- Insights into the new cadmium(II) metalloporphyrin: Synthesis, X-ray crystal structure, Hirshfeld surface analysis, photophysical and cyclic voltammetry characterization of the (morpholine){(meso-tetra(para-chloro-phenyl)porphyrinato}cadmium(II)
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In this work we report the synthesis of the cadmium(II)-meso-tetra(para-chloro-phenyl)porphyrin with the morpholine O-donor axial ligand with formula [Cd(TClPP)(morph)] (I). This coordination compound adopts a distorted five-coordinate square pyramidal ge
- Mchiri, Chadlia,Dhifaoui,Ezzayani, Khaireddine,Guergueb, Mouhieddinne,Roisnel, Thierry,Loiseau, Fredérique,Nasri
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- UV–visible and fluorescence spectroscopic assessment of meso?tetrakis?(4?halophenyl) porphyrin; H2TXPP (X = F, Cl, Br, I) in THF and THF-water system: Effect of pH and aggregation behaviour
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The current study determines optical and fluorescence response of halogen substituted series of meso?tetrakis?(4?halophenyl) porphyrin; H2TXPP (Halo = F, Cl, Br, I) dye in tetrahydrofuran; THF and THF-water system at changing pH in relationship with changing medium of allure. Effects produced by varying the pH and medium, over spectral and aggregation were discussed in detail. Results show sequential protonation and deprotonation of H2TXPP series in acidic (pH = 4) and (pH =10) basic medium. Specific structural changes of monomeric absorption band were put in evidence on lowering pH, which includes broadening and splitting of soret or B band. Other changes include increasing in intensity and red-shifting of Q1 band indicating some degree of aggregation. The side-by-side aggregation and formation of J-aggregate were quite evident. The red shift of B band featured self-aggregation through head-to-tail molecular ordering which is consonant with absorption-emission data.
- Dar, Umar Ali,Shah, Shakeel A.
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- A One-Step Route to CO2-Based Block Copolymers by Simultaneous ROCOP of CO2/Epoxides and RAFT Polymerization of Vinyl Monomers
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The one-step synthesis of well-defined CO2-based diblock copolymers was achieved by simultaneous ring-opening copolymerization (ROCOP) of CO2/epoxides and RAFT polymerization of vinyl monomers using a trithiocarbonate compound bearin
- Wang, Yong,Zhao, Yajun,Ye, Yunsheng,Peng, Haiyan,Zhou, Xingping,Xie, Xiaolin,Wang, Xianhong,Wang, Fosong
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- Synthesis of novel single site tin porphyrin complexes and the catalytic activity of tin tetrakis(4-fluorophenyl)porphyrin over -caprolactone
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Tin tetrakis(4-fluorophenyl)porphyrin, tin tetrakis(4-chlorophenyl)porphyrin and tin tetrakis(4-bromophenyl)porphyrin complexes were prepared by reaction of butyltin trichloride with tetrakis(4-fluorophenyl)porphyrin, tetrakis(4-chlorophenyl)porphyrin, and tetrakis(4-bromophenyl)porphyrin in tetrahydrofuran and toluene, respectively. These novel complexes were characterized by 1H, 13C NMR, FTIR, mass spectroscopy and elemental analysis. The single site tin complex including fluoride was tested as a catalyst in polymerization of -caprolactone and was very effective. Polycaprolactone was characterized by 1H, 13C NMR, and gel permeation chromatography.
- Yaman, Hanifi,Kayan, Asgar
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- Synthesis and single crystal structure of a new polymorph of 5, 10, 15, 20-tetrakis-(4-chlorophenyl) porphyrin, H2TTPCl4: Spectroscopic investigation of aggregation of H2TTPCl4
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5, 10, 15, 20-tetrakis-(4-chlorophenyl) porphyrin, H2TTPCl4, has been isolated as a new polymorph following the modified Adler’s method and its X-ray crystal structure solved. The new polymorph (I) crystallises in the monoclinic spac
- Dechan, Padma,Bajju, Gauri Devi,Sood, Puneet,Dar, Umar Ali
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- PH-switchable porphyrin receptor for binding halide ions
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Main properties of 5,10,15,20-tetra(4-chlorophenyl)porphyrin in the acetonitrile-perchloric acid system were studied by the method of spectrophotometric titration at standard temperature. The protonation of nitrogen atoms of the tetrapyrrole macrocycle wa
- Ivanova, Yu. B.,Kulikova,Mamardashvili, N. Zh.
