37161-81-2Relevant academic research and scientific papers
REACTIONS OF HALOGEN FLUORIDES. VII. FLUORINATION OF UNSATURATED COMPOUNDS WITH BROMINE TRIFLUORIDE AND AN EQUIMOLAR MIXTURE OF BROMINE TRIFLUORIDE WITH MOLECULAR BROMINE
Boguslavskaya, L. S.,Chuvatkin, N. N.,Kartashov, A. V.,Ternovskoi, L. A.
, p. 230 - 236 (2007/10/02)
The reactions of bromine trifluoride and an equimolar mixture of bromine trifluoride and bromine with halogen-substituted alkenes and methyl α-substituted acrylates were investigated.With sufficient dilution of the substrate by Freon 113 (20-25:1) it is possible to obtain the bromofluoro and difluoro adducts with good yiels.The best results (overall yields of fluorination products 80-83percent) were obtained with alkenes containing a halogen at the multiple bond; in the case of more reactive substrates the reaction becomes nonpreparative.The bromofluorination of E- and Z-1,2-dichloroethylenes and E- and Z-1,3-dichloropropenes with pure bromine trifluoride is antistereospecific.The bromofluorination of E- and Z-1,2-dichloroethylenes by the BrF3-Br2 system gives a mixture of diastereomeric bromofluoro adducts as a result of isomerization of the initial olefins in the presence of the bromine.The formation of the difluorides of the halogenated olefins is nonstereospecific and is accompanied by migration of the halogens.
REACTIONS OF CHLORINE MONOFLUORIDE. SUBSTITUTION OF CHLORINE ATOMS BY FLUORINE IN CHLORINE-SUBSTITUTED ALKANES AND ESTERS
Chuvatkin, N. N.,Panteleeva, I. Yu.,Boguslavskaya, L. S.
, p. 821 - 827 (2007/10/02)
In anhydrous hydrogen fluoride under mild conditions chlorine monofluoride selectively substitutes the chlorine atoms in chlorine-substituted alkanes and esters by fluorine with the formation of high yields of the corresponding fluorides.The presence of an alkoxycarbonyl group or difluoromethylene group at the α position to the CHCl group deactivates the chlorine atom, and substitution by fluorine does not occur.In chloroalkanes, from which elimination of the chloride ion leads to sufficiently stable carbocations, substitution by fluorine can be realized in the absence of hydrogen fluoride at temperatures between -20 and -60 deg C.The fluorinating capacity of chlorine monofluoride is increased in the presence of catalytic amounts (3-5percent) of antimony pentachloride.Here the reaction is less selective than in hydrogen fluoride.In certain cases substitution is accompanied by hydride transfers.
