4-Methylpyrazole → 4-methyl-1-(3-nitro-5-(trifluoromethyl)phenyl)-1H-pyrazole

HRID 1050147ノート

反応式

HRID 1050147 の反応式
F[C:2]1[CH:7]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:5]=[C:4]([N+:12]([O-:14])=[O:13])[CH:3]=1.C([O-])([O-])=O.[K+].[K+].[CH3:21][C:22]1[CH:23]=[N:24][NH:25][CH:26]=1>CN(C=O)C>[CH3:21][C:22]1[CH:23]=[N:24][N:25]([C:2]2[CH:7]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:5]=[C:4]([N+:12]([O-:14])=[O:13])[CH:3]=2)[CH:26]=1

参加物

5

反応物 3

HCID 34064-MethylpyrazoleHCID 11430Potassium CarbonateHCID 152724001-Fluoro-3-nitro-5-(trifluoromethyl)benzene

生成物 1

HCID 904234844-methyl-1-(3-nitro-5-(trifluoromethyl)phenyl)-1H-pyrazole収率 70.2%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
110 °C

実験手順

To a solution of 1-fluoro-3-nitro-5-(trifluoromethyl)benzene (500 mg, 2.391 mmol) and K2CO3 (496 mg, 3.59 mmol) in DMF (3 mL) was added 4-methyl-1H-pyrazole (196 mg, 2.391 mmol) in one portion. Then the mixture stirred under N2 was heated to 110° C. and reacted for 15 h. LCMS analysis showed the starting material disappeared. The solvent was removed in vacuo. The residue was dissolved in DCM (60 mL) and washed with H2O (20 mL) and brine (20 mL). The organic layer was dried over Na2SO4, filtered and concentrated to give crude material which was purified by silica column chromatography (PE/EA=10/1 to 5/1) to afford pure product 4-methyl-1-(3-nitro-5-(trifluoromethyl)phenyl)-1H-pyrazole (500 mg, 1.678 mmol, 70.2% yield): 1H NMR (400 MHz, CD3OD): δ 8.83 (s, 1H), 8.46 (s, 1H), 8.35 (s, 1H), 8.30 (s, 1H), 7.64 (s, 1H), 2.18 (s, 3H). ES-LCMS: m/z 272.2 (M+H).

後処理

  1. customreacted for 15 h
  2. customThe solvent was removed in vacuo
  3. dissolutionThe residue was dissolved in DCM (60 mL)
  4. washwashed with H2O (20 mL) and brine (20 mL)
  5. dry with materialThe organic layer was dried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto give crude material which
  9. customwas purified by silica column chromatography (PE/EA=10/1 to 5/1)

出典と根拠

ORDレコード
ord-5f52a61366fb4b65b5e60df8f17f4288
出典データセット
uspto-grants-2016_07
特許番号
US09382238B2

反応ノート

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