Dimethyl Sulfate → 5-Chloro-o-anisic acid

HRID 1658594Notes

Reaction equation

HRID 1658594 reaction equation
[Cl:1][C:2]1[CH:11]=[C:6]([C:7]([O:9]C)=[O:8])[C:5]([OH:12])=[CH:4][CH:3]=1.[OH-].[Na+].S(OC)(O[CH3:19])(=O)=O>CC(C)=O>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([O:12][CH3:19])=[C:6]([CH:11]=1)[C:7]([OH:9])=[O:8]

Participants

5

Reactant 3

HCID 6497Dimethyl Sulfate2×HCID 14798Sodium Hydroxide2×HCID 77684Benzoic acid, 5-chloro-2-hydroxy-, methyl ester

Product 1

HCID 769705-Chloro-o-anisic acid

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

To a solution of methyl 5-chlorosalicylate (20 g.) in acetone 110 ml.) was added 2 N sodium hydroxide (66 ml.) and dimethyl sulphate (13.86 g.). The mixture was stirred for 10 minutes, sodium hydroxide 33 ml., 2N) and dimethyl sulphate (6.93 g.) added, and the mixture was heated under reflux for 45 minutes. The product was then cooled, the acetone evaporated off, and the residue was taken up in ether. The ether was extracted with dilute sodium hydroxide, evaporated off, and the residue heated under reflux for 1 hour with 10 aqueous sodium hydroxide (100 ml.). The product was cooled and acidified. The precipitate acid was filtered off and recrystallized from ethanol-water to give 8 g., m.p. 80°-81° (45%) with a second crop of 0.8 g., m.p. 77°-79° (4.5%).

Workup

  1. temperaturethe mixture was heated
  2. temperatureunder reflux for 45 minutes
  3. temperatureThe product was then cooled
  4. customthe acetone evaporated off
  5. extractionThe ether was extracted with dilute sodium hydroxide
  6. customevaporated off
  7. temperaturethe residue heated
  8. temperatureunder reflux for 1 hour with 10 aqueous sodium hydroxide (100 ml.)
  9. temperatureThe product was cooled
  10. filtrationThe precipitate acid was filtered off
  11. customrecrystallized from ethanol-water
  12. customto give 8 g

Sources & evidence

ORD record
ord-112465c1013f4611a44a4aebf679efd8
Source dataset
uspto-grants-1976_06
Patent number
US03965173

Reaction notes

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