Oxygen → Ethyl 4-(3,4-dimethoxybenzoyl)-1H-1,2,3-triazole-5-carboxylate

HRID 1293117Notes

Reaction equation

HRID 1293117 reaction equation
[N-:1]=[N+:2]=[N-:3].[Na+].O=O.[CH3:7][O:8][C:9]1[CH:10]=[C:11]([C:17](=[O:25])[CH:18]=[CH:19][C:20]([O:22][CH2:23][CH3:24])=[O:21])[CH:12]=[CH:13][C:14]=1[O:15][CH3:16].N([O-])=O.[Na+].S(=O)(=O)(O)O>CN(C)C=O.[Cu]Cl.O>[CH3:7][O:8][C:9]1[CH:10]=[C:11]([CH:12]=[CH:13][C:14]=1[O:15][CH3:16])[C:17]([C:18]1[NH:3][N:2]=[N:1][C:19]=1[C:20]([O:22][CH2:23][CH3:24])=[O:21])=[O:25]

Participants

9

Reactant 5

HCID 977OxygenHCID 1118Sulfuric AcidHCID 33557Sodium AzideHCID 23668193Sodium NitriteHCID 53400457Ethyl 4-(3,4-dimethoxyphenyl)-4-oxo-2-butenoate2×

Product 1

HCID 178470512Ethyl 4-(3,4-dimethoxybenzoyl)-1H-1,2,3-triazole-5-carboxylateYield 163.1%

Reagents, catalysts & solvents 3

HCID 62652Cuprous chlorideCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent3×

Procedure

Copper(I) chloride (190 mg, 1.91 mmol) was added at room temperature to a solution (40 mL) of sodium azide (1.84 g, 28.3 mmol) in N,N-dimethylformamide, and the air in the system was replaced by oxygen. A solution (10 mL) of ethyl 4-(3,4-dimethoxyphenyl)-4-oxo-2-butenoate (2.50 g, 9.46 mmol) in N,N-dimethylformamide was added to this mixed solution at 5° C. over a period of 30 min. The temperature of the reaction solution was raised to room temperature before the reaction solution was stirred for 3 hr. Thereafter, the reaction temperature was lowered to 5° C., and a solution (10 mL) of ethyl 4-(3,4-dimethoxyphenyl)-4-oxo-2-butenoate (2.50 g, 9.46 mmol) in N,N-dimethylformamide was added thereto. The temperature of the reaction solution was raised to room temperature before the reaction solution was stirred for 4 hr. After the completion of the reaction, the reaction solution was poured into iced water (75 mL), and sodium nitrite (636 mg, 9.22 mmol) was added thereto. The mixture was adjusted to pH 1.8 by the addition of 6 N sulfuric acid and was extracted with ethyl acetate. To the organic layer was added 5 wt % brine. The mixture was adjusted to pH 1.5 by the addition of 1 N hydrochloric acid, followed by separation. The organic layer was dried over anhydrous sodium sulfate, and the solvent was removed by evaporation under the reduced pressure. Toluene was added to the residue, and the solvent was removed by evaporation under the reduced pressure. The resultant crystal was washed with toluene and was then dried under the reduced pressure to give ethyl 5-(3,4-dimethoxybenzoyl)-1H-1,2,3-triazole-4-carboxylate (4.71 g, 81%).

Workup

  1. customwas lowered to 5° C.
  2. temperatureThe temperature of the reaction solution was raised to room temperature before the reaction solution
  3. stirringwas stirred for 4 hr
  4. customAfter the completion of the reaction
  5. additionwas added
  6. extractionwas extracted with ethyl acetate
  7. additionTo the organic layer was added 5 wt % brine
  8. additionThe mixture was adjusted to pH 1.5 by the addition of 1 N hydrochloric acid
  9. customfollowed by separation
  10. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  11. customthe solvent was removed by evaporation under the reduced pressure
  12. additionToluene was added to the residue
  13. customthe solvent was removed by evaporation under the reduced pressure
  14. washThe resultant crystal was washed with toluene
  15. customwas then dried under the reduced pressure

Sources & evidence

ORD record
ord-d786c839f0ad460c999905d1a08ce840
Source dataset
uspto-grants-2007_07
Patent number
US07238719B2

Reaction notes

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