HALOGEN FLUOROSULFATE REACTIONS WITH FLUOROCARBONS

Article abstract of DOI:10.1016/S0022-1139(00)85149-0

The scope of the reaction of simple fluorocarbon halides with chlorine fluorosulfate and mixtures of chlorine and bromine fluorosulfate to produce R_fOSO2F compounds has been investigated.It is shown that in many cases even primary chlorine in -CF2Cl groups can be replaced by -OSO2F.Primary bromine or iodine in -CF2X are more readily replaced.The mechanism of this replacement reaction has been established by the isolation of the metastable iodine III intermediate R_fI(OSO2F)2.Neither secondary chlorine nor bromine in -CFX- groups is affected.With the secondary iodide, i-C3F7I, the salt <(i-C3F7)2I>^{+ -} is formed.Furthermore, it has been found that ClOSO2F is capable of converting fluorocarbon acids or their derivatives into fluorocarbon halides.A combination of these two ClOSO2F reactions with the known conversion of R_fCF2OSO2F to the corresponding fluorocarbon acid offers a novel, high yield chain shortening reaction for the otherwise unreactive fluorocarbon halides according to: