Formic Acid → Methyl 3-amino-5-nitrobenzoate

HRID 1819797Notes

Reaction equation

HRID 1819797 reaction equation
[CH3:1][O:2][C:3](=[O:16])[C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[CH:7]=[C:6]([N+:13]([O-])=O)[CH:5]=1.C(N(CC)CC)C.C(O)=O>CC#N.[Pd]>[CH3:1][O:2][C:3](=[O:16])[C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[CH:7]=[C:6]([NH2:13])[CH:5]=1

Participants

6

Reactant 3

HCID 284Formic AcidHCID 8471TriethylamineHCID 222067Methyl 3,5-dinitrobenzoate

Product 1

HCID 2756518Methyl 3-amino-5-nitrobenzoateYield 59%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 6342AcetonitrileSolvent2×

Procedure

3,5-Dinitro-benzoic acid methyl ester (Example 312, 13.7 g, 60.6 mmol), Pd/C (Aldrich, 1.34 g, 10%, 0.61 mmol), triethylamine (Aldrich, 36.4 mL, 273 mmol) was dissolved in 30 mL of CH3CN. To the above solution was added a solution of HCOOH (Aldrich, 9.7 mL, 261 mmol) in 30 mL of CH3CN dropwise. The mixture was then refluxed for 2 h. After cooled to room temperature, the mixture was filtered through a Celite pad, washed with EtOAc, and the filtrate was concentrated. The residue was purified by chromatography (5%-10% EtOAc/CH2Cl2) to give 7.0 g (59%) of product. 1H NMR (400 MHz, DMSO-d6) δ 7.74 (t, J=2.0 Hz, 1H), 7.59 (t, J=2.2 Hz, 1H), 7.55 (t, J=2.0 Hz, 1H), 6.16 (s, 2H), 3.87 (s, 3H).

Workup

  1. temperatureThe mixture was then refluxed for 2 h
  2. filtrationthe mixture was filtered through a Celite pad
  3. washwashed with EtOAc
  4. concentrationthe filtrate was concentrated
  5. customThe residue was purified by chromatography (5%-10% EtOAc/CH2Cl2)

Sources & evidence

ORD record
ord-02d45ac9e0774bfdbaea83ad9b2e216d
Source dataset
uspto-grants-2009_10
Patent number
US07601841B2

Reaction notes

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