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In organophosphorus chemistry, the Kinnear–Perren reaction is used to prepare alkylphosphonyl dichlorides Cl2] and alkylphosphonate esters 2]. The reactants are alkyl chloride, phosphorus trichloride, and aluminium trichloride as catalyst. The reaction proceeds via the alkyltrichlorophosphonium salt:
Reduction of this trichlorophosphonium intermediate with aluminium powder gives alkyldichlorophosphines.
Partial hydrolysis of the same intermediate gives the alkylphosphonyl dichloride:
The reaction was first reported by Clay and expanded upon by Kinnear and Perren, who demonstrated that the four chlorinated methanes give the corresponding CH3-, CH2Cl-, CHCl2-, and CCl3-substituted derivatives. They also demonstrated workup with hydrogen sulfide to give the alkylthiophosphoryl dichlorides.