Chlorosulfonic acid → 262589-79-7

HRID 2303441Notes

Reaction equation

HRID 2303441 reaction equation
[CH3:1][O:2][C:3]1[CH:13]=[CH:12][C:6]([C:7]([O:9][CH2:10][CH3:11])=[O:8])=[CH:5][CH:4]=1.[Cl:14][S:15](O)(=[O:17])=[O:16]>C(Cl)(Cl)(Cl)Cl>[Cl:14][S:15]([C:4]1[CH:5]=[C:6]([CH:12]=[CH:13][C:3]=1[O:2][CH3:1])[C:7]([O:9][CH2:10][CH3:11])=[O:8])(=[O:17])=[O:16]

Participants

4

Reactant 2

HCID 24638Chlorosulfonic acidHCID 60979Ethyl anisate

Product 1

HCID 11129636262589-79-7

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

A solution of ethyl 4-methoxybenzoate (10.25 g, 57 mmol) in CCl4 (40 ml) is cooled to −15° C. and treated dropwise with chlorosulfonic acid (10.4 ml, 156 mmol) in the course of 15 min, the temperature rising to −10° C. After addition is complete, the reaction mixture is warmed to RT with stirring in the course of 30 min and then stirred at 40-50° C. for 1.5 h. The heating is removed and the reaction mixture is stirred at RT in a gentle stream of argon for 64 h to complete the chlorination. The reaction mixture is added to a suspension of ice (25 g) in CCl4 (50 ml) with ice-cooling and vigorous stirring. It is stirred vigorously for 3 min. The organic phase is separated off and the aqueous phase is extracted 3 times with further CH2Cl2 (150 ml). The combined organic extracts are washed with saturated NaCl solution, dried over Na2SO4 sicc. and concentrated: a crystalline, white residue of a mixture of ester and free acid in the ratio 1:1 remains, which is dried on an oil pump, yield 6.7 g (42%)

Workup

  1. customrising to −10° C
  2. additionAfter addition
  3. stirringstirred at 40-50° C. for 1.5 h
  4. customThe heating is removed
  5. stirringthe reaction mixture is stirred at RT in a gentle stream of argon for 64 h
  6. additionThe reaction mixture is added to a suspension of ice (25 g) in CCl4 (50 ml) with ice-
  7. temperaturecooling
  8. stirringIt is stirred vigorously for 3 min
  9. customThe organic phase is separated off
  10. extractionthe aqueous phase is extracted 3 times with further CH2Cl2 (150 ml)
  11. washThe combined organic extracts are washed with saturated NaCl solution
  12. dry with materialdried over Na2SO4 sicc
  13. concentrationand concentrated
  14. additiona crystalline, white residue of a mixture of ester and free acid in the ratio 1:1
  15. customwhich is dried on an oil pump, yield 6.7 g (42%)

Sources & evidence

ORD record
ord-ef9227870a38439cb67b839be0c63d2d
Source dataset
uspto-grants-2002_08
Patent number
US06432988B1

Reaction notes

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