Dimethyl acetylenedicarboxylate → HCID 178418309, compound

HRID 1598609Notes

Reaction equation

HRID 1598609 reaction equation
[NH2:1][C:2]1[CH:11]=[CH:10][CH:9]=[C:8]([Cl:12])[C:3]=1[C:4]([O:6]C)=O.[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>[Cl:12][C:8]1[CH:9]=[CH:10][CH:11]=[C:2]2[C:3]=1[C:4]([OH:6])=[C:13]([C:19]([O:21][CH3:22])=[O:20])[C:14]([C:15]([O:17][CH3:18])=[O:16])=[N:1]2

Participants

5

Reactant 3

HCID 12980Dimethyl acetylenedicarboxylateHCID 592849Methyl 2-amino-6-chlorobenzoateHCID 23665647Potassium tert-butoxide

Product 1

HCID 178418309HCID 178418309, compoundYield 80.4%

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

A solution of methyl 2-amino-6-chlorobenzoate (3.00 g, 16.2 mM) and dimethyl acetylenedicarboxylate (2.64 g, 18.6 mM) in t-butanol (25 mL) was refluxed under a nitrogen atmosphere for 18 hr. The reaction mixture was cooled to room temperature and potassium t-butoxide (2.09 g, 18.6 mM) was added in one portion whereupon a precipitate formed. After refluxing this mixture for 1.5 hr, it was cooled to room temperature and filtered to separate the solids. The solids were dissolved in water and the resulting solution acidified with 1N H2SO4 to form a precipitate. The mixture was filtered and the collected solids were washed with water and air dried to give dimethyl 5-chloro-4-hydroxyquinoline-2,3-dicarboxylate (3.84 g, 80.2%) as a tan solid. An 0.25 g portion of this material was recrystallized from ethyl acetate to provide an analytical sample (0.152 g) of the title compound as an off-white solid, mp 174°-176° C.; MS(CI): 296 (M+H).

Workup

  1. customformed
  2. temperatureAfter refluxing this mixture for 1.5 hr
  3. temperatureit was cooled to room temperature
  4. filtrationfiltered
  5. customto separate the solids
  6. dissolutionThe solids were dissolved in water
  7. customto form a precipitate
  8. filtrationThe mixture was filtered
  9. washthe collected solids were washed with water and air
  10. customdried

Sources & evidence

ORD record
ord-21f53e0882994e2d915c4be3ae957b38
Source dataset
uspto-grants-1998_04
Patent number
US05739133

Reaction notes

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