- Design and synthesis of porphyrins bearing catechols
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The synthesis of meso-tetraarylporphyrines bearing 1-4 catechoylamid groups was achieved. Among the four new compounds prepared, the structure of the disubstituted ligand was elucidated in the solid state by an X-ray analysis.
- Drexler, Cathy,Hosseini, Mir Wais,De Cian, Andre,Fischer, Jean
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- Cyclotriphosphazene ring as a platform for multiporphyrin assemblies
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A simple method has been employed to synthesize a cyclotriphosphazene appended with six porphyrins. The reaction of one equivalent of hexachlorocyclotriphosphazene with six equivalents of 5-(4-hydroxyphenyl)-10,15, 20-tri(p-tolyl)porphyrin or -21-thiaporp
- Rao, M. Rajeswara,Gayatri,Kumar, Amit,Sastry, G. Narahari,Ravikanth
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- Unexpected one-pot synthesis of A3-type unsymmetrical porphyrin
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The first direct synthesis of A3-type unsymmetrical porphyrin is achieved via conventional pyrrole-aldehyde condensation in a one-pot procedure in an appreciable yield. Generalization of this approach to a variety of other aldehydes revealed th
- Mahmood, Mian Hr,Liu, Hai-Yang,Wang, Hua-Hua,Jiang, Yi-Yu,Chang
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- Solution Characterization of Copper(II) and Silver(II) Porphyrins and the One-Electron Oxidation Products by Nuclear Magnetic Resonance Spectroscopy
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The Cu(II) and Ag(II) complexes of tetraphenylporphyrin, octaethylporphyrin, etioporphyrin I, and the one-electron oxidation products of these metalloporphyrin species have been examined by nuclear magnetic resonance (NMR) spectroscopy.Deuterium NMR spect
- Godziela, Gregory M.,Goff, Harold M.
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- Tetraphenylporphyrin derivatives possessing piperidine group as potential agents for photodynamic therapy
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Photodynamic therapy (PDT) is a noninvasive therapeutic and promising procedure in cancer treatment and has attracted considerable attention in recent years. In the present paper, 2-piperidinetetraphenylporphyrin derivatives (P1–P3) conjugated with differ
- Liao, Ping-Yong,Gao, Ying-Hua,Wang, Xin-Rong,Bao, Lei-Lei,Bian, Jun,Hu, Tai-Shan,Zheng, Mei-Zhen,Yan, Yi-Jia,Chen, Zhi-Long
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- Thiaporphyrins with one, two and four unsubstituted meso-carbons: Synthesis and functionalization
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Thiaporphyrins with one, two and four unsubstituted meso carbons were synthesized from easily available thiophene diols. The reactivity at these carbons was demonstrated by carrying out series of reactions and some very useful functional groups were introduced. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).
- Agarwal, Neeraj,Hung,Ravikanth
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- Novel fullerene receptors based on calixarene-porphyrin conjugates
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Several different synthetic approaches enabling a direct covalent connection between the meso-position of porphyrin and the upper rim of calix[4]arene have been studied. The best results were obtained via condensation of an excess of pyrrole and p-methylb
- Ká?, Martin,Lang, Kamil,Stibor, Ivan,Lhoták, Pavel
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- Cobalt Porphyrin-Polypyridyl Surface Coatings for Photoelectrosynthetic Hydrogen Production
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Hybrid materials that link light capture and conversion technologies with the ability to drive reductive chemical transformations are attractive as components in photoelectrosynthetic cells. We show that thin-film polypyridine surface coatings provide a molecular interface to assemble cobalt porphyrin catalysts for hydrogen evolution onto a visible-light-absorbing p-type gallium phosphide semiconductor. Spectroscopic techniques, including grazing angle attenuated total reflection Fourier transform infrared spectroscopy, confirm that the cobalt centers of the porphyrin macrocycles coordinate to pyridyl nitrogen sites of the organic surface coating. The cobalt porphyrin surface concentration and fraction of pyridyl sites coordinated to a cobalt center are quantified using complementary methods of ellipsometry, inductively coupled plasma mass spectrometry, and X-ray photoelectron spectroscopy. In aqueous solutions under simulated solar illumination the modified cathode is photochemically active for hydrogen production, generating the product gas with near-unity Faradaic efficiency at a rate of ≈10 μL min-1 cm-2 when studied in a three-electrode configuration and polarized at the equilibrium potential of the H+/H2 couple. This equates to a photoelectrochemical hydrogen evolution reaction activity of 17.6 H2 molecules s-1 Co-1, the highest value reported to date for a molecular-modified semiconductor. Key features of the functionalized photocathode include (1) the relative ease of synthetic preparation made possible by application of an organic surface coating that provides molecular recognition sites for immobilizing the cobalt porphyrin complexes at the semiconductor surface and (2) the use of visible light to drive cathodic fuel-forming reactions in aqueous solutions with no added organic acids or sacrificial chemical reductants.
- Beiler,Khusnutdinova,Wadsworth,Moore
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- FSM-16: Recyclable Mesoporous Acid Promoter for meso-Tetraarylporphyrin Synthesis
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A new porous silicate, FSM-16 with a pore size of 2.8 nm in diameter is remarkably effective for meso-tetraarylporphyrin synthesis and can be used repeatedly without any efficiency loss after calcination at 500 deg C in air.
- Shinoda, Tomotaka,Izumi, Yusuke,Onaka, Makoto
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- Structurally controlled porphyrin-aggregation process in phospholipid membranes
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Structurally controlled aggregation course for five porphyrins (etioporphyrin [EP], 5-mono- and 5,15-di-[p-tolyl]etioporphyrin [TP and DTP], 5,10,15,20-tetrakis[p-tolyl]porphin [TTP], and 5,10,15,20-tetrakis[3,5-di-tert-butylphenyl]porphin [TBP]) in dipal
- Borovkov, Victor V.,Anikin, Michael,Wasa, Kiyotaka,Sakata, Yoshiteru
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- Synthesis of meso-furyl porphyrins with N4, N3S, N2S2 and N3O porphyrin cores
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A series of meso-furyl porphyrins with four different porphyrin cores (N4, N3S, N2S2 and N3O) were synthesized and characterized. The comparison of NMR, optical and fluorescence properties of meso-furyl porphyrins with porphyrins with six-membered aryl groups indicates that electronic properties of porphyrins were changed drastically on the introduction of furyl groups at meso positions. The maximum shifts in spectral bands were observed for meso-furyl porphyrins with N2S2 core. On protonation, the absorption bands of meso-furyl porphyrins were further red shifted. All these changes were ascribed to the possibility of more planarity of the meso-furyl porphyrins due to the small size of the furyl groups which results in extending the π-delocalisation of the porphyrin ring in to the furyl groups.
