Ethyl Acetate → 4-(3-Aminophenyl)-6-bromo-5,7-dimethyl-2H-chromen-2-one

HRID 1483188Notes

Reaction equation

HRID 1483188 reaction equation
[Br:1][C:2]1[C:3]([CH3:23])=[C:4]2[C:9](=[CH:10][C:11]=1[CH3:12])[O:8][C:7](=[O:13])[CH:6]=[C:5]2[C:14]1[CH:19]=[CH:18][CH:17]=[C:16]([N+:20]([O-])=O)[CH:15]=1.CCOC(C)=O.C([O-])([O-])=O.[Na+].[Na+]>CCO.C(O)(=O)C.O.[Fe]>[NH2:20][C:16]1[CH:15]=[C:14]([C:5]2[C:4]3[C:9](=[CH:10][C:11]([CH3:12])=[C:2]([Br:1])[C:3]=3[CH3:23])[O:8][C:7](=[O:13])[CH:6]=2)[CH:19]=[CH:18][CH:17]=1

Participants

8

Reactant 3

HCID 8857Ethyl AcetateHCID 10340Sodium CarbonateHCID 894780386-Bromo-5,7-dimethyl-4-(3-nitrophenyl)-2H-chromen-2-one

Product 1

HCID 894779214-(3-Aminophenyl)-6-bromo-5,7-dimethyl-2H-chromen-2-oneYield 17.2%

Reagents, catalysts & solvents 4

HCID 23925IronCatalystHCID 176Acetic AcidSolventHCID 702EthanolSolventHCID 962WaterSolvent

Conditions

Temperature
110 °C

Procedure

To a stirred solution of 6-bromo-5,7-dimethyl-4-(3-nitrophenyl)-2H-chromen-2-one (6-3) (15.41 g, 41.18 mmol) in EtOH (100 mL) and acetic acid (40 mL) was added iron (11.50 g, 205.9 mmol) at room temperature. The mixture was heated at 110° C. for 2 h. The reaction mixture was cooled at room temperature and filtrated. To the filtrate was added EtOAc and Na2CO3 (37 g, 0.35 mol) in water (200 mL). After being stirred at room temperature, the mixture was filtrated. Then the filtrated was diluted with EtOAc and extracted with EtOAc. The organic layers were washed with brine, dried over Na2SO4, and concentrated. To the concentrate added CH2Cl2-MeOH (1:9), and the precipitated solid was collected by filtration. The solid was washed with CH2Cl2-MeOH (1:9) and purified by silica gel column chromatography (hexanes:EtOAc=2:1˜1:1) to give the title compound 6-4 (2.44 g, 17% yield) as a yellow solid.

Workup

  1. temperatureThe reaction mixture was cooled at room temperature
  2. filtrationfiltrated
  3. filtrationthe mixture was filtrated
  4. additionThen the filtrated was diluted with EtOAc
  5. extractionextracted with EtOAc
  6. washThe organic layers were washed with brine
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated
  9. additionTo the concentrate added CH2Cl2-MeOH (1:9)
  10. filtrationthe precipitated solid was collected by filtration
  11. washThe solid was washed with CH2Cl2-MeOH (1:9)
  12. custompurified by silica gel column chromatography (hexanes:EtOAc=2:1˜1:1)

Sources & evidence

ORD record
ord-76d85d5ba2c148159de46099b98d6717
Source dataset
uspto-grants-2016_08
Patent number
US09416121B2

Reaction notes

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