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

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 Full article

Journal

Journal of Fluorine Chemistry
ISSN: 0022-1139

Output data

Year: 2013, Volume: 156, Pages: 290-297 Pages count : DOI: 10.1016/j.jfluchem.2013.07.011

Tags

Pentafluorophenyltrifluoroborate; N-nucleophile; Nucleophilic substitution; NMR spectroscopy

Authors

Shabalin Anton Yu ¹ , Adonin Nicolay Yu ¹ , Bardin Vadim V. ^1,2 , Taran Oksana P. ¹ , Ayusheev Artemiy B. ¹ , Parmon Valentin N. ¹

Affiliations

1	(Данные Web of science) RAS, SB, GK Boreskov Inst Catalysis, Novosibirsk 630090, Russia
2	(Данные Web of science) RAS, SB, NN Vorozhtsov Novosibirsk Inst Organ Chem, Novosibirsk 630090, Russia

Nucleophilic substitution of fluorine atom in K[C6F5BF3] with alkali metal azol-1-ides in polar aprotic solvent (DMF, DMSO) at 60-130 degrees C gives potassium 4-(azol-1-yl)-2,3,5,6-tetrafluorophenyltrifluorborates, K[4-AzC(6)F(4)BF(3)] (AzH = pyrrole, pyrazole, imidazole, indole, and benzimidazole). Unexpectedly, diethylamine and morpholine do not react with K[C6F5BF3] under the same conditions while pentafluorobenzene and R2NC6F4H form at 150 degrees 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. (C) 2013 Elsevier B.V. All rights reserved.

Shabalin A.Y. , Adonin N.Y. , Bardin V.V. , Taran O.P. , Ayusheev A.B. , Parmon V.N.
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
Journal of Fluorine Chemistry. 2013. V.156. P.290-297. DOI: 10.1016/j.jfluchem.2013.07.011 WOS Scopus РИНЦ

Published print:

Dec 1, 2013

Web of science	WOS:000329257000046
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