Dimethyl acetylenedicarboxylate → HCID 178418430, compound

HRID 1449553Notes

Reaction equation

HRID 1449553 reaction equation
[NH2:1][C:2]1[CH:11]=[C:10]([Cl:12])[CH:9]=[C:8]([Cl:13])[C:3]=1[C:4]([O:6]C)=O.[C:14]([C:20]([O:22][CH3:23])=[O:21])#[C:15][C:16]([O:18][CH3:19])=[O:17].CC(C)([O-])C.[K+]>C(O)(C)(C)C>[Cl:13][C:8]1[CH:9]=[C:10]([Cl:12])[CH:11]=[C:2]2[C:3]=1[C:4]([OH:6])=[C:14]([C:20]([O:22][CH3:23])=[O:21])[C:15]([C:16]([O:18][CH3:19])=[O:17])=[N:1]2

Participants

5

Reactant 3

HCID 12980Dimethyl acetylenedicarboxylateHCID 12363232Methyl 2-amino-4,6-dichlorobenzoateHCID 23665647Potassium tert-butoxide

Product 1

HCID 178418430HCID 178418430, compoundYield 59%

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

A solution of methyl 2-amino-4,6-dichlorobenzoate (1.30 g, 5.91 mM) and dimethyl acetylenedicarboxylate (0.96 g, 6.78 mM) in t-butanol (14 mL) was refluxed for 18 hr under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and potassium t-butoxide (0.76 g, 6.8 mM) was added to the stirred mixture whereupon a precipitate formed. After refluxing for 1.5 hr, the reaction mixture was cooled to room temperature and filtered to separate the precipitated solids. The solids were washed with t-butanol and then dissolved in water. The resulting solution was acidified with IN H2SO4 and the resulting precipitate was collected, washed thoroughly with water and dried to give the title compound as a light green solid (1.15 g, 59%). An analytical sample was obtained by recrystallization of a portion from toluene to provide the title compound as a light tan solid, mp 109.5°-111° C. (d); MS(CI): 330 (M+H).

Workup

  1. customformed
  2. temperatureAfter refluxing for 1.5 hr
  3. temperaturethe reaction mixture was cooled to room temperature
  4. filtrationfiltered
  5. customto separate the precipitated solids
  6. washThe solids were washed with t-butanol
  7. dissolutiondissolved in water
  8. customthe resulting precipitate was collected
  9. washwashed thoroughly with water
  10. customdried

Sources & evidence

ORD record
ord-3ba1df11190c4078bd208846b6838b64
Source dataset
uspto-grants-1997_02
Patent number
US05599814

Reaction notes

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