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

HRID 423312

反応式

HRID 423312 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 (D22) (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). MS (ES): no mass ion observed.

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-ff61b594fe674a9da734248857ad1d5b
出典データセット
uspto-grants-2012_01
特許番号
US08101775B2

関連ノート

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