Ethanol → Diethyl methyl(3-oxocyclohexyl)propanedioate

HRID 903026Notes

Reaction equation

HRID 903026 reaction equation
[CH2:1]([OH:3])[CH3:2].[Na].C[CH2:6][CH:7]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[C:8](OC)=[O:9].[C:17]1(=[O:23])[CH2:22][CH2:21][CH2:20][CH:19]=[CH:18]1>C(O)(=O)C>[CH2:1]([O:3][C:8](=[O:9])[C:7]([CH3:6])([CH:19]1[CH2:20][CH2:21][CH2:22][C:17](=[O:23])[CH2:18]1)[C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH3:2]

Participants

6

Reactant 4

HCID 702Ethanol2×HCID 135942-Cyclohexen-1-oneHCID 5088009HCID 5088009, compoundHCID 5360545Sodium2×

Product 1

HCID 103616Diethyl methyl(3-oxocyclohexyl)propanedioate

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

Into a 2 l. 3-neck flask equipped with stirrer, condenser, thermometer, dropping funnel, and under a nitrogen atmosphere is placed 325 ml. of ethanol, and 2.5 g. of freshly cut sodium is added. When solution of the sodium is effected, 200 g. of diethyl methyl malonate is added in 5 minutes, and the mixture is stirred at room temperature for 1 hour. At the end of this period a solution of 100 g. of 2-cyclohexen-1-one in 130 ml. of ethanol is added through the dropping funnel over a period of 1 hour. The ensuing mild exothermic reaction causes the temperature to rise to 42°. Stirring is continued overnight at room temperature, after which 20 ml. of acetic acid is added, and the mixture is evaporated at reduced pressure. The residual oil is dissolved in 1.31 l. of ether, transferred to a separatory funnel and washed with three 230 ml. portions of water. The ether solution is dried over anhydrous sodium sulfate, filtered, and dried over anhydrous calcium sulfate. The ether is removed at reduced pressure and the residual oil distilled under high vacuum using a 6-inch Vigreux column. After removal of a forerun of 22.5 g., bp 49°-129°/0.14-0.21 mm, α-methyl-3-oxocyclohexane malonic acid diethyl ester distills at 129°-130°/0.2 mm; 211.5 g, 75.4% of theory.

Workup

  1. custom3-neck flask equipped with stirrer, condenser
  2. customThe ensuing mild exothermic reaction
  3. customto rise to 42°
  4. stirringStirring
  5. waitis continued overnight at room temperature
  6. customthe mixture is evaporated at reduced pressure
  7. dissolutionThe residual oil is dissolved in 1.31 l
  8. customof ether, transferred to a separatory funnel
  9. washwashed with three 230 ml
  10. dry with materialThe ether solution is dried over anhydrous sodium sulfate
  11. filtrationfiltered
  12. dry with materialdried over anhydrous calcium sulfate
  13. customThe ether is removed at reduced pressure
  14. distillationthe residual oil distilled under high vacuum
  15. customAfter removal of a forerun of 22.5 g
  16. distillation, bp 49°-129°/0.14-0.21 mm, α-methyl-3-oxocyclohexane malonic acid diethyl ester distills at 129°-130°/0.2 mm

Sources & evidence

ORD record
ord-5f89ae48a6ab408f8975c4d2dc1b8079
Source dataset
uspto-grants-1980_10
Patent number
US04226774

Reaction notes

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