Ethyl Acetate → 4-Chloro-2-(2-chloro-6-fluorophenyl)-2H-pyrazolo[4,3-c]pyridine

HRID 626676ノート

反応式

HRID 626676 の反応式
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([F:8])[C:3]=1[N:9]1[CH:18]=[C:12]2[CH:13]=[N+:14]([O-])[CH:15]=[CH:16][C:11]2=[N:10]1.C(OCC)(=O)C.C(=O)([O-])O.[Na+].P(Cl)(Cl)([Cl:32])=O>[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC>[Cl:32][C:13]1[C:12]2=[CH:18][N:9]([C:3]3[C:4]([F:8])=[CH:5][CH:6]=[CH:7][C:2]=3[Cl:1])[N:10]=[C:11]2[CH:16]=[CH:15][N:14]=1

参加物

6

反応物 4

HCID 8857Ethyl AcetateHCID 24813Phosphorus oxychlorideHCID 516892Sodium BicarbonateHCID 696711682-(2-Chloro-6-fluorophenyl)-2H-pyrazolo[4,3-c]pyridine 5-oxide

生成物 1

HCID 866970434-Chloro-2-(2-chloro-6-fluorophenyl)-2H-pyrazolo[4,3-c]pyridine収率 27%

試薬・触媒・溶媒 1

HCID 70681Tetrabutylammonium Chloride触媒

反応条件

温度
85 °C

実験手順

2-(2-Chloro-6-fluorophenyl)-2H-pyrazolo[4,3-c]pyridine 5-oxide (2.13 g, 8.1 mmol) was added to a solution of tetrabutylammonium chloride (2.24 g, 8.1 mmol) in phosphorous oxychloride (16 mL) and the reaction mixture was heated at 85° C. for 5 hours. The reaction mixture was cooled to room temperature and poured into a mixture of ethyl acetate and sodium hydrogen carbonate (sat. aq.). The organic phase was separated, washed with sodium hydrogen carbonate (sat. aq.) and brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (20% ethyl acetate in cyclohexane) to afford the title compound as a white solid (606 mg, 27% yield). 1H NMR (400 MHz, CDCl3): δ 8.36 (s, 1H), 8.12 (d, J=6.3 Hz, 1H), 7.57 (d, J=6.5 Hz, 1H), 7.55-7.50 (m, 1H), 7.45 (d, J=8.3 Hz, 1H), 7.27 (m, 1H). LCMS (Method D): RT=3.29 min, m/z: 282 [M+H+].

後処理

  1. temperatureThe reaction mixture was cooled to room temperature
  2. customThe organic phase was separated
  3. washwashed with sodium hydrogen carbonate (sat. aq.) and brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified by silica gel flash chromatography (20% ethyl acetate in cyclohexane)

出典と根拠

ORDレコード
ord-cb32466da680419d8593dbca86f1ab14
出典データセット
uspto-grants-2016_04
特許番号
US09309240B2

反応ノート

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