Ethyl Acetate → 2-Bromo-6-(8-tert-butyl-5-oxo-2,3-dihydro-5H-benzo[f][1,4]oxazepin-4-yl)benzaldehyde

HRID 1879679노트

반응식

HRID 1879679 반응식
[C:1]([C:5]1[CH:16]=[CH:15][C:8]2[C:9](=[O:14])[NH:10][CH2:11][CH2:12][O:13][C:7]=2[CH:6]=1)([CH3:4])([CH3:3])[CH3:2].[Br:17][C:18]1[CH:25]=[CH:24][CH:23]=[C:22](Br)[C:19]=1[CH:20]=[O:21].C(=O)([O-])[O-].[Cs+].[Cs+].C(OCC)(=O)C>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.O>[Br:17][C:18]1[CH:25]=[CH:24][CH:23]=[C:22]([N:10]2[C:9](=[O:14])[C:8]3[CH:15]=[CH:16][C:5]([C:1]([CH3:4])([CH3:2])[CH3:3])=[CH:6][C:7]=3[O:13][CH2:12][CH2:11]2)[C:19]=1[CH:20]=[O:21]

참가 물질

9

반응물 4

HCID 8857Ethyl AcetateHCID 10796Cesium carbonateHCID 126486412,6-DibromobenzaldehydeHCID 595485458-tert-Butyl-3,4-dihydro-2H-benzo[f][1,4]oxazepin-5-one

생성물 1

HCID 595485352-Bromo-6-(8-tert-butyl-5-oxo-2,3-dihydro-5H-benzo[f][1,4]oxazepin-4-yl)benzaldehyde

시약·촉매·용매 4

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)촉매HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladium촉매HCID 962Water용매HCID 312751,4-Dioxane용매

반응 조건

온도
100 °C

실험 절차

8-tert-Butyl-3,4-dihydro-2H-benzo[f][1,4]oxazepin-5-one (600 mg, 2.74 mmol, 2,6-Dibromo-benzaldehyde (3.62 g, 5eq), Xanthphos (71 mg, 0.045eq), and cesium carbonate (1.25 g, 1.4 eq) were taken up in dioxane (5.3 mL) and a stream of Argon gas was bubbled through the mixture for 10 minutes. The catalyst Pd(dba)2 (47 mg, 0.03 eq) was added and the resulting mixture was placed under argon and stirred at 100° C. for three hours. By TLC, the reaction was complete and after cooling the mixture to room temperature, ethyl acetate (150 mL) and water (50 mL) were added and the layers were partitioned and separated. The organic layer was further washed with water (3×50 mL) and finally washed with brine (1×50 mL) before it was dried over magnesium sulfate, filtered and concentrated. Purification by column chromatography on silica gel eluting with a gradient of 5% ethyl acetate to 30% ethyl acetate afforded the title compound as an off-white powder (793 mg) (M+H)+=404.

후처리

  1. customa stream of Argon gas was bubbled through the mixture for 10 minutes
  2. temperatureafter cooling the mixture to room temperature
  3. customthe layers were partitioned
  4. customseparated
  5. washThe organic layer was further washed with water (3×50 mL)
  6. washfinally washed with brine (1×50 mL) before it
  7. dry with materialwas dried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customPurification by column chromatography on silica gel eluting with a gradient of 5% ethyl acetate to 30% ethyl acetate

출처 및 근거

ORD 기록
ord-526df6a040d44c0f8346d26455f1fd64
출처 데이터셋
uspto-grants-2012_11
특허 번호
US08318719B2

반응 노트

불러오는 중…