5-Chloro-2-nitrobenzoic acid → 3-Amino-5-chloro-2-nitrobenzoic acid

HRID 85136

Reaction equation

HRID 85136 reaction equation
CC(C)([O-])C.[K+].Cl.CO[NH2:10].[Cl:11][C:12]1[CH:13]=[C:14]([C:18]([N+:21]([O-:23])=[O:22])=[CH:19][CH:20]=1)[C:15]([OH:17])=[O:16]>CN(C=O)C.O.C([O-])(=O)C.[Cu+2].C([O-])(=O)C>[NH2:10][C:19]1[C:18]([N+:21]([O-:23])=[O:22])=[C:14]([CH:13]=[C:12]([Cl:11])[CH:20]=1)[C:15]([OH:17])=[O:16]

Participants

6

Reactant 3

HCID 172865-Chloro-2-nitrobenzoic acidHCID 521874O-Methylhydroxylamine hydrochlorideHCID 23665647Potassium tert-butoxide

Product 1

HCID 107274793-Amino-5-chloro-2-nitrobenzoic acidYield 60.5%

Reagents, catalysts & solvents 2

HCID 165397Cupric acetate monohydrateCatalystHCID 6228DimethylformamideSolvent2×

Procedure

To a mixture of potassium tert-butoxide (38.9 g, 0.347 mol) and copper-(II) acetate monohydrate (0.9 g, 4.96 mmol) in DMF (160 ml) was added a solution of O-methylhydroxylamine hydrochloride (8.3 g, 99.3 mmol) and 3-chloro-6-nitrobenzoic acid (69; 10 g, 49.6 mmol) in DMF (160 ml) at 0° C. The resulting reaction mixture was stirred at that temperature for 3 h. It was then quenched with water, acidified with 10% HCl and extracted with EtOAc. The combined organic layers were dried (Na2SO4) and concentrated under reduced pressure. The residue was taken up in EtOAc and extracted with 10% aqueous NaOH. The combined aqueous layers were acidified with concentrated HCl to a pH=3 and then extracted with EtOAc. The combined organic layers were dried (Na2SO4) and concentrated under reduced pressure to afford 3-amino-5-chloro-2-nitrobenzoic acid 70 (6.5 g, 60.5%) as a brown red solid.

Workup

  1. customThe resulting reaction mixture
  2. customIt was then quenched with water
  3. extractionextracted with EtOAc
  4. dry with materialThe combined organic layers were dried (Na2SO4)
  5. concentrationconcentrated under reduced pressure
  6. extractionextracted with 10% aqueous NaOH
  7. extractionextracted with EtOAc
  8. dry with materialThe combined organic layers were dried (Na2SO4)
  9. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-18c1db3467fd4e33b5684e007a97df51
Source dataset
uspto-grants-2014_09
Patent number
US08846947B2

Linked notes

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