N,N'-Dimethylethylenediamine → Ethyl 1-(1-ethoxyethyl)-3-[4-(4-methylpiperazin-1-yl)benzoylamino]-1H-thieno[2,3-c]pyrazole-5-carboxylate

HRID 736280ノート

反応式

HRID 736280 の反応式
Br[C:2]1[C:3]2[CH:14]=[C:13]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[S:12][C:4]=2[N:5]([CH:7]([O:9][CH2:10][CH3:11])[CH3:8])[N:6]=1.[CH3:20][N:21]1[CH2:26][CH2:25][N:24]([C:27]2[CH:35]=[CH:34][C:30]([C:31]([NH2:33])=[O:32])=[CH:29][CH:28]=2)[CH2:23][CH2:22]1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].CNCCNC>[Cu]I.O1CCOCC1>[CH2:10]([O:9][CH:7]([N:5]1[C:4]2[S:12][C:13]([C:15]([O:17][CH2:18][CH3:19])=[O:16])=[CH:14][C:3]=2[C:2]([NH:33][C:31](=[O:32])[C:30]2[CH:29]=[CH:28][C:27]([N:24]3[CH2:23][CH2:22][N:21]([CH3:20])[CH2:26][CH2:25]3)=[CH:35][CH:34]=2)=[N:6]1)[CH3:8])[CH3:11]

参加物

7

反応物 4

HCID 8070N,N'-DimethylethylenediamineHCID 62657Potassium Phosphate, TribasicHCID 223215944-(4-Methylpiperazin-1-yl)benzamideHCID 57487832ethyl 3-bromo-1-(1-ethoxyethyl)-1H-thieno[2,3-c]pyrazole-5-carboxylate

生成物 1

HCID 57848799Ethyl 1-(1-ethoxyethyl)-3-[4-(4-methylpiperazin-1-yl)benzoylamino]-1H-thieno[2,3-c]pyrazole-5-carboxylate収率 27%

試薬・触媒・溶媒 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 312751,4-Dioxane溶媒

反応条件

温度
110 °C

実験手順

Ethyl 3-bromo-1-(1-ethoxyethyl)-1H-thieno[2,3-c]pyrazole-5-carboxylate (10.9 g, 31 mmol), 4-(4-methylpiperazin-1-yl)benzamide (9 g, 41 mmol, 1.3 eq.), copper(I)iodide (0.601 g, 3.1 mmol, 0.1 eq.), preground tripotassium phosphate (20.1 g, 94 mmol, 3 eq.) and 70 mL of anhydrous dioxane degassed beforehand with argon are placed in a 500 mL round-bottomed flask under argon. N,N′-Dimethylethylenediamine (0.336 mL, 3.16 mmol, 0.1 eq.) is added to this suspension by syringe. The reaction mixture is then heated at a temperature in the region of 110° C. for a period of 24 hours. The dioxane is then evaporated off under vacuum and the residue is diluted with ethyl acetate (300 mL) and 150 mL of water. The organic phase is washed with 100 mL of water, dried over magnesium sulfate and then concentrated to dryness under reduced pressure. The residue is purified by chromatography on silica gel, eluting at the start with a dichloromethane/methanol mixture (90/10 by volume). Ethyl 1-(1-ethoxyethyl)-3-[4-(4-methylpiperazin-1-yl)benzoylamino]-1H-thieno[2,3-c]pyrazole-5-carboxylate (4.05 g, 27%) is thus obtained in the form of a pale yellow oil, which product is used directly in the following step.

後処理

  1. customThe dioxane is then evaporated off under vacuum
  2. additionthe residue is diluted with ethyl acetate (300 mL) and 150 mL of water
  3. washThe organic phase is washed with 100 mL of water
  4. dry with materialdried over magnesium sulfate
  5. concentrationconcentrated to dryness under reduced pressure
  6. customThe residue is purified by chromatography on silica gel
  7. washeluting at the start with a dichloromethane/methanol mixture (90/10 by volume)

出典と根拠

ORDレコード
ord-0743ef441dc74a659e897fce55178aef
出典データセット
uspto-grants-2009_09
特許番号
US07595320B2

反応ノート

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