Citric Acid → Methyl 2-amino-3-chloro-4-methoxybenzoate

HRID 420073Notes

Reaction equation

HRID 420073 reaction equation
[NH2:1][C:2]1[C:10]([Cl:11])=[C:9]([O:12][CH3:13])[CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].[C:14]([O-])([O-])=O.[K+].[K+].CI.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>CN(C=O)C>[CH3:14][O:5][C:4](=[O:6])[C:3]1[CH:7]=[CH:8][C:9]([O:12][CH3:13])=[C:10]([Cl:11])[C:2]=1[NH2:1]

Participants

6

Reactant 4

HCID 311Citric AcidHCID 6328Methyl iodideHCID 11430Potassium CarbonateHCID 666505632-Amino-3-chloro-4-methoxybenzoic acid

Product 1

HCID 66650895Methyl 2-amino-3-chloro-4-methoxybenzoateYield 50%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a stirred solution of compound 104d (1.9 g, 9.6 mmol) in dry DMF (25 mL) was added K2CO3 (1.32 g, 9.6 mmol) at room temperature. The reaction mixture was stirred for 30 min and methyl iodide (0.77 mL, 12.4 mmol) was added. After 2 hrs at room temperature, 5% aqueous citric acid was added. The mixture was extracted with EtOAc. Organics were washed with water, dried over Na2SO4, filtered, concentrated under reduced pressure, and purified by chromatography on silica gel (petroleum ether/EtOAc) to yield compound 105d as beige solid in 50% yield.

Workup

  1. waitAfter 2 hrs at room temperature
  2. extractionThe mixture was extracted with EtOAc
  3. washOrganics were washed with water
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. custompurified by chromatography on silica gel (petroleum ether/EtOAc)

Sources & evidence

ORD record
ord-db4749b12bbc496b8f8110bd91e17135
Source dataset
uspto-grants-2012_01
Patent number
US08093379B2

Reaction notes

Loading…