Benzene → HCID 18182300, compound

HRID 1359269Notes

Reaction equation

HRID 1359269 reaction equation
[Cl-].[Al+3].[Cl-].[Cl-].Cl[C:6]1[N:14]=[CH:13][CH:12]=[CH:11][C:7]=1[C:8](O)=O.[CH:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.O.[C:22](OCC)(=[O:24])C>>[CH2:8]([C:7]1[C:6]([O:24][CH3:22])=[N:14][CH:13]=[CH:12][CH:11]=1)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

Participants

6

Reactant 5

HCID 241BenzeneHCID 962WaterHCID 8857Ethyl AcetateHCID 762582-Chloronicotinic acidHCID 6451240Aluminum(III) Chloride

Product 1

HCID 18182300HCID 18182300, compound

Procedure

16 g of aluminum chloride was added to a mixture of 8.6 g of 2-chloronicotinic acid and 120 ml of benzene in an ice bath under stirring. After stirring at room temperature for 2 hours, water and ethyl acetate were added thereto. Insoluble matters were filtered off using Celite, and the organic phase was washed with brine, dried over anhydrous magnesium sulfate and the solvent was removed. To the residue were added 100 ml of methanol and 30 ml of 28% sodium methoxide methanol solution, followed by heating under reflux overnight. After cooling as it was, the solvent was removed and the mixture was partitioned by adding water and ethyl acetate thereto. The organic phase was washed with water and brine, dried over anhydrous magnesium sulfate and the solvent was removed. To the residue were added 90 ml of diethylene glycol, 6.8 g of potassium carbonate and 4.3 ml of hydrazine mono hydrate. The mixture was heated under stirring for one hour in a 100° C. oil bath and then for 3 hours in a 170° C. oil bath. After cooling as it was, the mixture was partitioned by adding water and ethyl acetate thereto. The organic phase was washed with brine, dried over anhydrous magnesium sulfate and the solvent was removed. The residue was subjected to silica gel column chromatography and eluted with 10% ethyl acetate/hexane, to give 4.2 g of the target compound.

Workup

  1. stirringAfter stirring at room temperature for 2 hours
  2. filtrationInsoluble matters were filtered off
  3. washthe organic phase was washed with brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. customthe solvent was removed
  6. additionTo the residue were added 100 ml of methanol and 30 ml of 28% sodium methoxide methanol solution
  7. temperatureby heating
  8. temperatureunder reflux overnight
  9. temperatureAfter cooling as it
  10. customthe solvent was removed
  11. customthe mixture was partitioned
  12. additionby adding water and ethyl acetate
  13. washThe organic phase was washed with water and brine
  14. dry with materialdried over anhydrous magnesium sulfate
  15. customthe solvent was removed
  16. additionTo the residue were added 90 ml of diethylene glycol, 6.8 g of potassium carbonate and 4.3 ml of hydrazine mono hydrate
  17. temperatureThe mixture was heated
  18. stirringunder stirring for one hour in a 100° C. oil bath
  19. temperatureAfter cooling as it
  20. customthe mixture was partitioned
  21. additionby adding water and ethyl acetate
  22. washThe organic phase was washed with brine
  23. dry with materialdried over anhydrous magnesium sulfate
  24. customthe solvent was removed
  25. washeluted with 10% ethyl acetate/hexane

Sources & evidence

ORD record
ord-4eb568c9b59144c5a0bff097246625b6
Source dataset
uspto-grants-2003_07
Patent number
US06599917B1

Reaction notes

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