Ethyl Acetate → HCID 15672397, compound

HRID 2248240Notes

Reaction equation

HRID 2248240 reaction equation
Br[CH:2](Br)[C:3]1[CH:4]=[C:5]([C:13]([O:15][CH3:16])=[O:14])[C:6]([C:9]([O:11][CH3:12])=[O:10])=[N:7][CH:8]=1.C(OCC)(=[O:20])C>O1CCOCC1.O.[N+]([O-])([O-])=O.[Ag+]>[CH:2]([C:3]1[CH:4]=[C:5]([C:13]([O:15][CH3:16])=[O:14])[C:6]([C:9]([O:11][CH3:12])=[O:10])=[N:7][CH:8]=1)=[O:20]

Participants

6

Reactant 2

HCID 8857Ethyl AcetateHCID 15672391HCID 15672391, compound

Product 1

HCID 15672397HCID 15672397, compoundYield 85%

Reagents, catalysts & solvents 3

HCID 24470Silver NitrateCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

To a solution of dimethyl 5-dibromomethylpyridine-2,3-dicarboxylate (8.32 g, 0.0227 mol) in dioxane (60 mL) and water (20 mL) is added silver nitrate (7.85 g, 0.0476 mol). The resulting slurry is heated at reflux for 3 hours. The reaction mixture is cooled to room temperature, filtered through a pad of diatomaceous earth and the diatomaceous earth is rinsed with tetrahydrofuran. The filtrate is concentrated in vacuo to remove the dioxane and tetrahydrofuran. The resultant aqueous solution is made basic by the addition to saturated aqueous sodium bicarbonate (100 mL) and extracted with methylene dichloride. The combined extracts are dried over anhydrous magnesium sulfate and concentrated in vacuo to give a residue. Chromatography of said residue using silica gel and 33% ethyl acetate in hexanes as eluant yields the title compound as a white solid, (4.31 g, 85%) mp 75° C.-77° C., identified by IR and NMR spectral analyses.

Workup

  1. temperatureThe resulting slurry is heated
  2. temperatureat reflux for 3 hours
  3. filtrationfiltered through a pad of diatomaceous earth
  4. washthe diatomaceous earth is rinsed with tetrahydrofuran
  5. concentrationThe filtrate is concentrated in vacuo
  6. customto remove the dioxane and tetrahydrofuran
  7. additionThe resultant aqueous solution is made basic by the addition to saturated aqueous sodium bicarbonate (100 mL)
  8. extractionextracted with methylene dichloride
  9. dry with materialThe combined extracts are dried over anhydrous magnesium sulfate
  10. concentrationconcentrated in vacuo
  11. customto give a residue

Sources & evidence

ORD record
ord-acc96b05c7cd48fbb5a7c0a4d0c65da9
Source dataset
uspto-grants-1991_08
Patent number
US05039333

Reaction notes

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