Trialkyl phosphites react with cyanoisopropylperoxyl radicals, generated by thermolysis of azobis(isobutyronitrile) in the presence of oxygen, to give the corresponding phosphates with rate constants of the order of 10 3 M −1 sec −1 at 65°C. Phenyl phosphites are oxidized also. A small amount of cyanoisopropyl phosphite is formed by substitution of the phosphite by alkyloxyl radicals leading to phenoxyl radicals. Sterically hindered aryl phosphites react with cyanoisopropylperoxyl radicals to yield the corresponding phosphates and alkoxyl radicals which in a second step react with phosphite by substitution releasing a sterically hindered phenoxyl radical. Therefore, sterically hindered phosphites are capable of acting as chain-terminating primary antioxidants. Because the rate constants of reaction of these phosphites with peroxyl radicals are only in the range of 10 2 M −1 sec −1 and 100 times smaller than those of phenols, phosphites should be less active as primary antioxidants than phenols.
