Dimethyl Carbonate → Methyl 6-oxospiro[4.5]decane-7-carboxylate

HRID 2070546Notes

Reaction equation

HRID 2070546 reaction equation
[H-].[Na+].CC(C)([O-])C.[K+].[C:9](=[O:14])([O:12][CH3:13])OC.[CH2:15]1[C:19]2([CH2:24][CH2:23][CH2:22][CH2:21][C:20]2=[O:25])[CH2:18][CH2:17][CH2:16]1>O1CCCC1.C(OCC)(=O)C.O.C(O)(=O)C>[CH3:13][O:12][C:9]([CH:21]1[CH2:22][CH2:23][CH2:24][C:19]2([CH2:15][CH2:16][CH2:17][CH2:18]2)[C:20]1=[O:25])=[O:14]

Participants

9

Reactant 4

HCID 12021Dimethyl CarbonateHCID 24758Sodium hydrideHCID 290662Spiro(4.5)decan-6-oneHCID 23665647Potassium tert-butoxide

Product 1

HCID 57429459Methyl 6-oxospiro[4.5]decane-7-carboxylate

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To a suspension of 60% sodium hydride (4.59 g) and potassium tert-butoxide (1.52 g) in tetrahydrofuran (100 mL) was added dimethyl carbonate (7.89 mL) under argon atmosphere at 85° C. To this mixture was added dropwise a solution of spiro[4.5]decan-6-one (8.74 g) obtained in the same manner as in Step 1 in tetrahydrofuran (70 mL) over 1.5 hours. The reaction mixture was heated under reflux for 3 hours. After ice-cooling, to the reaction mixture were added successively acetic acid (7.3 mL), water (85 mL) and ethyl acetate (175 mL), followed by separation of the organic layer. The organic layer was washed with saturated brine, dried and concentrated. The residue was purified by column chromatography on silica gel (ethyl acetate:hexane (volume ratio)=1:100 to 1:90) to give 6-oxo-spiro[4.5]decane-7-carboxylic acid methyl ester (9.99 g).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureunder reflux for 3 hours
  3. temperatureAfter ice-cooling, to the reaction mixture
  4. customfollowed by separation of the organic layer
  5. washThe organic layer was washed with saturated brine
  6. customdried
  7. concentrationconcentrated
  8. customThe residue was purified by column chromatography on silica gel (ethyl acetate:hexane (volume ratio)=1:100 to 1:90)

Sources & evidence

ORD record
ord-31b4eb60bb534bb0a782e5ec46040602
Source dataset
uspto-grants-2012_10
Patent number
US08299296B2

Reaction notes

Loading…