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

HRID 1525355ノート

反応式

HRID 1525355 の反応式
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]

参加物

7

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 3

HCID 23938Palladium触媒HCID 167845palladium(II) acetate触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
100 °C

実験手順

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)+.

後処理

  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

出典と根拠

ORDレコード
ord-a7bd80ae2a0148ca945ecd7f166cd470
出典データセット
uspto-grants-2015_07
特許番号
US09079929B2

反応ノート

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