106117-28-6Relevant articles and documents
A novel synthetic route to sapphyrins
Paolesse, Roberto,Licoccia, Silvia,Spagnoli, Mariangela,Boschi, Tristano,Khoury, Richard G.,Smith, Kevin M.
, p. 5133 - 5137 (1997)
New methodology has been developed for the synthesis of so-called sapphyrins, pentapyrrolic 'expanded porphyrins'. An efficient approach involving acid-catalyzed condensation of 1,19-diunsubstituted a,c-biladienes and 3,4-dialkylpyrrole-2-carbaldehydes eliminates the preparation of bipyrrolic intermediates and allows the synthesis of sapphyrins with an unsymmetrical array of peripheral substituents. The β-substitution pattern of 2,3,13,17-tetraethyl-7,8,12,18,22,23-hexamethylsapphyrin has been unambiguously confirmed by single crystal X-ray crystallography. 1H NMR spectra of the dication salts of sapphyrins are strongly dependent upon the counterions, and the pattern of resonances observed in solution is related to the stacking interactions between the macrocycles.
Molecular Fossils of Chlorophyll c of the 17-nor-DPEP Series. Structure Determination, Synthesis, Geochemical Significance.
Verne-Mismer, J.,Ocampo, R.,Callot, H. J.,Albrecht, P.
, p. 371 - 374 (1988)
Two porphyrins 1 and 2, having totally (1) or partially (2) lost the C-17 substituent, have been isolated from two Moroccan oil shales of Cretaceous age.An origin from chlorophyll c, which possesses a 17-acrylic side-chain, can explain this transformation.A synthesis of 1 from chlorophyll (a+b) is described.Porphyrin 1 is widely distributed in sediments and its relative abundance with regard to other molecular fossils of chlorophyll c is discussed briefly.
Dissociation kinetics of copper and cobalt complexes with sterically distorted porphyrins
Kuvshinova,Kuz'min,Dudkina,Pukhovskaya,Semeikin,Golubchikov
, p. 133 - 136 (2002)
The dissociation kinetics of the cobalt and copper complexes with octaethylporphyrin, its 5-phenyl, 5,15-diphenyl, and 5,10,15,20-tetraphenyl derivatives, and dodecaphenylporphyrin in acetic acid with small additions of trifluoroacetic acid were studied. In this series of complexes, the steric distortion of the tetrapyrrole macrocycle sequentially increases, which results in a regular decrease in the kinetic stability of the metal porphyrins: The dissociation rate increases by three orders of magnitude.
Tripyrrin - The missing link in the series of oligopyrrolic ligands
Broering,Brandt
, p. 499 - 500 (2001)
The first derivative of the hitherto elusive tripyrrin 2 was prepared and characterized; the X-ray structural analysis of its trifluoracetato-palladium(II) complex 7 displays a highly flexible N3 ligand.
Der Einbau von Magnesium in Liganden der Chlorophyll-Reihe mit (2,6-Di-t-butyl-4-methylphenoxy)magnesiumjodid
Zass, Engelbert,Isenring, Hans Peter,Etter, Rolf,Eschenmoser, Albert
, p. 1048 - 1067 (1980)
Experimental details are given for the new method of introducing magnesium into porhpinoid ligands by (2,6-di-t-butyl-4-methylphenoxy)magnesium iodide (1), previously published in preliminary form .Besides magnesium octaethylporphyrinate (14), methyl pyrochlorophyllide a (10), methyl chlorophyllide a (8), and methyl bacteriochlorophyllide a (12), the complexation of pheophytin a (2) to chlorophyll a (3) and of pheophytin b (4) to chlorophyll b (5) are described.
Syntheses of highly distorted meso-trifluoromethyl-substituted β-octaalkylporphyrins
Suzuki, Masaaki,Ishii, Shuto,Hoshino, Tyuji,Neya, Saburo
, p. 1563 - 1565 (2014)
Treatment of 5,5′-d icarboxy-3,3′,4,4′-tetraalkyl-2,2′-dipyrromethanes with trifluoroacetic acid and subsequent oxidation resulted in formation of meso-trifluoromethy l-substituted β-octaalkylporphyrins. The structura l characterizations and the spectrosc
Structure-stability relationships of phthalocyanine copper complexes
Sokolova,Lomova,Klueva,Suslova,Mayzlish,Shaposhnikov
, p. 775 - 785 (2000)
The influence of NO2, Br, and COOH function substituents in various positions of Cu(II)Pc on the reactivity of the latter concerning the dissociation of the metal - nitrogen bonds in proton donor solvents is discussed.
Paley's watchmaker analogy and prebiotic synthetic chemistry in surfactant assemblies. Formaldehyde scavenging by pyrroles leading to porphyrins as a case study
Alexy, Eric J.,Hintz, Carl W.,Hughes, Hubert M.,Taniguchi, Masahiko,Lindsey, Jonathan S.
, p. 10025 - 10031 (2015)
The formation of elaborate molecules is regarded as an essential first step in prebiotic chemistry, but how such transformations could spontaneously occur, particularly in dilute aqueous conditions, remains poorly understood. Here, micromolar concentrations of a 3,4-dialkylpyrrole and excess formaldehyde in aqueous micellar solution (pH 7) at 25 or 50 °C were found to give good yield (up to 40%) of the lipophilic octaalkylporphyrin. The reaction occurs despite a mean occupancy number of ～0.1 pyrrole molecules/micelle, and 1 of 10 000 micelles initially containing the requisite 4 pyrrole molecules to form the porphyrin assuming a (random) Poisson distribution. Yields of up to 13% were observed in large, unilamellar phosphatidylcholine vesicles, wherein there are ～15 000 pyrrole molecules per vesicle membrane. Double-labeling crossover experiments (of 3,4-diethylpyrrole and 3,4-dimethylpyrrole) examined by mass spectrometry revealed facile exchange processes of reactive constituents among both micelle and vesicle surfactant assemblies. Together, the exchange of pyrrolic reactants among micelles and the thermodynamic driving force for tetrapyrrole formation overcome the apparent statistical odds against reaction. The fruitful exchange, accumulation and reaction of minute quantities of reactants in aqueous-surfactant assemblies suggest a general means for formation of prebiotically valuable constituents, even when the statistical odds at the outset are overwhelmingly improbable.
Synthesis of Octaalkyl- and Octaarylporphyrins from Nitroalkenes
Ono, Noboru,Maruyama, Kazuhiro
, p. 1511 - 1514 (1988)
Symmetrically substituted octaalkyl- and octaarylporphyrins are readily prepared by the reduction of 2-ethoxycarbonyl-3,4-dialkyl (or diaryl)pyrroles with LiAlH4 followed by treatment with acetic acid and oxidizing agents.
Phenyl-substituted porphyrins. 1. Synthesis of meso-phenyl-substituted porphyrins
Syrbu,Lyubimova,Semeikin
, p. 1262 - 1270 (2004)
A method was developed for the synthesis of a series of meso-phenyl-substituted octaalkylporphyrins with various numbers of phenyl groups at various positions. Some of their properties were studied.
