Dimethylformamide → 5-Bromo-1-methyl-3-nitropyridin-2(1H)-one

HRID 888451Notes

Reaction equation

HRID 888451 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([N+:9]([O-:11])=[O:10])[C:5]([OH:8])=[N:6][CH:7]=1.[CH3:12]N(C=O)C.C(=O)([O-])[O-].[K+].[K+].CI>O>[Br:1][C:2]1[CH:3]=[C:4]([N+:9]([O-:11])=[O:10])[C:5](=[O:8])[N:6]([CH3:12])[CH:7]=1

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 6328Methyl iodideHCID 11430Potassium CarbonateHCID 178418997HCID 178418997, compound

Product 1

HCID 529112535-Bromo-1-methyl-3-nitropyridin-2(1H)-oneYield 85%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A 1-L round-bottomed flask equipped with a magnetic stirrer was purged with nitrogen and charged with 5-bromo-3-nitro-2-hydroxypyridine (24.0 g, 0.11 mol), anhydrous DMF (280 mL) and powdered potassium carbonate (−350 mesh, 33.4 g, 0.24 mol), and the suspension stirred for 15 min at ambient temperature. After this time methyl iodide (17.1 g, 0.124 mol) was added, and the mixture stirred at room temperature for 18 h. The reaction mixture was then diluted with water (750 mL) and extracted with ethyl acetate (3×1.0 L). The organic extracts were combined, washed with brine (500 mL) and dried over sodium sulfate. After removing the drying agent by filtration, the filtrate was evaporated to dryness under reduced pressure. The resulting residue was purified by flash chromatography on silica to afford an 85% yield (21.7 g) of 41 as a yellow solid: mp 122-423° C.; 1H NMR (300 MHz, CDCl3) δ 8.37 (d, 1H, J=2.7 Hz), 7.26 (s, 1H), 3.68 (s, 3H); MS (ESI+) m/z 234 (M+H).

Workup

  1. customA 1-L round-bottomed flask equipped with a magnetic stirrer
  2. customwas purged with nitrogen
  3. stirringthe mixture stirred at room temperature for 18 h
  4. extractionextracted with ethyl acetate (3×1.0 L)
  5. washwashed with brine (500 mL)
  6. dry with materialdried over sodium sulfate
  7. customAfter removing the drying agent
  8. filtrationby filtration
  9. customthe filtrate was evaporated to dryness under reduced pressure
  10. customThe resulting residue was purified by flash chromatography on silica

Sources & evidence

ORD record
ord-13f472339ecf4d0f9cbdae812203d227
Source dataset
uspto-grants-2012_08
Patent number
US08247550B2

Reaction notes

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