Water → 2-Amino-6-methylpyridin-3-ol

HRID 1924045Notes

Reaction equation

HRID 1924045 reaction equation
[OH:1][C:2]1[C:3]([N+:9]([O-])=O)=[N:4][C:5]([CH3:8])=[CH:6][CH:7]=1.O.O.[SH-].[Na+]>CO.CCO>[NH2:9][C:3]1[C:2]([OH:1])=[CH:7][CH:6]=[C:5]([CH3:8])[N:4]=1

Participants

6

Reactant 3

HCID 962WaterHCID 848016-Methyl-2-nitropyridin-3-olHCID 16211346Sodium hydrosulfide hydrate

Product 1

HCID 885002-Amino-6-methylpyridin-3-olYield 89.5%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 887MethanolSolvent

Procedure

7.00 g of 3-hydroxy-6-methyl-2-nitropyridine (Aldrich, 0.045 mol) was dissolved in 250 mL of MeOH and 20 mL of H2O along with 15 g of sodium hydrosulfide hydrate (6 eq, 0.27 mol). The reaction mixture was stirred under reflux for 5 hours. The reaction mixture was cooled to room temperature and diluted with 300 mL of absolute EtOH and concentrated to dryness. The resulting residue was dissolved in 300 mL of CH2Cl2 and 10 mL of MeOH. The mixture was sonicated for 10 min and allowed to stand at room temperature for 3 hours. The resulting salts that precipitated out at this point were removed by filtration. The filtrate was concentrated to afford the crude amine. This was purified by passing through a short plug of silica gel and eluting with 95% CH2Cl2, 4% MeOH and 1% Et3N. A total of 5.0 g of the desired amine was obtained (89% yield).

Workup

  1. temperatureunder reflux for 5 hours
  2. concentrationconcentrated to dryness
  3. dissolutionThe resulting residue was dissolved in 300 mL of CH2Cl2
  4. customThe mixture was sonicated for 10 min
  5. customThe resulting salts that precipitated out at this point
  6. customwere removed by filtration
  7. concentrationThe filtrate was concentrated
  8. customto afford the crude amine
  9. customThis was purified
  10. washeluting with 95% CH2Cl2, 4% MeOH and 1% Et3N

Sources & evidence

ORD record
ord-cdaaf42f295c413e92cfacc85cd5b90b
Source dataset
uspto-grants-2012_05
Patent number
US08178536B2

Reaction notes

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