Ethyl 3-bromo-4-chlorobenzoate → 4-Chloro-3-(1-methylethyl)-benzoic acid ethyl ester

HRID 499944ノート

反応式

HRID 499944 の反応式
[CH2:1]([O:3][C:4](=[O:13])[C:5]1[CH:10]=[CH:9][C:8]([Cl:11])=[C:7](Br)[CH:6]=1)[CH3:2].[CH:14]([Zn]C(C)C)([CH3:16])[CH3:15]>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH2:1]([O:3][C:4](=[O:13])[C:5]1[CH:10]=[CH:9][C:8]([Cl:11])=[C:7]([CH:14]([CH3:16])[CH3:15])[CH:6]=1)[CH3:2]

参加物

5

反応物 2

HCID 12594300Ethyl 3-bromo-4-chlorobenzoateHCID 178461828HCID 178461828、化合物

生成物 1

HCID 577427574-Chloro-3-(1-methylethyl)-benzoic acid ethyl ester

試薬・触媒・溶媒 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 312751,4-Dioxane溶媒

実験手順

3-Bromo-4-chlorobenzoic acid ethyl ester (1.05 g, 3.99 mmol) was added in one portion to a solution of diisopropylzinc (10.0 mmol, 1M toluene, Aldrich) in 10 mL of 1,4-dioxane followed by addition of Pd(dppf)2Cl2 (4.0 mmol). The mixture was heated to reflux 3 hours, cooled to ambient temperature and stirred overnight. The mixture was quenched with 1N aqueous HCl, diluted with ethyl acetate, and filtered through celite. The separated organic layer was washed sequentially with 1N aqueous HCl, brine, dried (Na2SO4), filtered and concentrated under reduced pressure. The residue was purified by chromatography eluting with 4% ethyl acetate/hexanes to provide the title compound. 1H NMR (DMSO-d6) δ 7.92 (d, 1H), 7.78 (dd, 1H), 7.58 (d, 1H), 4.32 (q, 2H), 3.35 (sept, 1H), 1.32 (t, 3H), 1.24 (d, 6H).

後処理

  1. temperatureThe mixture was heated
  2. temperatureto reflux 3 hours
  3. customThe mixture was quenched with 1N aqueous HCl
  4. additiondiluted with ethyl acetate
  5. filtrationfiltered through celite
  6. washThe separated organic layer was washed sequentially with 1N aqueous HCl, brine
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was purified by chromatography
  11. washeluting with 4% ethyl acetate/hexanes

出典と根拠

ORDレコード
ord-8a252da9e39c438f9144f26008103793
出典データセット
uspto-grants-2010_08
特許番号
US07767705B2

反応ノート

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