Water → 4-Chloro-3-(2,4-dichloro-5-formylphenyl)-5-difluoromethoxy-1-methyl-1H-pyrazole

HRID 1086748Notes

Reaction equation

HRID 1086748 reaction equation
O.Br[CH2:3][C:4]1[C:5]([Cl:22])=[CH:6][C:7]([Cl:21])=[C:8]([C:10]2[C:14]([Cl:15])=[C:13]([O:16][CH:17]([F:19])[F:18])[N:12]([CH3:20])[N:11]=2)[CH:9]=1.C1N2CN3CN(C2)CN1C3.S(=O)(=O)(O)[OH:34]>C(O)(=O)C>[Cl:15][C:14]1[C:10]([C:8]2[C:7]([Cl:21])=[CH:6][C:5]([Cl:22])=[C:4]([CH:9]=2)[CH:3]=[O:34])=[N:11][N:12]([CH3:20])[C:13]=1[O:16][CH:17]([F:19])[F:18]

Participants

6

Reactant 4

HCID 962WaterHCID 1118Sulfuric AcidHCID 4101HexamethylenetetramineHCID 156723413-(5-bromomethyl-2,4-dichlorophenyl)-4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazole

Product 1

HCID 156721724-Chloro-3-(2,4-dichloro-5-formylphenyl)-5-difluoromethoxy-1-methyl-1H-pyrazoleYield 56.3%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

After addition of 100 ml water to a solution of 3-(5-bromomethyl-2,4-dichlorophenyl)-4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazole (26.60 g, 63.3 mmoles) in 100 ml glacial acetic acid, hexamethylenetetramine (8.87 g, 63.3 mmoles) was added and reacted under reflux for 2 hours. Further, 40 ml conc. sulfuric acid was added and reacted under reflux for 13 hours. Then the reaction product mixture, poured into ice-cold water, was extracted with ethyl acetate. The extract solution was washed with 5% aqueous NaHCO3 and then with water, dehydrated, and concentrated. Purification of the residue by column chromatography gave the title compound (12.66 g), m.p. 138.2° C., yield 56.3%.

Workup

  1. additionwas added
  2. customreacted
  3. temperatureunder reflux for 2 hours
  4. customreacted
  5. temperatureunder reflux for 13 hours
  6. additionThen the reaction product mixture, poured into ice-cold water
  7. extractionwas extracted with ethyl acetate
  8. washThe extract solution was washed with 5% aqueous NaHCO3
  9. concentrationconcentrated
  10. customPurification of the residue by column chromatography

Sources & evidence

ORD record
ord-330fb680762b492da87de43e2b562490
Source dataset
uspto-grants-1991_07
Patent number
US05032165

Reaction notes

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