Potassium Carbonate → 3-(5-chloro-3-difluoromethyl-1-methyl-1H-pyrazol-4-ylmethylthio)-5,5-dimethyl-2-isoxazoline

HRID 1172079Notes

Reaction equation

HRID 1172079 reaction equation
O.[SH-].[Na+].[CH3:4][C:5]1([CH3:15])[O:9][N:8]=[C:7]([S:10]([CH2:13][CH3:14])(=O)=O)[CH2:6]1.C(=O)([O-])[O-].[K+].[K+].C(S([O-])=O)O.[Na+].BrCC1[C:31]([CH:37]([F:39])[F:38])=[N:32][N:33]([CH3:36])[C:34]=1[Cl:35]>CN(C)C=O.O>[Cl:35][C:34]1[N:33]([CH3:36])[N:32]=[C:31]([CH:37]([F:39])[F:38])[C:14]=1[CH2:13][S:10][C:7]1[CH2:6][C:5]([CH3:15])([CH3:4])[O:9][N:8]=1

Participants

8

Reactant 5

HCID 11430Potassium CarbonateHCID 16211346Sodium hydrosulfide hydrateHCID 178628584-bromomethyl-5-chloro-3-difluoromethyl-1-methyl-1H-pyrazoleHCID 178629235,5-Dimethyl-3-ethylsulfonyl-2-isoxazolineHCID 23689980Sodium Formaldehyde Sulfoxylate

Product 1

HCID 178628833-(5-chloro-3-difluoromethyl-1-methyl-1H-pyrazol-4-ylmethylthio)-5,5-dimethyl-2-isoxazolineYield 68%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

1.2 g of sodium hydrosulfide hydrate (purity: 70%, 15.0 mmoles) was added to a solution of 1.9 g (10.0 mmoles) of 5,5-dimethyl-3-ethylsulfonyl-2-isoxazoline dissolved in 30 ml of N,N-dimethylformamide. The mixture was stirred for 2 hours. Thereto were added 2.1 g (15.0 mmoles) of anhydrous potassium carbonate, 2.3 g (15.0 mmoles) of Rongalit and 2.6 g (10.0 mmoles) of 4-bromomethyl-5-chloro-3-difluoromethyl-1-methyl-1H-pyrazole. The resulting mixture was stirred at room temperature for 15 hours to give rise to a reaction. After the completion of the reaction, the reaction mixture was poured into water, followed by extraction with ethyl acetate. The resulting organic layer was washed with an aqueous sodium chloride solution and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein. The residue was purified by silica gel column chromatography (developing solvent: hexane-ethyl acetate mixed solvent) to obtain 2.1 g (yield: 68.0%) of 3-(5-chloro-3-difluoromethyl-1-methyl-1H-pyrazol-4-ylmethylthio)-5,5-dimethyl-2-isoxazoline as a colorless viscous liquid (nD20=1.5183).

Workup

  1. stirringThe resulting mixture was stirred at room temperature for 15 hours
  2. customto give rise
  3. customto a reaction
  4. customAfter the completion of the reaction
  5. extractionfollowed by extraction with ethyl acetate
  6. washThe resulting organic layer was washed with an aqueous sodium chloride solution
  7. dry with materialdried over anhydrous magnesium sulfate
  8. distillationThe resulting solution was subjected to vacuum distillation
  9. customto remove the solvent
  10. customThe residue was purified by silica gel column chromatography (developing solvent: hexane-ethyl acetate mixed solvent)

Sources & evidence

ORD record
ord-4c41a68c99464955b1535c42fae7c71a
Source dataset
uspto-grants-2010_11
Patent number
US07833939B2

Reaction notes

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