This paper describes the successful application of the Suzuki polycondensation (SPC) to the synthesis of high molecular weight polyphenylenes using aryl dichloride monomers. From readily available starting material, two meta‐dichloromonomers ( 2b and 2c ) were prepared and subjected to SPC with benzene 1,4‐diboronic acid ester to produce reasonably high molar mass poly(para‐meta‐phenylene)s 4a and 4b , respectively, if freshly prepared Pd‐catalyst, Buchwald ligand and the base K3PO4 were used. The polymer with butoxy substituent ( 4a ) was compared regarding GPC molar mass and glass transition temperature with its exact same congener which had been synthesized in a previous work starting from a meta‐dibromo monomer. This comparison unequivocally confirms the molar masses achieved and, thus, establishes the first reported case of a SPC using aryl chloride monomers, instead of the more expensive and less amply available aryl bromides which had to be used otherwise.
