Lithium Hydroxide → 4-[(Diethoxyphosphorylmethyl)-ethoxyphosphinoyl)-benzoic acid

HRID 48935Notes

Reaction equation

HRID 48935 reaction equation
C([O:3][C:4](=[O:25])[C:5]1[CH:10]=[CH:9][C:8]([P:11]([CH2:16][P:17]([O:22][CH2:23][CH3:24])([O:19][CH2:20][CH3:21])=[O:18])([O:13][CH2:14][CH3:15])=[O:12])=[CH:7][CH:6]=1)C.[OH-].[Li+]>CO.O>[CH2:20]([O:19][P:17]([CH2:16][P:11]([O:13][CH2:14][CH3:15])([C:8]1[CH:7]=[CH:6][C:5]([C:4]([OH:25])=[O:3])=[CH:10][CH:9]=1)=[O:12])([O:22][CH2:23][CH3:24])=[O:18])[CH3:21]

Participants

5

Reactant 2

HCID 3939Lithium HydroxideHCID 213024024-[(Diethoxyphosphorylmethyl)-ethoxyphosphinoyl]-benzoic acid ethyl ester

Product 1

HCID 218979184-[(Diethoxyphosphorylmethyl)-ethoxyphosphinoyl)-benzoic acid

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Procedure

To a solution of 4-[(Diethoxyphosphorylmethyl)-ethoxyphosphinoyl]-benzoic acid ethyl ester (3c) (1 g, 2.55 mmol) in methanol (25 mL) was slowly added lithium hydroxide (monohydrate, 0.11 g, 2.55 mmol) in water (25 mL). The resulting reaction mixture was stirred at room temperature for 4 hours. The reaction mixture was concentrated to remove methanol and diluted with brine, then extracted with EtOAc (3×100 mL) until the aqueous layer showed little or no evidence of product by HPLC. The combined organics were dried over Na2SO4 and concentrated on rotary evaporator. The desired product (3d) was purified by silica gel flash chromatography as a pale yellow oil (0.91 g). 1H NMR (300 MHz, DMSO-d6) δ (ppm)): 1.13 (m, 9H), 2.94 (t, J=18.2 Hz, 2H), 3.85 (m, 6H), 7.88 (m, 2H), 8.02 (m, 2H), 12.60 (bs, 1H), 31P NMR (121 MHz, DMSO-d6)δ, 37.59 and 24.59

Workup

  1. customThe resulting reaction mixture
  2. concentrationThe reaction mixture was concentrated
  3. customto remove methanol
  4. additiondiluted with brine
  5. extractionextracted with EtOAc (3×100 mL) until the aqueous layer
  6. dry with materialThe combined organics were dried over Na2SO4
  7. concentrationconcentrated on rotary evaporator
  8. customThe desired product (3d) was purified by silica gel flash chromatography as a pale yellow oil (0.91 g)

Sources & evidence

ORD record
ord-2e9a4a5e46494f249575f34298245891
Source dataset
uspto-grants-2004_03
Patent number
US06706699B2

Reaction notes

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