- Gupta, Iti,Ravikanth, Mangalampalli
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- Synthesis and characterization of new molecular complexation between free base meso-tetraarylporphyrins and nitrosonium ion as π-acceptor
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NOBF4 reacts with para-substituted meso-tetraarylporphyrins, H2t(4-Xp)p, at room temperature for formation of green molecular complexes, [H2t(4-Xp)p(NO)]BF4. Mole ratio for the porphyrins and nitrosonium ion in the molecular complexes was 1:1, [H 2T(4-X)PP(NO)]BF4. FT-IR, UV-Vis, (1H and 13C) NMR spectral data, elemental analysis and molar conductivity indicated that NO+ (as electron acceptor) is bound to the lone electron pairs of the two pyrrolenine nitrogens in a side of the porphyrin plane. In these molecular complexes, two pyrrolic nitrogen atoms of the porphyrin core coordinate to the acceptor and two protons of the pyrrolic nitrogen atoms have been remained on the porphyrin macrocycles. Molecular complexation of meso-tetraarylporphyrins with NO+ produces a large downfield shift for the NH signal.
- Molaei, Halimeh,Dehghani, Hossein
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- Synthesis and characterization of tetraarylporphyrins in the presence of nano-TiCl4·SiO2
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[MediaObject not available: see fulltext.] Synthesis of tetraarylporphyrins by the coupling of an aromatic aldehyde and pyrrole using nano-TiCl4·SiO2 as mild, inexpensive, and highly efficient catalyst is studied in the present article.
- Zamani, Leila,Mirjalili, Bi Bi Fatemeh
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- Beneficial effects of salts on an acid-catalyzed condensation leading to porphyrin formation
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Addition of one of a variety of salts to the room temperature, two-step, one flask reaction at 0.1 M forming tetraphenylporphyrin (TPP) gave yield increases of up to 2-fold. Among 21 insoluble salts, 12 gave increased yields, 6 had no effect, and 3 gave diminished yields. The salts that gave increases encompassed diverse cations but were restricted to the anions Cl-, Br-, I-, and Ph4B- while SO42-, F-, or BF4- did not give improved yields. All 7 soluble tetraalkylammonium or tetraphenylphosphonium salts (F-, Cl-, Ph4B-, PF6-, or HSO4- counterions) that were surveyed gave yield increases of > 1.5 fold. Thus a 10-1 M pyrrole-benzaldehyde condensation catalyzed with 10-2 M BF3·O(Et)2 in CH2Cl2 containing 0.1 equiv of NaCl (5.85 mg/10 mL CH2Cl2) or 0.0031 equiv of benzyltributylammonium chloride (Bu3BzlNCl) (based on [benzaldehyde]) gave ~50% yield compared with ~25% in the reaction without salt. The pyrrole-aldehyde condensation is much faster in the presence of salt, as measured by the rate of disappearance of benzaldehyde and the rate of formation of the porphyrin. Yield increases in the presence of salt were observed with catalysis by BF3·O(Et)2, BF3·2H2O, and CF3CO2H. Significant salt effects also were observed with BF3·O(Et)2 or CF3CO2H in the solvent diethyl ether, but the maximum yield was 15%. A survey of nine aldehydes showed yield improvements of up to 2-fold in six cases in the presence of salt. During the pyrrole-aldehyde reaction in CH2Cl2 either in the presence or absence of soluble salts, the medium becomes heterogeneous (measured by nephelometry). The addition of water to BF3·O(Et)2 in CH2Cl2 also yields a heterogeneous medium; in the presence of salt this medium affords twice the yield of porphyrin as that formed in the absence of salt. 11B NMR and 19F NMR experiments failed to unveil any new species formed by interaction of chloride-containing salts with BF3·O(Et)2. The complexity of the reaction medium, as well as insufficient information about the nature of the pyrrole-aldehyde condensation, preclude an assignment of mechanisms underlying the salt effects. However, a rank ordering of salts in the porphyrin reaction does not correlate with their desiccative power, and the generality of the salt effects is at odds with the selective anion templating of tetrapyrrolic macrocycles. Irreversible features of the pyrrole-aldehyde condensation have been identified via exchange experiments during the course of the reaction and 13C NMR labeling experiments. The improved reaction conditions can be used for preparative-scale syntheses, as 720 mg tetra(nphenylporphyrin (47% yield) was obtained from a 100 mL-scale reaction with 0.1 M reactants at room temperature.
- Li, Feirong,Yang, Kexin,Tyhonas, John S.,MacCrum, Kristy A.,Lindsey, Jonathan S.
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- Clay-Mediated meso-Tetraarylporphyrin Synthesis
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meso-Tetraphenylporphyrin syntheses from aromatic aldehydes and pyrrole in clay nanospaces were investigated.The clay-promoted porphyrin synthesis was also contrasted with the Lindsey BF3-catalyzed system.
- Onaka, Makoto,Shinoda, Tomotaka,Izumi, Yusuke,Nolen, Ernest
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- Phenomenological statistical physics modeling of metalloporphyrins adsorption at the molecular level
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This paper is aimed to investigate the copper chloride and tin chloride adsorption phenomenon by using a quartz-crystal-adsorbent operating with both auspicious porphyrins: (i) the 5,10,15,20-tetrakis-(4-tolylphenyl)-porphyrin and (ii) the 5,10,15,20-tetr
- Aouaini, Fatma,Ben Yahia, Mohamed,M. Alanazi, Meznah
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- Diboryl and diboranyl porphyrin complexes: Synthesis, structural motifs, and redox chemistry: Diborenyl porphyrin or diboranyl isophlorin?
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The syntheses of diboryl porphyrin complexes [(BX2) 2(ttp)] (ttp: dianion of tetra-p-tolylporphyrin) and the B - B single-bond diboranyl complexes [(BX)2(ttp)] (X = F, Cl, Br, I) are given. The former are prepared from the
- Weiss, Andre,Hodgson, Michael C.,Boyd, Peter D. W.,Siebert, Walter,Brothers, Penelope J.
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- Structural elucidation and study of intermolecular interactions in meso-tetratolylporphyrins
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Synthesis and crystal structure analysis of meso-tetratolylporphyrins, 1-5 combined with computational Hirshfeld surface analysis were investigated. The crystal packing of porphyrins 1, 3 and 4 are arranged in an "orthogonal fashion" whereas 2 and 5 are i
- Soman, Rahul,Sujatha, Subramaniam,Arunkumar, Chellaiah
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- Ionic liquids for tetraarylporphyrin preparation
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In place of widely used dichloromethane, a series of ionic liquids, ILs, was employed as a reaction medium for the one-flask preparation of tetraarylporphyrins. The porphyrin yield in the IL was comparable to that in the dichloromethane, as long as both the water content and the fluidity were conditioned to be in the optimum state. When acidic IL, [C4-SAbim] [CF3SO3] possessing a sulfonic acid moiety was used as the reaction medium, nothing but a black tarry by-product was obtained due to its strong acidity. However, using the acidic IL in a biphasic mode together with dichloromethane enabled porphyrins to form, even at a high reactant concentration. Furthermore, the phase-separated acidic IL was reusable for at least 10 times without any loss of catalytic activity.
