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

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 : DOI: 10.1016/j.jfluchem.2011.09.011

Ключевые слова

Organyltrifluoroborate salts; Halogenation; Halodeboration; Halofluorination; NMR spectroscopy

Авторы

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

Организации

1	(Данные Web of science) Univ Duisburg Essen, D-47048 Duisburg, Germany
2	(Данные Web of science) RAS, SB, NN Vorozhtsov Novosibirsk Inst Organ Chem, Novosibirsk 630090, Russia
3	(Данные Web of science) RAS, SB, GK Boreskov Inst Catalysis, Novosibirsk 630090, Russia

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 similar to(CF3)(2)CFC 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(P)BF3] as a by-product. The electrophilic halofluorination of perfluoroalkenyltrifluoroborate salts with NCS or NBS in aHF (anhydrous HF) led to K[R(F)CFHal-CF2BF3] (from K[RFCF=CFBF3]) and K[R(F)CHal(2)-CF2BF3] (from K[R(F)CHal=CFBF3] and K[RFC-CBF3]) (Hal = Cl, Br). Treatment of K[RFCF=CFBF3] and K[RFC CBF3] with 5% F-2/N-2 in MeCN gave the corresponding salts K[RFCF2-CF2BF3] in 16-25% isolated yield. Reactions of K[trans-C4F9CF=CFBF3] with Cl-2 in MeOH resulted in K[C4F9CFCl-C(O)BF3] (major product). The latter was also obtained in reactions of K[trans-C4F9CF CFBF3] with Cl-2 in MeCN or sulfolane after sequential methanolysis of the primarily formed products. In contrast, the salts K[RCF=CFBF3](R = CnF2n+1, trans-C4H9) 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. (C) 2011 Elsevier B.V. All rights reserved.

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

Опубликована в печати:

1 мар. 2012 г.

Web of science	WOS:000301806400014
Scopus	2-s2.0-84857368712
РИНЦ	17977183
OpenAlex	W2017425355