Ethyl propiolate → Ethyl 1-[(3,4-dichlorophenyl)methyl]-1H-1,2,3-triazole-4-carboxylate

HRID 222367Notes

Reaction equation

HRID 222367 reaction equation
Br[CH2:2][C:3]1[CH:8]=[CH:7][C:6]([Cl:9])=[C:5]([Cl:10])[CH:4]=1.[N-:11]=[N+:12]=[N-:13].[Na+].[C:15]([O:19][CH2:20][CH3:21])(=[O:18])[C:16]#[CH:17]>CN(C=O)C>[Cl:10][C:5]1[CH:4]=[C:3]([CH2:2][N:11]2[CH:17]=[C:16]([C:15]([O:19][CH2:20][CH3:21])=[O:18])[N:13]=[N:12]2)[CH:8]=[CH:7][C:6]=1[Cl:9]

Participants

5

Reactant 3

HCID 12182Ethyl propiolate2×HCID 33557Sodium AzideHCID 6397264-(Bromomethyl)-1,2-dichlorobenzene

Product 1

HCID 59583668Ethyl 1-[(3,4-dichlorophenyl)methyl]-1H-1,2,3-triazole-4-carboxylateYield 60%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of 4-(bromomethyl)-1,2-dichlorobenzene (2 g, 8.3 mmol), in DMF (30 mL) was added sodium azide (0.65 g, 1.2 eq). The reaction was stirred at 80° C. for 3 hours. The solvent was then evaporated and the residue was dissolved in DCM and washed with water. The organic phase was dried over sodium sulphate and the solvent was evaporated. The crude azido compound was dissolved in ethanol (100 mL) and ethyl 2-propynoate (1 mL, 1.2 eq) was added. The reaction was stirred to reflux for 24 hours. The reaction was not completed and 0.3 mL of ethyl 2-propynoate was added and the reaction was stirred to refleux for more 24 hours. Ethanol was evaporated and the reaction was dissolved in DCM and washed with water, dried over sodium sulphate and concentrated in vacuo. Purification by flash chromatography eluting with DCM and DCM/MeOH 99/1 gave the title compound as a white solid (1.5 g, 60%). LC/MS: m/z 300 (M+H)+. Rt: 3.12 min.

Workup

  1. customThe solvent was then evaporated
  2. dissolutionthe residue was dissolved in DCM
  3. washwashed with water
  4. dry with materialThe organic phase was dried over sodium sulphate
  5. customthe solvent was evaporated
  6. dissolutionThe crude azido compound was dissolved in ethanol (100 mL)
  7. stirringThe reaction was stirred
  8. temperatureto reflux for 24 hours
  9. stirringthe reaction was stirred
  10. waitto refleux for more 24 hours
  11. customEthanol was evaporated
  12. dissolutionthe reaction was dissolved in DCM
  13. washwashed with water
  14. dry with materialdried over sodium sulphate
  15. concentrationconcentrated in vacuo
  16. customPurification by flash chromatography
  17. washeluting with DCM and DCM/MeOH 99/1

Sources & evidence

ORD record
ord-1972ebdbcb1a4c1197868c1601cc1280
Source dataset
uspto-grants-2012_06
Patent number
US08207204B2

Reaction notes

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