o-Pleiadienequinones. Part 3. Ring enlargement of o-pleiadienequinones with diazoalkanes

Abstract

The reactions of o-pleiadienequinones (1) and (2) with various diazoalkanes are described. In the absence of catalyst pyrazoline derivatives (3) and (4) were obtained. In the presence of Lewis acid catalysts ring-enlarged cyclo-octa[de]naphthalenones (5a), (6), and (7a) were obtained, achieving syntheses of the first known higher analogues of phenalenone. The reaction of the quinone (2) with trimethylsilyldiazomethane gave cyclo-octa[de]naphthalenedione (8). The physical properties of these compounds are described and the mechanism of formation is discussed. The quinone (1) formed 1 : 1 complexes with divalent metal ions.