Phosphorus oxychloride → ethyl 4-chloro-1-ethyl-1H-pyrazolo[3,4-b]pyridine-5-carboxylate

HRID 451206

반응식

HRID 451206 반응식
C(O[C:4](=O)[C:5](=[CH:11][NH:12][C:13]1[N:14]([CH2:18][CH3:19])[N:15]=[CH:16][CH:17]=1)[C:6]([O:8][CH2:9][CH3:10])=[O:7])C.O=P(Cl)(Cl)[Cl:23]>>[CH2:9]([O:8][C:6]([C:5]1[C:4]([Cl:23])=[C:17]2[CH:16]=[N:15][N:14]([CH2:18][CH3:19])[C:13]2=[N:12][CH:11]=1)=[O:7])[CH3:10]

참가 물질

3

반응물 2

HCID 24813Phosphorus oxychlorideHCID 12845080Diethyl {[(1-ethyl-1H-pyrazol-5-yl)amino]methylene}malonate

생성물 1

HCID 10491120ethyl 4-chloro-1-ethyl-1H-pyrazolo[3,4-b]pyridine-5-carboxylate수율 69%

반응 조건

온도
135 °C

실험 절차

A solution of 2-[(2-ethyl-2H-pyrazol-3-ylamino)-methylene]-malonic acid diethyl ester (11.75 g, 0.041 mol) in POCl3 (70 mL) was heated at reflux (135° C.) for 8 hours. The excess of POCl3 were distilled off and the reaction mixture cooled to 0° C., before careful addition of water (100 mL) and then aqueous NaOH (3N) until pH reached 7. The product was extracted with CH2Cl2 several times, and the combined orgnic phase were dried over Na2SO4 and concentrated under vacuo. Column chromatography (SiO2, EtOAc/Heptane 1/5) afforded 7.22 g (69%) of the title product as a white solid. ES-MS m/e: 254.2 (M+H+).

후처리

  1. distillationThe excess of POCl3 were distilled off
  2. temperaturethe reaction mixture cooled to 0° C., before careful addition of water (100 mL)
  3. extractionThe product was extracted with CH2Cl2 several times
  4. dry with materialthe combined orgnic phase were dried over Na2SO4
  5. concentrationconcentrated under vacuo

출처 및 근거

ORD 기록
ord-9179ab2bd5b84a39a150d267fd730d56
출처 데이터셋
uspto-grants-2013_07
특허 번호
US08487102B2

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