Nucleophilic character of alkyl radicals. Part 17. Absolute rate constants and the alternating effect in the addition of alkyl radicals to styrene and acrylic monomers

The absolute rate constants for the addition of alkyl radicals to styrene and acrylic monomers are determined by two kinetic models. The first evaluates the ratio of electron-transfer oxidation by copper(II) acetate and addition to the double bonds, and the second determines the relative rates of alternating addition to acrylic monomers. The results are compared with the values in gas-phase reactions and are discussed in terms of polar effects and frontier orbital theory. The synthetic interest of the reactions involved is emphasized.