Lithium Hydroxide → 4-(Diethoxyphosphoryl)benzoic acid

HRID 719247

Reaction equation

HRID 719247 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, 1H). 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-3e4420040f774f96a0ef13572d009796
Source dataset
uspto-grants-2006_11
Patent number
US07132427B2

Linked notes

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