Formaldehyde → HCID 86627072, compound

HRID 1159490Notes

Reaction equation

HRID 1159490 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.[CH2:20](Br)[C:21]#[CH:22]>CN(C=O)C.O.C(OCC)(=O)C>[CH2:22]([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])[C:21]#[CH:20]

Participants

8

Reactant 4

HCID 712FormaldehydeHCID 7842Propargyl bromideHCID 11430Potassium Carbonate2×HCID 178481859HCID 178481859, compound

Product 1

HCID 86627072HCID 86627072, compoundYield 49.2%

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 23.8 g (0.20 mole) of propargyl bromide. The reaction mixture was heated to 60° C. and stirred for 2 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 31.2 g (purity: 36.9%, yield: 49.2%) of a crude solution of title compound. The crude solution was subjected to vacuum distillation to obtain a title compound as a light yellow 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 2 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-796eca66ea564d4180af1851a3b59c53
Source dataset
uspto-grants-2010_10
Patent number
US07812175B2

Reaction notes

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