Free radical addition to olefins. Part XVIII. Addition of chloroiodo-and di-iodo-methane to fluoroalkenes

The free-radical addition of chloroiodo- and di-iodo-methane to ethylene, vinyl fluoride, 1,1-difluoroethylene, trifluoroethylene, tetrafluoroethylene, and hexafluoropropene, has been investigated in sealed-tube experiments employing di-t-butyl peroxide as initiator. The main reaction products were 1:1 adducts derived from chloromethyl and iodomethyl radicals respectively. The addition of bromotrichloromethane to hexafluoropropene has been examined under similar experimental conditions. The relative rates of addition of chloromethyl radicals to the alkenes, and the orientation ratios for the unsymmetrical alkenes have been estimated. It is shown that the orientation of radical addition can be successfully accommodated within the 'Patterns of Reactivity' scheme developed for polymer radical reactions.