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

HRID 1424717Notes

Reaction equation

HRID 1424717 reaction equation
[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]

Participants

6

Reactant 2

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

Product 1

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

Reagents, catalysts & solvents 3

HCID 962WaterSolvent4×HCID 6342AcetonitrileSolventHCID 312751,4-DioxaneSolvent

Procedure

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 water (60 mL) was added in portions over 10 min. The solution was then heated to reflux for 4 h, cooled, and diluted with water (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 KOH (5 g, 90 mmol) in water (20 mL). The solution was heated to reflux for 2 h, then cooled and diluted with water (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).

Workup

  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

Sources & evidence

ORD record
ord-3c1ae78402c843e8984c97fbed73d07b
Source dataset
uspto-grants-2015_01
Patent number
US08927729B2

Reaction notes

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