Überführung von Mesoporphyrin IX in eine Porphyrin‐monopropionsäure, sowie über einige Porphyrin‐Synthesen

Fischer, Hartmut; Rothhaas, Alexander

doi:10.1002/jlac.19304840106

Cited by 13 publications

(3 citation statements)

References 6 publications

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“…Compound 6a was prepared from a , c -biladiene 13a (0.640 g) by the procedure reported above. Recrystallization of the residue from chloroform−methanol gave the title porphyrin (0.316 g; 64%) as violet crystals: mp 201.5−202.5 °C (lit . mp 199 °C; lit .…”

Section: Methodsmentioning

confidence: 99%

Normal and Abnormal Heme Biosynthesis. 1. Synthesis and Metabolism of Di- and Monocarboxylic Porphyrinogens Related to Coproporphyrinogen-III and Harderoporphyrinogen: A Model for the Active Site of Coproporphyrinogen Oxidase

et al. 1998

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Coproporphyrinogen oxidase (copro'gen oxidase), which catalyses the conversion of coproporphyrinogen-III via a monovinylic intermediate to protoporphyrinogen-IX, is one of the least well understood enzymes in the heme biosynthetic pathway. To develop a model for the substrate recognition and binding recognition for this enzyme, a series of substrate analogues were prepared with two alkyl substituents on positions 13 and 17 in place of the usual propionate residues. Although the required substrate probes are porphyrinogens (hexahydroporphyrins), the corresponding porphyrin methyl esters were initialy synthesized via a,c-biladiene intermediates. These were hydrolyzed and reduced with 3% sodium amalgam to give the unstable porphyrinogens needed for the biochemical investigations. These modified structures were metabolized by avian preparations of copro'gen oxidase to give monovinylic products, but the second propionate residue was not further metabolized. In three cases, the metabolites were isolated and further characterized by proton NMR spectroscopy and mass spectrometry. When methyl or ethyl groups were placed at the 13 and 17 positions, the resulting porphyrinogens were very good substrates (although the ethyl version, mesoporphyrinogen-VI, gave slightly better results), but when propyl units were introduced metabolism was significantly inhibited and the butyl-substituted structure was only slightly transformed after long incubation periods. These results suggest the presence of an active-site lipophobic region near the catalytic site for copro'gen oxidase. The observation that the related 3-vinyl- and 3-ethylporphyrinogens with 13,17-diethyl substituents were not substrates for this enzyme confirmed the need for a second propionate residue to hold the substrate in place at the catalytic site.

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Section: Methodsmentioning

confidence: 99%

Normal and Abnormal Heme Biosynthesis. 1. Synthesis and Metabolism of Di- and Monocarboxylic Porphyrinogens Related to Coproporphyrinogen-III and Harderoporphyrinogen: A Model for the Active Site of Coproporphyrinogen Oxidase

et al. 1998

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“…This was surprising if only because any "scrambling" of the porphinogens in hot acid6 would result in the loss of translocation of bridges. 6"Scrambling" refers to intermolecular redistribution reactions of porphinogens in hot acid leading to new porphinogens in which the pyrrole nuclei are randomized (22) and added formaldehyde may form the bridges (23). Analogous reactions have been observed in dipyrrylmethanes (24) and in their meso-alkyl derivatives (25); the latter may also lose their bridges with KOMe-MeOH at 220" (6,26).…”

mentioning

confidence: 99%

The Analytical Reduction of Porphyrins to Pyrroles

Chapman¹,

Roomi²,

Morton³

et al. 1971

Can. J. Chem.

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When porphyrins or related pigments are reduced by HI-AcOH, their meso-substituents (R = H or alkyl) appear as a-CH2R groups in the resulting pyrroles. The identification of the pyrroles, as by g.l.p.c., defines and orders the meso-substituents flanking each pair of peripheral substituents in the porphyrin. If one meso-substituent differs from the others, all the substituents about the two adjacent pyrrole nuclei are then ordered.The pyrroles can be reductively alkylated in situ, and symmetry then reduces their number when the aldehyde used (R.CH0) corresponds to a bridge and its meso-substituent. This may simplify the pyrrole mixtures, identify meso-substituents, or make pyrroles distinguishable by g.1.p.c.The critical pyrrole -propionic acids are separable as methyl esters by g.1.p.c. Desoxophylloerythrin and pyrophaeophorbides (the latter first reduced with potassium borohydride) are reduced to cyclopenteno-pyrroles which reveal the isocyclic rings and the 5-substituents. The r.r.t.3 of relevant pyrroles are reported.La reduction des porphyrines et des pigments du mCme genre par HI-AcOH fait que les substituants mtso (R = H OLI alkyle) apparaissent sous forme de groupements CH2R en cc des pyrroles resultants. L'identification des pyrroles par c.p.l.g., par exemple, definit et classe les substituants meso qui se trouvent a cBte de chaque paire de substituants peripheriques dans la porphyrine. Si un des substituants meso differe des autres, tous les substituants autour des deux noyaux pyrroles adjacents sont alors clasds.L'alkylation reductive irz situ des pyrroles peut riduire par symitrie le nombre de pyrroles lorsque l'aldehyde utilise (R.CH0) correspond au pont et au substituant meso de la porphyrine initiale. Ceci peut simplifier le melange des pyrroles, identifier les substituant meso et differentier les pyrroles par c.p.1.g.Les acides critiques pyrrole -propioniques sont separables de leurs esters methyliques par c.p.1.g. La dCsoxophylloerythrine et les pyrophaephorbides (ces dernieres d'abord reduites par le borohydrure de potassium) sont reduites en cyclopenteno-pyrroles, ce qui revele les noyaux isocycliques et les substituants en 5. Les donnees t.r.r, des pyrroles correspondants sont rapportkes.

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“…Fischer and Rotthaus had previously noted that the reduction of mesoporphyrin with zinc dust in hot acetic acid, followed by autoxidation, produced porphyrins having one to three carboxyl groups per molecule. 3 Reduction in the cold or in alkaline solution did not form such mixtures. This isomerization offered a unique opportunity to study the thermodynamic stability of a macrocyclic compound.…”

Section: Arch=c-c=0 I Imentioning

confidence: 94%

On the Reactivity of the Exocyclic Double Bond in 5-Arylidene-3-aryl-2,4-thiazolidinediones; Their Reaction with Diazoalkanes, p-Thiocresol and Piperidine

Mustafa¹,

Asker²,

Sobhy³

1960

J. Am. Chem. Soc.

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Überführung von Mesoporphyrin IX in eine Porphyrin‐monopropionsäure, sowie über einige Porphyrin‐Synthesen

Cited by 13 publications

References 6 publications

Normal and Abnormal Heme Biosynthesis. 1. Synthesis and Metabolism of Di- and Monocarboxylic Porphyrinogens Related to Coproporphyrinogen-III and Harderoporphyrinogen: A Model for the Active Site of Coproporphyrinogen Oxidase

Normal and Abnormal Heme Biosynthesis. 1. Synthesis and Metabolism of Di- and Monocarboxylic Porphyrinogens Related to Coproporphyrinogen-III and Harderoporphyrinogen: A Model for the Active Site of Coproporphyrinogen Oxidase

The Analytical Reduction of Porphyrins to Pyrroles

On the Reactivity of the Exocyclic Double Bond in 5-Arylidene-3-aryl-2,4-thiazolidinediones; Their Reaction with Diazoalkanes, p-Thiocresol and Piperidine

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