Methanol → 2-Amino-6-nitro-benzoic acid

HRID 1844298Notes

Reaction equation

HRID 1844298 reaction equation
[N+:1]([C:4]1[CH:12]=[CH:11][CH:10]=[C:9]([N+:13]([O-])=O)[C:5]=1[C:6]([OH:8])=[O:7])([O-:3])=[O:2].[NH4+]=S.C(Cl)Cl.CO>C(O)C>[N+:1]([C:4]1[CH:12]=[CH:11][CH:10]=[C:9]([NH2:13])[C:5]=1[C:6]([OH:8])=[O:7])([O-:3])=[O:2]

Participants

5

Reactant 3

HCID 887MethanolHCID 6344DichloromethaneHCID 119206Benzoic acid, 2,6-dinitro-

Product 1

HCID 957952-Amino-6-nitro-benzoic acid

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

2,6-Dinitrobenzoic acid (0.5 g, 2.36 mmol) in ethanol (5 mL) was heated to 80° C. Ammonium sulfide (40-48% in water) (0.36 mL, 2.36 mmol) was then added (the yellow solution became a bright orange suspension) the mixture was heated under reflux for 0.5 h. TLC (DCM 80%, MeOH 20%) showed a faint spot below the starting material. Ammonium sulfide (3.6 mL, 20.4 mmol) was added and the mixture became a darker orange. This mixture was then heated under reflux for 1 h after which time TLC indicated that the reaction had gone to completion. The solvents were removed under reduced pressure and then the residue washed with methanol. The methanol solution was decanted off and evaporated to dryness to afford 2-nitro-6-amino benzoic acid as a orange solid. This was then purified using flash chromatography (DCM 90%/MeOH 10%->20% MeOH over 60CV, 12 g column) to afford the desired material (0.2 g, 46%).

Workup

  1. temperaturewas heated
  2. temperatureunder reflux for 0.5 h
  3. temperatureThis mixture was then heated
  4. temperatureunder reflux for 1 h after which time TLC
  5. customThe solvents were removed under reduced pressure
  6. washthe residue washed with methanol
  7. customThe methanol solution was decanted off
  8. customevaporated to dryness

Sources & evidence

ORD record
ord-ed5b770b6e0342b5ba1eeb228d93b02a
Source dataset
uspto-grants-2015_02
Patent number
US08946410B2

Reaction notes

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