Kinnear–Perren reaction
In organophosphorus chemistry, the Kinnear–Perren reaction (sometimes the Clay-Kinnear-Perren reaction) is used to prepare alkylphosphonyl dichlorides (RP(O)Cl2) and alkylphosphonate esters (RP(O)(OR')2).[1] The reactants are alkyl chloride, phosphorus trichloride, and aluminium trichloride as catalyst.[2] The reaction proceeds via the alkyltrichlorophosphonium salt:
- RCl + PCl3 + AlCl3 → [RPCl3]+AlCl4−
Reduction of this trichlorophosphonium intermediate with aluminium powder gives alkyldichlorophosphines (RPCl2).
Partial hydrolysis of the same intermediate gives the alkylphosphonyl dichloride:
- [RPCl3]+AlCl4− + H2O → RP(O)Cl2 + AlCl3 + 2 HCl
The reaction was first reported by Clay[3] and expanded upon by Kinnear and Perren, who demonstrated that the four chlorinated methanes (CH4−xClx) give the corresponding CH3-, CH2Cl-, CHCl2-, and CCl3-substituted derivatives. They also demonstrated workup with hydrogen sulfide to give the alkylthiophosphoryl dichlorides.[4]
References
- ^ "Phosphorus Compounds, Organic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. 2008. doi:10.1002/14356007.a19_545.pub2.
{{cite encyclopedia}}: Cite uses deprecated parameter|authors=(help). - ^ "The Synthesis of Dialkyl α-Halogenated Methylphosphonates". Synthesis: 727–743. 1997. doi:10.1055/s-1997-1417.
{{cite journal}}: Cite uses deprecated parameter|authors=(help) - ^ Clay, John P. (June 1951). "A New Method for the Preparation Of Alkane Phosphonyl Dichlorides". The Journal of Organic Chemistry. 16 (6): 892–894. doi:10.1021/jo01146a010.
- ^ "Formation of Organo-Phosphorus Compounds by the Reaction of Alkyl Chlorides with Phosphorus Trichloride in the Presence of Aluminium Chloride". J. Chem. Soc.: 3437–3445. 1952. doi:10.1039/JR9520003437.
{{cite journal}}: Cite uses deprecated parameter|authors=(help)