Interaction of a Lithiated Nitronyl Nitroxide with Polyfluorinated 1,4-Naphthoquinones
Научная публикация
| Общее |
Язык:
Английский,
Жанр:
Статья (Full article),
Статус опубликования:
Опубликована,
Оригинальность:
Оригинальная
|
| Журнал |
Tetrahedron
ISSN: 0040-4020
, E-ISSN: 1464-5416
|
| Вых. Данные |
Год: 2018,
Том: 74,
Страницы: 3924-3930
Страниц
: 7
DOI:
10.1016/j.tet.2018.05.075
|
| Ключевые слова |
Nitronyl nitroxides Iminonitroxides 1,4-Naphthoquinones Organic diradicals X-ray diffraction study ESR spectra |
| Авторы |
Zhivetyeva S.I.
1
,
Zayakin I.A.
1,2
,
Bagryanskaya I.Yu.
1,2
,
Zaytseva E.V.
1
,
Bagryanskaya E.G.
1
,
Tretyakov E.V.
1,2
|
| Организации |
| 1 |
N. N. Vorozhtsov Institute of Organic Chemistry, 9 Ac. Lavrentiev Avenue, Novosibirsk, 630090, Russia
|
| 2 |
Novosibirsk State University, 2 Pirogova Str, Novosibirsk, 630090, Russia
|
|
Информация о финансировании (1)
|
1
|
Российский научный фонд
|
17-73-10238 (АААА-А17-117073110021-4)
|
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.