Alkylation of Dimethyl Acetonedicarboxylate with Halogen-Containing Compounds

The results of the alkylation of dimethyl acetonedicarboxylate with halogen-containing compounds in the presence of potassium carbonate in dimethyl sulfoxide at 60–70°C are presented, leading to Cand O-alkylation products. At temperatures above 180°C, the O-alkylation product undergoes rearrangement to form the C-alkylation product. The reaction with α-bromopropionate or 1,3-dichloroacetone under similar conditions proceeds via both methylene groups of the synthon. The O-alkylation product of dimethyl acetonedicarboxylate with diethylacetaldehyde bromuxus derivative is stable at temperaturesup to 200°C. However, its hydrolysis product undergoes isomerization to a C-alkylated compound, followed by conversion into a furan derivative. In the case of the reaction of dimethyl acetonedicarboxylate with chloroacetonitrile, the obtained C-alkylation product in an acidic medium converts into α-amino-furan.

dimethyl acetonedicarboxylate, alkylation, rearrangement, diethylacetaldehyde, bromopropionate, dichloroacetone, chloroacetonitrile