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.
