462-72-6Relevant articles and documents
REACTIONS OF HALOGEN FLUORIDES. XI. MECHANISM OF REACTIONS OF ALKYL HALIDES WITH BROMINE TRIFLUORIDE
Kartashov, A. V.,Chuvatkin, N. N.,Kurskii, Yu. A.,Boguslavskaya, L. S.
, p. 2279 - 2284 (2007/10/02)
The effects of the substituted halogen, the neighboring groups, and the polarity of the medium on the nature of the fluorination products were studied for the reactions of δ-substituted halogenobutanes and 1,2,3-trihalogenobutanes with bromine tetrachloride.A mechanism involving formation of linear halogenonium ions at the rate-determining stage is proposed.
REACTIONS OF HALOGENS FLUORIDES. VIII. SUBSTITUTIVE FLUORINATION OF BROMINE-CONTAINING ALKANES AND ESTERS WITH BROMINE TRIFLUORIDE
Chuvatkin, N. N.,Kartashov, A. V.,Morozova, T. V.,Boguslavskaya, L. S.
, p. 237 - 242 (2007/10/02)
The conditions were found for selective liquid-phase substitutive fluorination of bromine-substituted alkanes and esters with pure bromine trifluoride, in which all three fluorine atoms of the BrF3 molecule are used effectively in the fluorination.The exchange of bromine for fluorine in monobromohalogenoalkanes is nonstereospecific and is in a number of cases accompanied by skeletal rearrangements, hydride shifts, and migration of the halogen.A carbocationic mechanism of fluorination is discussed.
REACTIONS OF CHLORINE MONOFLUORIDE. VI. RELATIVE RATES OF SUBSTITUTIVE FLUORINATION OF BROMINE-SUBSTITUTED ALKANES. HYDRIDE SHIFTS AND OTHER MIGRATIONS DURING FLUORINATION
Morozova, T. V.,Chuvatkin, N. N.,Panteleeva, I. Yu.,Boguslavskaya, L. S.
, p. 1255 - 1263 (2007/10/02)
The relative rates of substitutive fluorination of bromoalkanes with various structures by chlorine monofluoride in a nonpolar medium at 20-40 deg C were investigated by the method of competing reactions.Halogen atoms vicinal with the substituted bromine greatly reduce the fluorination rate.The reactivity of the secondary bromides decreases in the order (CH3)2CHBr>>CH3CHBrCH2Cl>>CH2ClCHBrCH2Cl.The geminal halogen atoms have little effect on the rate of substitutive fluorination.The fluorination rates of the bromoalkanes CH2BrCH2Br, CH2BrCHClBr, and CH2BrCCl2Br are in ratios 10:3:1 respectively, while the fluorination rate of CH3CHClBr is much higher than that of CH2ClCH2Br.As a rule the debromination of primary bromides containing vicinal halogens (Br, Cl) is accompanied by migration of the latter and gives fluorides with iso structures.Hydride shifts take place in cases where stable tertiary or secondary carbocations are formed as a result of migration of the hydride; for example, the fluorination of CH3CHFCH2Br leads to the geminal difluoroalkane CH3CF2CH3.The mechanism of substitutive fluorination is discussed.