Lithium Hydroxide → 4-(Diethoxyphosphoryl)benzoic acid

HRID 48933

Reaction equation

HRID 48933 reaction equation
C([O:3][C:4](=[O:19])[C:5]1[CH:10]=[CH:9][C:8]([P:11]([O:16][CH2:17][CH3:18])([O:13][CH2:14][CH3:15])=[O:12])=[CH:7][CH:6]=1)C.[OH-].[Li+]>CO.O>[CH2:17]([O:16][P:11]([C:8]1[CH:9]=[CH:10][C:5]([C:4]([OH:19])=[O:3])=[CH:6][CH:7]=1)([O:13][CH2:14][CH3:15])=[O:12])[CH3:18]

Participants

5

Reactant 2

HCID 3939Lithium HydroxideHCID 2773693Ethyl 4-(diethoxyphosphoryl)benzoate

Product 1

HCID 27736884-(Diethoxyphosphoryl)benzoic acid

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Procedure

To a solution of 4-(diethoxyphosphoryl)-benzoic acid ethyl ester (2b) (2.46 g, 8.59 mmol) in methanol (86 mL) was slowly added lithium hydroxide (monohydrate, 0.36 g, 8.59 mmol) in water (86 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 a rotary evaporator. The desired product was purified by crystallization from hexane/ethyl acetate (2.37 g), m.p. 101° C. 1H NMR (300 MHz, CDCl3) δ (ppm)): 1.27 (t, J=7.03 Hz, 6H), 4.03 (q, J=7.03 Hz, 4H), 7.85 (m, 2H), 8.09 (m, 2H), 12.65 (bs, 11H). 31P NMR (121 MHz, CDCl3) δ 21.611.

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 a rotary evaporator
  8. customThe desired product was purified by crystallization from hexane/ethyl acetate (2.37 g), m.p. 101° C

Sources & evidence

ORD record
ord-54c14f4bf0f14469a0384788b65a07bc
Source dataset
uspto-grants-2004_03
Patent number
US06706699B2

Linked notes

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