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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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- Preparation of a porphyrin-polyoxometalate hybrid and its photocatalytic degradation performance for mustard gas simulant 2-chloroethyl ethyl sulfide
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By combining 5,10,15,20-tetra(4-chlorine)phenylporphyrin (TClPP) and α-Keggin polyoxometalate H5PV2Mo10O40 (H5PVMo) via a simple ion-exchange method, an organic-inorganic hybrid material [C44H28N4Cl4]1.5[H2PMo10V2O40]·2C2H6O (H2TClPP-H2PVMo) was prepared and thoroughly characterized by a variety of techniques. The homogeneous photocatalytic degradation of 2-chloroethyl ethyl sulfide (CEES) (5 μL) by H2TClPP-H2PVMo (1 × 10?6 mol/L) was studied in methanol and methanol-water mixed solvent (v/v = 1:1), in which the degradation rate of CEES reached 99.52% and 99.14%, respectively. The reaction followed first-order reaction kinetics, and the half-life and kinetic constant in methanol and the mixed solvent were respectively 33.0 min, ?0.021 min?1 and 15.7 min, ?0.043 min?1. Mechanism analysis indicated that under visible light irradiation in the air, CEES was degraded via oxidation and alcoholysis/hydrolysis in methanol and the mixed solvent. O2·? and 1O2 generated by H2TClPP-H2PVMo selectively oxidized CEES into a nontoxic sulfoxide. Singlet oxygen capture experiments showed that H2TClPP-H2PVMo (? = 0.73) had a higher quantum yield of singlet oxygen than TClPP (? = 0.35) under an air atmosphere and visible light irradiation.
- Tao, Fangsheng,Tian, Shubo,Wang, Yong'an,Yang, Ying,Zhang, Lijuan,Zhong, Yuxu,Zhou, Yunshan
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supporting information
(2022/01/03)
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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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- Spectroscopic characterization, X-ray molecular structures and cyclic voltammetry study of two (piperazine) cobalt(II) meso-arylporphyin complexes. Application as a catalyst for the degradation of 4-nitrophenol
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Two new cobaltous-porphyrin complexes, namely (μ-piperazine)-bis[(meso-tetra(para-methoxyphenyl)porphyrinato)]cobalt(II) and (piperazine)[meso-tetra(para-chlorophenyl)porphyrin]cobalt(II) dichloromethane disolvate, with the formulas [{CoII(TMPP)}2(μ2-pipz)] (complex 1) and [CoII(TClPP)(pipz)]·2CH2Cl2 (complex 2), were used efficiently as catalysts in the degradation of 4-nitrophenol (4-NP) in an aqueous hydrogen peroxide solution. These cobalt(II)-pipz porphyrin complexes were characterized by a variety of spectroscopic methods including infrared, UV–visible, fluorescence, proton nuclear magnetic resonance, electron paramagnetic resonance (EPR) as well as mass spectrometry. A cyclic voltammetry investigation was also carried out on these two Co(II) metalloporphyrins. The EPR results indicate that both complexes 1 and 2 are paramagnetic low-spin (S = 1/2) cobalt(II) porphyrin complexes. Furthermore, the X-ray diffraction crystal structures of 1 and 2 were determined, and the intermolecular interactions were investigated by Hirshfeld surface analysis.
- Al-Ghamdi, Youssef O.,Brahmi, Jihed,Guergueb, Mouhieddinne,Guerineau, Vincent,Loiseau, Frédérique,Molton, Florian,Nasri, Habib,Nasri, Soumaya,Roisnel, Thierry
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- Synthesis of meso-substituted corroles and porphyrins using iodine as a catalyst
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Abstract: Different types of corroles and porphyrins are synthesized from substituted aldehydes and pyrrole. The current synthetic method involves iodine as catalyst and proceeds at room temperature itself. By varying the amounts of reactants (i.e., pyrrole and aldehydes), the corrole and porphyrins were obtained in good to excellent yields. These products were characterized by 1H-NMR, UV-visible, and HRMS techniques. The reaction approach utilizes the readily available pyrrole and substituted aldehydes as starting materials and makes this reaction highly attractive in diversity-oriented synthesis. Graphic abstract: Different types of porphyrins and corroles are synthesized from substituted aldehydes and pyrrole using iodine as a catalyst and the reaction proceeds at room temperature itself. By varying the amount of reactants (i.e. pyrrole and aldehydes), the porphyrins and corroles are obtained in good to excellent yields.[Figure not available: see fulltext.]
