Diethyl Malonate → 5-(2H-1,3-Benzodioxol-5-yl)-3-hydroxycyclohex-2-en-1-one

HRID 1980791Notes

Reaction equation

HRID 1980791 reaction equation
C(OCC)(=O)[CH2:2][C:3](OCC)=[O:4].[Na].[CH2:13]1[O:21][C:20]2[CH:19]=[CH:18][C:17]([CH:22]=[CH:23][C:24](=[O:26])[CH3:25])=[CH:16][C:15]=2[O:14]1.[OH-].[K+]>C(O)C>[OH:4][C:3]1[CH2:2][CH:22]([C:17]2[CH:18]=[CH:19][C:20]3[O:21][CH2:13][O:14][C:15]=3[CH:16]=2)[CH2:23][C:24](=[O:26])[CH:25]=1

Participants

6

Reactant 4

HCID 7761Diethyl MalonateHCID 14797Potassium HydroxideHCID 184804-(1,3-Benzodioxol-5-yl)but-3-en-2-oneHCID 5360545Sodium

Product 1

HCID 139829245-(2H-1,3-Benzodioxol-5-yl)-3-hydroxycyclohex-2-en-1-one

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

Diethyl malonate (17.34 g) was added to a solution of sodium metal (2.35 g) in anhydrous absolute ethanol (40 ml). 1-(3,4-methylenedioxyphenyl)-but-1-en-3-one (20 g) was added to the solution and the volume of ethanol was made up to 80 ml. The mixture was heated under reflux with stirring for 2-4 hr. An aqueous solution of potassium hydroxide (25.0 g in 120 ml of water) was added and the mixture was heated under reflux for a further 6 hours. Subsequently, the ethanol was distilled off and the aqueous residue was acidified with dilute hydrochloric acid. After cooling to room temperature, the mixture was extracted with ethyl acetate and the organic phase was washed consecutively with water and an aqueous 10% sodium hydroxide solution. The basic extract was acidified with dilute aqueous hydrochloric acid and the resulting solution was extracted with ethyl acetate. The organic phase was washed with water, dried over anhydrous sodium sulfate, and the solvent was evaporated to give 3-hydroxy-5-(3,4-methylenedioxyphenyl)cyclohex-2-en-1-one as a crystalline solid, mp 181° C.

Workup

  1. temperatureThe mixture was heated
  2. temperatureunder reflux
  3. temperaturethe mixture was heated
  4. temperatureunder reflux for a further 6 hours
  5. distillationSubsequently, the ethanol was distilled off
  6. extractionthe mixture was extracted with ethyl acetate
  7. washthe organic phase was washed consecutively with water
  8. extractionThe basic extract
  9. extractionthe resulting solution was extracted with ethyl acetate
  10. washThe organic phase was washed with water
  11. dry with materialdried over anhydrous sodium sulfate
  12. customthe solvent was evaporated

Sources & evidence

ORD record
ord-136a4683b5fd49f6b63f339c98716a6f
Source dataset
uspto-grants-1985_04
Patent number
US04511391

Reaction notes

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