- Kitaoka, Satoshi,Nobuoka, Kaoru,Ishikawa, Yuichi
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- SYNTHESIS AND CHARACTERIZATION OF A DIRECTLY LINKED PORPHYRIN-ANTHRAQUINONE MOLECULE
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We have synthesized a porphyrin-anthraquinone molecule (PAQ) in which the AQ moiety is attached directly at a meso-position of tritolylporphyrin.The absorption spectrum shows pronounced perturbations in the bands of both the P and AQ groups that are independent of solvent polarity; a charge-transfer band was not observed.In contrast, the spectrum of the porphyrin fluorescence in PAQ is only moderately red-shifted, but the lifetimes and intensities depend markedly on solvent dielectric constant: the fluorescence is quenched negligibly in solvents with εss s >= 7.In methylene chloride, the major emitting component has a lifetime of ca. 30 ps as compared to ca. 9.0 ns for both tetratolylporphyrin (TTP) and an ester-linked TTP-AQ molecule.An electron transfer mechanism is implicated even though the energetics for net electron transfer do not appear to be favorable (the sum of the redox potentials being essentially isoenergetic with the porphyrin S1 state in benzonitril).We infer that the short distance between the P and AQ moieties (ca. 1.4 Angstroem edge-to-edge) compensates for the otherwise marginal energetics in accord with Marcus theory.However, calculations of the reorganization energy, based on a two-sphere dielectronic continuum model, and estimates of the solvent-dependent reaction energetics, using the Weller equation, do not yield a meaningful correlation with the fluorescence data measured in 19 solvents and binary solvent mixtures.Electron transfer in this intimately linked donor-acceptor molecule may involve an inner-sphere and/or adiabatic mechanism.
- Cormier, Russel A.,Posey, Mary R.,Bell, William L.,Fonda, Harold N.,Connolly, John S.
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- A simple method for efficient synthesis of tetrapyridyl-porphyrin using Adler method in acidic ionic liquids
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We investigated the preparation of tetraphenylporphyrin (TPP) using the several acidic ionic liquids, [HC4im][X] (X- = CF 3SO3-, ClO4-, Cl -, CF3CO2-, and BF4 -), as acid catalytic media. For such ionic liquids, the anion (X-) of [HC4im][X] is related to the acidity of the ionic liquid, and affects porphyrin formation. This synthetic method using acidic ionic liquids can also be applied to other meso-substituted phenyl porphyrins and 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (TPyP), which has 4-pyridyl moieties at four meso positions. In [HC4im][CF3CO 2], TPyP could be obtained in 11% yield, and the [HC 4im][CF3CO2] could be reused at least 3 times without any loss of its catalytic activity. The TPyP synthesis methodology using acidic ionic liquids can remove the ionic liquids from TPyP by easy filtration in contrast to the traditional Alder method, which needs vacuum distillation or liquid-liquid extraction for removing propionic acid. Our proposed porphyrin preparation method using the acidic ionic liquids potentially have wide applications to various useful porphyrin analogues. This journal is the Partner Organisations 2014.
- Kitaoka, Satoshi,Nobuoka, Kaoru,Ihara, Keita,Ishikawa, Yuichi
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- Synthesis and Spectroscopic Investigation of Directly Azobenzene Bridged Diporphyrins
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The synthesis of new directly azobenzene bridged diporphyrins is described.The spectroscopic properties of the new compounds are discussed.
- Hombrecher, Hermann K.,Luedtke, Kerstin
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- Donor-acceptor conjugates derived from cobalt porphyrin and fullerene via metal-ligand axial coordination: Formation and excited state charge separation
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Two types of cobalt porphyrins, viz., meso-tetrakis(tolylporphyrinato)cobalt(II), (TTP)Co (1), and meso-tetrakis(triphenylamino porphyrinato)cobalt(II), [(TPA)4P]Co, (2) were self-assembled via metal-ligand axial coordination of phenyl imidazole functiona
- Subedi, Dili R.,Jang, Youngwoo,Ganesan, Ashwin,Schoellhorn, Sydney,Reid, Ryan,Verbeck, Guido F.,D'Souza, Francis
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p. 533 - 546
(2021/04/28)
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- Efficient oxidation of cycloalkanes with simultaneously increased conversion and selectivity using O2 catalyzed by metalloporphyrins and boosted by Zn(AcO)2: A practical strategy to inhibit the formation of aliphatic diacids
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The direct sources of aliphatic acids in cycloalkanes oxidation were investigated, and a strategy to suppress the formation of aliphatic acids was adopted through enhancing the catalytic transformation of oxidation intermediates cycloalkyl hydroperoxides to cycloalkanols by Zn(II) and delaying the emergence of cycloalkanones. Benefitted from the delayed formation of cycloalkanones and suppressed non-selective thermal decomposition of cycloalkyl hydroperoxides, the conversion of cycloalkanes and selectivity towards cycloalkanols and cycloalkanones were increased simultaneously with satisfying tolerance to both of metalloporphyrins and substrates. For cyclohexane, the selectivity towards KA-oil was increased from 80.1% to 96.9% meanwhile the conversion was increased from 3.83 % to 6.53 %, a very competitive conversion level with higher selectivity compared with current industrial process. This protocol is not only a valuable strategy to overcome the problems of low conversion and low selectivity lying in front of current cyclohexane oxidation in industry, but also an important reference to other alkanes oxidation.
- Shen, Hai-Min,Wang, Xiong,Ning, Lei,Guo, A-Bing,Deng, Jin-Hui,She, Yuan-Bin
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- K2S2O8mediated synthesis of 5-Aryldipyrromethanes and meso-substituted A4-Tetraarylporphyrins
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The synthesis of dipyrromethanes from pyrrole and arylglyoxylic acids in the presence of K2S2O8at 90 C is reported affording dipyrromethanes in very good yields. Unlike an excess pyrrole traditionally used in dipyrromethane synthesis, the current method uses a stoichiometric amount of pyrrole avoiding any use of Br?nsted or Lewis acid. A gram scale synthesis of 5-phenyldipyrromethane is also achieved demonstrating potential scale up of dipyrromethanes using this method feasible. Subsequently, dipyrromethanes were converted to A4tetraarylporphyrins also in the presence of K2S2O8at 90C. A direct synthesis of A4-tetraphenylporphyrin from excess pyrrole and phenylglyoxylic acid in the presence of K2S2O8 at 90C is also reported.
