Phosphorus oxychloride → 4-chloro-2-(2,6-dichlorophenyl)-2H-pyrazolo[4,3-c]pyridine

HRID 626659

反応式

HRID 626659 の反応式
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Cl: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.P(Cl)(Cl)([Cl:21])=O.C(=O)([O-])O.[Na+]>[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.C(OCC)(=O)C>[Cl:21][C:13]1[C:12]2=[CH:18][N:9]([C:3]3[C:2]([Cl:1])=[CH:7][CH:6]=[CH:5][C:4]=3[Cl:8])[N:10]=[C:11]2[CH:16]=[CH:15][N:14]=1

参加物

6

反応物 3

HCID 24813Phosphorus oxychlorideHCID 516892Sodium BicarbonateHCID 677015532-(2,6-Dichlorophenyl)-2H-pyrazolo[4,3-c]pyridine 5-oxide

生成物 1

HCID 866970364-chloro-2-(2,6-dichlorophenyl)-2H-pyrazolo[4,3-c]pyridine収率 49%

試薬・触媒・溶媒 2

HCID 70681Tetrabutylammonium Chloride触媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
80 °C

実験手順

2-(2,6-Dichlorophenyl)-2H-pyrazolo[4,3-c]pyridine 5-oxide (1.12 g, 4 mmol) was slowly added to phosphorous oxychloride (8 mL). Tetrabutylammonium chloride (1.11 g, 4 mmol) was then added. The reaction mixture was heated at 80° C. for 5 hours and then cooled to room temperature. The reaction was poured into a mixture of ethyl acetate and sodium hydrogen carbonate (sat. aq.) and the layers were partitioned. The organic layer was washed with sodium hydrogen carbonate (sat. aq.) and brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resultant residue was purified by silica gel flash chromatography (20% ethyl acetate in cyclohexane) to afford the title compound as a white solid (590 mg, 49% yield). 1H NMR (400 MHz, DMSO-d6): δ 9.33 (d, J=1.0 Hz, 1H), 8.11 (d, J=6.0 Hz, 1H), 7.83 (d, J=1.3 Hz, 1H), 7.82-7.81 (m, 1H), 7.75-7.71 (m, 1H). LCMS (Method D): RT=3.42 min, m/z: 298 [M+H+].

後処理

  1. temperaturecooled to room temperature
  2. customthe layers were partitioned
  3. washThe organic layer was washed with sodium hydrogen carbonate (sat. aq.) and brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customThe resultant residue was purified by silica gel flash chromatography (20% ethyl acetate in cyclohexane)

出典と根拠

ORDレコード
ord-4dd650f0ed7046cb95d4f42a57c97827
出典データセット
uspto-grants-2016_04
特許番号
US09309240B2

関連ノート

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