Methyl iodide → Methyl 2-methyl-4-(methylamino)-3-nitrobenzoate

HRID 906129Notes

Reaction equation

HRID 906129 reaction equation
I[CH3:2].[NH2:3][C:4]1[CH:13]=[CH:12][C:7]([C:8]([O:10][CH3:11])=[O:9])=[C:6]([CH3:14])[C:5]=1[N+:15]([O-:17])=[O:16].[H-].[Na+]>O1CCCC1>[CH3:14][C:6]1[C:5]([N+:15]([O-:17])=[O:16])=[C:4]([NH:3][CH3:2])[CH:13]=[CH:12][C:7]=1[C:8]([O:10][CH3:11])=[O:9]

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 67404328HCID 67404328, compound

Product 1

HCID 67403462Methyl 2-methyl-4-(methylamino)-3-nitrobenzoateYield 72.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Iodomethane (125 uL, 2.0 mmol) was added to a mixture of the methyl 4-amino-2-methyl-3-nitrobenzoate (400 mg, 1.9 mmol) and sodium hydride (60% oil dispersion, 84 mg, 2.1 mmol) in tetrahydrofuran (10 mL) at 0° C. The reaction mixture was slowly warmed to room temperature and stirred for 18 hours. The reaction mixture was quenched with saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The combined extract was washed with water (2×30 mL), brine (30 mL), dried over sodium sulfate, filtered and concentrated, then purified by flash chromatography (25% ethyl acetate in hexanes) to give methyl 2-methyl-4-(methylamino)-3-nitrobenzoate (308 mg, 72% yield). 1H NMR (400 MHz, CDCl3): 7.94 (d, 1H), 6.63 (d, 1H), 5.68 (br, 1H), 3.86 (d, 2H), 2.58 (s, 3H); MS (EI) for C10H12N2O4: 225 (MH+).

Workup

  1. customThe reaction mixture was quenched with saturated aqueous ammonium chloride solution
  2. extractionextracted with ethyl acetate
  3. extractionThe combined extract
  4. washwas washed with water (2×30 mL), brine (30 mL)
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. custompurified by flash chromatography (25% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-c96b4f8d9d74455e93f6c16fffb51a11
Source dataset
uspto-grants-2011_09
Patent number
US08012956B2

Reaction notes

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