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

HRID 1467789ノート

反応式

HRID 1467789 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].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]

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 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)+.

後処理

  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

出典と根拠

ORDレコード
ord-b25057ed7e084dfab904c01e3528c212
出典データセット
uspto-grants-2015_04
特許番号
US09000172B2

反応ノート

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