Benzoic Acid → Benzoic acid, 3-(chlorosulfonyl)-

HRID 352643Notes

Reaction equation

HRID 352643 reaction equation
[C:1]([OH:9])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Cl:10][S:11](O)(=[O:13])=[O:12]>>[Cl:10][S:11]([C:4]1[CH:3]=[C:2]([CH:7]=[CH:6][CH:5]=1)[C:1]([OH:9])=[O:8])(=[O:13])=[O:12]

Participants

3

Reactant 2

HCID 243Benzoic AcidHCID 24638Chlorosulfonic acid

Product 1

HCID 77641Benzoic acid, 3-(chlorosulfonyl)-Yield 85%

Conditions

Temperature
122.5 °C

Procedure

Benzoic acid (250 g, 2.05 mol) was placed in a 1-L round-bottom flask, and chlorosulfonic acid (1L, 1760 g, 15.1 mol) was added. The mixture was heated with stirring at 120-125° C. for 2 h, allowed to cool to 40-50° C., and added dropwise to an excess of crushed ice. The precipitated product was collected by filtration and dissolved in 1 L of ethyl acetate; then the aqueous layer that formed was separated, and the organic layer was washed with 100 mL of water, dried over sodium sulfate, and concentrated by evaporation to near dryness. After trituration with 300 mL of hexane, the product was collected by filtration, washed on the filter with 200 mL of hexane, and dried in air to give 384.1 g (85%) of 3-chlorosulfonylbenzoic acid, mp 134-135° C. (lit. mp 134-135° C.); 1H NMR (400 MHz, in CDCl3 w/TMS, ppm) 11.43 (broad s, CO2H), 7.81 (t, J=8.0 Hz, H-5), 8.32 and 8.50 (2d, J=8.0 Hz, H-4 and H-6), 8.79 (t, J=1.6 Hz, H-2); {1H}13C NMR (100 MHz, in CDCl3 w/TMS, ppm) 170.00 (C═O), 145.06 (C-3), 136.71 (C-6), 131.92 (C-4), 131.31 (C-1), 130.63 (C-5), 128.91 (C-2).

Workup

  1. temperatureThe mixture was heated
  2. temperatureto cool to 40-50° C.
  3. additionadded dropwise to an excess of crushed ice
  4. filtrationThe precipitated product was collected by filtration
  5. dissolutiondissolved in 1 L of ethyl acetate
  6. customthen the aqueous layer that formed
  7. customwas separated
  8. washthe organic layer was washed with 100 mL of water
  9. dry with materialdried over sodium sulfate
  10. concentrationconcentrated by evaporation
  11. filtrationAfter trituration with 300 mL of hexane, the product was collected by filtration
  12. washwashed on the
  13. filtrationfilter with 200 mL of hexane
  14. customdried in air

Sources & evidence

ORD record
ord-9df566f5bc554a05ac49cc3782b9dabb
Source dataset
uspto-grants-2004_06
Patent number
US06747081B2

Reaction notes

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