Hydrochloric Acid → 1,3-Diethyl 2-(1-oxopropyl)propanedioate

HRID 1671332Notes

Reaction equation

HRID 1671332 reaction equation
[O-]CC.[Mg+2].[O-]CC.[C:8]([O:16][CH2:17][CH3:18])(=[O:15])[CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11].[C:19](Cl)(=[O:22])[CH2:20][CH3:21].Cl.C([O-])(O)=O.[Na+]>C1(C)C=CC=CC=1>[C:19]([CH:9]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[C:8]([O:16][CH2:17][CH3:18])=[O:15])(=[O:22])[CH2:20][CH3:21]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 7761Diethyl MalonateHCID 62324Propionyl chlorideHCID 164963Magnesium ethanolateHCID 516892Sodium Bicarbonate

Product 1

HCID 307201,3-Diethyl 2-(1-oxopropyl)propanedioate

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Conditions

Temperature
50 °C

Procedure

To a stirred suspension of magnesium ethoxide (3.56 g, 31.2 mmol) in anhydrous toluene (10 ml) at RT is added a solution of diethyl malonate (5 g, 31.2 mmol) in toluene (40 ml). The mixture is stirred at 50° C. for 2.5 hrs (until all the solid dissolved) then cooled to 8-10° C. (note: solidification occurs at 5° C.). To this solution is added slowly propionyl chloride (2.7 ml, 31.2 mmol). The reaction mixture is warmed to ambient temperature and stirring continues for 2 hrs. The reaction mixture is cooled to 5-10° C. and treated with 1M HCl (approx. 35 ml, 1.1 equiv.) to adjust the pH to approx. 1-3. The mixture is allowed to warm to RT and treated with sat. aq. NaHCO3 to give a pH of 6-7. The layers are separated and the organic layer is washed with brine, dried (Na2SO3) and concentrated in vacuo to afford the title compound as a viscous orange oil; 1H NMR (400 MHz, CDCl3) δ [13.45 (s) and 4.47 (s) combined 1H], 4.15-4.30 (4H, m), [2.66 (q, J 7.2) and 2.48 (q, J 7.5) combined 2H], 1.30 (6H, m), [1.21 (t, J 7.5) and 1.12 (t, J 7.2) combined 3H].

Workup

  1. dissolutiondissolved)
  2. temperaturethen cooled to 8-10° C. (note: solidification occurs at 5° C.)
  3. temperatureThe reaction mixture is warmed to ambient temperature
  4. stirringstirring
  5. waitcontinues for 2 hrs
  6. temperatureThe reaction mixture is cooled to 5-10° C.
  7. temperatureto warm to RT
  8. customto give a pH of 6-7
  9. customThe layers are separated
  10. washthe organic layer is washed with brine
  11. dry with materialdried (Na2SO3)
  12. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-e7728efe5eb74619babc3dda6c3b6838
Source dataset
uspto-grants-2011_08
Patent number
US07994203B2

Reaction notes

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