2-Chloro-3-methyl-5-nitropyridine → 6-Chloro-5-methylpyridin-3-amine

HRID 2185728Notes

Reaction equation

HRID 2185728 reaction equation
[Cl:1][C:2]1[C:7]([CH3:8])=[CH:6][C:5]([N+:9]([O-])=O)=[CH:4][N:3]=1>O.CC(O)=O.[Fe]>[NH2:9][C:5]1[CH:6]=[C:7]([CH3:8])[C:2]([Cl:1])=[N:3][CH:4]=1

Participants

4

Reactant 1

HCID 896482-Chloro-3-methyl-5-nitropyridine

Product 1

HCID 122956076-Chloro-5-methylpyridin-3-amineYield 89%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 21899381Acetic acid--water (1/1)Solvent

Procedure

2-Chloro-3-methyl-5-nitropyridine (3.2 g, 18.5 mmol; Maybridge Chemical Co.) was dissolved in a mechanically stirred solution of H2O/HOAc (60 mL, 5:1). Iron powder was added over a 5 h period, maintaining the temperature below 40° C., and stirring was continued until starting material had be consumed. The reaction mixture was filtered, and the filter cake was washed with EtOAc. The aqueous filtrate was extracted with EtOAc, and the combined organic fractions were washed with saturated NaHCO3 solution, dried (MgSO4) and concentrated. The residue was chromatographed (silica gel; CHCl3/MeOH, 98:2) to afford 5-amino-2-chloro-3-methylpyridine as an orange solid (2.34 g, 89%): MS (CI/NH3) m/z: 143 (M+H)+; NMR (DMSO-d6, 300 MHz) δ2.17 (s, 3H), 5.40 (br s, 2H), 6.90 (d, J=2.2 Hz, 1H), 7.54 (d, J=2.2 Hz, 1H).

Workup

  1. temperaturemaintaining the temperature below 40° C.
  2. customhad be consumed
  3. filtrationThe reaction mixture was filtered
  4. washthe filter cake was washed with EtOAc
  5. extractionThe aqueous filtrate was extracted with EtOAc
  6. washthe combined organic fractions were washed with saturated NaHCO3 solution
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated
  9. customThe residue was chromatographed (silica gel; CHCl3/MeOH, 98:2)

Sources & evidence

ORD record
ord-a7ca6cb336b54c71bfaa424883294a4b
Source dataset
uspto-grants-2002_06
Patent number
US06403575B1

Reaction notes

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