Ammonium formate → Methyl 3,4-diamino-2-methylbenzoate

HRID 906099Notes

Reaction equation

HRID 906099 reaction equation
[NH2:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([CH3:12])[C:3]=1[N+:13]([O-])=O.C([O-])=O.[NH4+]>O1CCCC1.O.[Fe]>[NH2:13][C:3]1[C:4]([CH3:12])=[C:5]([CH:10]=[CH:11][C:2]=1[NH2:1])[C:6]([O:8][CH3:9])=[O:7]

Participants

6

Reactant 2

HCID 2723923Ammonium formateHCID 67404328HCID 67404328, compound

Product 1

HCID 67403564Methyl 3,4-diamino-2-methylbenzoateYield 98%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of methyl 4-amino-2-methyl-3-nitrobenzoate (1.10 g, 5.22 mmol) in tetrahydrofuran (75 mL) and water (25 mL) was added ammonium formate (6.6 g, 104 mmol) and iron powder (2.92 g, 52.2 mmol). This mixture was refluxed for 12 hours then filtered and the filter cake rinsed with ethyl acetate. The filtrate layers were separated and the organic layer was dried (magnesium sulfate), filtered and concentrated to give 0.92 g (98% yield) of crude methyl 3,4-diamino-2-methylbenzoate, which was used without further purification. 1H NMR (400 MHz, d6-DMSO): 7.05 (d; 1H), 6.40 (d, 1H), 3.69 (s, 3H), 2.29 (s, 3H). MS (EI) for C9H12N2O2: 181 (MH+).

Workup

  1. temperatureThis mixture was refluxed for 12 hours
  2. filtrationthen filtered
  3. washthe filter cake rinsed with ethyl acetate
  4. customThe filtrate layers were separated
  5. dry with materialthe organic layer was dried (magnesium sulfate)
  6. filtrationfiltered
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-3eca5cd7bf5f44cabea27c30ec8fa22a
Source dataset
uspto-grants-2011_09
Patent number
US08012956B2

Reaction notes

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