Synthesis of New Cyclopenta-Fused PAH Isomers of Cata-Annelated Benzenoid Systems

Article abstract of DOI:10.1021/jo00391a006

The syntheses of three new benz-annelated derivatives of aceanthrylene and acephenanthrylene are reported.These systems are of interest in studies on mechanisms of bioactivation and structure-activity correlations because of their predicted high level of biological activity.Of the three isomers, benzaceanthrylene (5) has been synthesized by two routes involving Friedel-Crafts acylations of 1,2,3,4-tetrahydronaphthacene with chloroacetyl chloride or oxalyl chloride as the key step.The cyclic ketone product from each route has been successfully elaborated to 5.Synthesis of benzaceanthrylene (9) involves preparation of acenaphthene-3,4-dicarboxylic anhydride and its smooth conversion to 9.A straightforward and high-yield synthesis of benzacephenanthrylene (27) is described utilizing a Robinson annelation reaction of methyl vinyl ketone with a previously reported ketonic precursor of acephenanthrylene.