Reactions of Fluoroalk-1-en-1-yltrifluoroborate and Perfluoroalk-1-yn-1-yltrifluoroborate Salts and Selected Hydrocarbon Analogues with Hydrogen Fluoride and with Halogenating Agents in aHF and in Basic Solvents Full article
| Journal |
Journal of Fluorine Chemistry
ISSN: 0022-1139 |
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| Output data | Year: 2012, Volume: 135, Pages: 114-128 Pages count : 15 DOI: 10.1016/j.jfluchem.2011.09.011 | ||||||
| Tags | Halodeboration, Halofluorination, Halogenation, NMR spectroscopy, Organyltrifluoroborate salts | ||||||
| Authors |
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| Affiliations |
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Funding (3)
| 1 | Russian Foundation for Basic Research | |
| 2 | German Research Foundation | |
| 3 | Verband der Chemischen Industrie |
Abstract:
The relative rate of the electrophilic hydrodeboration of K[R′BF3] with HF (27–100%) diminishes in the series R′ = C4H9CC > C4F9CFCFCC > CF2C(CF3) > C3F7CC в€ј (CF3)2CFCC > CF3CC. When R′ = CF3CC the new salt K[CF3CH2–CF2BF3] was obtained by addition of HF besides CF3CCH and K[BF4]. Small amounts of water caused the formation of K[CF3CH2–C(O)BF3] as a by-product. The electrophilic halofluorination of perfluoroalkenyltrifluoroborate salts with NCS or NBS in aHF (anhydrous HF) led to K[RFCFHal–CF2BF3] (from K[RFCFCFBF3]) and K[RFCHal2–CF2BF3] (from K[RFCHalCFBF3] and K[RFCCBF3]) (Hal = Cl, Br). Treatment of K[RFCFCFBF3] and K[RFCCBF3] with 5% F2/N2 in MeCN gave the corresponding salts K[RFCF2–CF2BF3] in 16–25% isolated yield. Reactions of K[trans-C4F9CFCFBF3] with Cl2 in MeOH resulted in K[C4F9CFCl–C(O)BF3] (major product). The latter was also obtained in reactions of K[trans-C4F9CFCFBF3] with Cl2 in MeCN or sulfolane after sequential methanolysis of the primarily formed products. In contrast, the salts K[RCFCFBF3] (R = CnF2n+1, trans-C4H9) and K[CF3CCBF3] underwent bromodeboration to RCFCFBr and CF3CCBr, respectively, when they were reacted with bromine in the polar solvents MeOH, MeCN, or sulfolane.
Cite:
Bardin V.V.
, Adonin N.Y.
, Frohn H-J.
Reactions of Fluoroalk-1-en-1-yltrifluoroborate and Perfluoroalk-1-yn-1-yltrifluoroborate Salts and Selected Hydrocarbon Analogues with Hydrogen Fluoride and with Halogenating Agents in aHF and in Basic Solvents
Journal of Fluorine Chemistry. 2012. V.135. P.114-128. DOI: 10.1016/j.jfluchem.2011.09.011 WOS Scopus РИНЦ ANCAN OpenAlex
Reactions of Fluoroalk-1-en-1-yltrifluoroborate and Perfluoroalk-1-yn-1-yltrifluoroborate Salts and Selected Hydrocarbon Analogues with Hydrogen Fluoride and with Halogenating Agents in aHF and in Basic Solvents
Journal of Fluorine Chemistry. 2012. V.135. P.114-128. DOI: 10.1016/j.jfluchem.2011.09.011 WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
| Submitted: | Aug 24, 2011 |
| Accepted: | Sep 25, 2011 |
| Published online: | Oct 1, 2011 |
| Published print: | Mar 1, 2012 |
Identifiers:
| Web of science: | WOS:000301806400014 |
| Scopus: | 2-s2.0-84857368712 |
| Elibrary: | 17977183 |
| Chemical Abstracts: | 2012:257600 |
| Chemical Abstracts (print): | 156:337357 |
| OpenAlex: | W2017425355 |