2-Aminophenol → 2-(4-chlorophenyl)-3-oxo 3,4-dihyro-2H-1,4-benzoxazine

HRID 1439868Notes

Reaction equation

HRID 1439868 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[OH:8].C(=O)([O-])O.[Na+].Br[CH:15]([C:19]1[CH:24]=[CH:23][C:22]([Cl:25])=[CH:21][CH:20]=1)[C:16](Cl)=[O:17]>C(OCC)(=O)C.O.C1(C)C=CC=CC=1>[Cl:25][C:22]1[CH:23]=[CH:24][C:19]([CH:15]2[C:16](=[O:17])[NH:1][C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=3[O:8]2)=[CH:20][CH:21]=1

Participants

7

Reactant 3

HCID 58012-AminophenolHCID 516892Sodium BicarbonateHCID 12575778Bromo-4-chlorophenylacetyl chloride

Product 1

HCID 108488972-(4-chlorophenyl)-3-oxo 3,4-dihyro-2H-1,4-benzoxazineYield 76.9%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 2-aminophenol (13.5 g) in ethyl acetate (150 ml) is added a solution of sodium hydrogen carbonate (15 g) in water (300 ml), and to the mixture is added dropwise a solution of α-bromo-4-chlorophenylacetyl chloride (32.2 g) in toluene with vigorous stirring under ice cooling. After the mixture is stirred at room temperature for one hour, the solvent in the organic layer is distilled off and the residue is dissolved in acetone. To the solution is added potassium carbonate (20 g), and the mixture is stirred at room temperature overnight. The solvent is distilled off and to the residue is added water. The mixture is extracted with ethyl acetate. The ethyl acetate layer is washed, dried and distilled to remove the solvent, and the residue is recrystallized from ethyl acetate-n-hexane to give 2-(4-chlorophenyl)-3-oxo-3,4-dihyro-2H-1,4-benzoxazine (24.0 g) as crystals. M.p. 180.5°-181.5° C.

Workup

  1. stirringAfter the mixture is stirred at room temperature for one hour
  2. distillationthe solvent in the organic layer is distilled off
  3. dissolutionthe residue is dissolved in acetone
  4. additionTo the solution is added potassium carbonate (20 g)
  5. stirringthe mixture is stirred at room temperature overnight
  6. distillationThe solvent is distilled off and to the residue
  7. additionis added water
  8. extractionThe mixture is extracted with ethyl acetate
  9. washThe ethyl acetate layer is washed
  10. customdried
  11. distillationdistilled
  12. customto remove the solvent
  13. customthe residue is recrystallized from ethyl acetate-n-hexane

Sources & evidence

ORD record
ord-4fb08c1d204a4bee84804cf7c61d8d01
Source dataset
uspto-grants-1996_03
Patent number
US05496815

Reaction notes

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