Toluene → Methyl 3-amino-4-(methyloxy)-5-nitrobenzoate

HRID 852591Notes

Reaction equation

HRID 852591 reaction equation
[CH3:1][O:2][C:3](=[O:18])[C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[C:7]([O:13][CH3:14])=[C:6]([N+:15]([O-])=O)[CH:5]=1.[C:19]1(C)C=CC=CC=1>CC(O)=O.[Fe]>[CH3:19][CH2:14][O:13][CH2:7][CH3:8].[CH3:7][CH2:6][CH2:5][CH:4]([CH3:9])[CH3:3].[NH2:15][C:6]1[CH:5]=[C:4]([CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[C:7]=1[O:13][CH3:14])[C:3]([O:2][CH3:1])=[O:18]

Participants

6

Reactant 2

HCID 1140TolueneHCID 14091421Methyl 4-methoxy-3,5-dinitrobenzoate

Product 2

HCID 21882825Ether isohexaneHCID 63022111Methyl 3-amino-4-(methyloxy)-5-nitrobenzoateYield 83%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 176Acetic AcidSolvent

Procedure

To a solution of methyl 4-(methyloxy)-3,5-dinitrobenzoate (D25) (5.0 g, 19.5 mmol, 1 equiv) in AcOH (150 ml) at room temperature was added iron powder (9.0 g, 161 mmol, 8.2 equiv) portionwise and the resulting mixture was stirred for 3 h. Toluene (500 ml) was added and the organic phase was filtered through a pad of celite then concentrated in vacuo. The residue was dissolved in AcOEt and the organic phase was washed with a saturated aqueous NaHCO3 solution, dried over MgSO4 and concentrated in vacuo. Trituration of the residue with Et2O/iso-hexane gave methyl 3-amino-4-(methyloxy)-5-nitrobenzoate (D163) (3.65 g, 83%) as a yellow solid which was used in the next step without further purification. [M+H]+=226.9, RT=2.76 min.

Workup

  1. filtrationthe organic phase was filtered through a pad of celite
  2. concentrationthen concentrated in vacuo
  3. dissolutionThe residue was dissolved in AcOEt
  4. washthe organic phase was washed with a saturated aqueous NaHCO3 solution
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-ba7707a8d4024b96b1a93ebb0794c908
Source dataset
uspto-grants-2007_08
Patent number
US07253198B2

Reaction notes

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