Thionyl Chloride → HCID 15292814, compound

HRID 259878Notes

Reaction equation

HRID 259878 reaction equation
[F:1][C:2]1[CH:10]=[CH:9][C:8]([Si:11]([CH3:14])([CH3:13])[CH3:12])=[CH:7][C:3]=1C(O)=O.S(Cl)(Cl)=O.[N-:19]=[N+]=[N-].[Na+]>O>[F:1][C:2]1[CH:10]=[CH:9][C:8]([Si:11]([CH3:14])([CH3:13])[CH3:12])=[CH:7][C:3]=1[NH2:19]

Participants

5

Reactant 3

HCID 24386Thionyl ChlorideHCID 33557Sodium AzideHCID 15292813HCID 15292813, compound

Product 1

HCID 15292814HCID 15292814, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
60 °C

Procedure

A mixture of 2.12 g (10 mmol) of 2-fluoro-5-trimethylsilyl-benzoic acid and 1.78 g (15 mmol) of thionyl chloride is heated 2 hours at 60° C. Then gases and excess of thionyl chloride are removed under reduced pressure. To the crude material dissolved in 10 ml of acetone is added dropwise 6.5 g (10 mmol) of sodium azide in 10 ml of water and the mixture is stirred one hour at 0° C. Acetone is removed under reduced pressure and the acyl azide was extracted with ethyl acetate. The organic phase is dried over MgSO4 and ethyl acetate is removed under reduced pressure. To the acyl azide 20 ml of benzene is added and the reaction mixture is stirred 30 minutes at reflux. Then the solution is cooled to 0° C., 10 ml of concentrated hydrochloric acid is added and the mixture is heated 30 minutes at reflux. Benzene and water are removed under reduced pressure and the hydrochloride salt is recrystallized from isopropanol. To the salt dissolved in 10 ml of water is added 10 ml of 1N sodium hydroxide and the aqueous mixture is extracted with ethyl acetate. The organic layer is washed with brine, dried over MgSO4 and concentrated to obtain pure 2-fluoro-5-trimethylsilyl-aniline.

Workup

  1. customThen gases and excess of thionyl chloride are removed under reduced pressure
  2. dissolutionTo the crude material dissolved in 10 ml of acetone
  3. customAcetone is removed under reduced pressure
  4. extractionthe acyl azide was extracted with ethyl acetate
  5. dry with materialThe organic phase is dried over MgSO4 and ethyl acetate
  6. customis removed under reduced pressure
  7. additionTo the acyl azide 20 ml of benzene is added
  8. stirringthe reaction mixture is stirred 30 minutes
  9. temperatureat reflux
  10. temperatureThen the solution is cooled to 0° C.
  11. addition10 ml of concentrated hydrochloric acid is added
  12. temperaturethe mixture is heated 30 minutes
  13. temperatureat reflux
  14. customBenzene and water are removed under reduced pressure
  15. customthe hydrochloride salt is recrystallized from isopropanol
  16. dissolutionTo the salt dissolved in 10 ml of water
  17. additionis added 10 ml of 1N sodium hydroxide
  18. extractionthe aqueous mixture is extracted with ethyl acetate
  19. washThe organic layer is washed with brine
  20. dry with materialdried over MgSO4
  21. concentrationconcentrated

Sources & evidence

ORD record
ord-73d79df8ed1d410bb653deddd344b87e
Source dataset
uspto-grants-1996_06
Patent number
US05523442

Reaction notes

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