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 | Sciact - CRIS-система Института катализа

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 Научная публикация

Журнал

Journal of Fluorine Chemistry
ISSN: 0022-1139

Вых. Данные

Год: 2012, Том: 135, Страницы: 114-128 Страниц : 15 DOI: 10.1016/j.jfluchem.2011.09.011

Ключевые слова

Halodeboration, Halofluorination, Halogenation, NMR spectroscopy, Organyltrifluoroborate salts

Авторы

Bardin Vadim V. ¹ , Adonin Nicolay Yu. ^1,2 , Frohn Hermann-Josef ³

Организации

1	N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, SB RAS, Acad. Lavrentjev Avenue 9, 630090 Novosibirsk, Russian Federation
2	G.K. Boreskov Institute of Catalysis, SB RAS, Acad. Lavrentjev Avenue 5, 630090 Novosibirsk, Russian Federation
3	Inorganic Chemistry, University of Duisburg-Essen, Lotharstrasse 1, D-47048 Duisburg, Germany

Информация о финансировании (3)

1	Российский фонд фундаментальных исследований
2	German Research Foundation
3	Verband der Chemischen Industrie

The relative rate of the electrophilic hydrodeboration of K[R′BF3] with HF (27–100%) diminishes in the series R′ = C4H9C≡C > C4F9CF=CFC≡C > CF2=C(CF3) > C3F7C≡C ~ (CF3)2CFC≡C > CF3C≡C. When R′ = CF3C≡C the new salt K[CF3CH2–CF2BF3] was obtained by addition of HF besides CF3C≡CH 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[RFCF=CFBF3]) and K[RFCHal2–CF2BF3] (from K[RFCHal=CFBF3] and K[RFC≡CBF3]) (Hal = Cl, Br). Treatment of K[RFCF=CFBF3] and K[RFC≡CBF3] with 5% F2/N2 in MeCN gave the corresponding salts K[RFCF2–CF2BF3] in 16–25% isolated yield. Reactions of K[trans-C4F9CF=CFBF3] with Cl2 in MeOH resulted in K[C4F9CFCl–C(O)BF3] (major product). The latter was also obtained in reactions of K[trans-C4F9CF=CFBF3] with Cl2 in MeCN or sulfolane after sequential methanolysis of the primarily formed products. In contrast, the salts K[RCF=CFBF3] (R = CnF2n+1, transC4H9) and K[CF3C≡CBF3] underwent bromodeboration to RCF=CFBr and CF3C≡CBr, respectively, when they were reacted with bromine in the polar solvents MeOH, MeCN, or sulfolane.

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 CAPlusCA OpenAlex

Поступила в редакцию:	24 авг. 2011 г.
Принята к публикации:	25 сент. 2011 г.
Опубликована online:	1 окт. 2011 г.
Опубликована в печати:	1 мар. 2012 г.

Web of science:	WOS:000301806400014
Scopus:	2-s2.0-84857368712
РИНЦ:	17977183
Chemical Abstracts:	2012:257600
Chemical Abstracts (print):	156:337357
OpenAlex:	W2017425355

БД	Цитирований
Web of science	7
Scopus	7
РИНЦ	9
OpenAlex	9