A Convenient Preparative Method of Dibromoterphenyl and Bis(bromophenyl)diene Monomers Using Zirconacyclopentadienes

Abstract
Zirconacyclopentadienes prepared from 4,4′-dibromodiphenyldiynes or 1-(4′-bromophenyl)-1-alkynes reacted with dimethylacetylene dicarboxylate in the presence of CuCl afforded polyphenylene monomers which contain three benzene rings. Hydrolysis, chlorination with NCS, or allylation of the zirconacyclopentadienes gave a variety of polyphenylenedienylene monomers. Polymerization of these monomers using the system NiCl2(PPh3)2 (cat.)/Zn produced the corresponding polymers.

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