Potassium Hydroxide → 4-[1-(4-pentafluoroethyloxy-phenyl)-1H-[1,2,4]triazol-3-yl]-benzaldehyde

HRID 1192796ノート

反応式

HRID 1192796 の反応式
[F:1][C:2]([F:26])([O:7][C:8]1[CH:13]=[CH:12][C:11]([N:14]2[CH:18]=[N:17][C:16]([C:19]3[CH:24]=[CH:23][C:22]([CH3:25])=[CH:21][CH:20]=3)=[N:15]2)=[CH:10][CH:9]=1)[C:3]([F:6])([F:5])[F:4].[OH-:27].[K+]>C(#N)C.O.O1CCOCC1>[F:26][C:2]([F:1])([O:7][C:8]1[CH:9]=[CH:10][C:11]([N:14]2[CH:18]=[N:17][C:16]([C:19]3[CH:20]=[CH:21][C:22]([CH:25]=[O:27])=[CH:23][CH:24]=3)=[N:15]2)=[CH:12][CH:13]=1)[C:3]([F:6])([F:5])[F:4]

参加物

6

反応物 2

HCID 14797Potassium HydroxideHCID 866333811-(4-pentafluoroethyloxy-phenyl)-3-p-tolyl-1H-[1,2,4]triazole

生成物 1

HCID 866333824-[1-(4-pentafluoroethyloxy-phenyl)-1H-[1,2,4]triazol-3-yl]-benzaldehyde収率 30.7%

試薬・触媒・溶媒 3

HCID 962Water溶媒4 回HCID 6342Acetonitrile溶媒HCID 312751,4-Dioxane溶媒

実験手順

The product from Step 1 (7.0 g, 18.7 mmol) was dissolved in acetonitrile (200 mL) and stirred at ambient temperature while ceric ammonium nitrate (32 g, 58 mmol) in H2O (60 mL) was added in portions over 10 min. The solution was then heated to reflux for 4 h, cooled, and diluted with H2O (200 mL). The solution was extracted with ether (2×200 mL), and the combined organic layer was dried and concentrated to give an orange oil. This material was dissolved in dioxane (40 mL) and treated with a solution of potassium hydroxide (KOH; 5 g, 90 mmol) in H2O (20 mL). The solution was heated to reflux for 2 h, then cooled and diluted with H2O (100 mL). The aldehyde precipitated and was collected by filtration. Recrystallization from MeOH/H2O gave the pure aldehyde as a white solid (2.2 g, 30%): mp 137-144° C.; 1H NMR (300 MHz, CDCl3) δ 10.1 (s, 1H), 8.65 (s, 1H), 8.40 (d, J=8.4 Hz, 2H), 8.0 (d, J=8.4 Hz, 2H), 7.85 (d, J=9 Hz, 2H), 7.45 (d, J=9 Hz, 2H); ESIMS m/z 384.2 (M+H).

後処理

  1. additionwas added in portions over 10 min
  2. temperatureThe solution was then heated
  3. temperatureto reflux for 4 h
  4. temperaturecooled
  5. extractionThe solution was extracted with ether (2×200 mL)
  6. customthe combined organic layer was dried
  7. concentrationconcentrated
  8. customto give an orange oil
  9. temperatureThe solution was heated
  10. temperatureto reflux for 2 h
  11. temperaturecooled
  12. customThe aldehyde precipitated
  13. filtrationwas collected by filtration
  14. customRecrystallization from MeOH/H2O

出典と根拠

ORDレコード
ord-6150edb62dbf40b5bb7e1c8f44d2ae62
出典データセット
uspto-grants-2014_03
特許番号
US08680269B2

反応ノート

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