Novel Versatile Synthesis of Substituted Tetrabenzoporphyrins

Abstract

A novel general synthetic route to tetraaryltetrabenzoporphyrins (Ar(4)TBP) with various peripheral functional groups is developed. The procedure includes (i) Barton-Zard condensation of 1-nitro- or 1-phenylsulfonylcyclohexenes with isocyanoacetic acid esters, (ii) condensation of the resulting 4,5,6,7-tetrahydroisoindoles with aromatic aldehydes to give fused tetraaryltetracylohexenoporphyrins (Ar(4)TCHP), and (iii) aromatization of the metal complexes of Ar(4)TCHP's into the corresponding Ar(4)TBP's. Cu and Zn complexes of Ar(4)TBP's are further demetalated to give the corresponding Ar(4)TBP free bases. The overall yields for the sequence range from 15% to 40%, making the method suitable for the preparation of gram quantities of Ar(4)TBP's in a single run. The scope of the method, the selection of the peripheral substituents, the choice of the metal ions, and their influence on the yields of aromatization are discussed. The basic spectroscopic properties of newly synthesized Ar(4)TBP's and Ar(4)TCHP's are reported together with the first X-ray crystallographic structure of the NiAr(4)TBP complex.

Dynamic quenching of porphyrin triplet states by two-photon absorbing dyes: Towards two-photon-enhanced oxygen nanosensors

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Synthesis of Metallated (Cu, Pd) Crown Substituted Tetracyclohexenoporphyrins. Crown-Containing Pd Tetrabenzoporphyrin and Its Phosphorescence

“…Сравнение полученных спектров с литературными данными [5,27] показало, что введение краун-эфирных фрагментов незначительно отражается на оптических свойствах рассматриваемых порфиринов (Таблица 1).…”

Synthesis and evaluation of the antiproliferative activity of novel isoindolo[2,1-a]quinoxaline and indolo[1,2-a]quinoxaline derivatives

“…Condensation of nitrocyclohexenes with ethyl isocyanoacetate in the presence of 1,8-diazabicyclo [5.4.0]undec-7-ene (DBU) afforded the corresponding fused pyrroles 2a-b using a Barton-Zard reaction [14][15][16] . The not commercially available, starting material 2-nitro-3,4-dihydronaphthalene was readily prepared by the nitration of the corresponding alkene 17 .…”