Dimethyl Sulfate → 2-Fluoro-3-methoxybenzoic acid

HRID 338993

반응식

HRID 338993 반응식
[F:1][C:2]1[C:10]([OH:11])=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].[C:12](=O)([O-])[O-].[K+].[K+].S(OC)(OC)(=O)=O.O[Li].O>CC(C)=O.O>[F:1][C:2]1[C:10]([O:11][CH3:12])=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5]

참가 물질

7

반응물 4

HCID 6497Dimethyl SulfateHCID 11430Potassium CarbonateHCID 168937Lithium hydroxide, monohydrateHCID 5936372-Fluoro-3-hydroxybenzoic acid

생성물 1

HCID 33906792-Fluoro-3-methoxybenzoic acid수율 94.1%

시약·촉매·용매 2

HCID 180Acetone용매HCID 962Water용매

실험 절차

A suspension of 2-fluoro-3-hydroxybenzoic acid (12.0 g, 76.9 mmol) and potassium carbonate (23.4 g, 169 mmol) in acetone (154 mL) was stirred at ambient temperature for 1 hour. To the mixture was added dimethyl sulfate (21.8 mL, 231 mmol) and the mixture stirred at ambient temperature for 30 minutes then heated at reflux for 4 hours. The mixture was cooled to ambient temperature, filtered and concentrated under reduced pressure. The residue was dissolved in anhydrous THF (154 mL) and the solution cooled to 0° C. in an ice bath. To this solution was added LiOH—H2O (12.9 g, 307 mmol) followed by water (30 mL) and the resulting mixture stirred at ambient temperature for 3 hours. The mixture was concentrated under reduced pressure and the residue partitioned between water and ethyl acetate and the layers separated. The aqueous layer was acidified with 1N HCl solution and extracted with ethyl acetate. The combined organic extracts were washed with brine and dried (MgSO4), filtered and concentrated under reduced pressure to afford 2-fluoro-3-methoxybenzoic acid (12.31 g, 94%).

후처리

  1. stirringthe mixture stirred at ambient temperature for 30 minutes
  2. temperaturethen heated
  3. temperatureat reflux for 4 hours
  4. temperatureThe mixture was cooled to ambient temperature
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. dissolutionThe residue was dissolved in anhydrous THF (154 mL)
  8. temperaturethe solution cooled to 0° C. in an ice bath
  9. stirringthe resulting mixture stirred at ambient temperature for 3 hours
  10. concentrationThe mixture was concentrated under reduced pressure
  11. customthe residue partitioned between water and ethyl acetate
  12. customthe layers separated
  13. extractionextracted with ethyl acetate
  14. washThe combined organic extracts were washed with brine
  15. dry with materialdried (MgSO4)
  16. filtrationfiltered
  17. concentrationconcentrated under reduced pressure

출처 및 근거

ORD 기록
ord-5310aa142b8646b999a7a345849ab2a2
출처 데이터셋
uspto-grants-2014_11
특허 번호
US08889704B2

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