Dimethyl 3-oxoglutarate → methyl 2-(5-oxo-1-(2-phenylpropan-2-yl)-4,5-dihydro-1H-pyrazol-3-yl)acetate

HRID 244942

反応式

HRID 244942 の反応式
[C:1]1([C:7]([NH:10][NH:11]C(OC(C)(C)C)=O)([CH3:9])[CH3:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.O.C1(C)C=CC(S(O)(=O)=O)=CC=1.C(=O)([O-])O.[Na+].CO[C:38]([CH2:40][C:41]([CH2:43][C:44]([O:46][CH3:47])=[O:45])=O)=[O:39]>C(Cl)Cl.C(O)(=O)C.C(OCC)(=O)C>[O:39]=[C:38]1[N:10]([C:7]([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)([CH3:9])[CH3:8])[N:11]=[C:41]([CH2:43][C:44]([O:46][CH3:47])=[O:45])[CH2:40]1

参加物

8

反応物 4

HCID 74591Dimethyl 3-oxoglutarateHCID 516892Sodium BicarbonateHCID 521998p-Toluenesulfonic acid monohydrateHCID 19606120tert-Butyl 2-(2-phenylpropan-2-yl)hydrazinecarboxylate

生成物 1

HCID 86697465methyl 2-(5-oxo-1-(2-phenylpropan-2-yl)-4,5-dihydro-1H-pyrazol-3-yl)acetate収率 35.1%

試薬・触媒・溶媒 3

HCID 176Acetic Acid溶媒HCID 6344Dichloromethane溶媒HCID 8857Ethyl Acetate溶媒

実験手順

tert-Butyl 2-(2-phenylpropan-2-yl)hydrazinecarboxylate (250 mg, 1.00 mmol) was dissolved in methylene chloride (2 mL), mixed with p-toluenesulfonic acid monohydrate (0.40 g, 2.1 mmol) and stirred at room temperature for 18 hours. The reaction solution was basified with saturated aqueous sodium hydrogen carbonate and separated. The organic layer was washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The resulting residue was dissolved in toluene (2.0 mL) and acetic acid (70 μL), mixed with dimethyl 1,3-acetonedicarboxylate (174 mg, 1.00 mmol) and stirred at 90° C. for 3 hours and at 105° C. for 3 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature and diluted with ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen carbonate and then with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The resulting residue was purified by intermediate pressure silica gel column chromatography (silica gel12 g, ethyl acetate:hexane=1:9 to 3:7) to give 96.3 mg of the desired product as a white solid.

後処理

  1. customseparated
  2. washThe organic layer was washed with saturated aqueous sodium chloride
  3. dry with materialdried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationthe filtrate was concentrated under reduced pressure
  6. dissolutionThe resulting residue was dissolved in toluene (2.0 mL)
  7. stirringstirred at 90° C. for 3 hours and at 105° C. for 3 hours
  8. customAfter completion of the reaction
  9. temperatureto cool to room temperature
  10. washThe organic layer was washed with saturated aqueous sodium hydrogen carbonate
  11. dry with materialwith saturated aqueous sodium chloride, dried over anhydrous sodium sulfate
  12. filtrationfiltered
  13. concentrationthe filtrate was concentrated under reduced pressure
  14. customThe resulting residue was purified by intermediate pressure silica gel column chromatography (silica gel12 g, ethyl acetate:hexane=1:9 to 3:7)

出典と根拠

ORDレコード
ord-e1d33a0014ef49b0a544c1fb1f20cbf7
出典データセット
uspto-grants-2014_02
特許番号
US08658686B2

関連ノート

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