Thionyl Chloride → HCID 21432728, compound

HRID 2399103Notes

Reaction equation

HRID 2399103 reaction equation
S(Cl)(Cl)=O.O[C:6]1[C:15]2[C:10](=[CH:11][CH:12]=[C:13]([C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=3)[CH:14]=2)[N:9]=[N:8][C:7]=1[C:22]([O:24][CH2:25][CH3:26])=[O:23]>CN(C)C=O>[C:16]1([C:13]2[CH:14]=[C:15]3[C:10](=[CH:11][CH:12]=2)[N:9]=[N:8][C:7]([C:22]([O:24][CH2:25][CH3:26])=[O:23])=[CH:6]3)[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1

Participants

4

Reactant 2

HCID 24386Thionyl ChlorideHCID 178470436HCID 178470436, compound

Product 1

HCID 21432728HCID 21432728, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideCatalyst

Procedure

Thionyl chloride (15 ml.) and dimethylformamide (1 drop) were added to ethyl 4-hydroxy-6-phenylcinnolin-3-yl carboxylate (0.30 g.). The mixture was gradually heated to boiling point and then heated under reflux until the evolution of gases ceased. The solution was evaporated under reduced pressure. The residue was dissolved in dry toluene (20 ml.) and the solution evaporated; this operation was then repeated. The residue was dissolved in a mixture of dimethylformamide (5 ml.) and ethyl acetate (30 ml.). The solution was stirred and sodium borohydride (0.25 g.) was added. The mixture was stirred for 2 hours and then added to a mixture of N-hydrochloric acid (10 ml.) and ethyl acetate (50 ml.). The mixture was separated and the ethyl acetate layer was washed with water (3 × 20 ml.), dried (MgSO4), filtered, and the filtrate evaporated under reduced pressure. The residue (which comprised ethyl 6-phenyl-1,4-dihydrocinnolin-3-yl carboxylate) was dissolved in dry toluene (50 ml.). Lead tetraacetate (1 g.) was added, and the mixture was stirred for 2 hours. The mixture was shaken with water (50 ml.), and separated. The organic layer was washed with water (3× 50 ml.), dried (MgSO4), filtered, and the filtrate evaporated under reduced pressure. The residue was crystallised from a mixture of ethyl acetate and petroleum ether (b.p. 60°-80° C.) to give ethyl 6-phenylcinnolin-3-yl carboxylate, m.p. 160°-2° C.

Workup

  1. temperatureThe mixture was gradually heated
  2. temperatureheated
  3. temperatureunder reflux until the evolution of gases
  4. customThe solution was evaporated under reduced pressure
  5. dissolutionThe residue was dissolved in dry toluene (20 ml.)
  6. customthe solution evaporated
  7. dissolutionThe residue was dissolved in a mixture of dimethylformamide (5 ml.) and ethyl acetate (30 ml.)
  8. additionsodium borohydride (0.25 g.) was added
  9. stirringThe mixture was stirred for 2 hours
  10. additionadded to a mixture of N-hydrochloric acid (10 ml.) and ethyl acetate (50 ml.)
  11. customThe mixture was separated
  12. washthe ethyl acetate layer was washed with water (3 × 20 ml.)
  13. dry with materialdried (MgSO4)
  14. filtrationfiltered
  15. customthe filtrate evaporated under reduced pressure
  16. dissolutionThe residue (which comprised ethyl 6-phenyl-1,4-dihydrocinnolin-3-yl carboxylate) was dissolved in dry toluene (50 ml.)
  17. additionLead tetraacetate (1 g.) was added
  18. stirringthe mixture was stirred for 2 hours
  19. stirringThe mixture was shaken with water (50 ml.)
  20. customseparated
  21. washThe organic layer was washed with water (3× 50 ml.)
  22. dry with materialdried (MgSO4)
  23. filtrationfiltered
  24. customthe filtrate evaporated under reduced pressure
  25. customThe residue was crystallised from a mixture of ethyl acetate and petroleum ether (b.p. 60°-80° C.)

Sources & evidence

ORD record
ord-b1935d6bbf6a4d45a246410184e7be1a
Source dataset
uspto-grants-1977_05
Patent number
US04027023

Reaction notes

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