Potassium Carbonate → Isoxazole, 3-[[(2,6-difluorophenyl)methyl]thio]-4,5-dihydro-5,5-dimethyl-

HRID 1760147Notes

Reaction equation

HRID 1760147 reaction equation
[CH3:1][S:2]([C:5]1[CH2:9][C:8]([CH3:11])([CH3:10])[O:7][N:6]=1)(=O)=O.O.S.[Na].C(=O)([O-])[O-].[K+].[K+].C(S([O-])=O)O.[Na+].[F:27][C:28]1[CH:42]=[CH:41][CH:40]=[C:39]([F:43])[C:29]=1CC(Br)C1C=CC=CC=1>CN(C=O)C.O>[F:27][C:28]1[CH:42]=[CH:41][CH:40]=[C:39]([F:43])[C:29]=1[CH2:1][S:2][C:5]1[CH2:9][C:8]([CH3:11])([CH3:10])[O:7][N:6]=1

Participants

8

Reactant 5

HCID 11430Potassium CarbonateHCID 121376563-Methylsulfonyl-5,5-dimethyl-2-isoxazolineHCID 22597338HCID 22597338, compoundHCID 23689980Sodium Formaldehyde SulfoxylateHCID 53442613Sodium hydrogen sulfide hydrate

Product 1

HCID 12137655Isoxazole, 3-[[(2,6-difluorophenyl)methyl]thio]-4,5-dihydro-5,5-dimethyl-Yield 80.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

To a solution of 5.0 g (28.2 mmoles) of 3-methylsulfonyl-5,5-dimethyl-2-isoxazoline (present compound No. 2-1) dissolved in 50 ml of DMF were added, with ice-cooling, 4.5 g (purity: 70%, 56.1 mmoles) of sodium hydrogensulfide hydrate, 7.8 g (56.4 mmoles) of potassium carbonate and 8.7 g (56.5 mmoles) of Rongalit. The mixture was stirred for 2 hours. Thereto was added 5.8 g (28.0 mmoles) of 2,6-difluorobenzylbenzyl bromide. The mixture was stirred at room temperature for 12 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 phase 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 (solvent system=hexane-ethyl acetate) to obtain 5.8 g (yield: 80.0%) of 3-(2,6-difluorobenzylthio)-5,5-dimethyl-2-isoxazoline as a white powder (melting point: 77 to 80° C.).

Workup

  1. additionwere added, with ice-
  2. temperaturecooling
  3. stirringThe mixture was stirred at room temperature for 12 hours
  4. customto give rise
  5. customto a reaction
  6. customAfter the completion of the reaction
  7. extractionfollowed by extraction with ethyl acetate
  8. washThe resulting organic phase was washed with an aqueous sodium chloride solution
  9. dry with materialdried over anhydrous magnesium sulfate
  10. distillationThe resulting solution was subjected to vacuum distillation
  11. customto remove the solvent
  12. customThe residue was purified by silica gel column chromatography (solvent system=hexane-ethyl acetate)

Sources & evidence

ORD record
ord-59c9adbd69be439aa9beb7ada96991da
Source dataset
uspto-grants-2005_01
Patent number
US06841519B1

Reaction notes

Loading…