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Synthesis of a Family of Highly Substituted Porphyrin Thioethers via Nitro Displacement in 2,3,7,8,12,13,17,18-Octaethyl-5,10,15,20-tetranitroporphyrin

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School of Chemistry, SFI Tetrapyrrole Laboratory, Trinity Biomedical Sciences Institute, Trinity College Dublin, The University of Dublin, 152-160 Pearse Street, Dublin 2, Ireland
Cite this: J. Org. Chem. 2017, 82, 10, 5122–5134
Publication Date (Web):April 28, 2017
Copyright © 2017 American Chemical Society

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    A series of highly substituted porphyrin thioethers was synthesized from 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetranitroporphyrin (H2OETNP). The reactions proceeded via a SNAr mechanism with a broad range of aromatic thiols in the presence of a base. This is a rapid way to prepare a large variety of meso-substituted porphyrins from only one precursor. Single crystal X-ray analysis revealed that these new porphyrin thioethers are highly distorted, exhibiting conformational properties that are distinctive of both meso-sulfur substitution and steric overcrowding in general. Additionally, denitration of H2OETNP under basic conditions was investigated, yielding products of stepwise desubstitution. This allowed a comparative X-ray crystallographic study to delineate the successive structural effects of an increasing degree of nitro substitution in the complete series of nitro-substituted octaethylporphyrins.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.7b00328.

    • A quantitative study on the influence of TEA on the consumption of 1, NMR spectra of the reaction products, crystal data for 12, and the UV–vis spectra of 1, 20, 21, 22, 23, and 32 (PDF)

    • Crystallographic data (CIF)

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