Dimethyl Carbonate → 6-bromo-1H,2H,4H-pyrido(2,3-d)(1,3)oxazin-2-one

HRID 2112670Notes

Reaction equation

HRID 2112670 reaction equation
[NH2:1][C:2]1[C:7]([CH2:8][OH:9])=[CH:6][C:5]([Br:10])=[CH:4][N:3]=1.[C:11](=O)(OC)[O:12]C.C[O-].[Na+]>CO>[Br:10][C:5]1[CH:4]=[N:3][C:2]2[NH:1][C:11](=[O:12])[O:9][CH2:8][C:7]=2[CH:6]=1

Participants

5

Reactant 3

HCID 12021Dimethyl CarbonateHCID 108913662-Amino-5-bromo-3-(hydroxymethyl)pyridineHCID 10942334Sodium Methoxide

Product 1

HCID 159259906-bromo-1H,2H,4H-pyrido(2,3-d)(1,3)oxazin-2-oneYield 51%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a stirred solution of 2-amino-5-bromo-3-(hydroxymethyl)pyridine (3.0 g, 15 mmole) in methanol (30 mL) was added dimethyl carbonate (5 mL, 60 mmole) and sodium methoxide (25 wt % solution in methanol, 4 mL, 17.4 mmole). The reaction was heated at reflux for 18 hr, cooled to RT, and concentrated to dryness. The remaining residue was triturated with saturated aqueous NH4Cl (50 mL), filtered, washed with cold H2O (50 mL), and dried under vacuum to give the title compound (1.75 g, 51%) as a beige solid: LCMS (ES) m/e 229.0 (M+H)+; 1H NMR (400 MHz, DMSO-d6) δ 10.90 (s, 1H), 8.31 (s, 1H), 7.90 (s, 1H), 5.31 (s, 2H).

Workup

  1. temperatureThe reaction was heated
  2. temperatureat reflux for 18 hr
  3. concentrationconcentrated to dryness
  4. customThe remaining residue was triturated with saturated aqueous NH4Cl (50 mL)
  5. filtrationfiltered
  6. washwashed with cold H2O (50 mL)
  7. customdried under vacuum

Sources & evidence

ORD record
ord-8198a09223f54bc78211f8e24061e7dc
Source dataset
uspto-grants-2009_04
Patent number
US07524843B2

Reaction notes

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