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
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Journal of Fluorine Chemistry
ISSN: 0022-1139 |
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| Output data | Year: 2013, Volume: 156, Pages: 290-297 Pages count : 8 DOI: 10.1016/j.jfluchem.2013.07.011 | ||||
| Tags | N-nucleophile, NMR spectroscopy, Nucleophilic substitution, Pentafluorophenyltrifluoroborate | ||||
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Funding (1)
| 1 | The Ministry of Education and Science of the Russian Federation | 2012-1.2.1-12-000-1004-038 |
Abstract:
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 do 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.
Cite:
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 ANCAN OpenAlex
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 ANCAN OpenAlex
Dates:
| Submitted: | May 27, 2013 |
| Accepted: | Jul 15, 2013 |
| Published online: | Jul 24, 2013 |
| Published print: | Dec 1, 2013 |
Identifiers:
| Web of science: | WOS:000329257000046 |
| Scopus: | 2-s2.0-84889094417 |
| Elibrary: | 21464698 |
| Chemical Abstracts: | 2013:1271682 |
| Chemical Abstracts (print): | 160:101344 |
| OpenAlex: | W1973832952 |