Trimethyl Phosphate → ([1,1'-Biphenyl]-4-ylmethyl)phosphonic acid dimethyl ester

HRID 1440664Notes

Reaction equation

HRID 1440664 reaction equation
Cl[CH2:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[CH:5][CH:4]=1.[CH3:15][O:16][P:17](OC)([O:19][CH3:20])=[O:18]>>[CH3:15][O:16][P:17]([CH2:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[CH:5][CH:4]=1)(=[O:18])[O:19][CH3:20]

Participants

3

Reactant 2

HCID 10541Trimethyl PhosphateHCID 154634-Phenylbenzyl chloride

Product 1

HCID 15359635([1,1'-Biphenyl]-4-ylmethyl)phosphonic acid dimethyl esterYield 72.8%

Procedure

A solution of 4-(chloromethyl)biphenyl (4.12 g, 0.020 M) in trimethylphosphate (10 mL, 10.5 g, 0.085 M) is heated at reflux temperature for 60 hours. The excess trimethylphosphite is removed under reduced pressure and the solid residue is chromatographed (400 g of 40-63 μm silica gel, 50 mL fractions). The sample is applied to the column in a minimum amount of EtOAc and the column is eluted with 50% EtOAc-hexane (1.2 L), 75% EtOAc-hexane (2 L), and with EtOAc. Fractions 88-136 contained the dimethyl ester (4.98 g, 0.0180 M, 90%) which is crystallized from ether-pentane to give 4.09 g of title compound as white crystals, mp 70°-71° C.(fused), 76.5°-77.5° C.

Workup

  1. temperatureat reflux temperature for 60 hours
  2. customThe excess trimethylphosphite is removed under reduced pressure
  3. customthe solid residue is chromatographed (400 g of 40-63 μm silica gel, 50 mL fractions)
  4. washthe column is eluted with 50% EtOAc-hexane (1.2 L), 75% EtOAc-hexane (2 L)
  5. customis crystallized from ether-pentane

Sources & evidence

ORD record
ord-4d2ae52265eb42d59d35a6b967857009
Source dataset
uspto-grants-1996_03
Patent number
US05500417

Reaction notes

Loading…