Synthesis of azaphthalocyanines bearing one 2,6-di(tert-butyl)phenol substituent

Charles University in Prague, Faculty of Pharmacy in Hradec Králové Department Department of Pharmaceutical Chemistry and Drug Control Candidate Miroslava Lásková Supervisor Doc. PharmDr. Petr Zimčík, Ph.D. Title of Thesis Synthesis of azaphthalocyanines bearing one 2,6-di(tert-butyl)phenol substituent In this work, azaphthalocyanines (AzaPc) bearing one 2,6-di(tert-butyl)phenol substituent were synthesized. Phenolic OH in this moiety is a weak donor for intramolecular charge transfer (ICT). However, this group can be ionized in basic media and the resulting phenolate anion is very strong donor. This was expected to cause ICT and quench fluorescence of this compound. The precursors for AzaPcs are substituted pyrazine-2,3-dicarbonitriles. They were prepared via one- step reaction of 5,6-dichloropyrazine-2,3-dicarbonitrile with 2-methylpropane-2-thiolate, respectively octanethiolate or via two-step reaction of 5,6-dichloropyrazine-2,3-dicarbonitrile with 2,6-di(tert- butyl)phenolate followed by nucleophilic substitution by 2-methylpropane-2-thiolate, respectively octanethiolate. Another precursor was prepared via reaction of glyoxylic acid with diaminomaleonitrile followed by chlorination with phosphoryl chloride and by subsequent nucleophilic substitution by 2,6- di(tert-butyl)phenolate. Resulting..