Uses
Diethyl Acetonylmalonate is a doubly functionalized reagent, the ketone acting as an internal trapping agent after the reaction of the malonate anion; for synthesis of five-membered rings.
Synthesis Reference(s)
The Journal of Organic Chemistry, 46, p. 4631, 1981
DOI: 10.1021/jo00335a084
Synthesis
A detailed procedure reports the alkylation of Diethyl Malonate by chloroacetone on a 100 g scale, giving diethyl acetonylmalonate (1) with a yield of 55% after distillation. Since chloroacetone is toxic and highly irritating to the eyes, skin, and mucous membranes, an alternative procedure using Isopropenyl Acetate, a mild irritant and a much less toxic compound than chloroacetone, should be seriously considered. Thus the reaction of dimethyl malonate with isopropenyl acetate in the presence of Cerium(IV) Ammonium Nitrate (CAN) followed by a mild basic treatment affords dimethyl acetonylmalonate in a yield of 82% on a 5-10 g scale (eq 1). This procedure offers advantages regarding the yield and reaction conditions, and it uses available starting materials.
References
1. Mercier C.; Addas A. R.; Deslongchamps P. CJC 1972, 50, 1882.
2. The Merck Index, 11th ed.; Merck: Rahway, NJ, 1989.
3. Baciocchi E.; Civitarese G.; Ruzziconi R. TL 1987, 28, 5357.
