Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2019 Feb 27;24(5):838.
doi: 10.3390/molecules24050838.

Isomers of β, β-Dinitro-5,10,15,20-tetraphenylporphy-rin Derivatives: Valuable Starting Materials for Further Transformations

Agnieszka Mikus  1 , Mariusz Rosa  2 , Stanisław Ostrowski  3
Affiliations

Isomers of β, β-Dinitro-5,10,15,20-tetraphenylporphy-rin Derivatives: Valuable Starting Materials for Further Transformations

Agnieszka Mikus et al. Molecules. .

Abstract

The synthesis, chromatographic isolation, and structure elucidation of β,β-substituted isomers of dinitro-5,10,15,20-tetraphenylporphyrin complexes are described. meso-Tetraphenyl-porphyrin chelates (CuII, NiII, CoII) upon reaction wit e.g., itric acid (yellow HNO₃, d = 1.52, diluted to 25⁻50%) in CHCl₃ formed a mixture of nitro-derivatives with combined yields of ca 80%. This nitration (under optimized conditions: 25⁻30% HNO₃, 30⁻40 min, r.t.) can be carried out selectively to give mainly β,β-dinitro-compounds in yields of up to 73%. From the above mixtures of five possible regioisomers that can be formed, usually two or three of them were isolated, for which the structures were assigned on the basis of ¹H NMR spectra including COSY and NOESY measure-ments. These types of products are attractive starting materials for synthesis of potential anticancer PDT agents with unique structures, being practically unavailable by any other alternative method.

Keywords: 2D NMR.; complexes; electrophilic substitution; nitric acid; porphyrins; β-nitration.

PubMed Disclaimer

Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Preparation of dinitro-isomers and all the possible structures of the products.
Figure 1
Figure 1
Structures of dinitro-isomers 6a–10a and 6b–10b.
Figure 2
Figure 2
Structures of 3db, 3dc, 3dd, and 3de.
Figure 3
Figure 3
1H NMR spectrum of product 3db (diagnostic region: 7.50–9.00 ppm).
Figure 4
Figure 4
The diagnostic 2D correlations observed for product 3db: COSY correlations—orange arches; NOESY correlations—black arches.
See this image and copyright information in PMC

References

    1. Kadish K.M., Smith K.M., Guilard R., editors. Handbook of Porphyrin Science. Volume 1–25 World Scientific Publishing Co.; New Jersey, NJ, USA: London, UK: Singapore: Beijing, China: Shanghai, China: Hong Kong: Taipei, Taiwan: Chennai, India: 2010–2012.
    1. Ostrowski S. Preparation of 2-nitro-5,10,15,20-tetraphenylporphyrin zinc(II) complex—post scriptum to electrophilic nitration of porphyrins at the β-pyrrolic position. Polish J. Chem. 2005;79:1169–1172.
    1. Mikus A., Ostrowski S. Synthesis of highly functionalized porphyrins—substituted in all β-positions of EASTERN HALF; Proceedings of the Petra International Conference of Chemistry (PICC) and Transmediterranean Colloquium on Heterocyclic Chemistry (TRAMECH–5); Tafila, Jordan. 25–28 June 2007; p. 28.
    1. Ostrowski S., Wyrębek P. The first example of Diels-Alder cycloaddition of ortho-xylylenes to meso-tetraarylporphyrins containing electron-deficient β,β-double bonds. Tetrahedron Lett. 2006;47:8437–8440. doi: 10.1016/j.tetlet.2006.09.006. - DOI
    1. Fang Y., Jiang X., Ou Z., Michelin C., Desbois N., Gros C.P., Kadish K.M. Redox properties of nitro-phenylporphyrins and electrosynthesis of nitrophenyl-linked Zn porphyrin dimers or arrays. J. Porphyrins Phthalocyanines. 2014;18:832–841. doi: 10.1142/S1088424614500540. - DOI

LinkOut - more resources