Formaldehyde → HCID 66718572, compound

HRID 1159489Notes

Reaction equation

HRID 1159489 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)([O-])[O-:13].[K+].[K+].C=O.Br[CH2:21][C:22]([O:24][CH2:25][CH3:26])=[O:23]>CN(C=O)C.O.C(OCC)(=O)C>[CH2:25]([O:24][C:22]([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:13])=[O:23])[CH3:26]

Participants

8

Reactant 4

HCID 712FormaldehydeHCID 7748Ethyl bromoacetateHCID 11430Potassium Carbonate2×HCID 178481859HCID 178481859, compound

Product 1

HCID 66718572HCID 66718572, compoundYield 81.9%

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 93.4 g (0.20 mole) of ethyl bromoacetate, followed by stirring at room temperature 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 44.7 g (purity: 63.0%, yield: 81.9%) of a crude solution of title compound. The crude solution was subjected to vacuum distillation to obtain a light yellow transparent solution. N-Hexane was added to the solution. The resulting white crystals were collected by suction filtration to obtain a title compound as white crystals.

Workup

  1. stirringby stirring at the same temperature for 1 hour
  2. stirringby stirring at room temperature for 2 hours
  3. customto give rise
  4. customto a reaction
  5. additionwere added
  6. customThe organic layer, which appeared by phase separation
  7. customwas separated
  8. extractionThe aqueous layer was subjected to re-extraction with 50 ml of ethyl acetate
  9. 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
  10. dry with materialThe resulting organic layer was dried over anhydrous sodium sulfate
  11. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-6c0ed4fd8acf498297a0c6ab61ea8e2b
Source dataset
uspto-grants-2010_10
Patent number
US07812175B2

Reaction notes

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