Dialkyl hydrogen phosphonates or dialkylphosphine oxides are conveniently and efficiently alkylated by alkyl chlorides to produce dialkyl alkylphosphonates or trialkylphosphine oxides, respectively, by aqueous sodium hydroxide in a liquid-liquid phase-transfer- catalyzed reaction. Despite the hydrolytic instability of dialkyl hydrogen phosphonates, their reaction with chloroacetamides in the two-phase system can provide dialkyl ( ...