First example of the topochemical polymerization of the (E,E)‐muconic acid derivative

The 1‐naphthylmethylammonium salts of not only (Z,Z)‐ but also (E,E)‐muconic acid were found to polymerize upon photoirradiation in the crystalline state to provide a stereoregular polymer in a high yield. The stereochemical structure of both polymers obtained from the monomers with different configurations was identical, i. e., a meso‐diisotactic‐trans‐2,5‐structure. The stereochemistry of the polymers obtained is discussed on the basis of the monomer configuration and the molecular packing in the crystals.