Dimethylformamide → ethyl 5-formyl-1-(4-methoxybenzyl)-1H-pyrazole-4-carboxylate

HRID 1520221ノート

反応式

HRID 1520221 の反応式
C([Li])CCC.C(NC(C)C)(C)C.[Li+].CC([N-]C(C)C)C.[CH3:21][O:22][C:23]1[CH:39]=[CH:38][C:26]([CH2:27][N:28]2[CH:32]=[C:31]([C:33]([O:35][CH2:36][CH3:37])=[O:34])[CH:30]=[N:29]2)=[CH:25][CH:24]=1.CN(C)[CH:42]=[O:43]>C1COCC1.CCOC(C)=O>[CH:42]([C:32]1[N:28]([CH2:27][C:26]2[CH:25]=[CH:24][C:23]([O:22][CH3:21])=[CH:39][CH:38]=2)[N:29]=[CH:30][C:31]=1[C:33]([O:35][CH2:36][CH3:37])=[O:34])=[O:43]

参加物

8

反応物 5

HCID 6228DimethylformamideHCID 7912DiisopropylamineHCID 2724682Lithium diisopropylamideHCID 44558860ethyl 1-(4-methoxybenzyl)-1H-pyrazole-4-carboxylateHCID 178418339Butyllithium

生成物 1

HCID 86658573ethyl 5-formyl-1-(4-methoxybenzyl)-1H-pyrazole-4-carboxylate収率 60.2%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
-78 °C

実験手順

According to Scheme 17 Step 1: Butyl lithium 2.5 M (16.9 mmol, 8.45 mL) was added to a solution of diisopropylamine (16.9 mmol, 2.37 mL) in THF (10 mL) at −78° C. and the reaction mixture was stirred at −78° C. for 5 minutes and then at room temperature. To the resulting LDA solution was added at −78° C. a solution of ethyl 1-(4-methoxybenzyl)-1H-pyrazole-4-carboxylate (7.68 mmol, 2 g) in THF (30 mL) and the reaction mixture was stirred for 5 minutes at −78° C. N,N-Dimethylformamide (61.5 mmol, 4.73 mL) was added and then the reaction mixture was stirred at room temperature. The reaction mixture was diluted with AcOEt and was washed with a saturated aqueous solution of NH4Cl. The combined organic phases were dried over MgSO4, were filtered and were evaporated. The crude mixture was purified by flash chromatography over silica gel using cyclohexane/AcOEt (100:0 to 80:20) as eluent to yield ethyl 5-formyl-1-(4-methoxybenzyl)-1H-pyrazole-4-carboxylate (4.62 mmol, 1.33 g, 60%).

後処理

  1. customat room temperature
  2. stirringthe reaction mixture was stirred for 5 minutes at −78° C
  3. stirringthe reaction mixture was stirred at room temperature
  4. washwas washed with a saturated aqueous solution of NH4Cl
  5. dry with materialThe combined organic phases were dried over MgSO4
  6. filtrationwere filtered
  7. customwere evaporated
  8. customThe crude mixture was purified by flash chromatography over silica gel

出典と根拠

ORDレコード
ord-06e583d12ffe451b9a33754eabef4349
出典データセット
uspto-grants-2015_07
特許番号
US09073907B2

反応ノート

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