Acetic Acid → Methyl 3-amino-5-chloro-2-hydroxybenzoate

HRID 1747463Notes

Reaction equation

HRID 1747463 reaction equation
[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:9]=[C:8]([Cl:10])[CH:7]=[C:6]([N+:11]([O-])=O)[C:5]=1[OH:14].C(O)(=O)C>CO.[Fe]>[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:9]=[C:8]([Cl:10])[CH:7]=[C:6]([NH2:11])[C:5]=1[OH:14]

Participants

5

Reactant 2

HCID 176Acetic AcidHCID 235651methyl 5-chloro-2-hydroxy-3-nitrobenzoate

Product 1

HCID 687991Methyl 3-amino-5-chloro-2-hydroxybenzoate

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 887MethanolSolvent

Procedure

5-Chloro-2-hydroxy-3-nitro-benzoic acid methyl ester 1 g (4.31 mmol) is dissolved in methanol (30 mL) and acetic acid (30 mL) and then iron powder is added (4.8 g, 86 mmol) at room temperature. The resulting suspension is stirred and heated to reflux for 1 hour. The reaction is allowed to cool to room temperature and then gravity filtered though a pad of celite. The celite cake is washed 3× with ethyl acetate (50 mL) and then the combined washings evaporated in vacuo. The oil is then taken up in ethyl acetate (250 mL) and washed with water (100 mL) and saturated sodium bicarbonate (100 mL). The organic layer is dried (MgSO4), decolorized with charcoal, filtered and evaporated to give the title compound that is used without further purification (730 mg, 3.6 mmol, 84%). LCMS (ESMS): m/z 202.5 (M+H+).

Workup

  1. temperatureheated
  2. temperatureto reflux for 1 hour
  3. filtrationgravity filtered though a pad of celite
  4. washThe celite cake is washed 3× with ethyl acetate (50 mL)
  5. customthe combined washings evaporated in vacuo
  6. washwashed with water (100 mL) and saturated sodium bicarbonate (100 mL)
  7. dry with materialThe organic layer is dried (MgSO4)
  8. filtrationfiltered
  9. customevaporated

Sources & evidence

ORD record
ord-03304eaf22a14b589a5d96d3a62e6f3c
Source dataset
uspto-grants-2015_10
Patent number
US09150556B2

Reaction notes

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