Diethyl Malonate → Isobutylmalonic acid

Participants

Reaction Steps

To a solution of sodium ethoxide obtained from 46.0 g (2.00 mol) of sodium lump and 1000 cm3 of anhydrous ethanol 320 g (2.00 mol) of diethyl malonate was added at room temperature. The obtained mixture was stirred for 30 min at this temperature, and then 274 g (2.00 mol) of isobutylbromide was added. The resulting mixture was refluxed for 5 h, and then ethanol was distilled off. To the cooled residue 1500 ml of cold water and 500 ml of ethyl acetate were added. The organic layer was separated, dried over Na2SO4 and then evaporated to dryness. Fractional rectification of the residue gave 357 g of colorless liquid, bp 177-187° C./220 mm Hg. This product contained ca. 10% of diethyl malonate. To a solution of 117.3 g (542 mmol) of diethyl isobutylmalonate in 500 ml of methanol a solution of 125 g of potassium hydroxide in 1000 cm3 of water was added. The resulting mixture was refluxed for 5 h, then ethanol and methanol were distilled off. Further on, 1000 cm3 of water was added, and then this mixture was acidified by 12 M HCl to pH 1.0. Isobutylmalonic acid was extracted by 4×500 ml of ether. The combined extract was evaporated to dryness. To the residue 300 ml of toluene was added. Again, the obtained mixture was evaporated to dryness to remove moisture. To a solution of the residue in 150 ml of toluene 500 ml of hexanes was added. The formed precipitate was filtered off, washed by 50 ml of hexanes and dried in vacuum. This procedure gave 72.8 g (84%) of the title product as white crystalline solid.

Provenance & Evidence