NOVEL REARRANGEMENT IN THE SYNTHESIS OF POLY(PHTHALIDYLIDENEARYLENE)SBY SELF-CONDENSATION OF 3-ARYL-3-CHLOROPHTHALIDES .2. EFFECT OF MONOMER STRUCTURE AND REACTION CONDITIONS

The Friedel-Crafts self-condensation of 3-aryl-3-chlorophthalides mono substituted in the phthalide ring has been studied. 3-Aryl-3-chloropht halides containing Cl, Br, F, and NO2 as substituents were polymerized in solutions of nitrobenzene and dichloroethane in the presence of Le wis acids as a catalyst. The structures of the polymers obtained were established by C-13 NMR spectroscopy. The monomers containing substitu ents at the 4- and 6-positions of the phthalide ring were found to par tially rearrange in the course of the polymer synthesis, giving rise t o isomeric units in the polymer. From the effect of reaction condition s on the monomer rearrangement a mechanism has been proposed.