Highly substituted 2,3,7,8,12,13,17,18-octaethylporphyrins with meso aryl residues for application in NLO and sensors

Abstract

The synthesis of novel free base meso mono- and 5,10-disubstituted (A2- and AB-type) 2,3,7,8,12,13,17,18-octaethylporphyrins (OEPs) and of several meso trisubstituted AB-and AAB-type OEPs is reported with optimization details, NMR and UV/vis characterization. Yields for meso mono aryl substituted OEPs were excellent (up to 89%) and the subsequent disubstitution step was carried out with ease and also in good yields (maximal 92%) producing meso 5,10-AB and 5,10-A2-type substituted OEPs. The observed regio selectivity of the disubstitution was furthermore described by M. O. Senge et al. and could be also observed for the formation ABA tri substituted OEPs (287 291), which were obtained directly from the meso monosubstituted OEPs 4-8 . With 5-(3-trifluoromethylphenyl)-10-(4-dimethylaminophenyl) OEP 253 a novel mini push-pull OEP was prepared in 45% yield and 5,10-bisphenyl OEP 236, which was previously described as not reactive towards phenyllithium, could be used for the preparation of 5,10,15-AAB-type OEPs with in situ generated aryllithium reagents and produced the OEPs 292-294 in 17%, 38% and 69% yield. Atropisomers were observed for 9-phenanthrenyl and 1-naphthyI substituted OEPs (chapter 3) and changes in the shape of the UV/vis spectra were encountered for several di- and trisubstituted OEPs (chapter 5) due to the introduced unsymmetry and distortion.