Polyaromatic heterocycles and azine oxidation chemistry
The oxidative polymerization of aromatic heterocycles is one of the subjects of this dissertation, specifically the polymerization of 2-amino-7-alkyl-phenazines and 2,2′ biindoles. Polyaminophenazine was prepared by oxidative coupling of the monomer. Great consideration was given to the design of the monomer so that the resulting material would be completely stereoregular with specific coupling. To achieve this, the introduction of an alkyl group in the 7 position of the monomer forces the coupling to the 6 position in the polymer. Thus, the preparation of the 2-amino-7-alkyl phenazine was the primary consideration. ^ Polybiindoles were prepared by oxidative coupling of the monomer 2,2 ′ biindole. Since no method was available to prepare the monomer in high yields with conditions that would tolerate sensitive functional groups, several novel syntheses were evaluated for their usefulness in the preparation of this monomer. It was found that the monomer could be synthesized in a single step in good yield by direct cyclization of an alpha diketone with 2 iodoaniline under mild conditions. Polymerization of these monomers yielded stereoregular polymers with properties tunable by appropriate functional groups. ^ The unusual oxidation chemistry of 1,4-Diphenyl-1,3-diazabutadienes was evaluated showing that an alkyl side group α to the azomethine bond could be oxidized by iodine to form a novel addition product. This reaction may explain the low conductivities associated with iodine doped polyazine systems. ^
Darrell J Koza,
"Polyaromatic heterocycles and azine oxidation chemistry"
Dissertations and Master's Theses (Campus Access).