Methyl propiolate → Methyl 1-[(6-bromopyridin-2-yl)methyl]-1H-1,2,3-triazole-4-carboxylate

HRID 386040Notes

Reaction equation

HRID 386040 reaction equation
[C:1]([O:5][CH3:6])(=[O:4])[C:2]#[CH:3].[N:7]([CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[C:13]([Br:17])[N:12]=1)=[N+:8]=[N-:9].O=C1O[C@H]([C@H](CO)O)C([O-])=C1O.[Na+]>CC(O)(C)C.O.C([O-])(O)=O.[Na+]>[Br:17][C:13]1[N:12]=[C:11]([CH2:10][N:7]2[CH:3]=[C:2]([C:1]([O:5][CH3:6])=[O:4])[N:9]=[N:8]2)[CH:16]=[CH:15][CH:14]=1

Participants

7

Reactant 3

HCID 13536Methyl propiolateHCID 23667548Sodium AscorbateHCID 453574032-(Azidomethyl)-6-bromopyridine

Product 1

HCID 58335253Methyl 1-[(6-bromopyridin-2-yl)methyl]-1H-1,2,3-triazole-4-carboxylate

Reagents, catalysts & solvents 3

HCID 962WaterSolvent3×HCID 6386tert-ButanolSolventHCID 516892Sodium BicarbonateSolvent

Procedure

Methyl propiolate (641 μL, 7.63 mmol) and 2-(azidomethyl)-6-bromopyridine (1.25 g, 5.87 mmol) were combined in t-BuOH (9.0 mL) and water (5.0 mL). A solution of CuSO4.5H2O (73 mg, 0.29 mmol) in water (2.0 mL) was added, followed by sodium ascorbate (232 mg, 1.17 mmol) in water (2.0 mL). The reaction was stirred at room temperature for 18 h, during which time it became a yellow suspension. The suspension was diluted with saturated NaHCO3 and extracted with EtOAc (3×). The combined organic layers were washed with brine, dried (MgSO4), filtered, and concentrated under reduced pressure. The crude solid was purified by flash chromatography (40-100% EtOAc/hexanes) to afford the title compound as a colorless solid.

Workup

  1. extractionextracted with EtOAc (3×)
  2. washThe combined organic layers were washed with brine
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customThe crude solid was purified by flash chromatography (40-100% EtOAc/hexanes)

Sources & evidence

ORD record
ord-77188be22dc445c88ffeda7909befadf
Source dataset
uspto-grants-2013_02
Patent number
US08367706B2

Reaction notes

Loading…