- Laha, Joydev K.,Hunjan, Mandeep Kaur
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p. 664 - 673
(2021/06/03)
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- Selective Solvent-Free and Additive-Free Oxidation of Primary Benzylic C–H Bonds with O2 Catalyzed by the Combination of Metalloporphyrin with N-Hydroxyphthalimide
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Abstract: A protocol for solvent-free and additive-free oxidation of primary benzylic C–H bonds with O2 was presented through adjusting the combination of metalloporphyrins and NHPI as binary catalysts to overcome the deficiencies encountered in current oxidation systems. The effects of reaction temperature, porphyrin structure, central metal, catalyst loading and O2 pressure were investigated systematically. For the optimized combination of T(2-OCH3)PPCo and NHPI, all the primary benzylic C–H bonds could be functionalized efficiently and selectively at 120 °C and 1.0?MPa O2 with aromatic acids as the primary products. The selectivity towards aromatic acids could reach up to 70–95% in the conversion of more than 30% for most of the substrates possessing primary benzylic C–H bonds in the metalloporphyrin loading of 0.012% (mol/mol). And the superior performance of T(2-OCH3)PPCo among the metalloporphyrins investigated was mainly attributed to its high efficiency in charge transfer and fewer positive charges around central metal Co (II) which favored the adduction of O2 to cobalt (II) forming the high-valence metal-oxo complex followed by the production of phthalimide N-oxyl radical (PINO) and the initiation of the catalytic oxidation cycle. This work would provide not only an efficient protocol in utilization of hydrocarbons containing primary benzylic C–H bonds, but also a significant reference in the construction of more efficient C–H bonds oxidation systems. Graphic Abstract: The solvent-free and additive-free oxidation of primary benzylic C–H bonds with O2 was presented through adjusting the combination of metalloporphyrins and NHPI as binary catalysts, and the highest selectivity towards aromatic acid reached up to 95.1% with the conversion of 88.5% in the optimized combination of T(2-OCH3)PPCo and NHPI.[Figure not available: see fulltext.].
- Shen, Hai-Min,Qi, Bei,Hu, Meng-Yun,Liu, Lei,Ye, Hong-Liang,She, Yuan-Bin
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p. 3096 - 3111
(2020/04/29)
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- Crystallographic elucidations of indium(III) porphyrin conformations, morphology and aggregation behaviour: Comparative optical study of free base porphyrins and their indium(III) derivatives at varying pH
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The supramolecular structural architectures of 5, 10, 15, 20-Tetrakis-(4-methoxyphenylporphyrinato) indium (III) chloride (I) and 5, 10, 15, 20-Tetrakis-(4-methylphenylporphyrinato) indium (III) chloride (II) have been determined from their three dimensio
- Dechan, Padma,Bajju, Gauri Devi,Sood, Puneet,Dar, Umar Ali
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- Synthesis, spectral and redox properties of closely spaced pyrrole-β-position-linked porphyrin-fullerene dyads
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Two free base meso-tetraphenylporphyrin-fullerene dyads, H2PMe-C60, H2POMe-C60, and their zinc complexes, ZnPMe-C60 and ZnPOMe-C60, which the para positions of the meso-tetrasubstituted phenyl groups of the porphyrin core were substituted by methyl(-Me) and methoxyl(-OMe) groups respectively, were synthesized. The porphyrin unit in the synthesized dyads is directly linked to the fullerene entity through the pyrrole-β- position rather than through the traditionally meso-substituted phenyl group, which may be more favorable for electron communication between the donor and the acceptor. They are fully characterized by mass spectrometry, nuclear magnetic resonance, infrared spectroscopy and ultraviolet visible spectroscopy. Experimental results obtained from steady-state fluorescence spectroscopy and cyclic voltammetry show that the coordination of the zinc ions lead to an increase in the singlet excited state energy of the metallated porphyrin unit by about 0.15 eV, and to a reduce in the HOMO level and in the HOMO-LUMO energy gap. The molecular reorganization energy decreases after the electron-donating groups of -Me or -OMe attaching to the para position of the meso-phenyl group of the porphyrin moiety. The results of the energy calculations show that photoinduced electron transfer is thermodynamically favorable for the synthesized porphyrin-C60 dyads. There exists a competition between the photoinduced electron transfer and energy transfer processes from the first singlet excited state of porphyrin core to fullerene moiety. The photoinduced electron transfer rate constant of the dyads were calculated according to Marcus theory. The results indicate that the coordination of metal zinc ions lead to great increase in the electron transfer rate constant. Further, the photoinduced electron transfer rate constant increases in the order ZnP-C60, ZnPMe-C60, ZnPOMe-C60.
- Wu, Zhen-Yi,Yang, Sheng-Yan
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p. 244 - 254
(2019/04/17)
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- A four-phenyl porphine preparation method
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The invention discloses a preparation method of meso-tetraphenylchlorin. The preparation method comprises the steps that 1, a mixed solution of pyrrole and aromatic aldehyde is prepared for standby; 2, a solvent is added into a polymerization reactor, nitrogen displacement is conducted till the concentration of tail oxygen is lower than 1%, the solvent is heated to backflow, the mixed solution obtained in the first step starts to be dropwise added, a reaction is started, after the mixed solution is dropwise added completely, the reaction is continuously conducted for 0.05 h to 0.5 h, and then the reaction is stopped; 3, oxygen-containing gas with the oxygen volume fraction ranging from 5% to 100% is fed into the polymerization reactor for oxidation, cooling is conducted after the oxidation is completed, filtration is conducted to obtain a filter cake and filtrate, and a product is obtained after the filter cake is washed and dried. The preparation method of the meso-tetraphenylchlorin has the advantages that the yield is high, safety and environmental protection are achieved, separation and purification are easy, and the product quality is stable.
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Paragraph 0060; 0082-0088
(2018/03/26)
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- A four-phenyl porphine production method (by machine translation)
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The invention discloses a production method for tetraphenyl porphin. The production method includes the steps that 1, pyrrole and aromatic aldehyde are prepared into a mixed solution for standby application; 2, solvent is added into a polymerization reactor, the pressure of the polymerization reactor is maintained at 1-5 atm, the mixed solution obtained in the step 1 starts to be dripped to start a polymerization reaction, after the reaction is finished, reaction products are cooled to normal temperature, and filter liquor and a filter cake are obtained through filtration; 3, the filter cake obtained in the step 2 and propionic acid are added into an oxidation reactor, oxygen-containing gas is introduced to carry out an oxidation reaction, cooling is carried out after oxidation is finished, a solid and filter liquor are obtained through filtration, and the solid is washed and dried to obtain the tetraphenyl porphin. The production method has the advantages of being high in yield, safe and environmentally friendly, separation and purification are easy, and the production quality is stable.
