Dimethyl acetylenedicarboxylate → HCID 178418477, compound

HRID 1005766Notes

Reaction equation

HRID 1005766 reaction equation
[NH2:1][C:2]1[CH:11]=[C:10]([Cl:12])[CH:9]=[CH:8][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:10]1[CH:11]=[C:2]2[C:3]([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)=[CH:8][CH:9]=1

Participants

5

Reactant 3

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

Product 1

HCID 178418477HCID 178418477, compoundYield 47%

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

A stirred mixture of methyl 2-amino-4-chlorobenzoate (2.50 g, 13.5 mmol) and dimethyl acetylenedicarboxylate (2.05 g, 14.4 mmol) in tert-butanol (22 ml) was refluxed for 7 hours under a nitrogen atmosphere. After adding additional dimethyl acetylenedicarboxylate (1.16 g, 8.13 mmol) and refluxing another 2.5 hours, the reaction mixture was allowed to cool to room temperature and potassium tert-butoxide (1.56 g, 13.9 mmol) 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 tert-butanol and ether. The solids were dissolved in water and acidified with 1 N 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 over MgSO4, filtered and concentrated to give a green solid. Recrystallization of this material from methanol provided the title compound (1.15 g, 47%) as an off-white solid, mp 232-233° C.; MS (Cl):296(M+H). Analysis for C13H10ClNO5: Calc'd: C, 52.81; H, 3.41; N, 4.74; Found: C, 52.75; H, 3.47; N, 4.69.

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 tert-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 over MgSO4
  14. filtrationfiltered
  15. concentrationconcentrated
  16. customto give a green solid
  17. customRecrystallization of this material from methanol

Sources & evidence

ORD record
ord-0effa98eca7a46a98cc806ba902d6aaf
Source dataset
uspto-grants-2004_09
Patent number
US06787547B2

Reaction notes

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