Phenylhydrazine hydrochloride → 3-(1,1-difluoroethyl)-1-phenyl-1H-pyrazol-5-amine

HRID 631661ノート

反応式

HRID 631661 の反応式
[F:1][C:2]([F:9])([CH3:8])[C:3](=O)[CH2:4][C:5]#[N:6].Cl.[C:11]1([NH:17][NH2:18])[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1>C(O)C>[F:1][C:2]([C:3]1[CH:4]=[C:5]([NH2:6])[N:17]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[N:18]=1)([F:9])[CH3:8]

参加物

4

反応物 2

HCID 60962Phenylhydrazine hydrochlorideHCID 86653534HCID 86653534、化合物

生成物 1

HCID 668761373-(1,1-difluoroethyl)-1-phenyl-1H-pyrazol-5-amine収率 31.5%

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

反応条件

温度
70 °C

実験手順

A stirred mixture of 4,4-difluoro-3-oxopentanenitrile (prepared as described in Example 152A Step 1) (1 g, 7.52 mmol) and phenyl hydrazine hydrochloride (1.08 g, 7.52 mmol) in ethanol (30 mL) was heated at 70° C. for 8 h. After cooling to rt, the mixture was concentrated under reduced pressure. The residue was partitioned between dichloromethane (200 mL) and saturated aqueous sodium hydrogen carbonate solution (200 mL). The organic layer was separated and dried over magnesium sulfate and filtered. Concentration under reduced pressure gave an oil, which was purified via silica gel column chromatography (eluting with a gradient of 5% to 65% ethyl acetate in hexanes) to afford 3-(1,1-difluoroethyl)-1-phenyl-1H-pyrazol-5-amine (528 mg, 31%) as a yellow oil. 1H NMR (300 MHz, CDCl3) δ 7.36-7.57 (m, 5H), 5.81 (s, 1H), 3.84 (brs, 2H), 2.01 (t, J=18 Hz, 3H); LC-MS (ESI) m/z 224 (M+H)+.

後処理

  1. temperatureAfter cooling to rt
  2. concentrationthe mixture was concentrated under reduced pressure
  3. customThe residue was partitioned between dichloromethane (200 mL) and saturated aqueous sodium hydrogen carbonate solution (200 mL)
  4. customThe organic layer was separated
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationConcentration under reduced pressure
  8. customgave an oil, which
  9. customwas purified via silica gel column chromatography (
  10. washeluting with a gradient of 5% to 65% ethyl acetate in hexanes)

出典と根拠

ORDレコード
ord-f90f17e0358944bea335b28bdd5359f4
出典データセット
uspto-grants-2016_04
特許番号
US09320739B2

反応ノート

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