Hydrogen Peroxide → 2-(((4-Chlorophenyl)sulfonyl)methyl)-1,4-difluorobenzene

HRID 1178861Notes

Reaction equation

HRID 1178861 reaction equation
S(=O)(=O)(O)[OH:2].[Cl:6][C:7]1[CH:12]=[CH:11][C:10]([S:13][CH2:14][C:15]2[CH:20]=[C:19]([F:21])[CH:18]=[CH:17][C:16]=2[F:22])=[CH:9][CH:8]=1.OO.[OH2:25]>CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)C.[Cl-].C1(C)C=CC=CC=1.O.O.[O-][W]([O-])(=O)=O.[Na+].[Na+]>[Cl:6][C:7]1[CH:12]=[CH:11][C:10]([S:13]([CH2:14][C:15]2[CH:20]=[C:19]([F:21])[CH:18]=[CH:17][C:16]=2[F:22])(=[O:2])=[O:25])=[CH:9][CH:8]=1

Participants

8

Reactant 4

HCID 784Hydrogen PeroxideHCID 962WaterHCID 1118Sulfuric AcidHCID 16681304(4-Chlorophenyl)(2,5-difluorobenzyl)sulfane

Product 1

HCID 99010282-(((4-Chlorophenyl)sulfonyl)methyl)-1,4-difluorobenzeneYield 96%

Reagents, catalysts & solvents 3

HCID 21218Trioctylmethylammonium chlorideCatalystHCID 150191Sodium Tungstate DihydrateCatalystHCID 1140TolueneSolvent

Conditions

Temperature
0 °C

Procedure

A mixture of sodium tungstate dihydrate (1.83 g, 5.54 mmol) as a solution in water (36.56 mL), 1M sulfuric acid (2.50 mL), 2-[[(4-chlorophenyl)thio]methyl]-1,4-difluorobenzene (Example 1) (100 g, 0.37 mol) and Aliquat 336™ (2.99 g, 7.39 mmol) in toluene (500 mL) was heated to 45° C., and 27.5% aqueous hydrogen peroxide (114.2 mL) was added slowly. The mixture was cooled and the unreacted peroxide was quenched by addition of 20 wt % sodium metabisulfite solution (120 mL). The layers were separated. The organic phase was washed with water (190 mL) and concentrated to a total volume of approximately 200 mL. Heptane (400 mL) was added and the resulting mixture was cooled to 0° C. and filtered. The wet cake was washed with 2:1 heptane:toluene (200 mL) and then heptane (200 mL). The product was dried in vacuo at 40° C. to yield 107.6 g of 2-[[(4-chlorophenyl)sulfonyl]methyl]-1,4-difluorobenzene (96% yield). 1H NMR CDCl3 7.61 (2H, d, J=8.6 Hz), 7.45 (2H, d, J=8.6 Hz), 7.13-7.08 (1H, m), 7.05-7.00 (1H, m), 6.99-6.87 (1H, m) and 4.36 (2H, s).

Workup

  1. temperatureThe mixture was cooled
  2. customthe unreacted peroxide was quenched by addition of 20 wt % sodium metabisulfite solution (120 mL)
  3. customThe layers were separated
  4. washThe organic phase was washed with water (190 mL)
  5. concentrationconcentrated to a total volume of approximately 200 mL
  6. additionHeptane (400 mL) was added
  7. filtrationfiltered
  8. washThe wet cake was washed with 2:1 heptane
  9. customThe product was dried in vacuo at 40° C.

Sources & evidence

ORD record
ord-c44573124b01457f96b753e4d2b110ee
Source dataset
uspto-grants-2007_10
Patent number
US07276637B2

Reaction notes

Loading…