Ethyl bromoacetate → 6-Nitro-2H-1,4-benzoxazin-3(4H)-one

HRID 1618591Notes

Reaction equation

HRID 1618591 reaction equation
[F-].[K+].Br[CH2:4][C:5](OCC)=[O:6].[NH2:10][C:11]1[CH:16]=[C:15]([N+:17]([O-:19])=[O:18])[CH:14]=[CH:13][C:12]=1[OH:20]>CN(C=O)C.[Cl-].[Na+].O>[N+:17]([C:15]1[CH:14]=[CH:13][C:12]2[O:20][CH2:4][C:5](=[O:6])[NH:10][C:11]=2[CH:16]=1)([O-:19])=[O:18]

Participants

6

Reactant 3

HCID 7748Ethyl bromoacetateHCID 522689Potassium FluorideHCID 36133892-Amino-4-Nitrophenol

Product 1

HCID 27636836-Nitro-2H-1,4-benzoxazin-3(4H)-one

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

To a stirred suspension of KF (4.9 g, 84.35 mmol) in DMF (25 mL) was added ethyl bromoacetate and the mixture was stirred at rt. After 25 minutes, to the mixture was added 2-amino-4-nitrophenol (5 g, 32.44 mmol) and the mixture was stirred at 60° C. After 25 h, the mixture was cooled to rt, poured into cold brine (200 mL), extracted with EtOAc (100 mL×3). The combined organics were washed with brine (200 mL×1), dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was suspended in MeOH, filtered, and washed the solid with MeOH to give 6-nitro-2H-benzo[b][1,4]oxazin-3(4H)-one as a brown solid: Spectrum (ESI) m/e=193.0 (M+1).

Workup

  1. stirringthe mixture was stirred at 60° C
  2. waitAfter 25 h
  3. temperaturethe mixture was cooled to rt
  4. extractionextracted with EtOAc (100 mL×3)
  5. washThe combined organics were washed with brine (200 mL×1)
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. filtrationfiltered
  10. washwashed the solid with MeOH

Sources & evidence

ORD record
ord-115ba5ed70244327b9a41dbccdc8c3b4
Source dataset
uspto-grants-2014_07
Patent number
US08765940B2

Reaction notes

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