Water → Ethyl diethoxymethyl(benzyl)phosphinate

HRID 1463643Notes

Reaction equation

HRID 1463643 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>[CH2:3]([O:5][CH:6]([P:10]([CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)(=[O:14])[O:11][CH2:12][CH3:13])[O:7][CH2:8][CH3:9])[CH3:4]

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 12 g of oil-free sodium hydride in 300 ml of absoluted tetrahydrofuran under an inert atmosphere is treated with a solution of 103.5 g of 95% ethyl diethoxymethylphosphinate in 100 ml of absolute tetrahydrofuran at such a rate so as to maintain the temperature at or just below 20° C. After the addition is complete, the suspension is stirred for 1 hour at room temperature and then cooled to approximately 10° C. before addition of 85.5 g of benzylbromide, maintaining the temperature below 15° C. Finally, the white suspension is stirred for 20 hours at room temperature. Water is then added and the tetrahydrofuran layer is separated. The aqueous layer is extractet with dichloromethane and the combined organic layers are dried and concentrated in vacuo. Distillation of the residue in high vacuum affords ethyl diethoxymethyl(benzyl)phosphinate as a colourless oil of b.p. 105-125 (10-2 mbar). 1H-NMR (CDCl3): δ (ppm)=7.29 (5H, m, Ph), 4.48 (1H, d, 5=9 Hz, CHP), 4.08 (2H, q, CH2OP), 3.83 (2H, m, CH2OC), 3.66 (2H, m, CH2OC), 3.21 (2H, ABq, d, 5=15×6 Hz, CH2P), 1.23 (9H, m, 3×CH3).

Workup

  1. temperatureto maintain the temperature at or just below 20° C
  2. additionAfter the addition
  3. temperaturemaintaining the temperature below 15° C
  4. stirringFinally, the white suspension is stirred for 20 hours at room temperature
  5. customthe tetrahydrofuran layer is separated
  6. customthe combined organic layers are dried
  7. concentrationconcentrated in vacuo
  8. distillationDistillation of the residue in high vacuum

Sources & evidence

ORD record
ord-e1585ef08c884a5e8dd7246d50347a74
Source dataset
uspto-grants-1994_04
Patent number
US05300679

Reaction notes

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