Potassium Carbonate → HCID 66876696、化合物

HRID 631662ノート

反応式

HRID 631662 の反応式
[F:1][C:2]([C:5]1[CH:9]=[C:8]([NH2:10])[N:7]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[N:6]=1)([F:4])[CH3:3].C(=O)([O-])[O-].[K+].[K+].Cl[C:24]([O:26][C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)=[O:25]>ClCCl>[F:1][C:2]([C:5]1[CH:9]=[C:8]([NH:10][C:24](=[O:25])[O:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[N:7]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[N:6]=1)([F:4])[CH3:3]

参加物

5

反応物 3

HCID 11430Potassium Carbonate2 回HCID 15891Phenyl chloroformate2 回HCID 668761373-(1,1-difluoroethyl)-1-phenyl-1H-pyrazol-5-amine

生成物 1

HCID 66876696HCID 66876696、化合物収率 49.2%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

A mixture of 3-(1,1-difluoroethyl)-1-phenyl-1H-pyrazol-5-amine (528 mg, 2.37 mmol), potassium carbonate (979 mg, 7.10 mmol) and phenyl chloroformate (556 mg, 3.55 mmol) in anhydrous dichloromethane (20 mL) was stirred at rt for 15 h. Additional phenyl chloroformate (556 mg, 3.55 mmol) and potassium carbonate (979 mg, 7.10 mmol) was added and the mixture stirred for a further 4 h. The mixture was concentrated under reduced pressure and the residue partitioned between ethyl acetate and saturated aqueous sodium hydrogen carbonate solution. The organic layer was separated, washed with water, saturated aqueous sodium hydrogen carbonate solution, then 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 12% ethyl acetate in hexanes to 100% ethyl acetate) to afford phenyl 3-(1,1-difluoroethyl)-1-phenyl-1H-pyrazol-5-ylcarbamate (400 mg, 49%) as an oil. 1H NMR (300 MHz, CDCl3) δ 7.51-7.58 (m, 5H), 7.35-7.41 (m, 2H), 7.26 (m, 1H), 7.15 (m, 2H), 7.00 (brs, 1H), 6.80 (s, 1H), 2.04 (t, J=18 Hz, 3H); LC-MS (ESI) m/z 344 (M+H)+.

後処理

  1. stirringthe mixture stirred for a further 4 h
  2. concentrationThe mixture was concentrated under reduced pressure
  3. customthe residue partitioned between ethyl acetate and saturated aqueous sodium hydrogen carbonate solution
  4. customThe organic layer was separated
  5. washwashed with water, saturated aqueous sodium hydrogen carbonate solution
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationConcentration under reduced pressure
  9. customgave an oil which
  10. customwas purified via silica gel column chromatography (
  11. washeluting with a gradient of 12% ethyl acetate in hexanes to 100% ethyl acetate)

出典と根拠

ORDレコード
ord-c133f8645b9242c78d6326bf93d83a9e
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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