7-Acetoxybicyclo[4,3,0]nonan-3-one → 6-Acetoxy-2-carboxybicyclo[3,3,0]octane

HRID 462783Notes

Reaction equation

HRID 462783 reaction equation
[OH2:1].O.O.[N+]([O-])(O)=O.[C:8]([O:11][CH:12]1[CH2:20][CH2:19][CH:18]2[CH:13]1[CH2:14][CH2:15][C:16](=[O:21])[CH2:17]2)(=[O:10])[CH3:9]>C(O)(=O)C>[C:8]([O:11][CH:12]1[CH2:20][CH2:19][CH:18]2[CH:13]1[CH2:14][CH2:15][CH:17]2[C:16]([OH:21])=[O:1])(=[O:10])[CH3:9]

Participants

4

Reactant 2

HCID 132410007-Acetoxybicyclo[4,3,0]nonan-3-oneHCID 21743480Nitric acid--water (1/3)

Product 1

HCID 132410016-Acetoxy-2-carboxybicyclo[3,3,0]octaneYield 12.2%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

Thallic nitrate trihydrate (133 g) was added to a stirred solution of 7-acetoxybicyclo[4,3,0]nonan-3-one (57 g; prepared as described in Reference Example 4) in glacial acetic acid (290 ml). After 30 minutes the resulting solid was filtered off and the filtrate was heated at reflux for 30 minutes. The acetic acid was distilled off under reduced pressure and the residue was neutralised by treatment with aqueous sodium hydroxide solution to pH 5 and then with aqueous sodium bicarbonate solution to neutral. The resulting solution was washed with diethyl ether, and then it was acidified by treatment with concentrated hydrochloric acid and extracted with chloroform. The combined chloroform extracts were washed with saturated aqueous sodium chloride solution, then dried over magnesium sulphate, and concentrated under reduced pressure. The residue was purified by medium pressure, short column chromatography on silica gel, eluting with a mixture of ethyl acetate, hexane, and acetic acid (45:55:1 by volume), to give 6-acetoxy-2-carboxybicyclo[3,3,0]octane (7.55 g), predominantly in the 2β-configuration.

Workup

  1. filtrationAfter 30 minutes the resulting solid was filtered off
  2. temperaturethe filtrate was heated
  3. temperatureat reflux for 30 minutes
  4. distillationThe acetic acid was distilled off under reduced pressure
  5. washThe resulting solution was washed with diethyl ether
  6. extractionextracted with chloroform
  7. washThe combined chloroform extracts were washed with saturated aqueous sodium chloride solution
  8. dry with materialdried over magnesium sulphate
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was purified by medium pressure, short column chromatography on silica gel
  11. washeluting with a mixture of ethyl acetate, hexane, and acetic acid (45:55:1 by volume)

Sources & evidence

ORD record
ord-35d27016b26d4e56aeae667dc362ebe7
Source dataset
uspto-grants-1985_05
Patent number
US04517202

Reaction notes

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