Sodium hydride → Diethyl {[2-(bromomethyl)phenyl]methyl}phosphonate

HRID 1646182Notes

Reaction equation

HRID 1646182 reaction equation
[H-].[Na+].[CH2:3]([O:5][P:6]([O-:10])[O:7][CH2:8][CH3:9])[CH3:4].[Br:11][CH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[CH2:19]Br.C(OP([O-])OCC)C.[Na+]>O1CCCC1>[CH2:3]([O:5][P:6]([CH2:19][C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][C:13]=1[CH2:12][Br:11])(=[O:10])[O:7][CH2:8][CH3:9])[CH3:4]

Participants

6

Reactant 4

HCID 24758Sodium hydrideHCID 66665o-Bis(bromomethyl)benzeneHCID 3780918DiethylphosphiteHCID 23684067Sodium diethyl phosphite

Product 1

HCID 15171995Diethyl {[2-(bromomethyl)phenyl]methyl}phosphonateYield 16.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

A suspension of sodium hydride (60% in oil, 1.4 g, 35 mmol) in anhydrous tetrahydrofuran (75 ml) is stirred under a nitrogen atmosphere and a solution of diethylphosphite (4.82 g, 34.9 mmol) in tetrahydrofuran (20 ml) is added dropwise. The reaction mixture is stirred an additional 20 minutes. A solution of 1,2-bis(bromomethyl)benzene (10.56 g, 40 mmol) in anhydrous tetrahydrofuran (150 ml) is treated dropwise with the solution of sodium diethylphosphite generated above. The reaction mixture is stirred 6.5 hours at room temperature, and then quenched with water and diluted with diethyl ether. The diethyl ether layer is separated, washed with water (2×100 ml), and dried over magnesium sulfate. After filtration and evaporation, the residue is chromatographed over silica gel (ethyl acetate as eluant) to give a clear oil (1.8 g).

Workup

  1. stirringThe reaction mixture is stirred an additional 20 minutes
  2. stirringThe reaction mixture is stirred 6.5 hours at room temperature
  3. customquenched with water
  4. additiondiluted with diethyl ether
  5. customThe diethyl ether layer is separated
  6. washwashed with water (2×100 ml)
  7. dry with materialdried over magnesium sulfate
  8. filtrationAfter filtration and evaporation
  9. customthe residue is chromatographed over silica gel (ethyl acetate as eluant)

Sources & evidence

ORD record
ord-54437e30675a4b45ac78d6ccb5d81d6f
Source dataset
uspto-grants-1993_01
Patent number
US05179085

Reaction notes

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