4-(2,4-dichlorophenyl)but-3-en-2-one → 5-(2,4-dichlorophenyl)cyclohexane-1,3-dione

HRID 1578087Notes

Reaction equation

HRID 1578087 reaction equation
[Na].C([C:4](CC)(C([O-])=O)[C:5]([O-])=[O:6])C.[Cl:13][C:14]1[CH:19]=[C:18]([Cl:20])[CH:17]=[CH:16][C:15]=1[CH:21]=[CH:22][C:23](=[O:25])[CH3:24]>C(O)C>[Cl:13][C:14]1[CH:19]=[C:18]([Cl:20])[CH:17]=[CH:16][C:15]=1[CH:21]1[CH2:4][C:5](=[O:6])[CH2:24][C:23](=[O:25])[CH2:22]1

Participants

5

Reactant 3

HCID 35189644-(2,4-dichlorophenyl)but-3-en-2-oneHCID 5360545SodiumHCID 69515632,2-Diethylpropanedioate

Product 1

HCID 5991285-(2,4-dichlorophenyl)cyclohexane-1,3-dione

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Conditions

Temperature
0 °C

Procedure

To a solution of 2.3 g of sodium in 200 ml of ethanol is added 15.7 g of diethylmalonate followed by a suspension of 20 g of 1-(2,4-dichlorophenyl)-1-butene-3-one in 100 ml ethanol. The mixture is heated under reflux for 2 hrs and then concentrated to dryness in vacuo. The solid is partitioned between 200 ml water and 200 ml ether. The ether layer is discarded and 20 ml 50% NaOH is added to the aqueous layer which is heated under reflux for 2 hrs. The mixture is filtered and the filtrate is made strongly acidic pH <2 with concentrated sulfuric acid. The mixture is heated on a steam bath for 2 hrs. The resulting solid is collected, pulverized and suspended in 500 ml of 10N sulfuric acid and heated on a steam bath for 2 hrs and cooled to 0° C. The solid is collected, washed with water and recrystallized from a mixture of dimethylformamide and ethyl acetate. Drying in vacuo at 80° C. for 6 hrs gives 5-(2,4-dichlorophenyl)cyclohexane-1,3dione; mp 192°-196° C.

Workup

  1. temperatureThe mixture is heated
  2. temperatureunder reflux for 2 hrs
  3. concentrationconcentrated to dryness in vacuo
  4. customThe solid is partitioned between 200 ml water and 200 ml ether
  5. addition20 ml 50% NaOH is added to the aqueous layer which
  6. temperatureis heated
  7. temperatureunder reflux for 2 hrs
  8. filtrationThe mixture is filtered
  9. temperatureThe mixture is heated on a steam bath for 2 hrs
  10. customThe resulting solid is collected
  11. temperatureheated on a steam bath for 2 hrs
  12. customThe solid is collected
  13. washwashed with water
  14. customrecrystallized from a mixture of dimethylformamide and ethyl acetate
  15. customDrying in vacuo at 80° C. for 6 hrs

Sources & evidence

ORD record
ord-60527b318a9f4f77a88210cd8de47ffc
Source dataset
uspto-grants-1981_09
Patent number
US04291034

Reaction notes

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