5-Chloro-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carbaldehyde → 1-methyl-5-(oxetan-3-yloxy)-3-trifluoromethyl-1H-pyrazole-4-carbaldehyde

HRID 1192944Notes

Reaction equation

HRID 1192944 reaction equation
[O:1]1[CH2:4][CH:3]([OH:5])[CH2:2]1.CC(C)([O-])C.[K+].Cl[C:13]1[N:17]([CH3:18])[N:16]=[C:15]([C:19]([F:22])([F:21])[F:20])[C:14]=1[CH:23]=[O:24]>C1COCC1>[CH3:18][N:17]1[C:13]([O:5][CH:3]2[CH2:4][O:1][CH2:2]2)=[C:14]([CH:23]=[O:24])[C:15]([C:19]([F:20])([F:21])[F:22])=[N:16]1

Participants

5

Reactant 3

HCID 14784595-Chloro-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carbaldehydeHCID 9942117Oxetan-3-olHCID 23665647Potassium tert-butoxide

Product 1

HCID 597395451-methyl-5-(oxetan-3-yloxy)-3-trifluoromethyl-1H-pyrazole-4-carbaldehydeYield 99.9%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Oxetane-3-ol (6.12 g, 82.7 mmol) was added dropwise to potassium tert-butoxide (1M in THF) (69.6 ml, 69.6 mmol) at room temperature. 5-Chloro-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carbaldehyde (9.86 g, 46.4 mmol) was dissolved in THF (40 ml) and added slowly to the solution. After 25 minutes the mixture was concentrated and the residue partitioned between ethyl acetate and water. The two phases were separated and the aqueous phase was extracted several times with ethyl acetate. The combined organic phases were washed with brine, dried over magnesium sulfate and concentrated to yield the product as brown oil (11.6 g) which was used in the next step without further purification.

Workup

  1. additionadded slowly to the solution
  2. concentrationAfter 25 minutes the mixture was concentrated
  3. customthe residue partitioned between ethyl acetate and water
  4. customThe two phases were separated
  5. extractionthe aqueous phase was extracted several times with ethyl acetate
  6. washThe combined organic phases were washed with brine
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-27f71bb8d7ae44309ca08b70a2098812
Source dataset
uspto-grants-2014_03
Patent number
US08680290B2

Reaction notes

Loading…