Please use this identifier to cite or link to this item:
https://hdl.handle.net/2440/39405
Citations | ||
Scopus | Web of Science® | Altmetric |
---|---|---|
?
|
?
|
Type: | Journal article |
Title: | Reaction of 5-nitro-octaethylporphyrins with nucleophiles |
Author: | Crossley, M. King, L. Pyke, S. Tansey, C. |
Citation: | Journal of Porphyrins and Phthalocyanines, 2002; 6(11-12):685-694 |
Publisher: | Soc Porphyrins & Phthalocyanines |
Issue Date: | 2002 |
ISSN: | 1088-4246 1099-1409 |
Statement of Responsibility: | Maxwell J. Crossley, Lionel G. King, Simon M. Pyke and Charles W. Tansey |
Abstract: | <jats:p> An investigation of the reactions of metallo-5-nitro-2,3,7,8,12,13,17,18-octaethylporphyrins with Grignard reagents, benzyl oxide, phenoxide and benzenethiolate nucleophiles shows that, except for benzenethiolate reactions, they are less efficient than related reactions of metallo-2-nitro-5,10,15,20-tetraarylporphyrins. Treatment of free-base and nickel(II) 5-nitro-octaethylporphyrin with the “soft” nucleophile benzenethiolate in DMF affords the corresponding 5-phenylthioporphyrins in 61 and 72% yield, respectively, by ipso-substitution of the nitro group. In contrast, with methylmagnesium iodide and benzyl oxide, “hard” nucleophiles, attack is at the diagonally opposite 15-position of the ring to give 15-substituted 5-nitroporphyrin while with phenoxide and more substituted Grignard reagents, electron-transfer reactions lead to denitration to (metallo)-octaethylporphyrin or reduction to the corresponding 5-aminoporphyrin. The lower efficiency of the latter reactions, compared to those on 2-nitro-tetraarylporphyrin analogues, is a consequence of two factors, higher energies being required for initial nucleophilic attack as macrocyclic aromaticity is lost in intermediates and the susceptibility of the resultant “non-aromatic” intermediates to further attack. </jats:p> |
Description: | Copyright © 2002-2007 Society of Porphyrins & Phthalocyanines. All rights reserved. |
DOI: | 10.1142/S1088424602000816 |
Published version: | http://www.u-bourgogne.fr/jpp/base_article/index.php?v=06&n=11&abs=685 |
Appears in Collections: | Aurora harvest Chemistry publications |
Files in This Item:
There are no files associated with this item.
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.