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

HRID 1293118Notes

Reaction equation

HRID 1293118 reaction equation
[N-:1]=[N+:2]=[N-:3].[Na+].[CH3:5][O:6][C:7]1[CH:8]=[C:9]([C:15](=[O:23])[CH:16]=[CH:17][C:18]([O:20][CH2:21][CH3:22])=[O:19])[CH:10]=[CH:11][C:12]=1[O:13][CH3:14].N([O-])=O.[Na+].Cl>CN(C)C=O.[Fe](Cl)(Cl)Cl.O>[CH3:5][O:6][C:7]1[CH:8]=[C:9]([CH:10]=[CH:11][C:12]=1[O:13][CH3:14])[C:15]([C:16]1[NH:3][N:2]=[N:1][C:17]=1[C:18]([O:20][CH2:21][CH3:22])=[O:19])=[O:23]

Participants

8

Reactant 4

HCID 313Hydrochloric 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 175.9%

Reagents, catalysts & solvents 3

HCID 24380Iron chloride (FeCl3)CatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent2×

Procedure

Iron(III) chloride (309 mg, 1.90 mmol) was added at room temperature to a solution (37.5 mL) of sodium azide (1.84 g, 28.3 mmol) in N,N-dimethylformamide. A solution (25 mL) of ethyl 4-(3,4-dimethoxyphenyl)-4-oxo-2-butenoate (2.50 g, 9.46 mmol) in N,N-dimethylformamide was then added to the mixture at 5° C. under an oxygen atmosphere. The temperature of the reaction solution was raised to room temperature before the reaction solution was stirred for 3 hr. Thereafter, ethyl 4-(3,4-dimethoxyphenyl)-4-oxo-2-butenoate (2.50 g, 9.46 mmol) was added to the reaction solution at room temperature, and the mixture was stirred for additional 4 hr. After the completion of the reaction, the reaction solution was poured into iced water, and sodium nitrite (636 mg, 9.22 mmol) was added thereto. The mixture was adjusted to pH 2 by the addition of 1 N hydrochloric acid and was extracted with ethyl acetate, and 5 wt % brine was then added. The mixture was adjusted to pH 2.0 by the addition of 1 N hydrochloric acid, followed by separation. The organic layer was dried over anhydrous sodium sulfate, and the solvent was then removed by evaporation under the reduced pressure. Toluene was added to the residue, and toluene was removed by evaporation under the reduced pressure. The resultant crystal was collected by filtration, 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 (5.08 g, 88%).

Workup

  1. stirringthe mixture was stirred for additional 4 hr
  2. customAfter the completion of the reaction
  3. additionwas added
  4. extractionwas extracted with ethyl acetate, and 5 wt % brine
  5. additionwas then added
  6. additionThe mixture was adjusted to pH 2.0 by the addition of 1 N hydrochloric acid
  7. customfollowed by separation
  8. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  9. customthe solvent was then removed by evaporation under the reduced pressure
  10. additionToluene was added to the residue, and toluene
  11. customwas removed by evaporation under the reduced pressure
  12. filtrationThe resultant crystal was collected by filtration
  13. washwas washed with toluene
  14. customwas then dried under the reduced pressure

Sources & evidence

ORD record
ord-21d90979bd1743faa9ebd2cb8c36d8d7
Source dataset
uspto-grants-2007_07
Patent number
US07238719B2

Reaction notes

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