Dimethyl oxalate → Methyl 4-cyclopropyl-2,4-dioxobutanoate

HRID 869054Notes

Reaction equation

HRID 869054 reaction equation
[CH3:1][C:2]([CH:4]1[CH2:6][CH2:5]1)=[O:3].C[O-].[Na+].[C:10](OC)(=[O:15])[C:11]([O:13][CH3:14])=[O:12]>CO>[CH3:14][O:13][C:11](=[O:12])[C:10](=[O:15])[CH2:1][C:2]([CH:4]1[CH2:6][CH2:5]1)=[O:3]

Participants

5

Reactant 3

HCID 11120Dimethyl oxalateHCID 13004Cyclopropyl methyl ketoneHCID 10942334Sodium Methoxide

Product 1

HCID 16227056Methyl 4-cyclopropyl-2,4-dioxobutanoateYield 49.5%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of cyclopropyl methyl ketone (5 g, 59.4 mmol) in MeOH (75 mL) was added sodium methoxide (4.8 g, 54.0 mmol) at rt. After a 15 min stirring, dimethyl oxalate (7 g, 59.4 mmol) was added. The reaction mixture was stirred for 16 h at rt and concentrated. The residue was taken up in a saturated aqueous solution of ammonium chloride and extracted with EtOAc. The organic layers were dried (Na2SO4), filtered, and concentrated. The residue was purified by silica gel column chromatography (hexane/EtOAc, 95:5) to provide 5 g of the title compound. Rf=0.59 (hexane/EtOAc, 4:1); 1H NMR (300 MHz, CDCl3) δ ppm 1.00-1.30 (m, 4H), 1.80-1.95 (m, 1H), 3.85 (s, 3H), 6.48 (s, 1H), 14.2-15.0 (br. s, 1H).

Workup

  1. stirringThe reaction mixture was stirred for 16 h at rt
  2. concentrationconcentrated
  3. extractionextracted with EtOAc
  4. dry with materialThe organic layers were dried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe residue was purified by silica gel column chromatography (hexane/EtOAc, 95:5)

Sources & evidence

ORD record
ord-812d291f92594e9f98e546779dfb355b
Source dataset
uspto-grants-2015_03
Patent number
US08969341B2

Reaction notes

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