- Chauhan, Shive M S,Dandia, Anshu
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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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- Selective synthesis of 5-aryl-10-(nitromethyl) substituted 15-azatripyrrane, 15-oxatripyrrane and 15-thiatripyrrane: Access to nitromethyl functionalized A3B-porphyrins
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A chemical strategy toward the selective synthesis of unsymmetrical tripyrranes was developed for the formation of meso-aryl and -nitromethyl substituted A3B porphyrins. The iodine catalyzed addition of meso-substituted dipyrromethanes to nitrovinylarenes to generate unsymmetrical 5-aryl-10-(nitromethyl) substituted 15-azatripyrranes, 15-oxatripyrranes and 15-thiatripyrrane under mild conditions has been investigated. The multicomponent reactions of 15-azatripyrranes provided the construction of meso-aryl and -nitromethyl substituted A3B-porphyrins. To the best of our knowledge, the first examples of 5-aryl-10-(nitromethyl) substituted 15-azatripyrranes, 15-oxatripyrranes and 15-thiatripyrrane, and 5-(nitromethyl)-10,15,20-tris(aryl)porphyrins are introduced in this study.
- Seyitdanlioglu, Pinar,Altundal, Gulberil,Cinar, Seda,Unaleroglu, Canan
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p. 14163 - 14169
(2018/08/28)
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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; 0061-0067
(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 0059-0070
(2020/02/07)
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- Temperature-responsive Catalyst for the Coupling Reaction of Carbon Dioxide and Propylene Oxide
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The selective synthesis of polypropylene carbonate (PPC) and cyclic propylene carbonate (CPC) from coupling reaction of CO2 and propylene oxide (PO) is a long term pursuing target. Here we report that a temperature controllable porphyrin alumin
- Zhuo, Chunwei,Qin, Yusheng,Wang, Xianhong,Wang, Fosong
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p. 299 - 305
(2018/02/21)
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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)
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- Reaction of a Nitrosyl Complex of Cobalt Porphyrin with Hydrogen Peroxide: Putative Formation of Peroxynitrite Intermediate
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The cobalt porphyrin complex [(Cl4TPP)Co], 1, {Cl4TPP = 5,10,15,20-tetrakis(4′-chlorophenyl)porphyrinate dianion} in dichloromethane solution was subjected to react with nitric oxide (NO) gas and resulted in the formation of the corr
- Saha, Soumen,Gogoi, Kuldeep,Mondal, Baishakhi,Ghosh, Somnath,Deka, Hemanta,Mondal, Biplab
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p. 7781 - 7787
(2017/07/22)
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- A method for preparing cyclic carbonic ester
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The invention provides a preparation method of cyclic carbonate. The preparation method comprises the following steps: under actions of a main catalyst and a co-catalyst, carrying out a cyclization reaction of carbon dioxide and an epoxide, and thus obtaining the cyclic carbonate. The main catalyst is a metalloporphyrin complex, and the metalloporphyrin complex has a structure represented by the formula I; the co-catalyst is one or more of a quaternary ammonium salt, a quaternary phosphonium salt and an organic base. Compared with the prior art, the metalloporphyrin complex can be used as the catalyst for catalyzing the cyclization reaction of carbon dioxide and the epoxide, and the metalloporphyrin complex as the main catalyst shows extremely high catalytic activity. In addition, in the cyclization reaction process, the metalloporphyrin complex as the main catalyst has relatively high selectivity on the reaction product, inhibits the polycarbonate generation, and improves the content of cyclic carbonate in the product; and the metalloporphyrin complex is recyclable and reused and keeps the high catalytic activity.
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Paragraph 0110; 0111; 0145
(2017/08/25)
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- Catalytic Aerobic Oxidation of Biomass-based Furfural into Maleic Acid in Aqueous Phase with Metalloporphyrin Catalysts
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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)
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- Copper porphyrin-catalyzed aerobic oxidative coupling of terminal alkynes with high TON
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Copper porphyrin-catalyzed Glaser-Hay-type couplings of terminal alkynes generating 1,3-diynes are described. This reaction features high TON (up to 950) and is complete in an hour, providing a facile, clean, and efficient protocol to access various 1,3-d
- Sheng, Wen-Bing,Chen, Tie-Qiao,Zhang, Ming-Zhong,Tian, Mi,Jiang, Guo-Fang,Guo, Can-Cheng
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supporting information
p. 1641 - 1643
(2016/04/04)
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- Synthesis, photophysical properties and biological evaluation of β-alkylaminoporphyrin for photodynamic therapy
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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)
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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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p. 213 - 219
(2016/11/18)
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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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p. 578 - 581
(2016/02/16)
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- An aluminum porphyrin complex with high activity and selectivity for cyclic carbonate synthesis
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An aluminum porphyrin complex with a quaternary ammonium salt cocatalyst exhibits high activity (i.e., a turnover frequency as high as 1.85 × 105 h-1) and selectivity (>99%) for cyclic carbonates synthesis from CO2 and epoxides; the catalyst can be reused at least 4 times with only a slight loss in activity.
