Diethyl Malonate → 3'-Acetyl-5-hydroxy-2',4',6'-trimethyl-1,6-dihydro[1,1'-biphenyl]-3(2H)-one

HRID 978990Notes

Reaction equation

HRID 978990 reaction equation
C(OCC)(=O)[CH2:2][C:3](OCC)=[O:4].[Na].[C:13]([C:16]1[C:17]([CH3:29])=[C:18]([CH:24]=[CH:25][C:26](=[O:28])[CH3:27])[C:19]([CH3:23])=[CH:20][C:21]=1[CH3:22])(=[O:15])[CH3:14].[OH-].[Na+]>C(O)C.O>[C:13]([C:16]1[C:17]([CH3:29])=[C:18]([CH:24]2[CH2:25][C:26](=[O:28])[CH:27]=[C:3]([OH:4])[CH2:2]2)[C:19]([CH3:23])=[CH:20][C:21]=1[CH3:22])(=[O:15])[CH3:14]

Participants

7

Reactant 4

HCID 7761Diethyl MalonateHCID 14798Sodium HydroxideHCID 5360545SodiumHCID 544302651-(3-Acetyl-2,4,6-trimethylphenyl)but-1-en-3-one

Product 1

HCID 212949533'-Acetyl-5-hydroxy-2',4',6'-trimethyl-1,6-dihydro[1,1'-biphenyl]-3(2H)-oneYield 84%

Reagents, catalysts & solvents 2

HCID 702EthanolSolvent2×HCID 962WaterSolvent

Procedure

Diethyl malonate (10.16 g; 69 mmole) was added to a solution of sodium metal (1.46 g; 63 mmole) in anhydrous absolute ethanol (50 ml) and the mixture was heated to reflux temperature. A mixture of 1-(3-acetyl-2,4,6-trimethylphenyl)but-1-en-3-one (14.60 g; 63 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. A 30% aqueous solution of sodium hydroxide (100 ml) 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 washed with diethyl ether (2×100 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. The product, 5-(3-acetyl-2,4,6-trimethylphenyl)-3-hydroxycyclohex-2-en-1-one (13.55 g; 84.0%), was obtained as a glassy solid. Proton magnetic resonance spectrum (D6 -dimethylsulfoxide; δ in ppm): 2.20 (3H, s); 2.24 (3H, s); 2.38 (3H, s); 2.45 (3H, s); 2.45-3.40 (4H, m); 3.90 (1H, m); 5.25 (1H, s); 6.85 (1H, s); 11.0 (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. washthe aqueous mixture was washed with diethyl ether (2×100 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

Sources & evidence

ORD record
ord-bac829a7f85c4e6d8b59b0ba6ddd58d8
Source dataset
uspto-grants-1987_05
Patent number
US04666510

Reaction notes

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