AcOH AcOAc → HCID 23366109, compound

HRID 1081213Notes

Reaction equation

HRID 1081213 reaction equation
[CH3:1][N:2]1[CH:7]2[CH2:8][CH2:9][CH:3]1[C:4](=[N:11]O)[C:5](=[O:10])[CH2:6]2.[C:13](O)(=[O:15])[CH3:14].C(OC(=O)C)(=O)C>[Ni]>[C:13]([NH:11][CH:4]1[C:5](=[O:10])[CH2:6][CH:7]2[N:2]([CH3:1])[CH:3]1[CH2:9][CH2:8]2)(=[O:15])[CH3:14]

Participants

4

Reactant 2

HCID 21895370AcOH AcOAcHCID 85194979HCID 85194979, compound

Product 1

HCID 23366109HCID 23366109, compoundYield 49%

Reagents, catalysts & solvents 1

HCID 935NickelCatalyst

Procedure

A solution of 8-methyl-8-azabicyclo[3.2.1]octane-2,3-dione-2-oxime (0.93 g, 5.5 mmol) in acetic acid/acetic anhydride (4:1, 40 mL) in a Parr bottle was treated with Raney nickel (Aldrich, 1/2 tsp.), then subjected to hydrogenation in a Parr apparatus at 45-50 psi for 5 h The solution was carefully evacuated of hydrogen, filtered through Celite® (wash filter cake carefully with methanol), and the filtrate was concentrated in vacuo. The residue was taken up in toluene and reconcentrated to remove most of the acetic acid. This residue was taken up in saturated sodium carbonate (40 mL), then treated with 15% sodium hydroxide (2 mL) and extracted with methylene chloride (3×50 mL) containing some 2-propanol. The combined extracts were dried (Na2SO4), concentrated in vacuo, and chromatographed on silica gel (eluted with 1:1 ethyl acetate/methanol) to afford a white solid, which contained some silica gel. This was removed by dissolving the product in warm ethyl acetate, filtering, and concentration in vacuo to afford 2-acetamido-8-methyl-8-azabicyclo[3.2.1]octan-3-one (0.53 g, 49%) as a white solid.

Workup

  1. customThe solution was carefully evacuated of hydrogen
  2. filtrationfiltered through Celite® (
  3. washwash
  4. filtrationfilter cake carefully with methanol), and the filtrate
  5. concentrationwas concentrated in vacuo
  6. customto remove most of the acetic acid
  7. additiontreated with 15% sodium hydroxide (2 mL)
  8. extractionextracted with methylene chloride (3×50 mL)
  9. additioncontaining some 2-propanol
  10. dry with materialThe combined extracts were dried (Na2SO4)
  11. concentrationconcentrated in vacuo
  12. customchromatographed on silica gel (eluted with 1:1 ethyl acetate/methanol)
  13. customto afford a white solid, which
  14. customThis was removed
  15. dissolutionby dissolving the product in warm ethyl acetate
  16. filtrationfiltering
  17. concentrationconcentration in vacuo

Sources & evidence

ORD record
ord-b5daaa2aa3604d87a5c58cba8f22c9cd
Source dataset
uspto-grants-1996_12
Patent number
US05583221

Reaction notes

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