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Insights into the Synthesis and the Solution Behavior of meso ‐Aryloxy‐ and Alkoxy‐Substituted Porphyrins
Author(s) -
Birin Kirill P.,
Gorbunova Yulia G.,
Tsivadze Aslan Yu.,
BessmertnykhLemeune Alla G.,
Guilard Roger
Publication year - 2015
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201500628
Subject(s) - chemistry , alkoxy group , alkyl , aryl , medicinal chemistry , derivative (finance) , zinc , metal , solvent , molecule , stereochemistry , organic chemistry , financial economics , economics
meso ‐RO‐appended (R = alkyl, aryl) porphyrins bearing one or two OR substituents at the tetrapyrrolic macrocycle were synthesized in good yields from 5,15‐dibromo‐10,20‐diphenylporphyrins 2H(Br 2 DPP), Ni(Br 2 DPP) and Zn(Br 2 DPP) using an S N Ar reaction. By varying the solvent, the base, the temperature, and the time of the reaction, the optimum conditions were established, and the selective introduction of one or two meso ‐RO substituents at the periphery of the macrocycle was achieved. Moreover, monofunctionalization of Ni(Br 2 DPP) according to an S N Ar reaction was used as a key step for the synthesis of rarely explored unsymmetrical porphyrinyl alkyl ethers. 1 H NMR studies of these ethers in CDCl 3 revealed concentration‐dependent aggregation of the zinc derivative through coordination of the central metal ion of one molecule to the peripheral oxygen atom of a second tetrapyrrolic macrocycle.