Methyl 3-methoxy-5-nitrobenzoate → Methyl 3-amino-5-methoxybenzoate

HRID 2266942Notes

Reaction equation

HRID 2266942 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:10]=[C:11]([N+:13]([O-])=O)[CH:12]=1)[C:6]([O:8][CH3:9])=[O:7].C([O-])=O.[NH4+]>CO.[Pd]>[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:10]=[C:11]([NH2:13])[CH:12]=1)[C:6]([O:8][CH3:9])=[O:7]

Participants

5

Reactant 2

HCID 877382Methyl 3-methoxy-5-nitrobenzoateHCID 2723923Ammonium formate

Product 1

HCID 11830046Methyl 3-amino-5-methoxybenzoateYield 98.2%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

2 g (9.5 mmol) methyl 3-methoxy-5-nitrobenzoate (7) were dissolved in 50 mL methanol by heating, then 0.3 g Pd/C (10%) were added under a stream of nitrogen, followed by 2.99 g (47.5 mmol) ammonium formate. The mixture was refluxed for 3 h, then stirred overnight at r.t.. The clear layer above the catalyst was decanted off portionwise and filtered through a syringe filter. The catalyst that remained in the flask was washed twice with methanol during this procedure. After concentration, 1.69 g of a brown solid were obtained, which were purified by column chromatography (hexanes/ethyl acetate, 7:3). Drying under vacuum afforded 1.25 g (73%) of a colorless solid. 1H NMR (CDCl3) δ 7.00-6.97 (m, 2H), 6.42 (t, J1=2.2 Hz, J2=2.2 Hz), 3.89 (s, 3H, OCH3), 3.80 (s, 3H, OCH3), 3.78 (sb, 2H); 13C NMR (CDCl3) δ 167.13 160.71, 147.49, 131.95, 109.01, 105.71, 104.36, 55.19, 51.880□ESI-MS m/z 314 [MH]+.

Workup

  1. temperatureby heating
  2. temperatureThe mixture was refluxed for 3 h
  3. customThe clear layer above the catalyst was decanted off portionwise
  4. filtrationfiltered through a syringe
  5. filtrationfilter
  6. washwas washed twice with methanol during this procedure
  7. concentrationAfter concentration

Sources & evidence

ORD record
ord-b83fc1221a1c478abb320c39ad21092c
Source dataset
uspto-grants-2010_12
Patent number
US07858737B2

Reaction notes

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