Water → 3-Methylthio-5,5-dimethyl-2-isoxazoline

HRID 1760148Notes

Reaction equation

HRID 1760148 reaction equation
Cl[C:2]1[CH2:6][C:5]([CH3:8])([CH3:7])[O:4][N:3]=1.[CH3:9][S-:10].[Na+].O>CN(C=O)C>[CH3:9][S:10][C:2]1[CH2:6][C:5]([CH3:8])([CH3:7])[O:4][N:3]=1

Participants

5

Reactant 3

HCID 962WaterHCID 4378561Sodium methanethiolateHCID 116654173-Chloro-5,5-dimethyl-4,5-dihydro-1,2-oxazole

Product 1

HCID 121376573-Methylthio-5,5-dimethyl-2-isoxazolineYield 74.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of 193.0 g (1.07 M) of 3-chloro-5,5-dimethyl-2-isoxazoline dissolved in 500 ml of DMF was dropwise added, with ice-cooling, 1.0 kg (content=15%, 2.14 M) of an aqueous sodium methanethiolate solution. 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, to obtain 115.0 g (yield: 74.1%) of 3-methylthio-5,5-dimethyl-2-isoxazoline. This residue (141.2 mmoles) was dissolved in 1 liter of chloroform. Thereto was added, with ice-cooling, 392.0 g (1.59 M) of m-chloroperbenzoic acid (purity: 70%), followed by stirring at that temperature for 1 hour and at room temperature for 12 hours to give rise to a reaction. After the completion of the reaction, the precipitated m-chloroperbenzoic acid was removed by filtration. The filtrate was washed with an aqueous sodium hydrogensulfite solution, water, an aqueous sodium hydrogencarbonate solution and an aqueous sodium chloride solution in this order, and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein. The residue was washed with diisopropyl ether to obtain 77.6 g (yield: 59.1%) of 3-methylsulfonyl-5,5-dimethyl-2-isoxazoline as a white powder (melting point: 82 to 84° C.).

Workup

  1. additionwas dropwise added, with ice-
  2. temperaturecooling
  3. customto give rise
  4. customto a reaction
  5. customAfter the completion of the reaction
  6. extractionfollowed by extraction with ethyl acetate
  7. washThe resulting organic phase was washed with an aqueous sodium chloride solution
  8. dry with materialdried over anhydrous magnesium sulfate
  9. distillationThe resulting solution was subjected to vacuum distillation
  10. customto remove the solvent

Sources & evidence

ORD record
ord-f7946a623cb342f792798199edf016f6
Source dataset
uspto-grants-2005_01
Patent number
US06841519B1

Reaction notes

Loading…