1361257-64-8Relevant academic research and scientific papers
Reactions of perfluorinated alkenyl-, alkynyl-, alkyltrifluoroborates, and selected hydrocarbon analogues with the halogenating agents Hal2 (Hal = F, Cl, Br), "brF" (BrF3-Br2 1:1), and ICl
Bardin, Vadim V.,Adonin, Nicolay Yu.,Frohn, Hermann-Josef
experimental part, p. 565 - 579 (2012/05/20)
Reactions of [Bu4N][RBF3] [R = CnF 2n+1CF=CF (cis, trans), CF2=CF, CF2=C(CF 3), trans-C4H9CF=CF, trans-C6H 5CF=CF, C4H9CH=CH (cis, trans), CF 3C≡C, and C4H9C≡C] with chlorine, bromine, BrF3 + Br2 (as equivalent of "BrF"), and ICl in solution (CH2Cl2, CHCl3, CF 3CH2CF2CH3) led to 1, 2-addition of halogen and/or replacement of boron by halogen (halodeboration). The reaction of [Bu4N][CF3C≡CBF3] with less than equimolar amounts of diluted fluorine (5 %) in 1, 1, 1, 3, 3-pentafluorobutane (PFB) showed only [Bu4N][CF3CF2CF 2BF3] as fluorine addition product besides extensive fluorodeboration. Suspensions of the insoluble K[CF2=CFBF 3] salt reacted with Cl2 and Br2 in CH 2Cl2 giving preferentially products of halogen addition across the C=C bond. In reactions with ICl iododeboration with formation of CF2=CFI occurred besides 1, 2-addition with formation of [CF 2I-CFClBF3]-. The halodeboration reaction of[Bu4N][trans-C4H9CF=CFBF3] with Br2, "BrF", and ICl, of K[trans-C6H 5CF=CFBF3] with Br2, and of [Bu 4N][trans-C4F9CF=CFBF3] with ICl proceeded stereospecifically. Copyright
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
Bardin, Vadim V.,Adonin, Nicolay Yu.,Frohn, Hermann-Josef
experimental part, p. 114 - 128 (2012/04/10)
The relative rate of the electrophilic hydrodeboration of K[R′BF 3] with HF (27-100%) diminishes in the series R′ = C 4H9CC > C4F9CFCFCC > CF 2C(CF3) > C3F7CC ～ (CF 3)2CFCC > CF3CC. When R′ = CF 3CC the new salt K[CF3CH2-CF2BF 3] was obtained by addition of HF besides CF3CCH and K[BF4]. Small amounts of water caused the formation of K[CF 3CH2-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-CF2BF 3] (from K[RFCFCFBF3]) and K[R FCHal2-CF2BF3] (from K[R FCHalCFBF3] and K[RFCCBF3]) (Hal = Cl, Br). Treatment of K[RFCFCFBF3] and K[R FCCBF3] with 5% F2/N2 in MeCN gave the corresponding salts K[RFCF2-CF2BF 3] in 16-25% isolated yield. Reactions of K[trans-C4F 9CFCFBF3] with Cl2 in MeOH resulted in K[C 4F9CFCl-C(O)BF3] (major product). The latter was also obtained in reactions of K[trans-C4F9CFCFBF 3] with Cl2 in MeCN or sulfolane after sequential methanolysis of the primarily formed products. In contrast, the salts K[RCFCFBF3] (R = CnF2n+1, trans-C 4H9) and K[CF3CCBF3] underwent bromodeboration to RCFCFBr and CF3CCBr, respectively, when they were reacted with bromine in the polar solvents MeOH, MeCN, or sulfolane.