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Paragraph 0059-0062; 0079-0086
(2020/02/07)
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- In silico study, synthesis, and cytotoxic activities of porphyrin derivatives
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Five known porphyrins, 5,10,15,20-tetrakis(p-tolyl)porphyrin (TTP), 5,10,15,20-tetrakis(pbromophenyl) porphyrin (TBrPP), 5,10,15,20-tetrakis(p-aminophenyl)porphyrin (TAPP), 5,10,15- tris(tolyl)-20-mono(p-nitrophenyl)porphyrin (TrTMNP), 5,10,15-tris(tolyl)-20-mono(paminophenyl) porphyrin (TrTMAP), and three novel porphyrin derivatives, 5,15-di-[bis(3,4- ethylcarboxymethylenoxy)phenyl]-10,20-di(p-tolyl)porphyrin (DBECPDTP), 5,10-di-[bis(3,4- ethylcarboxymethylenoxy)phenyl]-15,20-di-(methylpyrazole-4-yl)porphyrin (cDBECPDPzP), 5,15-di- [bis(3,4-ethylcarboxymethylenoxy)phenyl]-10,20-di-(methylpyrazole-4-yl)porphyrin (DBECPDPzP), were used to study their interaction with protein targets (in silico study), and were synthesized. Their cytotoxic activities against cancer cell lines were tested using 3-(4,5-dimetiltiazol-2-il)-2,5- difeniltetrazolium bromide (MTT) assay. The interaction of porphyrin derivatives with carbonic anhydrase IX (CAIX) and REV-ERBβ proteins were studied by molecular docking and molecular dynamic simulation. In silico study results reveal that DBECPDPzP and TrTMNP showed the highest binding interaction with REV- ERBβ and CAIX, respectively, and both complexes of DBECPDPzPREV- ERBβ and TrTMNP-CAIX showed good and comparable stability during molecular dynamic simulation. The studied porphyrins have selective growth inhibition activities against tested cancer cells and are categorized as marginally active compounds based on their IC50.
- Kurniawan, Fransiska,Miura, Youhei,Kartasasmita, Rahmana Emran,Mutalib, Abdul,Yoshioka, Naoki,Tjahjono, Daryono Hadi
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- Iron-based metalloporphyrins as efficient catalysts for aerobic oxidation of biomass derived furfural into maleic acid
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A series of porphyrin type catalysts with the metal active sites of Fe were prepared and investigated in aerobic oxidation of biomass-based furfural to maleic acid (MAD) in aqueous phase. The catalytic performance of meso-tetrakis(4-bromophenyl)porphyrin iron (III) chloride (FeT(p-Br)PPCl) immobilized on different supports was evaluated. It was interesting to find that the catalytic activity varied with the supports and followed the trend: FeT(p-Br)PPCl/SBA–15 > FeT(p-Br)PPCl/meso-ZSM–5 > FeT(p-Br)PPCl/MCM-41. The effect of reaction conditions were discussed in detail over FeT(p-Br)PPCl/SBA-15 catalyst, and 56.1% yield and 73.8% selectivity of MAD were obtained from renewable furfural under the optimal conditions. Moreover, the FeT(p-Br)PPCl/SBA-15 catalyst could be reused five times without a significant decrease of activity in recycling examinations.
- Xie, Yongdi,Huang, Yi,Wu, Chunyan,Yuan, Wenwen,Xia, Yongmei,Liu, Xiang,Wang, Haijun
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- Photodynamic effect of meso-(aryl)porphyrins and meso-(1-methyl-4-pyridinium)porphyrins on HaCaT keratinocytes
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Sixteen porphyrins, including neutral, anionic and cationic meso-(aryl)porphyrins and meso-(1-methyl-4-pyridinium)porphyrins were herein evaluated in terms of their photosensitizing properties against HaCaT keratinocytes. After an initial screening, the cationic porphyrins were studied in more details, by both determining their log POWand performing PDT assays in lower porphyrin concentrations. Porphyrins presenting two or more adjacent positively charged groups, directly linked to the macrocycle meso positions, appeared to be the most effective photosensitizers. The present study also included the dicationic 5,10-diphenyl-15,20-di(1-methylpyridinium-4-yl)porphyrin (14b), which has previously shown promising results on a psoriasis-like in vivo model. Overall results indicated that the beneficial effect related to porphyrins on psoriasis can be related to the decreasing of keratinocyte viability. Furthermore, some of the cationic porphyrins studied appeared as candidates to be utilized as photosensitizers for psoriasis treatment.
- Slomp, Amanda M.,Barreira, Sandra M.W.,Carrenho, Luise Z.B.,Vandresen, Camila C.,Zattoni, Ingrid F.,Ló, Stephanie M.S.,Dallagnol, Juliana C.C.,Ducatti, Diogo R.B.,Orsato, Alexandre,Duarte, M. Eugênia R.,Noseda, Miguel D.,Otuki, Michel F.,Gon?alves, Alan G.
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supporting information
p. 156 - 161
(2016/12/27)
-
- ANTIMICROBIAL AGENT FOR THE BIOCIDAL FINISH OF POLYMERS
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An antimicrobial agent for the biocidal finish of polymers based on biocides is described, whose molecules have at least one nitrogen atom with a free electron pair. In order to achieve an extensive insolubility without loss of the biocidal effect, it is
- -
-
Paragraph 0020
(2017/11/29)
-
- Catalytic Aerobic Oxidation of Biomass-based Furfural into Maleic Acid in Aqueous Phase with Metalloporphyrin Catalysts
-
Catalytic oxidation of renewable furfural into valuable maleic acid in aqueous solutions using metalloporphyrin catalysts was investigated for the first time. The synthesized catalysts were characterized by FT-IR, UV–vis, 1H NMR, elemental analysis, and TGA. The catalysts varied in metal active sites and functional groups, which had different effects on their catalytic activity. Furthermore, the effects of temperatures, reaction time, catalyst loading, and oxygen pressure were studied in detail. Maleic acid could be achieved in 44% yield by using FeT(p-Cl)PPCl as catalyst under optimal conditions. Finally, FeT(p-Cl)PPCl could be reused in five consecutive runs without a significant loss of activity.
