有機リンラジカルの反応

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Chlorophosphonation and its related free radical reaction of phosphorus compounds were revie wed. In the chlorophosphonation of substituted hydrocarbons, the resonance effect of substituents on the intermediatealkyl radical is of importance in the determination the process of the reaction. The unstabilized alkyl radical reacts rapidly with phosphorus trichloride to give alkylphosphoranyl radical which leads further to alkylphosphonyl dichloride as a final product. But the resonance-stabilized alkyl radical reacts with oxygen rather than with phosphorus trichloride to give alkyl peroxy radical. In the cases of benzylic radicals or halogenbridged alkyl radical, they lead to diphenylmethane derivatives or β-haloalkylphosphorodichloridates as final products. The mechanisms of the formation of these products were discussed.<BR>In the chlorophosphonation of unsaturated hydrocarbons, besides the addition of chlorine atom, the addition of intermediate PCl<SUB>4</SUB> radical to double bond are also of importance.<BR>The bromophosphonation of unsaturated hydrocarbons was also discussed.
社団法人有機合成化学協会の論文