Formaldehyde → HCID 66718631, compound

HRID 1159485Notes

Reaction equation

HRID 1159485 reaction equation
[OH:1][C:2]1[N:6]([CH3:7])[N:5]=[C:4]([C:8]([F:11])([F:10])[F:9])[CH:3]=1.[C:12](=[O:15])([O-])[O-].[K+].[K+].C=O.Br[CH2:21][CH3:22]>CN(C=O)C.O.C(OCC)(=O)C>[CH2:21]([O:1][C:2]1[N:6]([CH3:7])[N:5]=[C:4]([C:8]([F:11])([F:10])[F:9])[C:3]=1[CH2:12][OH:15])[CH3:22]

Participants

8

Reactant 4

HCID 712FormaldehydeHCID 6332Ethyl BromideHCID 11430Potassium Carbonate2×HCID 178481859HCID 178481859, compound

Product 1

HCID 66718631HCID 66718631, compoundYield 83%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

In 100 ml of DMF were suspended 16.6 g (0.10 mole) of the 5-hydroxy-1-methyl-3-trifluoromethylpyrazole synthesized in Reference Example 1 and 20.9 g (0.15 mole) of potassium carbonate. In this suspension being stirred at room temperature was placed 4.5 g (0.15 mole) of paraformaldehyde, followed by stirring at the same temperature for 1 hour. Then, 41.8 g (0.30 mole) of potassium carbonate was added. Thereto was dropwise added 21.8 g (0.20 mole) of bromoethane. The reaction mixture was heated to 60° C. and stirred for 8 hours to give rise to a reaction. After the reaction, 200 ml of ethyl acetate and 200 ml of water were added. The organic layer, which appeared by phase separation, was separated. The aqueous layer was subjected to re-extraction with 50 ml of ethyl acetate. The two organic layers were combined and washed with 50 ml of water, 30 ml of a saturated aqueous ammonium chloride solution and 30 ml of a saturated aqueous sodium chloride solution in this order. The resulting organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure to obtain 22.5 g (purity: 82.7%, yield: 83.0%) of a crude solution of title compound. The crude solution was subjected to vacuum distillation to obtain a title compound as a colorless transparent solution.

Workup

  1. stirringby stirring at the same temperature for 1 hour
  2. temperatureThe reaction mixture was heated to 60° C.
  3. stirringstirred for 8 hours
  4. customto give rise
  5. customto a reaction
  6. additionwere added
  7. customThe organic layer, which appeared by phase separation
  8. customwas separated
  9. extractionThe aqueous layer was subjected to re-extraction with 50 ml of ethyl acetate
  10. washwashed with 50 ml of water, 30 ml of a saturated aqueous ammonium chloride solution and 30 ml of a saturated aqueous sodium chloride solution in this order
  11. dry with materialThe resulting organic layer was dried over anhydrous sodium sulfate
  12. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-f4f7e72414d14245bcef25294af67131
Source dataset
uspto-grants-2010_10
Patent number
US07812175B2

Reaction notes

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