Water → 2-(3-(2,6-Difluorophenyl)pyrazol-1-yl)-3-(1-methyl-3,5-dichloropyrazol-4-yl)-3-hydroxyacrylonitrile

HRID 990727ノート

反応式

HRID 990727 の反応式
[C:1]([CH2:3][N:4]1[CH:8]=[CH:7][C:6]([C:9]2[C:14]([F:15])=[CH:13][CH:12]=[CH:11][C:10]=2[F:16])=[N:5]1)#[N:2].[H-].[Na+].[CH3:19][N:20]1[C:24]([Cl:25])=[C:23]([C:26](N2C=CC=N2)=[O:27])[C:22]([Cl:33])=[N:21]1.O>C1COCC1>[F:15][C:14]1[CH:13]=[CH:12][CH:11]=[C:10]([F:16])[C:9]=1[C:6]1[CH:7]=[CH:8][N:4]([C:3](=[C:26]([C:23]2[C:22]([Cl:33])=[N:21][N:20]([CH3:19])[C:24]=2[Cl:25])[OH:27])[C:1]#[N:2])[N:5]=1

参加物

6

反応物 4

HCID 962WaterHCID 24758Sodium hydrideHCID 221694981-Cyanomethyl-3-(2,6-difluorophenyl)pyrazoleHCID 221695221-(1-Methyl-3,5-dichloropyrazole-4-carbonyl)pyrazole

生成物 1

HCID 573044512-(3-(2,6-Difluorophenyl)pyrazol-1-yl)-3-(1-methyl-3,5-dichloropyrazol-4-yl)-3-hydroxyacrylonitrile収率 57.5%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒3 回

実験手順

3.0 g of 3-(2,6-difluorophenyl)pyrazole was dissolved in 20 ml of acetonitrile, and 2.52 g of chloroacetonitrile and 4.61 g of potassium carbonate were added thereto at room temperature, and heated under reflux for 5 hours. After acetonitrile was distilled off under reduced pressure, ethyl acetate was added to the residue, which was then washed with a small amount of water. The organic layer was dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The residual product was recrystallized from a mixed solvent of isopropylether and diethyl ether to obtain 1.74 g of l-cyanomethyl-3-(2,6-difluorophenyl)pyrazole. 2) A solution of 0.5 g of 1-cyanomethyl-3-(2,6-difluorophenyl)pyrazole dissolved in 10 ml of THF was dropwise added to a suspension of 0.15 g of 55% sodium hydride in 10 ml of THF, at; 50° C. After the resulting product was stirred for 30 minutes, a solution of 0.67 g of 1-(1-methyl-3,5-dichloropyrazole-4-carbonyl)pyrazole dissolved in 10 ml of THF was dropwise added thereto at 50° C. and then stirred overnight at room temperature. The reaction mixture was poured into water, then extracted with ethyl acetate and washed with a small amount of water. The resulting product was dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The residual product was recrystallized from a mixed solvent of isopropyl ether/ethyl acetate=3/1 to obtain 0.52 g of 2-(3-(2,6-difluorophenyl)pyrazol-1-yl)-3-(1-methyl-3,5-dichloropyrazol-4-yl)-3-hydroxyacrylonitrile.

後処理

  1. custom50° C
  2. additionwas dropwise added
  3. stirringat 50° C. and then stirred overnight at room temperature
  4. extractionextracted with ethyl acetate
  5. washwashed with a small amount of water
  6. dry with materialThe resulting product was dried over sodium sulfate
  7. distillationthe solvent was distilled off under reduced pressure
  8. customThe residual product was recrystallized from a mixed solvent of isopropyl ether/ethyl acetate=3/1

出典と根拠

ORDレコード
ord-9046dea90b0d477db96205bec0095be2
出典データセット
uspto-grants-2002_10
特許番号
US06462049B1

反応ノート

読み込み中…