Dimethyl acetylenedicarboxylate → HCID 178418477, compound

HRID 323606Notes

Reaction equation

HRID 323606 reaction equation
CO[C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([Cl:10])=[CH:6][C:5]=1[NH2:11].[C:13]([C:19]([O:21][CH3:22])=[O:20])#[C:14][C:15]([O:17][CH3:18])=[O:16].CC(C)([O-])C.[K+]>C(O)(C)(C)C>[CH3:18][O:17][C:15]([C:14]1[C:13]([C:19]([O:21][CH3:22])=[O:20])=[C:3]([OH:12])[C:4]2[C:5](=[CH:6][C:7]([Cl:10])=[CH:8][CH:9]=2)[N:11]=1)=[O:16]

Participants

5

Reactant 3

HCID 12980Dimethyl acetylenedicarboxylate2×HCID 80001Methyl 4-chloroanthranilateHCID 23665647Potassium tert-butoxide

Product 1

HCID 178418477HCID 178418477, compoundYield 28.9%

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

A stirred mixture of methyl-2-amino-4-chlorobenzoate (2.50 g, 13.5 mM) and dimethyl acetylenedicarboxylate (2.05 g, 14.4 mM) in t-butanol (22 mL) was refluxed for 7 hours under a nitrogen atmosphere. After adding additional dimethyl acetylenedicarboxylate (1.16 g, 8.13 mM) and refluxing another 2.5 hours, the reaction mixture was allowed to cool to room temperature and potassium t-butoxide (1.56 g, 13.9 mM) was added in one portion. A precipitate formed and the resulting mixture was refluxed for 1.5 hours. The mixture was cooled to room temperature and filtered to separate the solids, which were washed with t-butanol and ether. The solids were dissolved in water and acidified with 1N sulfuric acid to form a precipitate. The resulting mixture was extracted with methylene chloride and the combined extracts were washed with brine and water, dried (MgSO4), filtered and concentrated to give a green solid. Recrystallization of this material from methanol provided dimethyl-7-chloro-4-hydroxyquinoline-2,3-dicarboxylate (1.15 g, 28.94) as an off-white solid, mp 232-233° C.; MS (Cl):296 (M+H).

Workup

  1. temperaturewas refluxed for 7 hours under a nitrogen atmosphere
  2. temperaturerefluxing another 2.5 hours
  3. customA precipitate formed
  4. temperaturethe resulting mixture was refluxed for 1.5 hours
  5. temperatureThe mixture was cooled to room temperature
  6. filtrationfiltered
  7. customto separate the solids, which
  8. washwere washed with t-butanol and ether
  9. dissolutionThe solids were dissolved in water
  10. customto form a precipitate
  11. extractionThe resulting mixture was extracted with methylene chloride
  12. washthe combined extracts were washed with brine and water
  13. dry with materialdried (MgSO4)
  14. filtrationfiltered
  15. concentrationconcentrated
  16. customto give a green solid
  17. customRecrystallization of this material from methanol

Sources & evidence

ORD record
ord-c2810f308ad94112a9cf272994196ca9
Source dataset
uspto-grants-2001_04
Patent number
US06214826B1

Reaction notes

Loading…