- Huang, Yi,Wu, Chunyan,Yuan, Wenwen,Xia, Yongmei,Liu, Xiang,Yang, Huamei,Wang, Haijun
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p. 786 - 794
(2017/07/24)
-
- Synthesis and characterization of some new thallium(III) macrocyclic complexes and their biological studies
-
New symmetrically para-substituted tetraphenylporphyrin Tl(III) salicylate complexes, having the general formula SA/5-SSATl(III)t(4-Y)PP (Y=-H, -CH3, -OCH3); SA=salicylates and 5-SSA=5-sulfosalicylates, were synthesized and character
- Bajju, Gauri D.,Katoch, Sapna,Devi, Gita,Kundan, Sujata,Ashu,Bhagat, Madhullika
-
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- Synthesis, photophysical properties and biological evaluation of β-alkylaminoporphyrin for photodynamic therapy
-
A series of β-alkylaminoporphyrins conjugated with different amines at β position (D1–D3) or with electron-donating and electron-withdrawing substituents at phenyl position (D4–D6) were synthesized. Their photophysical and photochemical properties, intracellular localization, photocytotoxicities in vitro and vivo were also investigated. All target compounds exhibited no cytotoxicities in the dark and excellent photocytotoxicities against HeLa cells. Among them, D6 showed the highest phototoxicity and the lowest dark toxicity, which was more phototoxic than Hematoporphyrin monomethyl ether (HMME). In addition, D6 exhibited best photodynamic antitumor efficacy on BALB/c nude mice bearing HeLa tumor. Therefore, D6 is a powerful and promising antitumor photosensitizer for photodynamic therapy.
- Liao, Ping-Yong,Wang, Xin-Rong,Gao, Ying-Hua,Zhang, Xiang-Hua,Zhang, Li-Jun,Song, Chun-Hong,Zhang, Dan-Ping,Yan, Yi-Jia,Chen, Zhi-Long
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p. 6040 - 6047
(2016/11/09)
-
- Synthesis and characterization of zirconium (IV) derivatives of meso-tetra(p-methylphenyl)porphyrin with acetylacetonate and different phenolates at axial positions
-
In continuation with the previous research work carried out with axially ligated Zirconium(IV)p-methoxy-meso-tetraphenylporphyrin[Zr(p-OCH 3TPP)(Y)(X) [Y = acac and X = different phenolates] here we have undertaken to synthesize meso-tetra(p-me
- Bajju, Gauri D.,Anand, Sunil Kumar,Kundan, Sujata,Deepmala,Ashu,Gita
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experimental part
p. 417 - 432
(2012/10/07)
-
- Synthesis, characterization and spectral properties of substituted tetraphenylporphyrin iron chloride complexes
-
A series of substituted tetraphenylporphyrin iron chloride complexes [RTPPFe(III)Cl, R=o/p-NO2, o/p-Cl, H, o/p-CH3, o/p-OCH3] were synthesized by a novel universal mixed-solvent method and the spectral properties of free b
- Sun, Zhi-Cheng,She, Yuan-Bin,Zhou, Yang,Song, Xu-Feng,Li, Kai
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scheme or table
p. 2960 - 2970
(2011/06/21)
-
- Diporphyrinylamines: Synthesis and electrochemistry
-
The synthesis of three possible diporphyrinylamines is described. All compounds were obtained by using the Buchwald-Hartwig aromatic amination reaction. The electronic spectra of the three porphyrin dimers showed characteristic features found in highly de
- Pereira, Ana M. V. M.,Neves, Maria G. P. M. S.,Cavaleiro, Jose A. S.,Jeandon, Christophe,Gisselbrecht, Jean-Paul,Choua, Sylvie,Ruppert, Romain
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supporting information; experimental part
p. 4742 - 4745
(2011/10/18)
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- Toward carboxylate group functionalized A4, A2B 2, A3B oxaporphyrins and zinc complex of oxaporphyrins
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Series of new oxaporphyrins were isolated from the reaction of furan-1,4-diol, pyrrole, and an aldehyde under Lindsey's conditions, which gives easy access to ester group functionalized oxaporphyrins. The ester substituents can be readily hydrolyzed to te
- Ambre, Ram,Yu, Chien-Yi,Mane, Sandeep B.,Yao, Ching-Fa,Hung, Chen-Hsiung
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p. 4680 - 4688
(2011/06/26)
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- Solvent-free synthesis of meso-tetraarylporphyrins in air: Product diversity and yield optimization
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The scope and optimization of a solvent-free method for the rapid preparation and facile purification of technologically important meso-substituted aryl porphyrins, such as 5,10,15,20-tetraphenylporphyrin is presented. This one-step method involves heating the aromatic aldehyde to ～200°C in a vial fitted with a septum-lined cap, followed by addition of the pyrrole and maintaining the temperature for about 20 minutes. The dioxygen in air serves as the oxidant. Present results show that the addition of benzoic acid as a catalyst improves the yield of 5,10,15,20-tetraphenylporphyrin from 22% to 32% and of para halogenated phenylporphyrins from 10% to ～25%. Herein is also presented an examination of the many factors that influence the yield, the ease of purification, and the ability to scale up the reaction. Since the tarry by-products from this method are much less soluble than in most other synthetic strategies, much less solvent is required for purification; simple extraction is often sufficient. This method can be scaled in the lab to > 300 mg, and provides an attractive route to many meso-substituted porphyrins because of its minimal waste generation in terms of both solvent and chromatography support.
- Nia, Shabnam,Gong, Xianchang,Drain, Charles Michael,Jurow, Matthew,Rizvi, Waqar,Qureshy, Meroz
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scheme or table
p. 621 - 629
(2011/10/11)
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- Synthesis of meso-tetraphenyl porphyrins via condensation of dipyrromethanes with N-tosyl imines
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A new synthetic route for the synthesis of 5,10,15,20-tetraphenyl porphyrins has been developed based on the reaction of 5-substituted dipyrromethanes with N-tosyl imines in the presence of a metal triflate catalyst. meso-Substituted tetraphenyl porphyrins were synthesized in a two-step process. The first step of the method is the metal triflate-catalyzed condensation of 5-substituted dipyrromethanes with N-tosyl imines to form a porphyrinogen intermediate and the second step is the oxidation of the porphyrinogen to porphyrin. The method was applied to the synthesis of trans-A2B2-tetraarylporphyrins and the products were obtained with only a trace amount of one scrambling product. The synthesis of two important building blocks for porphyrin synthesis, mono and di-sulfonamide alkylated 5-substituted dipyrromethanes, was achieved by the addition of 5-substituted dipyrromethane to N-tosyl imine. The application of mono and di-sulfonamide alkylated 5-substituted dipyrromethanes in '2+2' porphyrin formation reactions is presented.
