CID 406 → Diethyl [chloro(4-chlorophenyl)methyl]phosphonate

Participants

Reaction Conditions

Reaction Steps

Under a nitrogen atmosphere a stirred solution of 6.7 grams (0.067 mole) of di(1-methylethyl)amine in 50 mL of tetrahydrofuran was cooled to -78° C., and 29 mL (0.0725 mole) of n-butyllithium (2.5M in hexanes) was added. Upon completion of addition the reaction mixture was stirred at -78° C. for 15 minutes. The reaction mixture was warmed to 0° C. where it stirred for 30 minutes, and then 15.1 grams (0.0575 mole) of diethyl (4-chlorophenyl)methylphosphonate was added. The reaction mixture was cooled to -78° C. In a second reaction vessel under a nitrogen atmosphere, a rapidly stirred solution of 11.4 grams (0.068 mole) of trifluoromethanesulfonyl chloride in 60 mL of tetrahydrofuran was cooled to -78° C., and the cold phosphonate solution prepared above was added. Upon completion of addition the reaction mixture was allowed to warm to ambient temperature where it stirred for 16 hours. The reaction mixture was stirred with aqueous ammonium chloride solution to quench any further reaction. The organic layer was taken up in diethyl ether and was washed first with an aqueous ammonium chloride solution and then with an aqueous sodium chloride solution. The organic layer was dried with magnesium sulfate and filtered through diatomaceous earth. The filtrate was concentrated under reduced pressure to a residue. The residue was subjected to column chromatography on silica gel. Elution was accomplished using 10% ethyl acetate in hexane. The appropriate fractions were combined and concentrated under reduced pressure to yield 8.9 grams of diethyl (4-chlorophenyl)chloromethylphosphonate.

Provenance & Evidence