Selective Reactions of Bromine Trifluoride in Organic Chemistry

Abstract

Although known for more than a century, bromine trifluoride is not a common reagent in day to day research work in organic chemistry. Its tendency to react exothermically with solvents containing Lewis base elements such as water, acetone or ethers distanced it from the mind of many. Still, under the proper conditions, it can perform quite a few selective reactions which are difficult to achieve by other reagents. We discuss in this review reactions which have been published in the last 30 years. They consist of fluorinating heteroatoms, substituting carbon-halogen bonds with carbon-fluorine bonds, syntheses of anesthetics, construction of the trifluoromethyl (CF 3 ) and the difluoromethylene (CF 2 ) groups, aromatic brominations and more.

Fluoro-Pummerer rearrangement and analogous reactions

“…p-(Difluoroiodo)toluene (DFIT) [139] as well as bromine trifluoride (BrF 3 ) [38,39], which efficiently combine electrophile and fluoride in one reagent, also proved their applicability for desulfurization-difluorination reactions. DFIT was able to convert 1,3-dithiolanes and 1,3-dithianes of diaryl ketones to gem-difluoro compounds in good yields [139].…”

“…These reactions have been extensively reviewed in several articles [38,105,125] and will not be discussed in this review.…”

“…Therefore, a variety of trifluoromethylated pharmaceuticals and agrochemicals have been developed in recent years. Besides different methods for the introduction of the whole CF 3 group into organic molecules [ the oxidative desulfurization-trifluorination approach can be utilized for the construction of CF 3 groups in strategic positions of various molecules [38,105,125].…”

“…Analogous, but more stable SF 3 -reagents like Desoxofluor 1 [34], Fluorinox 1 [35], Morpholino sulfur trifluoride [36], Fluolead TM [37] were also applied for nucleophilic fluorination reactions. For many substrates also bromine trifluoride (BrF 3 ) has been used [38,39].…”

Investigating the Synthesis and Thermal Stability of Barium Tetrafluorobromate (III)

“…It is quite interesting to consider alkali and alkali-earth metals fluorobromates as solid state analogues of BrF 3 3 . The common formulae of these compounds looks like MeBrF 4 for alkali metals fluorobromates and Me(BrF 4 ) 2 for alkali-earth metals fluorobromates.…”