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

HRID 1470801Notes

Reaction equation

HRID 1470801 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]-benzaldehyde

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 200 mL of acetonitrile and stirred at ambient temperature while ceric ammonium nitrate (32 g, 58 mmol) in 60 mL of water was added in portions over 10 min. The solution was then heated to reflux for 4 h, cooled, and diluted with 200 mL of water. The solution was extracted with 2×200 mL of ether, and the combined organic layer was dried and concentrated to give an orange oil. This material was dissolved in 40 mL of dioxane and treated with a solution of KOH (5 g, 90 mmol) in 20 mL of water. The solution was heated to reflux for 2 h, then cooled and diluted with 100 mL of water. The aldehyde precipitated and was collected by filtration. Recrystallization from MeOH/H2O gave the pure aldehyde as a white solid. 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 384.2 (M+H); mp 137-144° C.

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 2×200 mL of ether
  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-61ae0b7f26fd4e65b09c5a5973ac17b3
Source dataset
uspto-grants-2015_04
Patent number
US09006468B2

Reaction notes

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