Water → Ethyl diethoxymethyl(benzyl)phosphinate

HRID 1612770Notes

Reaction equation

HRID 1612770 reaction equation
[H-].[Na+].[CH2:3]([O:5][CH:6]([PH:10](=[O:14])[O:11][CH2:12][CH3:13])[O:7][CH2:8][CH3:9])[CH3:4].[CH2:15](Br)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.O>O1CCCC1>[CH2:12]([O:11][P:10]([CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)([CH:6]([O:7][CH2:8][CH3:9])[O:5][CH2:3][CH3:4])=[O:14])[CH3:13]

Participants

6

Reactant 4

HCID 962WaterHCID 7498Benzyl BromideHCID 24758Sodium hydrideHCID 178472284HCID 178472284, compound

Product 1

HCID 9994134Ethyl diethoxymethyl(benzyl)phosphinate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A suspension of 16.5 g of sodium hydride (80% in oil) in 100 ml of anhydrous tetrahydrofuran under an inert atmosphere at 20° is treated with 100 ml of an anhydrous tetrahydrofuran solution of 104.4 g of ethyl (diethoxymethyl)phosphinate at such a rate so that the temperature does not exceed 25°. After the addition is complete, the resulting suspension is stirred for 1 hour at room temperature. This suspension is then treated with 85.5 g of benzylbromide and the reaction mixture stirred overnight at room temperature. The reaction mixture is then cooled in an ice/water bath and 200 ml of water are carefully added. The clear solution is then partitioned between dichloromethane and water. Separation of the dichloromethane layer followed by drying and removal of the solvent affords a pale yellow oil. Distillation in high vacuum affords ethyl-P-benzyl-P-diethoxymethylphosphinate of b.p. 105°-125° (10-2 mbar); 1H-NMR (CDCl3): δ (ppm)=7.29 (5H, m, Ph), 4.58 (1H, d, J= 9 Hz, CHP), 4.08 (2H, q, CH2OP), 3.83 and 3.66 (4H, m, 2×CH2OC), 3.21 (2H, ABqJ=15×6.0 Hz, CH2Ph), 1.23 (9H, m, 3×CH3).

Workup

  1. customdoes not exceed 25°
  2. additionAfter the addition
  3. stirringthe reaction mixture stirred overnight at room temperature
  4. temperatureThe reaction mixture is then cooled in an ice/water bath
  5. customThe clear solution is then partitioned between dichloromethane and water
  6. customSeparation of the dichloromethane layer
  7. customby drying
  8. customremoval of the solvent
  9. customaffords a pale yellow oil
  10. distillationDistillation in high vacuum

Sources & evidence

ORD record
ord-ee887bbd7efc4bcea4c91a57a68ceca9
Source dataset
uspto-grants-1993_03
Patent number
US05190934

Reaction notes

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