Diethyl Malonate → 5-(5-Chloro-2-methylphenyl)cyclohexane-1,3-dione

HRID 1700722Notes

Reaction equation

HRID 1700722 reaction equation
[O-:1][CH2:2][CH3:3].[Na+].C(OCC)(=O)CC(OCC)=O.[Cl:16][C:17]1[CH:18]=[CH:19][C:20]([CH3:28])=[C:21]([CH:23]=[CH:24][C:25](=[O:27])[CH3:26])[CH:22]=1>C(O)C>[Cl:16][C:17]1[CH:18]=[CH:19][C:20]([CH3:28])=[C:21]([CH:23]2[CH2:3][C:2](=[O:1])[CH2:26][C:25](=[O:27])[CH2:24]2)[CH:22]=1

Participants

5

Reactant 3

HCID 7761Diethyl MalonateHCID 2723922Sodium ethoxideHCID 536366744-(5-Chloro-2-methylphenyl)-3-buten-2-one

Product 1

HCID 183174935-(5-Chloro-2-methylphenyl)cyclohexane-1,3-dione

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a solution of 20% sodium ethoxide in ethanol (9.5 g) was added at room temperature diethyl malonate (4.5 g) and then added little by little 4-(5-chloro-2-methylphenyl)-3-buten-2-one (5.5 g). The mixture was stirred at room temperature for 30 minutes, refluxed for 2 hours and cooled. The solvent was evaporated, and to the residue was added water. The aqueous layer was washed with ethyl acetate and concentrated. To the residue was added 2M sodium hydroxide (15 ml), and the mixture was refluxed for 2 hours and cooled. To the mixture was added 2.5M sulfuric acid (15 ml) for 15 minutes, and the mixture was refluxed for 30 minutes and cooled. Precipitated crystals were filtered and washed with water and isopropylether to give 5-(5-chloro-2-methylphenyl)cyclohexane-1,3-dione (2.9 g) as colorless crystals.

Workup

  1. temperaturerefluxed for 2 hours
  2. temperaturecooled
  3. customThe solvent was evaporated
  4. additionto the residue was added water
  5. washThe aqueous layer was washed with ethyl acetate
  6. concentrationconcentrated
  7. additionTo the residue was added 2M sodium hydroxide (15 ml)
  8. temperaturethe mixture was refluxed for 2 hours
  9. temperaturecooled
  10. additionTo the mixture was added 2.5M sulfuric acid (15 ml) for 15 minutes
  11. temperaturethe mixture was refluxed for 30 minutes
  12. temperaturecooled
  13. customPrecipitated crystals
  14. filtrationwere filtered
  15. washwashed with water and isopropylether

Sources & evidence

ORD record
ord-76807d30803b4e7190c431794976d4bd
Source dataset
uspto-grants-2002_02
Patent number
US06350749B1

Reaction notes

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