Acetic Acid → [4-(Chlorosulfonyl)phenyl]methylene diacetate

HRID 216276Notes

Reaction equation

HRID 216276 reaction equation
[C:1]1([CH3:11])[CH:6]=[CH:5][C:4]([S:7]([Cl:10])(=[O:9])=[O:8])=[CH:3][CH:2]=1.C([O:15][C:16](=[O:18])[CH3:17])(=O)C.S(=O)(=O)(O)O.[C:24]([OH:27])(=[O:26])[CH3:25]>[O-2].[O-2].[O-2].[Cr+6]>[C:24]([O:27][CH:11]([O:15][C:16](=[O:18])[CH3:17])[C:1]1[CH:2]=[CH:3][C:4]([S:7]([Cl:10])(=[O:9])=[O:8])=[CH:5][CH:6]=1)(=[O:26])[CH3:25]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 1118Sulfuric AcidHCID 73974-Toluenesulfonyl chlorideHCID 7918Acetic Anhydride

Product 1

HCID 11849277[4-(Chlorosulfonyl)phenyl]methylene diacetateYield 38%

Reagents, catalysts & solvents 1

HCID 10219390chromium (VI) trioxideCatalyst

Conditions

Temperature
7.5 °C

Procedure

A solution of p-toluenesulfonyl chloride (40.2 g) in acetic acid:acetic anhydride (800 mL, 1:1) was treated with conc. sulfuric acid (64 mL, 5 equivalents) at 0-5° C. Chromium trioxide (80 g, 4 equivalents) was added at such a rate that the temperature remained below 10° C. The mixture was stirred at 5-10° C. until reaction was completed as indicated by TLC. The mixture was quenched with ice water (2 L), and the solids were filtered, washed with water, and dried. The solids were combined with saturated NaHCO3 (1 L) at 25° C. for 2 hrs, filtered, dissolved in dichloromethane (1 L), dried over Na2SO4, filtered and concentrated. The residue was recrystallized from 2-3 volumes of hot acetone/pentane and cooling for 16 hrs. The crystals are filtered, and washed with cold pentane to give the product (24 g, 38%). 1H NMR (CDCl3): δ 8.09 (d, J=9 Hz, 2H), 7.77 (d, J=9 Hz, 2H), 7.73 (s, 1H), 2.16 (s, 6H).

Workup

  1. customremained below 10° C
  2. customThe mixture was quenched with ice water (2 L)
  3. filtrationthe solids were filtered
  4. washwashed with water
  5. customdried
  6. filtrationfiltered
  7. dissolutiondissolved in dichloromethane (1 L)
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe residue was recrystallized from 2-3 volumes of hot acetone/pentane
  12. temperaturecooling for 16 hrs
  13. filtrationThe crystals are filtered
  14. washwashed with cold pentane

Sources & evidence

ORD record
ord-8f66a9e2b0d44de4b6d149af4c89e7bb
Source dataset
uspto-grants-2012_06
Patent number
US08193227B2

Reaction notes

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