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Cu‐Mediated Syntheses of N‐Fused and Ring‐Modified Trithiahexaphyrins
Author(s) -
Hung ChenHsiung,
Jong JingPing,
Ho MuYih,
Lee GeneHsiang,
Peng ShieMing
Publication year - 2002
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20021004)8:19<4542::aid-chem4542>3.0.co;2-3
Subject(s) - ring (chemistry) , antiaromaticity , chemistry , nitrogen , tricyclic , chloride , crystal structure , carbon fibers , crystallography , stereochemistry , aromaticity , molecule , organic chemistry , materials science , composite number , composite material
The reaction of the antiaromatic [28]trithiahexaphyrin (TTHP) with Cu I in DMF gives a novel fused‐ring trithiahexaphyrin with the elimination of a chloride on a dichlorophenyl ring and bond formation to the outward oriented pyrrolic nitrogen to form a 5,5,6‐tricyclic internal ring system. The NMR spectra, which display characteristics of an antiaromatic compound, agree with the proposed structure. Meanwhile, reactions of TTHP with amines in the presence of Cu I give amino‐group‐inserted hexaphyrins with the amino nitrogen joined to a β ‐thiophenic carbon and the α ‐carbon of the alkylamine cyclized to the inward pyrrolic nitrogen to form a 5,7,5‐tricyclic rings. The crystal structure of the fused‐ring product indicates a rectangular geometry with a tilted tricyclic ring system, while the ring‐modified TTHP‐DMA complex gives a triangular trithiahexaphyrin core. This report demonstrates methods to incorporate functionalized heterocyclic rings into expanded porphyrins.