Tetrahydrofuran → Ethyl 3-chloro-4-(2-methylpropyl)benzoate

HRID 2189747

反応式

HRID 2189747 の反応式
[Br-].[CH2:2]([Zn+])[CH:3]([CH3:5])[CH3:4].C1COCC1.Br[C:13]1[CH:23]=[CH:22][C:16]([C:17]([O:19][CH2:20][CH3:21])=[O:18])=[CH:15][C:14]=1[Cl:24]>>[Cl:24][C:14]1[CH:15]=[C:16]([CH:22]=[CH:23][C:13]=1[CH2:2][CH:3]([CH3:5])[CH3:4])[C:17]([O:19][CH2:20][CH3:21])=[O:18]

参加物

4

反応物 3

HCID 8028TetrahydrofuranHCID 12594301Ethyl 4-bromo-3-chlorobenzoateHCID 178448254HCID 178448254、化合物

生成物 1

HCID 59316731Ethyl 3-chloro-4-(2-methylpropyl)benzoate

実験手順

A solution of isobutylzinc bromide in THF (0.5 M, 30 mL, 15.0 mmol) was added under argon to ethyl 4-bromo-3-chlorobenzoate (D16) (2.00 g, 7.60 mmol) and then 1,1′-bis(diphenylphosphino)ferrocene-palladium(II) dichloride dichloromethane complex (930 mg, 1.14 mmol) was added. The reaction was heated to reflux for 4.5 h. The mixture concentrated in vacuo and the residue partitioned between ethyl acetate (125 mL) and water (125 mL). A solid formed, which was filtered off and discarded. The organic layer was washed with water (100 mL), dried (phase separator) and concentrated in vacuo. The crude product was purified by silica chromatography, eluting with 0-5% EtOAc in hexane over 30 minutes to give the title compound as a colourless oil (1.76 g, 7.33 mmol). δH (d6-DMSO, 400 MHz): 7.91 (1H, d), 7.80 (1H, dd), 7.46 (1H, d), 4.30 (2H, q), 2.66 (2H, d), 1.88-2.01 (1H, m), 1.32 (3H, t), 0.89 (6H, d).

後処理

  1. addition1,1′-bis(diphenylphosphino)ferrocene-palladium(II) dichloride dichloromethane complex (930 mg, 1.14 mmol) was added
  2. temperatureThe reaction was heated
  3. temperatureto reflux for 4.5 h
  4. concentrationThe mixture concentrated in vacuo
  5. customthe residue partitioned between ethyl acetate (125 mL) and water (125 mL)
  6. customA solid formed
  7. filtrationwhich was filtered off
  8. washThe organic layer was washed with water (100 mL)
  9. customdried (phase separator)
  10. concentrationconcentrated in vacuo
  11. customThe crude product was purified by silica chromatography
  12. washeluting with 0-5% EtOAc in hexane over 30 minutes

出典と根拠

ORDレコード
ord-e097eab6fd8141a5a56cf02e82c39a73
出典データセット
uspto-grants-2012_12
特許番号
US08324254B2

関連ノート

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