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

HRID 904800Notes

Reaction equation

HRID 904800 reaction equation
S(Cl)(Cl)=O.[CH2:5]([O:7][P:8]([CH:13](O)[C:14]1[CH:19]=[CH:18][C:17]([Cl:20])=[CH:16][CH:15]=1)(=[O:12])[O:9][CH2:10][CH3:11])[CH3:6].C(Cl)[Cl:23].N1C=CC=CC=1>O>[CH2:5]([O:7][P:8]([CH:13]([Cl:23])[C:14]1[CH:19]=[CH:18][C:17]([Cl:20])=[CH:16][CH:15]=1)(=[O:12])[O:9][CH2:10][CH3:11])[CH3:6]

Participants

6

Reactant 4

HCID 1049PyridineHCID 6344DichloromethaneHCID 24386Thionyl ChlorideHCID 89363Diethyl P-((4-chlorophenyl)hydroxymethyl)phosphonate

Product 1

HCID 12881548Diethyl [chloro(4-chlorophenyl)methyl]phosphonateYield 97.7%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

9.2 g (0.0768 mol) of thionyl chloride were added to a mixture of 20.2 g (0.0725 mol) of 4-chloro-α-hydroxybenzylphosphonic acid diethyl ester, 65 g of methylene chloride and 5.8 g (0.0725 mol) of pyridine at 20°-40° C. in the course of about 1 hour, while cooling slightly with water. The reaction mixture was then heated under reflux for 3 hours and subsequently stirred for 12 hours, without further action of heat. The mixture was poured onto about 100 g of ice-water and the organic phase was separated off and dried. After distilling off the solvent, the residue was concentrated under 6 mm Hg and at 45° C. 21 g (97.7% of theory) of 4-chloro-α-chloro-benzylphosphonic acid diethyl ester were obtained as a yellow viscous oil with a purity of 98.6% (gas chromatogram) and a refractive index of nD24 : 1.5250.

Workup

  1. temperatureThe reaction mixture was then heated
  2. temperatureunder reflux for 3 hours
  3. temperatureof heat
  4. customthe organic phase was separated off
  5. customdried
  6. distillationAfter distilling off the solvent
  7. concentrationthe residue was concentrated under 6 mm Hg and at 45° C

Sources & evidence

ORD record
ord-e4cbe53b57d24d6f841effe41071e003
Source dataset
uspto-grants-1983_12
Patent number
US04420435

Reaction notes

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