Acetic Acid → 6,7,8-Trihydroxy-1-(hydroxymethyl)-2-oxa-4-azabicyclo[3.3.1]nonan-3-one

HRID 543532Notes

Reaction equation

HRID 543532 reaction equation
[BH4-].[Na+].Br[CH:4]1[CH:9]2[CH:10]([OH:15])[CH:11]([OH:14])[CH:12]([OH:13])[C:5]1([CH2:17][OH:18])[O:6][C:7](=[O:16])[NH:8]2.C(O)(=O)C>O>[OH:15][CH:10]1[CH:11]([OH:14])[CH:12]([OH:13])[C:5]2([CH2:17][OH:18])[CH2:4][CH:9]1[NH:8][C:7](=[O:16])[O:6]2

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 4311764Sodium borohydrideHCID 13174066HCID 13174066, compound

Product 1

HCID 131740726,7,8-Trihydroxy-1-(hydroxymethyl)-2-oxa-4-azabicyclo[3.3.1]nonan-3-oneYield 87%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

Sodium borohydride (55 g) is added by portions to a solution of 9-bromo-6,7,8-trihydroxy-1-hydroxymethyl-3-oxo-2-oxa-4-azabicyclo[3.3.1]nonane (100 g) in water (1.3 l) at 25°-30° C. with stirring. After stirring for 2 hours at the same temperature, the reaction mixture is adjusted to pH 6-7 with acetic acid and concentrated to about 800 ml under reduced pressure. The concentrate is chromatographed on a column of activated carbon (4.8 l), and the column is washed with water (5 l) and eluted with 50% aqueous methanol. The eluate is concentrated under reduced pressure. Methanol (350 ml) is added to the residue and refluxed for 10-20 minutes to remove a methanol soluble by-product. The mixture is allowed to stand in a refrigerator overnight, and the resulting crystals are collected by filtration, followed by washing with cold methanol and drying in a desiccator under reduced pressure to give 6,7,8-trihydroxy-1-hydroxymethyl-3-oxo-2-oxa-4-azabicyclo[3.3.1]nonane (64 g).

Workup

  1. stirringAfter stirring for 2 hours at the same temperature
  2. concentrationconcentrated to about 800 ml under reduced pressure
  3. customThe concentrate is chromatographed on a column of activated carbon (4.8 l)
  4. washthe column is washed with water (5 l)
  5. washeluted with 50% aqueous methanol
  6. concentrationThe eluate is concentrated under reduced pressure
  7. additionMethanol (350 ml) is added to the residue
  8. temperaturerefluxed for 10-20 minutes
  9. customto remove a methanol soluble by-product
  10. customto stand in a refrigerator overnight
  11. filtrationthe resulting crystals are collected by filtration
  12. washby washing with cold methanol
  13. customdrying in a desiccator under reduced pressure

Sources & evidence

ORD record
ord-7811d1d3ae564fc8a5f5ad27e12fec5b
Source dataset
uspto-grants-1984_05
Patent number
US04446319

Reaction notes

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