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

HRID 499944노트

반응식

HRID 499944 반응식
[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]

참가 물질

5

반응물 2

HCID 12594300Ethyl 3-bromo-4-chlorobenzoateHCID 178461828HCID 178461828, 화합물

생성물 1

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

시약·촉매·용매 2

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

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-8a252da9e39c438f9144f26008103793
출처 데이터셋
uspto-grants-2010_08
특허 번호
US07767705B2

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