Addition to fluoroalkenes

The rates and orientation of free radical additions to fluoroalkenes depend upon the nature of the attacking radical and the alkene, but polar effects again are important For instance, methyl radical adds 9 5 times faster to tetrafluoroethylene than to ethylene at 164 °C, but the tnfluoromethyl radical adds 10 times taster to ethylene [7551 The more favorable polar transition states combine the nucleophilic radical with the electron deficient olefin 17 and vice versa (18) These polar effects account for the tendency of perfluoroalkenes and alkenes to produce highly regular, alternating copolymers (see Chapter starting on page 1101)... 

Carboxylic acid fluorides undergo addition to fluoroalkenes in the presence of a fluoride ion catalyst, e.g. antimony(V) fluoride to give products 1, or cesium fluoride to give products 2 ... 

Conversely, when the rate of propagation is faster than chain transfer, products arising from telomerisation and polymerisation are formed in greater concentration. In this section, free-radical addition to fluoroalkenes will be dealt with first, in order to establish... 

Table 7.10 Regiochemistry of trifluoromethyl radical additions to fluoroalkenes ratio of attack at A B (Figure 7.58) [182, 184, 187]...

Many examples of free-radical addition to fluoroalkenes have been recorded some examples are listed in Table 7.11. 

Polyfluoroalkanes, Polyfluoroalkenes, Polyfluoroalkynes and Derivatives 199 Table 7.11 Free-radical additions to fluoroalkenes... 

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