Polymerization of aromatic nuclei. XIV. Polymerization of toluene with aluminum chloride–cupric chloride

The polymerization of toluene with aluminum chloride and cupric chloride was performed in carbon disulfide and in a neat system. The solvent reaction produced an insoluble, light‐brown product which did not melt below 350°C. In the neat system, polymerization was much more vigorous, yielding a dark, purple‐brown solid with mp ∼250°C and molecular weight of 634. Infrared, NMR, and ultraviolet spectroscopy, along with elemental analysis and oxidative degradation, indicated that the backbone chain contains o‐polyphenylene units with the methyl group situated in the 4‐position. Some p‐polyphenylene structures may also be present. Evidence for small amounts of benzyl and polynuclear moieties was obtained. The mechanistic aspects are discussed. Our principal conclusions concerning oligomer structure are in disagreement with those of Kuwata.