Robert S. Marmor

Halomethyl—metal compounds : LXIII. Diethyl lithiodichloromethylphosphonate and tetraethyl lithiochloromethylenediphosphonate☆

Abstract The action of n-butyllithium in THF at low temperature on diethyl trichloromethylphosphonate and tetraethyl dichloromethylenediphosphonate gave the reagents LiCCl 2 P (O) (OEt) 2 and [(EtO) 2 (O)P] 2 CClLi, respectively. The hydrolyses of these reagents, some coupling reactions with dimethyl sulfate, allyl bromide and trimethylchlorosilane and their use in the synthesis of chloroolefins are described.

The mercuration of phosphonate esters

The reactions of [(EtO)2(O)P]2CH2, (EtO)2(O)PCH2CO2Et, (EtO)2(O)PCH2CN and [(EtO)2(o)P]2CHCl with mercuric acetate in refluxing THF gave [(EtO)2(O)P]2C(HgOAc)2, (EtO)2(O)PC(CO2Et)(HgOAc)2, (EtO)2(O)PC(CN)(HgOAc)2 and [(EtO)2(O)P]2CClHgOAc, respectively. Redistribution reactions were used to prepare [(EtO)2(O)P]2C(HgX)2 (X = Cl, Br or Ph). The CHg bonds of tetraethyl bis(acetoxymercuri)methylenediphosphonate were cleaved by chlorine to give [(EtO)2(O)P]2CCl2· HgCl2 and by hydrogen sulfide in ethanol to give [(EtO)2(O)P]2CH2.