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

HRID 1772142

Reaction equation

HRID 1772142 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([N+:9]([O-:11])=[O:10])[C:5](=[O:8])[NH: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 851475-Bromo-3-nitro-2-pyridone

Product 1

HCID 529112535-Bromo-1-methyl-3-nitropyridin-2(1H)-oneYield 89%

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-nitropyridin-2(1H)-one (25.0 g, 114 mmol), anhydrous DMF (500 mL) and potassium carbonate (34.7 g, 251 mmol), and the suspension stirred for 15 min at ambient temperature. After this time, methyl iodide (17.8 g, 126 mmol) was added, and the mixture stirred at room temperature for 16 h. The reaction mixture was then diluted with water (500 mL) and extracted with methylene chloride (3×500 mL). The organic extracts were combined, washed with 10% aqueous lithium chloride (300 mL) and water (300 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 flash chromatographed eluting with a gradient from 50% to 100% of ethyl acetate in hexanes, and the fractions containing 122a were collected to afford, after concentrating under reduced pressure, an 89% yield (23.6 g) of 122a as a yellow solid: mp 122-123° 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 16 h
  4. extractionextracted with methylene chloride (3×500 mL)
  5. washwashed with 10% aqueous lithium chloride (300 mL) and water (300 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. customchromatographed
  11. washeluting with a gradient from 50% to 100% of ethyl acetate in hexanes
  12. additionthe fractions containing 122a
  13. customwere collected
  14. customto afford
  15. concentrationafter concentrating under reduced pressure

Sources & evidence

ORD record
ord-1dc56f21a48d4e0a82dcdd3c9ddd2e4d
Source dataset
uspto-grants-2016_02
Patent number
US09249123B2

Linked notes

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