Two approaches to α,α-bis-Mannich salts of N-monosubstituted amides

Two generally applicable syntheses of 2-bis-(dimethylaminomethyl)acetamides 9 are described. The first one involves reaction of N-mono substituted acetamides 3 with dimethyl(methylene)ammonium chloride in the presence of phosphorus oxychloride using diethyl ether as a solvent. Starting from ketoximes, the amines 9 are obtained under the same reaction conditions via Beckmann rearrangement. C-Aminomethylation observed in all cases may be the result of the formation of imidoyl chlorides 5 as intermediates.