Methyl acetoacetate → 1-Hydroxybicyclo[3.3.1]nonan-3-one

HRID 1699740Notes

Reaction equation

HRID 1699740 reaction equation
[C:1]1(=O)[CH2:6][CH2:5]C[CH:3]=[CH:2]1.[C:8]([O:14]C)(=O)[CH2:9][C:10]([CH3:12])=[O:11].C[O-].[Na+].[OH-].[K+]>CO>[OH:11][C:10]12[CH2:12][CH:2]([CH2:1][CH2:6][CH2:5]1)[CH2:3][C:8](=[O:14])[CH2:9]2

Participants

6

Reactant 4

HCID 7757Methyl acetoacetateHCID 135942-Cyclohexen-1-oneHCID 14797Potassium HydroxideHCID 10942334Sodium Methoxide

Product 1

HCID 124262571-Hydroxybicyclo[3.3.1]nonan-3-oneYield 50.8%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

50.58 g of cyclohexenone and 72.95 g of methyl acetoacetate were measured and placed in a 1,000 ml flask. 300 ml of methanol was added to prepare the homogeneous solution. The solution was gradually mixed with 101.53 g of 28% sodium methoxide, and the mixture was refluxed in the flask equipped with a Dimroth condenser for 72 hours. The reaction solution was cooled, mixed with 100 ml of an aqueous solution containing 72.12 g of potassium hydroxide, and further refluxed for 13 hours. After the reaction was finished, the solvent was distilled away from the reaction solution under reduced pressure, and the residue was extracted with dichloromethane. The obtained organic layers were integrated, washed with a saturated aqueous solution of sodium chloride, and then dried over MgSO4. The solvent was distilled away under reduced pressure, and the residue was again dissolved in diethyl ether. The solution was reversibly extracted with water, and the obtained water layers were integrated and concentrated. The residue was recrystallized from diethyl ether to obtain the title compound as white crystals (41.19g, 50%).

Workup

  1. customplaced in a 1,000 ml flask
  2. customto prepare the homogeneous solution
  3. temperaturethe mixture was refluxed in the flask
  4. customequipped with a Dimroth condenser for 72 hours
  5. temperatureThe reaction solution was cooled
  6. temperaturefurther refluxed for 13 hours
  7. distillationthe solvent was distilled away from the reaction solution under reduced pressure
  8. extractionthe residue was extracted with dichloromethane
  9. washwashed with a saturated aqueous solution of sodium chloride
  10. dry with materialdried over MgSO4
  11. distillationThe solvent was distilled away under reduced pressure
  12. dissolutionthe residue was again dissolved in diethyl ether
  13. extractionThe solution was reversibly extracted with water
  14. concentrationconcentrated
  15. customThe residue was recrystallized from diethyl ether

Sources & evidence

ORD record
ord-406ceb94f7cb456eb3dc7a84ff2ef2ba
Source dataset
uspto-grants-2002_02
Patent number
US06348478B1

Reaction notes

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