Tributylamine → (E)-tert-butyl 3-(2-acetyl-5-chlorophenyl)acrylate

HRID 1467789노트

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HRID 1467789 반응식
Br[C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:9](=[O:11])[CH3:10].C(N(CCCC)CCCC)CCC.[C:25]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])(=[O:28])[CH:26]=[CH2:27]>CN(C=O)C.[Pd].C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:9]([C:3]1[CH:4]=[CH:5][C:6]([Cl:8])=[CH:7][C:2]=1/[CH:27]=[CH:26]/[C:25]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])(=[O:11])[CH3:10]

참가 물질

7

반응물 3

HCID 7622TributylamineHCID 15458tert-Butyl acrylateHCID 47126441-(2-Bromo-4-chlorophenyl)ethanone

생성물 1

HCID 89499883(E)-tert-butyl 3-(2-acetyl-5-chlorophenyl)acrylate수율 63.2%

시약·촉매·용매 3

HCID 23938Palladium촉매HCID 167845palladium(II) acetate촉매HCID 6228Dimethylformamide용매

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온도
100 °C

실험 절차

To a degassed solution of 1-(2-bromo-4-chlorophenyl)ethanone (1.0 g, 4.28 mmol), tributylamine (2.041 mL, 8.57 mmol), and tert-butyl acrylate (1.255 mL, 8.57 mmol) in DMF (10 mL) was added palladium on carbon (0.456 g, 0.428 mmol) and palladium (II) acetate (0.096 g, 0.428 mmol). The reaction mixture was warmed to 100° C. After 16 h, the reaction was cooled to rt and filtered. The solid was rinsed with DMF and the filtrate was diluted with EtOAc and washed with H2O (2×) followed by brine. The crude product was then dried over Na2SO4, filtered and concentrated. Purification by normal phase chromatography afforded Intermediate 4A (0.760 g, 63%), as a brown oil. MS (ESI) m/z: 225.0 (M-C4H8+H)+.

후처리

  1. temperaturethe reaction was cooled to rt
  2. filtrationfiltered
  3. washThe solid was rinsed with DMF
  4. additionthe filtrate was diluted with EtOAc
  5. washwashed with H2O (2×)
  6. dry with materialThe crude product was then dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customPurification by normal phase chromatography

출처 및 근거

ORD 기록
ord-b25057ed7e084dfab904c01e3528c212
출처 데이터셋
uspto-grants-2015_04
특허 번호
US09000172B2

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