- Temelli, Baris,Unaleroglu, Canan
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experimental part
p. 2043 - 2050
(2009/07/18)
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- Efficient synthesis of meso-tetraarylporphyrins using i2 as catalyst and ibx as oxidant
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meso-Tetraarylporphyrins are synthesized from pyrrole and substituted benzaldehydes by a catalytic amount of I2 as catalyst and o-iodoxybenzoic acid (IBX) as oxidant in two steps and one flask. The advantages of this method include the use of inexpensive and easily available catalyst, avoidance of heavy consumption of CH2Cl2, innocuous oxidant, and good yields.
- Liu, Fenghua,Duan, Le,Wang, Yu-Lu,Zhang, Qian,Wang, Jin-Ye
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experimental part
p. 3990 - 3998
(2009/12/24)
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- Cyclic oligomers based on complementary Zn(ii) and Sn(iv)-porphyrins
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The aggregation of a 1: 1 mixture of complementary Sn(iv)- and Zn(ii)-porphyrins into cyclic decameric and dodecameric assemblies has been demonstrated by 1H NMR, GPC, DOSY and MALDI-TOF spectrometry.
- Metselaar, Gerald A.,Ballester, Pablo,De Mendoza, Javier
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experimental part
p. 777 - 783
(2009/06/19)
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- Synthesis and spectroscopic studies of axially ligated aluminium(III)-p- methyl-meso-tetraphenylporphyrins
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Treatment of p-methyl-meso-tetraphenylporphyrin (p-CH3TPP) with aluminium(III) acetylacetonate (Al(acac)3) and phenol affords the corresponding axially ligated aluminium(III)-pi-methyl-meso-tetraphenylpoiphyrin (Al(III)-p-CH3/s
- Dubey, Sunesh,Bajju, Gauri D.,Javed, Rabia,Sadiq, Tabraiz
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p. 529 - 534
(2008/12/20)
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- Synthesis and anion-binding studies of thiaphlorins and covalently linked thiaphlorin-porphyrin dyads
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A series of thiaphlorins with N2S2 and N3S cores have been prepared in decent yields from readily available precursors. The thiaphlorins were characterized by all spectroscopic techniques and the structures of two thiaphlo
- Gupta, Iti,Froehlich, Roland,Ravikanth, Mangalampalli
-
experimental part
p. 1884 - 1900
(2009/04/04)
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- Novel synthesis of meso-tetraarylporphyrins by using I2 as catalyst and air as oxidant under thermal or UV conditions
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An efficient and novel synthesis of meso-tetraarylporphyrins is accomplished through iodine-catalyzed condensation of pyrrole, and aryl aldehydes and subsequent oxidation by air under thermal or ultraviolet (UV) irradiation conditions. The advantages of this procedure include good yields and a green nature. Copyright
- Duan, Le,Wang, Yu-Lu,Fan, Xue-Sen,Wang, Jin-Ye
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p. 112 - 113
(2008/09/20)
-
- Synthesis of calix[3]dipyrrins by a modified Lindsey protocol
-
(Figure Presented) Bowled over: Calix[3]dipyrrins were synthesized from pyrrole and aryl aldehyde precursors by the Lindsey protocol, modified by the presence of a small amount of water. These bowl-shaped macrocycles can accommodate three metal (M) ions such as NiII and CuII in a hexagonal M3O3 manner (see structure; Cu green, N blue, O red, C black).
- Inoue, Mitsunori,Ikeda, Chusaku,Kawata, Yuji,Venkatraman, Sundararaman,Furukawa, Ko,Osuka, Atsuhiro
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p. 2306 - 2309
(2008/03/12)
-
- Porphyrin, phthalocyanine and porphyrazine derivatives with multifluorenyl substituents as efficient deep-red emitters
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The synthesis and photophysical properties are described for a series of porphyrin, phthalocyanine and pyrazinoporphyrazine derivatives which bear four or eight peripheral fluorenyl substituents as antennae. Representative examples are 5,10,15,20-tetra(9,9-dihexyl-9H-fluoren-2-yl)porphyrin (2), 5,10,15,20-tetrakis[4-(9,9-dihexyl-9H-fluoren-2-yl)phenyl]porphyrin (3), 2,3,9,10,16,17,23,24-octakis(9,9-dihexyl-9H-fluoren-2-yl)-29H, 31H-phthalocyanine (8) and 2,3,9,10,16,17,-23,24-octakis[4-(9,9-dihexyl-9tf- fluoren-2-yl)phenyl]-29H31H-tetrapyrazinoporphyrazine (9). Palladiummediated Suzuki-Miyaura cross-coupling reactions have been key steps for attaching the substituents. The compounds are deep-red emitters: λmax(em) = 659 (3), 737 (8) and 684 nm (9). Their absorption and emission spectra, their fluorescence lifetimes and quantum yields are correlated with the structures of the macrocycles and the substituents. The solution fluorescence quantum yields of porphyrin derivatives substituted with fluorene (2-4) and terphenyl substituents (7) (Φf = 0.21-0.23) are approximately twice that of tetraphenylporphyrin. For phthalocyanine derivative 8, Φf was very high (0.88). Specific excitation of the fluorene units of 8 produced emission from both of them (λmax = 480nm) and also from the phthalocyanine core (λmax = 750 nm), indicating a competitive rate of energy transfer and radiative decay of the fluorenes. Organic light-emitting devices (OLEDs) were made by spincoating techniques by using a polyspirobifluorene (PSBF) copolymer as the host blended with 3 (5 wt. % ) in the configuration ITO/PEDOT:PSS/PSBF copolymer:3/Ca/Al. Deep-red emission (λmax= 663nm; CIE coordinates x = 0.70, y = 0.27) was observed with an external quantum efficiency of 2.5 % (photons/electron) (at 7.5 mA cm-2), a low turn-on voltage and high emission intensity (luminance) of 5500 cdm-2 (at 250 mA/m-2).
- Barker, Carl A.,Zeng, Xianshun,Bettington, Sylvia,Batsanov, Andrei S.,Bryce, Martin R.,Beeby, Andrew
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p. 6710 - 6717
(2008/03/14)
-
- Synthesis and spectral properties of N4, N3S, and N2S2 porphyrins containing one, two, three, and four meso-furyl groups
-
Porphyrins with N4, N3S, and N2S2 cores having one, two, three, and four furyl groups at the meso-positions were synthesized by following various methodologies and characterized by using mass spectrometry, NMR s
- Santosh,Ravikanth
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p. 7833 - 7844
(2008/02/07)
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- The thermodynamic studies of the molecular interactions of tetracyanoethylene with free base meso-tetraarylporphyrins
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The interactions of tetracyanoethylene (TCNE) with 4-substituted meso-tetraphenylporphyrins (H2T(4-X)PP) results adducts of composition 2:1 of TCNE to H2T(4-X)PP, [(TCNE)2H 2T(4-X)PP)]. Formation constants, K, a
- Zabardasti, Abedien,Mirzaeian, Mohammam
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p. 1348 - 1349
(2007/10/03)
-
- Aspects of investigating scrambling in the synthesis of porphyrins: Different analytical methods
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Herein, we discuss the analyses and quantification of the different components in porphyrin mixtures, prepared from p-anisaldehyde, p-tolualdehyde, and 5-(4-bromophenyl)-dipyrromethane with acid catalysis, using NMR and HPLC. The advantages and disadvantages of these analytical methods are emphasized. Due to the similar size of a bromine atom and a methyl group it was possible to grow crystals suitable for X-ray crystallographic studies from a mixture of porphyrins, where the 4-position of the meso-phenyl rings was either substituted with methyl groups or bromine atoms. We also show that X-ray studies are inferior to NMR analysis for determining the components in a porphyrin mixture.
