Chloroacetic Acid → 2-Chloro-4-(methylsulfonyl)benzoic acid

HRID 466789

Reaction equation

HRID 466789 reaction equation
S([O-])([O-])=O.[Na+].[Na+].[C:7](=O)(O)[O-].[Na+].[Cl:12][C:13]1[CH:21]=[C:20]([S:22](Cl)(=[O:24])=[O:23])[CH:19]=[CH:18][C:14]=1[C:15]([OH:17])=[O:16].ClCC(O)=O.[OH-].[Na+].ClC1CC(=S=O)C=CC=1C(O)=O.Cl>O>[Cl:12][C:13]1[CH:21]=[C:20]([S:22]([CH3:7])(=[O:24])=[O:23])[CH:19]=[CH:18][C:14]=1[C:15]([OH:17])=[O:16]

Participants

9

Reactant 7

HCID 300Chloroacetic AcidHCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 24437Sodium SulfiteHCID 1884272-Chloro-4-(chlorosulfonyl)benzoic acidHCID 516892Sodium BicarbonateHCID 867462152-Chloro-4-sulfinylbenzoic acid

Product 1

HCID 7358632-Chloro-4-(methylsulfonyl)benzoic acidYield 105.9%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
50 °C

Procedure

A 250 mL round bottom flask equipped with a reflux condenser, thermometer, and magnetic stirrer was charged with 9.2 g (73 mmol) of sodium sulfite, 24.6 g (292 mmol) of sodium bicarbonate and 80 mL of water. The resulting slurry was heated to 50° C., and 20.0 g (70 mmol) of 2-chloro-4-(chlorosulfonyl)benzoic acid was added over 15 minutes. After heating at 50° C. for three hours, chloroacetic acid (10.4 g, 110 mmol) and 5.7 mL (110 mmol) of 50% aqueous sodium hydroxide were added sequentially to the aqueous solution of 2-chloro-4-sulfinylbenzoic acid, and the reaction mixture heated to reflux. After heating for 19 hours, the reaction mixture was allowed to cool to ambient temperature and acidified with dilute HCl. The precipitated solids were collected by filtration, washed with dilute HCl and dried to give 17.4 g of 2-chloro-4-(methylsulfonyl)benzoic acid as a white solid. The solid was assayed at 85% purity, corresponding to an overall yield of 89%.

Workup

  1. customA 250 mL round bottom flask equipped with a reflux condenser
  2. temperatureAfter heating at 50° C. for three hours
  3. temperaturethe reaction mixture heated to reflux
  4. temperatureAfter heating for 19 hours
  5. temperatureto cool to ambient temperature
  6. filtrationThe precipitated solids were collected by filtration
  7. washwashed with dilute HCl
  8. customdried

Sources & evidence

ORD record
ord-bd1ad13c0e614bd0b9b7539c51c775b6
Source dataset
uspto-grants-1992_10
Patent number
US05157150

Linked notes

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