Dimethyl Carbonate → 1-Oxo-spiro[5.5]undecane-2-carboxylic acid methyl ester

HRID 2070581

Reaction equation

HRID 2070581 reaction equation
[H-].[Na+].CC(C)([O-])C.[K+].[C:9](=[O:14])([O:12][CH3:13])OC.[C:15]1(=[O:26])[C:20]2([CH2:25][CH2:24][CH2:23][CH2:22][CH2:21]2)[CH2:19][CH2:18][CH2:17][CH2:16]1>O1CCCC1.[Cl-].[Na+].O.C(O)(=O)C>[CH3:13][O:12][C:9]([CH:16]1[CH2:17][CH2:18][CH2:19][C:20]2([CH2:21][CH2:22][CH2:23][CH2:24][CH2:25]2)[C:15]1=[O:26])=[O:14]

Participants

8

Reactant 4

HCID 12021Dimethyl CarbonateHCID 24758Sodium hydrideHCID 573924Spiro(5.5)undecan-1-oneHCID 23665647Potassium tert-butoxide

Product 1

HCID 157014041-Oxo-spiro[5.5]undecane-2-carboxylic acid methyl ester

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolvent2×HCID 57417360Sodium chloride; waterSolvent

Procedure

To a suspension of 60% sodium hydride (5.7 g) and potassium tert-butoxide (1.6 g) in tetrahydrofuran (200 mL) was added dimethyl carbonate (9.6 mL) at room temperature while stirring. The reaction mixture was heated under reflux. To the reaction mixture was added dropwise a solution of spiro[5.5]undecan-1-one (11.85 g) obtained in Step 1 in tetrahydrofuran (40 mL) over 1 hour, followed by heating the reaction mixture under reflux for 2 hours. After ice-cooling, acetic acid (14.6 mL) was added dropwise to the reaction mixture. Then, the reaction mixture was poured into saturated brine, followed by extraction with ethyl acetate. 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)=1:15) to give 1-oxo-spiro[5.5]undecane-2-carboxylic acid methyl ester (13.02 g).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureunder reflux
  3. temperatureby heating the reaction mixture
  4. temperatureunder reflux for 2 hours
  5. temperatureAfter ice-cooling
  6. extractionfollowed by extraction with ethyl acetate
  7. washThe organic layer was washed with saturated brine
  8. customdried
  9. concentrationconcentrated
  10. customThe residue was purified by column chromatography on silica gel (ethyl acetate:hexane (volume ratio)=1:15)

Sources & evidence

ORD record
ord-65f5429401d14c5d9d02ae3beff46eda
Source dataset
uspto-grants-2012_10
Patent number
US08299296B2

Linked notes

Loading…