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

HRID 1525355

반응식

HRID 1525355 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].CC([O-])=O.CC([O-])=O.[Pd+2]>[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

반응 조건

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 Pd(OAc)2 (0.096 g, 0.428 mmol). The reaction mixture was warmed to 100° C. After 16 h, the reaction was cooled to rt. The reaction was filtered and the solid was rinsed with DMF. The filtrate was diluted with EtOAc, washed with H2O (2×), brine, 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)+. Intermediate 4: A solution of Intermediate 4A (0.048 g, 0.171 mmol) in 50% TFA/DCM (2 mL) was stirred at rt. After 1 h, the reaction was concentrated to give Intermediate 4 (0.038 g, 100% yield) as a yellow solid. The material was carried onto the next step without further purification. MS (ESI) m/z: 225.1 (M+H)+.

후처리

  1. temperaturethe reaction was cooled to rt
  2. filtrationThe reaction was filtered
  3. washthe solid was rinsed with DMF
  4. additionThe filtrate was diluted with EtOAc
  5. washwashed with H2O (2×), brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customPurification by normal phase chromatography

출처 및 근거

ORD 기록
ord-a7bd80ae2a0148ca945ecd7f166cd470
출처 데이터셋
uspto-grants-2015_07
특허 번호
US09079929B2

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