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

HRID 1483188ノート

反応式

HRID 1483188 の反応式
[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

参加物

8

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 4

HCID 23925Iron触媒HCID 176Acetic Acid溶媒HCID 702Ethanol溶媒HCID 962Water溶媒

反応条件

温度
110 °C

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-76d85d5ba2c148159de46099b98d6717
出典データセット
uspto-grants-2016_08
特許番号
US09416121B2

反応ノート

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