Synthesis of Polyphenylenes and Polynaphthalenes by Thermolysis of Enediynes and Dialkynylbenzenes

Described are the syntheses of substituted enediynes and dialkynylbenzenes using Pd- or PdCu-catalyzed cross coupling procedures. The products were then thermalized, generally in benzene, to afford the corresponding polyp-phenylenes and poly1,4-naphthalenes. Thirteen examples are provided that show the scope of the polymerization process based upon substituent patterns and cyclization moieties. The superb thermal resiliency of the newly derived polymers is demonstrated using thermogravimetric analysis. The polymer structure was generally confirmed using IR data correlations to small molecules that resembled the polymers repeat unit structure. Radical trapping of dimeric intermediates, that were analyzed by GCMS, further substantiated the proposed mechanistic route. The step-growth polymerization pattern was determined by monitoring the degree of monomer consumption versus the polymer molecular weight.