Methyl 4-acetamido-5-chloro-2-methoxy-3-nitrobenzoate → Methyl 4-amino-5-chloro-2-methoxy-3-nitrobenzoate

HRID 39662Notes

Reaction equation

HRID 39662 reaction equation
[CH3:1][O:2][C:3](=[O:20])[C:4]1[CH:9]=[C:8]([Cl:10])[C:7]([NH:11]C(=O)C)=[C:6]([N+:15]([O-:17])=[O:16])[C:5]=1[O:18][CH3:19]>CO>[CH3:1][O:2][C:3](=[O:20])[C:4]1[CH:9]=[C:8]([Cl:10])[C:7]([NH2:11])=[C:6]([N+:15]([O-:17])=[O:16])[C:5]=1[O:18][CH3:19]

Participants

3

Reactant 1

HCID 10402690Methyl 4-acetamido-5-chloro-2-methoxy-3-nitrobenzoate

Product 1

HCID 12097752Methyl 4-amino-5-chloro-2-methoxy-3-nitrobenzoateYield 94%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Compound 11 (6.2 g, 20.5 mmol) was dissolved in methanol (70 mL), H2SO4 concentrated (4 mL) was added and the solution heated to reflux for 9 h. After cooling to r.t., the mixture was poured into ice (600 mL) and the precipitate formed was collected by filtration. Drying under hv gave 5.0 g (94%) of 12 as a yellow solid. Data of 12: Rf 0.85 (hexane/EtOAc 1:4). 1H NMR (300 MHz, DMSO-d6): δ 3.77 (s, 6H), 6.85 (brs, 2H), 7.82 (s, 1H). 13C NMR (75 MHz, DMSO-d6): δ 52.80, 64.68, 110.40, 114.21, 133.80, 142.29, 153.60, 163.48. MS (ESI): m/z (rel intensity) 261 (100). HRMS (FAB): m/z calcd for C9H9N2O5Cl, 260.0200; found, 260.0197.

Workup

  1. concentrationH2SO4 concentrated (4 mL)
  2. additionwas added
  3. temperaturethe solution heated
  4. temperatureto reflux for 9 h
  5. additionthe mixture was poured into ice (600 mL)
  6. customthe precipitate formed
  7. filtrationwas collected by filtration
  8. customDrying under hv

Sources & evidence

ORD record
ord-8a90f92c8b5f4054ba246788d41df462
Source dataset
uspto-grants-2013_09
Patent number
US08524899B2

Reaction notes

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