engleski

Synthesis and application of functionalized macrocyclic oligopyrroles

Porphyrins and their derivatives are pigments which occur widely in Nature. They play very important roles in various biological processes, including catalysis and transfer of small molecules and electrons. Synthetic porphyrins have found a broad range of applications in science and technology. The subjects of the work described in this thesis are various cyclic tetrapyrrolic compounds related to porphyrins and precursors and derivatives of these compounds. In the first part oxidative N-alkylation of a tetraphenolic porphyrin has been examined. This reaction, poorly documented in the literature, has been carried out using various sets of experimental conditions and with several alkylating agents. A number of novel compounds have been prepared while the syntheses of some known products have been improved. It has been shown that the degree of N-alkylation could be controlled. This enabled the preparation of partially alkylated products as well as products of mixed alkylation. A doubly bridged product with the adjacent pyrrole rings two by two connected in an unusual way has also been prepared. Secondly, syntheses of aromatically substituted trans-A2B-corroles (derivatives of porphyrins lacking one bridging carbon atom) and their application have been described. Several synthetic methods have been used, which allowed some generalization of the reaction conditions required for different types of starting aldehydes. Some of the corroles synthesized have successfully been used in analytical systems for determination of small molecules. In the last part of the work an optimized synthetic pathway to novel selectively substituted 2, 2’ -bipyrroles has been developed. The latter could be used as building blocks for porphyrin-related compounds and pyrrole polymers. The first experiments in these directions have been done.

oligopyrrole; cyclic tetrapyrrole; porphyrin; corrole; 2; 2'-bipyrrole; pyrrole polymer; organic synthesis; oxidative N-alkylation

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