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

HRID 631661노트

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HRID 631661 반응식
[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]

참가 물질

4

반응물 2

HCID 60962Phenylhydrazine hydrochlorideHCID 86653534HCID 86653534, 화합물

생성물 1

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

시약·촉매·용매 1

HCID 702Ethanol용매

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온도
70 °C

실험 절차

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)+.

후처리

  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)

출처 및 근거

ORD 기록
ord-f90f17e0358944bea335b28bdd5359f4
출처 데이터셋
uspto-grants-2016_04
특허 번호
US09320739B2

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