Synthesis of Highly Substituted Nitro/Ha­lo-meso-tetraaryl­porphyrins by Tandem Cyclocondensation/Aromatic Electrophilic Nitration Reactions

Abstract

Synthesis of highly functionalized nitro 10,15, with F, Cl, Br, and I)

Nitration of Porphyrin Systems: A Toolbox of Synthetic Methods

“…The above procedure could also be applied to synthesis of other meso‐ tetraaryl‐substituted porphyrins. Interestingly, contrary to the previous studies, tetranitro‐derivatives were isolated from the mixtures obtained in these experiments, sometimes with reasonable yield [96] . The substituents on meso ‐phenyl rings (3‐CH 3 , 3‐OCH 3 , 3‐Cl and other halogens; but not strong electron‐withdrawing groups, e. g .…”

“…Porphyrins bearing aryl moieties in meso ‐positions (5, 10, 15, 20) can also be successfully nitrated in these rings. In this case, the only mechanism described in the literature was the electrophilic one [21,88–92,95–101,103] . For the first time, this type of nitration taking place on meso ‐phenyl rings was reported by Kruper et al [88] .…”

“…The substituents on meso ‐phenyl rings (3‐CH 3 , 3‐OCH 3 , 3‐Cl and other halogens; but not strong electron‐withdrawing groups, e. g . CN, NO 2 ; see Chapter 3.4 ) did not change the site of nitration [21,92,96–98] . They only affect the reaction yield and – in some cases – the ratio of isomers.…”

Synthesis and Photodynamic Activity of 5,10,15-Tris(p-chlorophenyl)-20-(2- hydroxy-3-methoxyphenyl)-21H,23H-porphyrin

“…Previous report compared the cytotoxic activity of porphyrins substituted at meso position with hydroxyl and methoxyl groups, showing better results in hydroxy meso-substituted porphyrins, perhaps methoxy-substituted porphyrins also yielded good results [18]. Additionally, halogenated tetrapyrrolic compounds have been considered as potential photosensitizers and their structure also present other groups on meso positions allowing for an amphiphilic character [19,20]. The structure of the synthesized porphyrin presents different groups at the meso position, p-chlorophenyl and 2hydroxy-3-methoxyphenyl and is a novel target molecule to evaluate the synergistic effect of these hydrophobic and hydrophilic moieties distributed unsymmetrically on the porphyrin macrocycle.…”

Attempts of the Synthesis of Highly Functionalized Porphyrins at the β-Positions: Nitration of Exhaustively Substituted Moieties in the ’Eastern Half ’ and Mass-Spectral Study of the Reaction Products

“…[3][4][5][6][7][8][9] Previously the preparation of poly-substituted derivatives in meso-aryl rings was demonstrated. [3,4,7] Herein, attempts of synthesizing β-multifunctionalized porphyrins are reported. The first four functional groups were introduced to the ring due to tandem reactions electrophilic nitration / nucleophilic substitution of hydrogen.…”