янв. 2019 г.

Web of science	WOS:000457660400001
Scopus	2-s2.0-85056483552
РИНЦ	38626069
OpenAlex	W2899101897