Hydrochloric Acid → Ethyl 4-cyclopropyl-2,4-dioxobutanoate

HRID 476036Notes

Reaction equation

HRID 476036 reaction equation
[Na].[CH:2]1([C:5](=[O:7])[CH3:6])[CH2:4][CH2:3]1.[C:8](OCC)(=[O:14])[C:9]([O:11][CH2:12][CH3:13])=[O:10].Cl>C(O)C.O>[CH:2]1([C:5](=[O:7])[CH2:6][C:8](=[O:14])[C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH2:4][CH2:3]1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 7268Diethyl OxalateHCID 13004Cyclopropyl methyl ketoneHCID 5360545Sodium

Product 1

HCID 16779961Ethyl 4-cyclopropyl-2,4-dioxobutanoate

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Procedure

Sodium metal (2.411 g, 105 mmol) was dissolved in ethanol (50 mL). The solution was heated to reflux followed by addition of a mixture of 1-cyclopropylethanone (8.4 g, 100 mmol) and diethyl oxalate (14.59 g, 100 mmol) dropwise over 30 minutes. The reaction mixture was heated at reflux for an additional 2 h, and then allowed to cool to room temperature over a 2 d period. The contents were diluted with water (200 mL) and acidified by dropwise addition of 6N HCl. The contents were extracted with EtOAc (3×75 mL), washed with water, brine, dried over MgSO4, filtered, and concentrated in vacuo. The final product was collected as 14.3 g (74%). LCMS E-S (M+H)=184.8 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.03 (d, J=7.83 Hz, 2H) 1.13-1.19 (m, 2H) 1.31 (t, J=7.07 Hz, 3H) 1.81-1.90 (m, 1H) 4.29 (q, J=7.16 Hz, 2H) 6.43 (s, 1H).

Workup

  1. temperatureThe solution was heated
  2. temperatureto reflux
  3. temperatureThe reaction mixture was heated
  4. temperatureat reflux for an additional 2 h
  5. extractionThe contents were extracted with EtOAc (3×75 mL)
  6. washwashed with water, brine
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customThe final product was collected as 14.3 g (74%)

Sources & evidence

ORD record
ord-4d9523b9c9dc437897f44d18da5c2d2a
Source dataset
uspto-grants-2014_01
Patent number
US08637509B2

Reaction notes

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