Synthesis of potassium 4-(1-azol-1-yl)-2,3,5,6-tetrafluorophenyltrifluoroborates from K[C6F5BF3] and alkali metal azol-1-ides. The dramatic distinction in nucleophilicity of alkali metal azol-1-ides and dialkylamides : научное издание

Описание

Тип публикации: статья из журнала

Год издания: 2013

Идентификатор DOI: 10.1016/j.jfluchem.2013.07.011

Ключевые слова: N-nucleophile, NMR spectroscopy, nucleophilic substitution, pentafluorophenyltrifluoroborate

Аннотация: Nucleophilic substitution of fluorine atom in K[C6F5BF3] with alkali metal azol-1-ides in polar aprotic solvent (DMF, DMSO) at 60–130 °C gives potassium 4-(azol-1-yl)-2,3,5,6-tetrafluorophenyltrifluoroborates, K[4-AzC6F4BF3] (AzH = pyrrole, pyrazole, imidazole, indole, and benzimidazole). Unexpectedly, diethylamine and morpholine dПоказать полностьюo not react with K[C6F5BF3] under the same conditions while pentafluorobenzene and R2NC6F4H form at 150 °C. Reaction of K[C6F5BF3] with Na[NR2] in diglyme or DMSO proceeds similar way. The assumed reason is the relatively low nucleophilicity of both secondary amines and alkali metal dialkylamides which results in destructive by-reaction with K[C6F5BF3] rather than in its aminodefluorination. This is confirmed by the competitive nucleophilic aminodefluorination of a model substrate, C6F5Ph, with sodium indolide/sodium morpholinide.

Ссылки на полный текст

Издание

Журнал: Journal of Fluorine Chemistry

Выпуск журнала: Т. 156

Номера страниц: 290-297

ISSN журнала: 00221139

Издатель: Elsevier Science Publishing Company, Inc.

Персоны

  • Shabalin A. Y. (G.K. Boreskov Institute of Catalysis,SB RAS)
  • Adonin N. Y. (G.K. Boreskov Institute of Catalysis,SB RAS)
  • Bardin V. V. (N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry,SB RAS)
  • Taran O. P. (G.K. Boreskov Institute of Catalysis,SB RAS)
  • Ayusheev A. B. (G.K. Boreskov Institute of Catalysis,SB RAS)
  • Parmon V. N. (G.K. Boreskov Institute of Catalysis,SB RAS)

Вхождение в базы данных