ChemInform Abstract: Porphyrins and Their Derivatives. Part 18. Vicarious Nucleophilic Substitution of Hydrogen in 2‐Nitro‐5,10,15,20‐tetraphenylporphyrin.

Malinovskii, Vladimir L.; Vodzinskii, S. V.; Жиліна, З. І.; Андронаті, С. А.

doi:10.1002/chin.199644119

Cited by 2 publications

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“…For this reason β ‐nitroporphyrins were used in a number of various transformations, e. g . nucleophilic addition, [58–60] nucleophilic substitution, [22,27,30,61–66] or cycloaddition reactions [67–73] …”

Section: Nitration Of Porphyrin Derivatives At the β‐Positionsmentioning

confidence: 99%

“…The NO 2 group introduced into parent porphyrin system changes its reactivity character, thus allowing a broad spectrum of post‐transformations, e. g . reduction of NO 2 to NH 2 [10–13] and subsequent diazotisation, [12,14,15] substitution of hydrogen in position ortho to NO 2 , [16–30] a variety of cyclizations, [31,32] etc. Nitroporphyrins can be also convenient substrates for S N Ar reactions with numerous nucleophiles [33–36] …”

Section: Introductionmentioning

confidence: 99%

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Nitration of Porphyrin Systems: A Toolbox of Synthetic Methods

Mikus

Łopuszyńska

2020

Chemistry An Asian Journal

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This review addresses nitration reactions of porphyrin derivatives. Simple porphyrins modifications afford valuable intermediates in this area of chemistry. They are useful materials for further transformations, as the NO2 group introduced into parent porphyrin system increases its electrophilic character, thus allowing a broad spectrum of subsequent reactions, e. g. reduction of NO2 to NH2, subsequent diazotisation, nucleophilic substitution of hydrogen (in ortho‐position to NO2), a variety of cyclizations, etc. Such reactions are often utilized in the first steps of the designed syntheses, leading to attractive and useful target porphyrin molecules. This approach (via nitro‐derivatives) allows synthesizing numerous porphyrin‐like compounds of a high degree of complexity, and has thus become one of the methods choice. The substitution by NO2 group can take place at all positions of the porphyrin systems: four meso‐positions (5, 10, 15, 20) and eight positions β (2, 3, 7, 8, 12, 13, 17, 18). The third possibility includes the nitration in meso‐aryl rings attached to positions 5, 10, 15, and 20. The latter derivatives (meso‐aryl substituted ones) are a large, well‐known group of synthetic porphyrins. The nitration reactions described herein follow three various mechanisms: (a) radical, (b) via π‐cation radicals and π‐dications, and (c) electrophilic. All the above cases are discussed in detail. According to our knowledge, this is the first such systematic account concerning these reactions.

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Section: Nitration Of Porphyrin Derivatives At the β‐Positionsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Nitration of Porphyrin Systems: A Toolbox of Synthetic Methods

Mikus

Łopuszyńska

2020

Chemistry An Asian Journal

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“…In the previous research, some examples of synthesis of β,β-disubstituted porphyrins and porphyrinates (all of them practically zinc complexes) were presented using carbanions and VNS methodology (Malinovskii et al 1996;Ostrowski and Raczko 2005). Recently, several papers concerning this type of substitution in meso-aryl rings have also been published (Ostrowski et al 2002;Ostrowski et al 2004;Ostrowski et al 2007;Ostrowski et al 2017).…”

Section: Resultsmentioning

confidence: 99%

“…1 H NMR spectra of copper and cobalt complexes are not readable due to paramagnetic effect of Cu 2+ and Co 2+ cations present in the structure. In these cases some products were decomplexed to free-base porphyrins and the spectral data recorded (including 1 H NMR) were compared with those described earlier (Malinovskii et al 1996). 1 H NMR spectra of nickel-products (8-10, 14) were very characteristic.…”

Section: Resultsmentioning

confidence: 99%

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Nucleophilic substitution of hydrogen and synthesis of nickel-, copper-, and cobalt-porphyrinates – double functionalized at the β-positions

Mikus

Ostrowski

2023

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2-Nitro-5,10,15,20-tetraphenylporphyrin–nickel(II), –copper(II), and –cobalt(II) complexes reacted with carbanions of halomethyl aryl sulphones and para-chlorophenoxyacetonitrile according to the vicarious nucleophilic substitution scheme (VNS). This leads to the substitution of hydrogen products, in the position ortho- to the NO2 group, thus giving β,β-disubstituted derivatives on the same pyrrole ring. The yields were satisfactory, up to 95%. These types of products, being practically unavailable by alternative methods, are attractive starting materials for synthesis of more complex porphyrinoid moieties.

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ChemInform Abstract: Porphyrins and Their Derivatives. Part 18. Vicarious Nucleophilic Substitution of Hydrogen in 2‐Nitro‐5,10,15,20‐tetraphenylporphyrin.

Cited by 2 publications

References 0 publications

Nitration of Porphyrin Systems: A Toolbox of Synthetic Methods

Nitration of Porphyrin Systems: A Toolbox of Synthetic Methods

Nucleophilic substitution of hydrogen and synthesis of nickel-, copper-, and cobalt-porphyrinates – double functionalized at the β-positions

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