Methyl triflate → ethyl 2,3-dihydro-1-methyl-3-oxo-2-phenyl-1H-pyrazole-4-carboxylate

HRID 2359672ノート

反応式

HRID 2359672 の反応式
[O:1]=[C:2]1[C:6]([C:7]([O:9][CH2:10][CH3:11])=[O:8])=[CH:5][NH:4][N:3]1[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.F[C:19](F)(F)S(OC)(=O)=O>ClCCl>[CH3:19][N:4]1[CH:5]=[C:6]([C:7]([O:9][CH2:10][CH3:11])=[O:8])[C:2](=[O:1])[N:3]1[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

参加物

4

反応物 2

HCID 9526Methyl triflateHCID 223722Ethyl 3-oxo-2-phenyl-2,3-dihydro-1h-pyrazole-4-carboxylate

生成物 1

HCID 15192740ethyl 2,3-dihydro-1-methyl-3-oxo-2-phenyl-1H-pyrazole-4-carboxylate収率 21.1%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

To a solution of ethyl 3-oxo-2-phenyl-2,3-dihydro-1H-pyrazole-4-carboxylate (1000 mg, 5.0 mmol) in dichloromethane (10 mL) was added methyl trifluoromethanesulfonate (1200 mg, 7.3 mmol). The red solution was stirred at room temperature. After 14 h, the mixture was partitioned between dichloromethane and NaHCO3 (sat). The aqueous was extracted with dichloromethane (2×). The combined organic was dried over Na2SO4, concentrated and purified on silica. The product was triturated with EtOAc-hexane-CHCl3 to give the pure product as crystals (260 mg, 21%). Calc'd for C12H12N2O3, 232.08; MS (ESI pos. ion) m/z: 233 (MH+). 1H NMR (400 MHz, CHLOROFORM-d): 1.36 (t, J=7.04 Hz, 3H), 3.39 (s, 3H), 4.32 (q, J=7.17 Hz, 2H), 7.32 (d, J=7.43 Hz, 2H), 7.42 (t, J=7.34 Hz, 1H), 7.50 (t, J=7.73 Hz, 2H), 7.99 (s, 1H).

後処理

  1. customthe mixture was partitioned between dichloromethane and NaHCO3 (sat)
  2. extractionThe aqueous was extracted with dichloromethane (2×)
  3. dry with materialThe combined organic was dried over Na2SO4
  4. concentrationconcentrated
  5. custompurified on silica
  6. customThe product was triturated with EtOAc-hexane-CHCl3

出典と根拠

ORDレコード
ord-b7ed76858f434d4ab5f9ed7d6f76bc1b
出典データセット
uspto-grants-2014_04
特許番号
US08685983B2

反応ノート

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