- Nielsen, Christian B.,Krebs, Frederik C.
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p. 5935 - 5939
(2007/10/03)
-
- Effects of aldehyde or dipyrromethane substituents on the reaction course leading to meso-substituted porphyrins
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To better understand the effects of diverse substituents on reactions leading to porphyrins, pyrrole+aldehyde condensations and related reactions of dipyrromethanes were examined. The course of pyrrole+aldehyde condensations was investigated by monitoring the yield of porphyrin (by UV-Vis spectroscopy), reaction of aldehyde (by TLC), and changes in the composition of oligomers (by laser desorption mass spectrometry). Reaction reversibility was examined via exchange experiments. Reversibility of reactions leading to porphyrin was further probed with studies of dipyrromethanes. The reaction course was found to depend on the nature of the substituent and the acid catalyst. Alkyl or electron-donating substituents displayed levels of reversibility (exchange/scrambling) on par or greater than that of the phenyl substituent, whereas electron-withdrawing or sterically bulky substituents exhibited little to no reversibility. The results obtained provide insight into the electronic and steric effects of different substituents and should facilitate the design of synthetic plans for preparing porphyrinic macrocycles. Graphical abstract.
- Geier III, G. Richard,Lindsey, Jonathan S.
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p. 11435 - 11444
(2007/10/03)
-
- Novel synthesis of meso-tetraarylporphyrins using CF3SO 2Cl under aerobic oxidation
-
meso-Tetraarylporphyrins are synthesized from pyrrole and aryl aldehydes cleanly and efficiently in one pot at room temperature using equimolar amount of CF3SO2Cl in the presence of air as oxidant. By this novel method 5,10,15,20-tetraarylporphyrins can be prepared in excellent yields.
- Sharghi, Hashem,Nejad, Alireza Hassani
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p. 1863 - 1868
(2007/10/03)
-
- One-flask synthesis of mono- and trifunctionalized 21-thia and 21-oxaporphyrin building blocks and their application in the synthesis of covalent and noncovalent unsymmetrical porphyrin arrays
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A rapid synthetic route has been developed to synthesize mono- and trifunctionalized 21-thia and 21-oxaporphyrin systems using simple precursors such as 2[α-(aryl)-α-hydroxvmethyl] thiophene (thiophene mono-ol) and 2[α-(aryl)-α-hydroxvmethyl] furan (furan mono-ol), respectively. Condensation of one equivalent of thiophene or furan mono-ol with two equivalents of aryl aldehyde and three equivalents of pyrrole under porphyrin forming conditions followed by column chromatography resulted in functionalized 21-thia or 21-oxaporphyrins. To synthesize monofunctionalized porphyrins, the mono-ol containing the functionalized aryl group was used. The functionalized aldehydes were used to synthesize trifunctionalized porphyrins. The mono-ol method is versatile and applicable to synthesize mono- and trifunctionalized 21-thia and 21-oxaporphyrins containing functional groups such as iodophenyl, ethynylphenyl, hydroxyphenyl, bromophenyl, and pyridyl groups. The monofunctionalized porphyrin building blocks containing iodophenyl and ethynylphenyl groups were used further to synthesize four unsymmetrical covalent porphyrin dimers containing two different porphyrin cores such as N 3S-N4, N3O-N4, and N 3S-N3O bridged via diaryl ethyne group and one symmetrical phenylethyne bridged dimer containing two N3S cores. A preliminary photophysical study on these dimers indicated a possibility of energy transfer from one subunit to another. We also demonstrated the use of trifunctionalized porphyrins in the synthesis of two noncovalent unsymmetrical porphyrin tetramers containing one N3S and three N4 porphyrin subunits.
- Gupta, Iti,Ravikanth, Mangalampalli
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p. 6796 - 6811
(2007/10/03)
-
- Facile synthesis of meso-substituted dipyrromethanes and porphyrins using cation exchange resins
-
The macroporosity and acidity of cation exchange resins play a crucial role in the synthesis of dipyrromethanes and porphyrins; for the first time, cation exchange resins have been used as heterogeneous solid acid catalysts to produce dipyrromethanes and porphyrins in good yields. The reaction, at room temperature, of substituted aromatic aldehydes with pyrrole catalysed by cation exchange resin afforded the corresponding meso-substituted dipyrromethane in yields ranging from 70 to 80%, indicating the broad scope of the reaction. Further, the condensation of meso-substituted dipyrromethane with similar or different substituted aromatic aldehydes, using cation exchange resins furnished meso-tetrakis-symmetrical and mixed porphyrins, respectively. One-pot synthesis of porphyrins can also be carried out directly from the aldehydes and pyrrole under the above conditions. Acidolysis of the dipyrromethane is negligible under the conditions of the porphyrin-forming reaction.
- Naik, Rajan,Joshi, Padmakar,Kaiwar, Sharada P.,Deshpande, Rajesh K.
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p. 2207 - 2213
(2007/10/03)
-
- Phosphorus pentachloride (PCl5) mediated synthesis of tetraarylporphyrins
-
A new synthesis of porphyrins from pyrrole and substituted benzaldehydes is described, with PCl5 as catalyst. Aromatic aldehydes condense irreversibly with pyrrole in the presence of this catalyst, and aerobic oxidation of porphyrinogen provides functionalized porphyrins in yields of 20-65%.
- Sharghi, Hashem,Nejad, Alireza Hassani
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p. 408 - 414
(2007/10/03)
-
- Synthesis of meso-tetraarylporphyrins in air with silica chloride as catalyst
-
Meso-tetraarylporphyrins (14 examples) are prepared efficiently by condensation of pyrrole with aromatic aldehydes in the presence of silica chloride, followed by air oxidation. The method is compared with other published procedures.
- Sharghi, Hashem,Nejad, Ali Reza Hassani
-
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