Bromine → 1,3-Dihydro-4-methoxy-1-methyl-2H-indol-2-one

HRID 1623536

반응식

HRID 1623536 반응식
[Br-].[K+].BrBr.[CH3:5][O:6][C:7]1[CH:15]=[CH:14][CH:13]=[C:12]2[C:8]=1[CH:9]=[CH:10][N:11]2[CH3:16].C(=O)(O)[O-:18].[Na+]>O.[Pd].C(O)(C)(C)C>[CH3:5][O:6][C:7]1[CH:15]=[CH:14][CH:13]=[C:12]2[C:8]=1[CH2:9][C:10](=[O:18])[N:11]2[CH3:16]

참가 물질

8

반응물 4

HCID 24408Bromine2회HCID 253877Potassium BromideHCID 516892Sodium BicarbonateHCID 5952384-Methoxy-1-methylindole

생성물 1

HCID 127130311,3-Dihydro-4-methoxy-1-methyl-2H-indol-2-one

시약·촉매·용매 3

HCID 23938Palladium촉매HCID 962Water용매2회HCID 6386tert-Butanol용매

실험 절차

To a solution of potassium bromide (3986 mg, 33.5 mmol) in water (26.5 ml) was added bromine (0.863 ml, 16.75 mmol). A separate flask containing 4-methoxy-1-methyl-1H-indole (900 mg, 5.58 mmol) was charged with t-butanol (20.00 ml) and water (20.0 ml). To this flask was added 22.5 mL of bromine solution dropwise. The mixture was permitted to stir for approximately 30 minutes and then was neutralized with saturated aqueous sodium bicarbonate and quenched with saturated aqueous sodium thiosulfate. The reaction was then diluted with dichloromethane and saturated aqueous sodium bicarbonate and the layers were separated. The aqueous layer was extracted two additional times with dichloromethane and the organic layers were combined, dried over anhydrous sodium sulfate, filtered, and concentrated. The resulting residue was dissolved in 50 mL EtOH and 5 mL of AcOH. The solution was then charged with 10% palladium on carbon (1.2 g, 1.13 mmol). The atmosphere over the reaction mixture was evacuated and the reaction was placed under an atmosphere of hydrogen gas via a balloon. The reaction was stirred for 18 hours. The reaction mixture was then filtered through a plug of Celite® and the filtrate was then concentrated to approximately 25% of its original volume. The reaction was then diluted with dichloromethane and saturated aqueous sodium bicarbonate and the layers were separated. The aqueous layer was extracted two additional times with dichloromethane and the organic layers were combined, dried over anhydrous sodium sulfate, filtered, and concentrated. The resulting residue was purified by silica gel flash chromatography (ethyl acetate-heptane, 0 to 60%) to afford 4-methoxy-1-methyl-1,3-dihydro-indol-2-one; MS: (ES+) m/z 178.0 (M+H)+.

후처리

  1. customquenched with saturated aqueous sodium thiosulfate
  2. additionThe reaction was then diluted with dichloromethane and saturated aqueous sodium bicarbonate
  3. customthe layers were separated
  4. extractionThe aqueous layer was extracted two additional times with dichloromethane
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. dissolutionThe resulting residue was dissolved in 50 mL EtOH
  9. customThe atmosphere over the reaction mixture was evacuated
  10. stirringThe reaction was stirred for 18 hours
  11. filtrationThe reaction mixture was then filtered through a plug of Celite®
  12. concentrationthe filtrate was then concentrated to approximately 25% of its original volume
  13. additionThe reaction was then diluted with dichloromethane and saturated aqueous sodium bicarbonate
  14. customthe layers were separated
  15. extractionThe aqueous layer was extracted two additional times with dichloromethane
  16. dry with materialdried over anhydrous sodium sulfate
  17. filtrationfiltered
  18. concentrationconcentrated
  19. customThe resulting residue was purified by silica gel flash chromatography (ethyl acetate-heptane, 0 to 60%)

출처 및 근거

ORD 기록
ord-61466750abb343e298b544803ed4ca76
출처 데이터셋
uspto-grants-2014_07
특허 번호
US08778972B2

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