Piotr Tomasik

Mechanism of direct side-chain acylamination and aminoarylation of 2- and 4-picoline 1-oxides

The isolation of radical coupling products and the observation of appropriate C.I.N.D.P. signals suggest that most of the title reactions proceed by homolysis of the anhydro-bases (4) or (9) followed by radical recombinations; a diaza-oxy-Cope rearrangement may still account for the formation of α-acylamination products.

Direct side-chain acylamination of 4-picoline 1-oxides and related compounds

The anhydro bases formed from the reaction of 4-picoline 1-oxides with N-substituted benzimidoyl chlorides and a strong base undergo a new molecular rearrangement to give mixtures of the side chain acylaminated (e.g.4) and acylaminoarylated products (e.g.5); 2-picoline 1-oxides behave similarly.