Hydrochloric Acid → 3-Acetyltricyclo[3.3.1.03,7]nonane-1-carboxylic acid

HRID 1015505Notes

Reaction equation

HRID 1015505 reaction equation
C1([C:7]23[CH2:15][CH:11]4C[CH:13]([CH2:14]2)[C:9]([C:16](=[O:18])C)([CH2:10]4)[CH2:8]3)C=CC=CC=1.C(Cl)(Cl)(Cl)Cl.I([O-])(=O)(=O)=[O:25].[Na+].Cl.C([O:34][CH:35]([CH3:37])[CH3:36])(C)C>O.[Ru](Cl)(Cl)Cl.O.C(#N)C>[C:35]([C:36]12[CH2:14][CH:7]3[CH2:8][C:9]([C:16]([OH:18])=[O:25])([CH2:10][CH:11]1[CH2:15]3)[CH2:13]2)(=[O:34])[CH3:37]

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 5943Carbon TetrachlorideHCID 7914Diisopropyl EtherHCID 23667635Sodium periodateHCID 593749561-(2-Phenylhexahydro-2,5-methanopentalen-3a-yl)ethanone

Product 1

HCID 593749503-Acetyltricyclo[3.3.1.03,7]nonane-1-carboxylic acidYield 57%

Reagents, catalysts & solvents 3

HCID 6093376Ruthenium trichloride hydrateCatalystHCID 962WaterSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
0 °C

Procedure

To a stirred mixture of 1-(1-Phenyltricyclo[3.3.1.03,7]non-3-yl)ethanone (8.0 g, 33.3 mmol) as obtained in preparation 1, carbontetrachloride (66 mL), acetonitrile (66 mL) and water (100 mL), cooled to 0° C., was added sodiumperiodate (31.9 g, 149 mmol) and ruthenium (III) chloride hydrate (0.44 g, 1.7 mmol). The reaction mixture was gradually warmed to ambient temperature and stirred for 2 h. The reaction mixture was diluted with diisopropylether (100 mL) and stirred for 15 minutes to precipitate black RuO2. The reaction mixture was then filtered through a pad of celite and the organic layer was extracted with 1N NaOH solution (3×25 mL). The organic layer was dried over Na2SO4 and the solvent was evaporated under vacuum to obtain unreacted starting material (3.04 g 12.67 mmol). The aqueous layer was acidified with conc. HCl and extracted with EtOAc. The combined organic layers were washed with brine, dried over Na2SO4, and the solvent was removed under reduced pressure to obtain 3-acetyltricyclo[3.3.1.03,7]nonane-1-carboxylic acid (4.0 g) as off-white solid in 57% yield. M.R: 90-95.0° C. m/z (M+1) 209. IR cm−1 2935, 1694, 1413, 1357, 974, 746. 1H NMR (CDCl3) 300 MHz δ 2.77-2.73 (m, 1H), 2.54-2.48 (m, 1H), 2.44-2.34 (m, 1H), 2.20 (s, 3H), 2.18-2.09 (m, 1H), 7.38-7.19 (m, 5H), 2.86-2.80 (m, 1H), 2.59-2.50 (m, 1H), 2.32-2.25 (m, 1H), 2.23 (s, 3H), 2.18-2.09 (m, 1H), 2.06-1.74 (m, 7H), 1.73-1.61 (m, 1H). 13C NMR (CDCl3) 75 MHz δ 211.0, 181.3, 61.5, 50.3, 47.9, 45.9, 45.6, 42.6, 41.9, 36.8, 35.6, 26.4.

Workup

  1. temperatureThe reaction mixture was gradually warmed to ambient temperature
  2. stirringstirred for 15 minutes
  3. customto precipitate black RuO2
  4. filtrationThe reaction mixture was then filtered through a pad of celite
  5. extractionthe organic layer was extracted with 1N NaOH solution (3×25 mL)
  6. dry with materialThe organic layer was dried over Na2SO4
  7. customthe solvent was evaporated under vacuum
  8. customto obtain unreacted
  9. extractionextracted with EtOAc
  10. washThe combined organic layers were washed with brine
  11. dry with materialdried over Na2SO4
  12. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-6098350990f74f0eac58af9efef0eec4
Source dataset
uspto-grants-2011_07
Patent number
US07985759B2

Reaction notes

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