Date of Award
Master of Science (MS)
Department of Chemistry
Timothy D. Lash
Carbaporphyrins have been the focus of many studies, and a wide variety of related carbaporphyrinoid systems have been reported. N-confused porphyrins are a class of carbaporphyrins where one pyrrole unit has been inverted. In this work, a newly discovered family of porphyrin isomers where one of the pyrrolic subunits is connected to the meso-bridges in a 1,3-fashion, called neo-confused porphyrins, has been investigated.
Reaction of pyrrole-3-carbaldehydes with acetoxymethylpyrroles and NaH in DMF gave neo-confused dipyrrylmethane dialdehydes. The resulting dialdehydes underwent an acid catalyzed condensation with a dipyrrylmethane to give neo-confused phlorins, and following oxidation with FeCl3 afforded new neo-confused porphyrins. These porphyrinoids differ from previous neo-confused porphyrins in that they do not possess fused benzo- units or electron withdrawing ester substituents. Instead, the neo-confused ring is substituted with a phenyl or bromo group. Reaction of neo-confused porphyrins with nickel(II) or palladium(II) acetate afforded the metaled complexes. The aromaticity of the neo-confused porphyrin and their derivatives were assured by proton NMR spectroscopy and UV-Vis spectroscopy.
Almejbel, Arwa Salem, "Synthesis and Characterization of Neo-Confused Porphyrins and Related Systems" (2015). Theses and Dissertations. 486.