Abstract
The work described in this thesis is concerned with the reaction of various five-membered heterocyclic diamines with diiminoisoindoline, leading to macrocyclic aza-linked compounds whose skeletal structure resembles phthalocyanine. However, the reaction of 2,5-diamino-3,4-dicyanothiophene and 1,3-diiminoisoindoline, in dimethylformamide, gave rise exclusively to an open chain compound, from the condensation of one unit of the first reagent with three units of the second. In 2-methoxyethanol the same reactants gave an intermediate two unit compound, l-imino-3-(5-amino-3,4-dicyano-2-thienyl)iminoisoindoline, which could be converted into the unsymmetrical four-unit compound above, but the latter failed to cyclise under a variety of conditions. In the course of the studies on the two-unit intermediate compound, an anomalous reaction was encountered with benzaldehyde, giving a reduced product rather than the simple Schiff!s base. Similar anomalous reactions were found with diiminoisoindoline and oxoisoindoline, giving reduced products postulated as arising via a hydride transfer reaction. Condensation of guanazole (3-5-diimino-1,2,4-tetrahydro-triazole) and diiminoisoindoline gave a macrocyclic compound in good yield, having a 2:2 structure. Analogous compounds were prepared from 1-phenylguanazole and from t-butyldiiminoisoindoline. Metal containing macrocycles were also obtained, using the above reactants and the bivalent transition metal acetates of Co, Ni, Cu, Zn and Hg, showing characteristics similar to those of previously reported cross-conjugated macrocycles. They were thermally stable and highly insoluble in organic solvents. Among the model compounds prepared, were two and three-unit products from oxoisoindoline or l-imino-3-phenyliminoisoindoline and guanazole or 1-phenylguanazole these had the expected characteristics. A series of condensations of the guanazoles with either benzaldehyde or anisaldehyde, gave a variety of Schiff's base products, either mono or dianils depending on the conditions used. The reaction of 2,5-diamino-3,4-dicyanothiophene and oxoisoindoline in 2-methoxy-and 2-ethoxyethanol gave unexpectedly complex products incorporating the solvent in a condensed macromolecule. In anhydrous ammonia, under pressure, the thiophene gave only linear polymeric products and no macrocyclic materials.