Diethyl isopropylmalonate → HCID 54462554, compound

HRID 1085658Notes

Reaction equation

HRID 1085658 reaction equation
[CH:1]1([CH2:7][CH:8](O)[CH:9]=[CH2:10])[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.C([O:14][C:15](=[O:25])[CH:16]([CH:22]([CH3:24])[CH3:23])C(OCC)=O)C>CCO.CCO.CCO.CCO.[Ti]>[CH:1]1([CH2:7][CH:8]=[CH:9][CH2:10][CH:16]([CH:22]([CH3:24])[CH3:23])[C:15]([OH:25])=[O:14])[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1

Participants

4

Reactant 2

HCID 12966Diethyl isopropylmalonateHCID 14261103HCID 14261103, compound

Product 1

HCID 54462554HCID 54462554, compound

Reagents, catalysts & solvents 1

HCID 2724286Titanium(IV)ethoxideCatalyst

Procedure

23.15 g (0.15 mol) of 1-cyclohexyl-3-buten-2-ol, 6.85 g (0.03 mol) of tetraethyl orthotitanate and 61.5 ml (0.30 mol) of isopropylmalonic acid diethyl ester are placed in a flask and stirred for 1 hour at 170° and then for 24 hours at 200°. Excess malonic acid ester is distilled off at 20 mbar, and the residue is dissolved in 120 ml of ethanol and, after the addition of 120 ml of 6N KOH, stirred under reflux for 7 hours. After cooling, the reaction mixture is filtered and the filtrate is extensively concentrated by evaporation in a rotary evaporator. The aqueous phase is extracted once with ether, acidified to pH 1 with 6N HCl while cooling with ice and then extracted three times with ether. The combined organic phases are washed with brine, dried with MgSO4 and concentrated by evaporation in a rotary evaporator. The residue is distilled at 137°-140°/-0.025 mbar.

Workup

  1. waitfor 24 hours at 200°
  2. distillationExcess malonic acid ester is distilled off at 20 mbar
  3. dissolutionthe residue is dissolved in 120 ml of ethanol
  4. additionafter the addition of 120 ml of 6N KOH
  5. stirringstirred
  6. temperatureunder reflux for 7 hours
  7. temperatureAfter cooling
  8. filtrationthe reaction mixture is filtered
  9. concentrationthe filtrate is extensively concentrated by evaporation in a rotary evaporator
  10. extractionThe aqueous phase is extracted once with ether
  11. temperaturewhile cooling with ice
  12. extractionextracted three times with ether
  13. washThe combined organic phases are washed with brine
  14. dry with materialdried with MgSO4
  15. concentrationconcentrated by evaporation in a rotary evaporator
  16. distillationThe residue is distilled at 137°-140°/-0.025 mbar

Sources & evidence

ORD record
ord-477064885c0545bb855f3c73fa9ef930
Source dataset
uspto-grants-1991_04
Patent number
US05010189

Reaction notes

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