Ethyl 3-bromo-4-chlorobenzoate → HCID 68507475, 화합물

HRID 2410079노트

반응식

HRID 2410079 반응식
[CH3:1][C:2]([CH3:8])([CH3:7])[CH2:3][CH2:4][Mg]Cl.[CH2:9]([O:11][C:12](=[O:21])[C:13]1[CH:18]=[CH:17][C:16]([Cl:19])=[C:15](Br)[CH:14]=1)[CH3:10]>O1CCOCC1.C(OCC)C.[Cl-].[Cl-].[Zn+2].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]>[CH2:9]([O:11][C:12](=[O:21])[C:13]1[CH:18]=[CH:17][C:16]([Cl:19])=[C:15]([CH2:4][CH2:3][C:2]([CH3:8])([CH3:7])[CH3:1])[CH:14]=1)[CH3:10]

참가 물질

7

반응물 2

HCID 12594300Ethyl 3-bromo-4-chlorobenzoateHCID 178444610HCID 178444610, 화합물

생성물 1

HCID 68507475HCID 68507475, 화합물

시약·촉매·용매 4

HCID 3007855Zincchloride촉매HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)촉매HCID 3283Diethyl Ether용매HCID 312751,4-Dioxane용매

실험 절차

3,3-dimethyl-1-butylmagnesium chloride (8.00 mmol, 0.5 M THF, Platte Valley Scientific) was added dropwise to a solution of ZnCl2 (4.00 mmol, 1M diethyl ether, Aldrich) in 1,4-dioxane (15 mL) at ambient temperature. The mixture was stirred 30 minutes followed by addition of 3-bromo-4-chlorobenzoic acid ethyl ester (1.05 g, 3.99 mmol) and Pd(dppf)2Cl2 (131 mg, 0.160 mmol). The mixture was heated to reflux for 30 minutes, cooled to ambient temperature, diluted with diethyl ether and quenched with H2O. The mixture was filtered through celite and the filtrate was washed with brine, dried (Na2SO4), filtered and concentrated under reduced pressure. Flash chromatography eluting with 5% to 15% ethyl acetate/hexanes provided the title compound. 1H NMR (DMSO-d6) δ 7.89 (d, 1H), 7.78 (dd, 1H), 7.56 (d, 1H), 4.32 (q, 2H), 2.73 (m, 2H), 1.41 (m, 2H), 1.32 (t, 3H), 0.97 (s, 9H); MS (DCI+) m/z 286 (M+NH4)+, 269 (M+H)+.

후처리

  1. temperatureThe mixture was heated
  2. temperatureto reflux for 30 minutes
  3. customquenched with H2O
  4. filtrationThe mixture was filtered through celite
  5. washthe filtrate was washed with brine
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. washFlash chromatography eluting with 5% to 15% ethyl acetate/hexanes

출처 및 근거

ORD 기록
ord-81b97b83705540a5a10363aab60a8aa5
출처 데이터셋
uspto-grants-2014_08
특허 번호
US08815930B2

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