Ethyl bromopyruvate → Ethyl 2-(pyridin-3-YL)thiazole-4-carboxylate

HRID 533322

반응식

HRID 533322 반응식
[C:1]([NH2:9])(=[S:8])[C:2]1[CH:7]=[CH:6][CH:5]=[N:4][CH:3]=1.Br[CH2:11][C:12](=O)[C:13]([O:15][CH2:16][CH3:17])=[O:14]>CCO>[N:4]1[CH:5]=[CH:6][CH:7]=[C:2]([C:1]2[S:8][CH:11]=[C:12]([C:13]([O:15][CH2:16][CH3:17])=[O:14])[N:9]=2)[CH:3]=1

참가 물질

4

반응물 2

HCID 66144Ethyl bromopyruvateHCID 737155Thionicotinamide

생성물 1

HCID 2824169Ethyl 2-(pyridin-3-YL)thiazole-4-carboxylate수율 47.4%

시약·촉매·용매 1

HCID 702Ethanol용매

실험 절차

To a suspension of thionicotinamide (30.0 g, 217.1 mmol) in EtOH (400 mL) at room temperature was added ethyl bromopyruvate (90% technical, 30.6 mL, 219 mmol). The reaction mixture was heated to reflux and stirred for 2.5 days. The reaction mixture was cooled to room temperature and the precipitate that formed upon cooling was collected via vacuum filtration. The cake was rinsed twice with hexanes. This solid was added to a separatory funnel containing ethyl acetate and saturated aqueous NaHCO3. The biphasic mixture was separated and the organic layer was washed with brine, dried over MgSO4, filtered, and concentrated in vacuo. The crude product was purified using silica gel chromatography, (0 to 100% ethyl acetate/hexanes) to afford the desired product as a tan solid (24.1 g, 47%): mp 73-75° C.; 1H NMR (300 MHz, CDCl3) δ 9.19 (dd, J=2.6, 1.0 Hz, 1H), 8.69 (dd, J=4.6, 1.6 Hz, 1H), 8.34 (dt, J=7.9, 1.6 Hz, 1H), 8.22 (s, 1H), 7.41 (ddd, J=7.9, 4.6, 1.0 Hz, 1H), 4.47 (q, J=6.9 Hz, 2H), 1.43 (t, J=6.9 Hz, 3H); ESIMS m/z 236.1 (M+2).

후처리

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux
  3. customthe precipitate that formed
  4. temperatureupon cooling
  5. filtrationwas collected via vacuum filtration
  6. washThe cake was rinsed twice with hexanes
  7. additionThis solid was added to a separatory funnel
  8. additioncontaining ethyl acetate and saturated aqueous NaHCO3
  9. customThe biphasic mixture was separated
  10. washthe organic layer was washed with brine
  11. dry with materialdried over MgSO4
  12. filtrationfiltered
  13. concentrationconcentrated in vacuo
  14. customThe crude product was purified

출처 및 근거

ORD 기록
ord-81661fd14b1f41e39398f2101bac5293
출처 데이터셋
uspto-grants-2014_10
특허 번호
US08853246B2

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