Ethanol → 1-(Thieno[2,3-b]pyridin-5-yl)ethanone

HRID 657720

반응식

HRID 657720 반응식
[N+:1]([C:4]1[S:5][CH:6]=[CH:7][CH:8]=1)([O-])=O.[Sn].CO[CH:12](OC)[CH2:13][C:14](=[O:16])[CH3:15].[OH-].[Na+].[CH3:21]CO>Cl.[Cl-].[Cl-].[Zn+2].CCOC(C)=O>[S:5]1[C:4]2=[N:1][CH:12]=[C:13]([C:14](=[O:16])[CH3:15])[CH:21]=[C:8]2[CH:7]=[CH:6]1

참가 물질

9

반응물 5

HCID 702Ethanol2회HCID 11866Thiophene, 2-nitro-HCID 14798Sodium HydroxideHCID 2285484,4-Dimethoxy-2-butanoneHCID 5352426Tin atom2회

생성물 1

HCID 124927351-(Thieno[2,3-b]pyridin-5-yl)ethanone수율 23%

시약·촉매·용매 3

HCID 3007855Zincchloride촉매HCID 313Hydrochloric Acid용매HCID 8857Ethyl Acetate용매

반응 조건

온도
75 °C

실험 절차

To a vigorously stirred mixture of 2-nitrothiophene (Aldrich, 12.9 g, 0.1 mol) in concentrated HCl (Aldrich, 36.5%, 195 mL) was carefully added tin (Aldrich, 100 mesh, 25 g, 0.21 mol) at 20-30° C. After most of tin metal had been dissolved, EtOH (Aldrich, 70 mL) and ZnCl2 (Aldrich, 6.0 g, 0.044 mol) were added and the mixture was then heated to 75° C. for 1 h. The brown solution was cooled down to ambient temperature and 4,4-dimethoxybutan-2-one (Aldrich, 39.6 g, 0.3 mol) in EtOH (50 mL) was added. The reaction mixture was stirred at 70° C. for 10 h. The cooled brown reaction mixture was poured into NaOH aqueous solution (50%. 160 mL) and extrated with EtOAc (3×500 mL). The combined extracts were washed with brine (2×50 mL) and concentrated. The residue was purified with chromatography (SiO2, EtOAc/hexane, v. 20/80, Rf=0.30) to give the title compound (4.20 g, yield, 23%). 1H NMR (300 MHz, CDCl3) δ ppm 2.72 (s, 3 H), 7.38 (d, J=6.10 Hz, 1 H), 7.64 (d, J=6.10 Hz, 1 H), 8.63 (d, J=2.03 Hz, 1 H), 9.14 (d, J=2.03 Hz, 1 H); MS (DCI/NH3) M/z 178 (M+1)+, 195 (M+NH4).

후처리

  1. customat 20-30° C
  2. temperatureThe brown solution was cooled down to ambient temperature
  3. washThe combined extracts were washed with brine (2×50 mL)
  4. concentrationconcentrated
  5. customThe residue was purified with chromatography (SiO2, EtOAc/hexane, v. 20/80, Rf=0.30)

출처 및 근거

ORD 기록
ord-93bb9b75b0174988be63156362a2737c
출처 데이터셋
uspto-grants-2011_12
특허 번호
US08076350B2

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