Diethyl Malonate → 3-Hydroxy-5-mesitylcyclohex-2-en-1-one

HRID 35760Notes

Reaction equation

HRID 35760 reaction equation
C(OCC)(=O)[CH2:2][C:3](OCC)=[O:4].[Na].[CH3:13][C:14]1[CH:19]=[C:18]([CH3:20])[CH:17]=[C:16]([CH3:21])[C:15]=1[CH:22]=[CH:23][C:24](=[O:26])[CH3:25].[OH-].[Na+]>C(O)C.O>[OH:26][C:24]1[CH2:23][CH:22]([C:15]2[C:16]([CH3:21])=[CH:17][C:18]([CH3:20])=[CH:19][C:14]=2[CH3:13])[CH2:2][C:3](=[O:4])[CH:25]=1

Participants

7

Reactant 4

HCID 7761Diethyl MalonateHCID 14798Sodium HydroxideHCID 40530234-(2,4,6-Trimethylphenyl)but-3-en-2-oneHCID 5360545Sodium

Product 1

HCID 137985663-Hydroxy-5-mesitylcyclohex-2-en-1-one

Reagents, catalysts & solvents 2

HCID 702EthanolSolvent2×HCID 962WaterSolvent

Procedure

Diethyl malonate (10.1 g; 60 mmole) was added to a solution of sodium metal (1.4 g; 60 mmole) in anhydrous absolute ethanol (50 ml) and the mixture was heated to reflux temperature. A mixture of 1-(2,4,6-trimethylphenyl)but-1-en-3-one (11.4 g; 61 mmole) in anhydrous absolute ethanol (50 ml) was added over a period of 2 minutes and the mixture was heated under reflux for a period of 2 hours. An aqueous solution of sodium hydroxide (7.3 g; 180 mmole in 100 ml of water) was added and the mixture was heated under reflux for a further 41/2 hours. The solution was poured into water (200 ml) and the aqueous mixture was extracted twice with ethyl acetate (100 ml). The aqueous phase was acidified with concentrated hydrochloric acid and warmed gently until the evolution of carbon dioxide ceased. The aqueous mixture was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and the solvent was removed by evaporation under reduced pressure using a rotary evaporator. The product, 3-hydroxy-5-mesitylcyclohex-2-en-1-one, was obtained as a pale yellow solid (10.9 g; 77.4%), mp 165° C. Proton magnetic resonance spectrum (dimethylsulfoxide; δ in ppm): 2.0-4.1 (14H, m); 5.2 (1H, s); 6.8 (2H, s); 11.2 (1H, br.s).

Workup

  1. temperaturethe mixture was heated
  2. temperatureto reflux temperature
  3. additionwas added over a period of 2 minutes
  4. temperaturethe mixture was heated
  5. temperatureunder reflux for a period of 2 hours
  6. temperaturethe mixture was heated
  7. temperatureunder reflux for a further 41/2 hours
  8. extractionthe aqueous mixture was extracted twice with ethyl acetate (100 ml)
  9. temperaturewarmed gently until the evolution of carbon dioxide
  10. extractionThe aqueous mixture was extracted with ethyl acetate
  11. dry with materialdried over anhydrous sodium sulfate
  12. customthe solvent was removed by evaporation under reduced pressure
  13. customa rotary evaporator

Sources & evidence

ORD record
ord-7e4825c453c444408c20b24f6f701213
Source dataset
uspto-grants-1988_08
Patent number
US04767879

Reaction notes

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