Hydrochloric Acid → 2-(3-Oxo-4-propylcyclohexyl)-malonic acid diethyl ester

HRID 349110Notes

Reaction equation

HRID 349110 reaction equation
[C:1]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].[CH2:12]([C:15]1[C:16](=[O:21])[CH2:17][CH2:18][CH2:19][CH:20]=1)[CH2:13][CH3:14].Cl>C(O)C.[Na]>[CH2:10]([O:9][C:1](=[O:8])[CH:2]([CH:18]1[CH2:19][CH2:20][CH:15]([CH2:12][CH2:13][CH3:14])[C:16](=[O:21])[CH2:17]1)[C:3]([O:5][CH2:6][CH3:7])=[O:4])[CH3:11]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 7761Diethyl MalonateHCID 109096372-Propylcyclohex-2-en-1-one

Product 1

HCID 574874362-(3-Oxo-4-propylcyclohexyl)-malonic acid diethyl esterYield 78.3%

Reagents, catalysts & solvents 2

HCID 5360545SodiumCatalystHCID 702EthanolSolvent2×

Procedure

A solution of sodium metal (30 mg, 1.30 mmol) in absolute ethanol (4.0 mL) was stirred at −10° C. for 0.5 h. Diethyl malonate (3.5 mL, 23 mmol) was added at −10° C. followed by addition of a solution of 2-propylcyclohexenone (3.0 g, 21.7 mmol) in absolute ethanol (3.0 mL). The reaction mixture was stirred an additional 12 h at room temperature. The reaction mixture was acidified to pH 3 with 10% hydrochloric acid and then extracted several times with diethyl ether. The combined ether extracts were washed with water, and saturated sodium chloride, dried (sodium sulfate), filtered, and concentrated under reduced pressure to yield a yellow oil. Purification by flash column chromatography (silica, 83:17 hexanes/ethyl acetate) gave 2-(3-oxo-4-propyl-cyclohexyl)-malonic acid diethyl ester (5.07 g): 1H NMR (300 MHz, CDCl3) δ 4.21 (q, J=7 Hz, 2H), 4.20 (q, J=7 Hz, 2H), 3.30 (s, 0.5H), 3.28 (s, 0.5H), 2.67–1.55 (m, 8H), 1.43–1.11 (m, 10H), 0.90 (t, J=7 Hz, 1.5H), 0.90 (t, J=7.0 Hz, 1.5H).

Workup

  1. extractionextracted several times with diethyl ether
  2. washThe combined ether extracts were washed with water, and saturated sodium chloride
  3. dry with materialdried (sodium sulfate)
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customto yield a yellow oil
  7. customPurification by flash column chromatography (silica, 83:17 hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-99a701640f1d4d44b8a0822c8fcd89cb
Source dataset
uspto-grants-2007_02
Patent number
US07176242B2

Reaction notes

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