- Qin, Yusheng,Guo, Hongchen,Sheng, Xingfeng,Wang, Xianhong,Wang, Fosong
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p. 2853 - 2858
(2015/05/27)
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- Palladium porphyrin catalyzed hydrogenation of alkynes: Stereoselective synthesis of cis -alkenes
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(Tetraphenylporphyrin)palladium was developed as a catalyst for the chemoselective and stereoselective hydrogenation of alkynes to cis-alkenes by the syn-addition of hydrogen. Alkynes containing various functional groups were tolerated in the reaction, which gave the corresponding cis-alkenes in good to excellent yields. Georg Thieme Verlag Stuttgart New York.
- Nishibayashi, Ryo,Kurahashi, Takuya,Matsubara, Seijiro
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supporting information
p. 1287 - 1290
(2014/06/10)
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- Synthesis of substituted meso-tetraphenylporphyrins in mixed solvent systems
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An efficient synthetic method of substituted meso-tetraphenylporphyrins with better isolated yields was proposed by using propionic acid, valeric acid and m-nitrotoluene as mixed-solvent systems. The porphyrin yields in mixed solvent systems were obviousl
- Sun, Zhicheng,She, Yuanbin,Cao, Meijuan,Zhou, Qing,Lu, Xingmei,Zhang, Suojiang
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p. 389 - 400
(2013/07/26)
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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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experimental part
p. 133 - 136
(2012/05/20)
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- Synthesis of meso-tetraarylporphyrins using SeO2 as oxidant
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The oxidative step of the two-step, one-flask synthesis of meso-tetraarylporphyrins is herein conducted with heterogeneous oxidant SeO 2 instead of the usual quinones DDQ or p-chloranil. Evaluation of BF3O(Et)2 or I2 amount for the condensation of the first step combined with the excess of SeO2 defined porphyrin synthesis conditions employing benzaldehydes and pyrrole (or 5-phenyldipyrromethane) as starting materials. The simplicity of the workup, allied with reaction mild conditions, makes this method a good option for the synthesis of this kind of compound.
- Ló, Stephanie M.S.,Ducatti, Diogo R.B.,Duarte, M. Eugênia R.,Barreira, Sandra M.W.,Noseda, Miguel D.,Gonalves, Alan G.
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experimental part
p. 1441 - 1443
(2011/06/10)
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- Synthesis, characterization and spectral properties of substituted tetraphenylporphyrin iron chloride complexes
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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)
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- Controlled porphyrinogen oxidation for the selective synthesis of meso-tetraarylchlorins
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Chlorins have been synthesized through the reduction of the corresponding porphyrins although theoretically they can be obtained from reduced macrocycle forms as porphyrinogens. A new method for the oxidation of meso- tetraarylporphyrinogens was developed generating a substantial amount of chlorin relatively to porphyrin. The structure of the porphyrinogen, particularly the presence of substituents on the meso-phenyl groups, is decisive for the final yield of chlorin. In the case of meso-tetrakis(2,6-dichlorophenyl)porphyrinogen, 92% of the corresponding chlorin is obtained.
- Serra, Arménio C.,Rocha Gonsalves, António M.D'A.
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supporting information; experimental part
p. 4192 - 4194
(2010/09/12)
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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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- Efficient synthesis of 5,10,15-triarylcorroles using Amberlyst 15 under solvent-free conditions
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(Chemical Equation Presented) An efficient and convenient synthesis of 5,10,15-triarylcorroles by the condensation of aryl aldehydes with pyrrole catalyzed by Amberlyst 15 followed by oxidative cyclization with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (D
- Kumari, Pratibha,Chauhan, Shive M. S.
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p. 779 - 783
(2008/09/20)
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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)
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- One-pot general synthesis of metalloporphyrins
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A new general one-pot method for the synthesis of various metalloporphyrins has been developed from pyrrole and substituted aldehydes using transition metal salts. This method allows higher working concentrations than those previously reported. Along with
- Kumar, Anil,Maji, Suman,Dubey, Prashant,Abhilash,Pandey, Sohini,Sarkar, Sabyasachi
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p. 7287 - 7290
(2008/03/13)
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- Synthesis of calix[3]dipyrrins by a modified Lindsey protocol
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(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)
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- A general and efficient palladium-catalyzed intramolecular cyclization reaction of β-brominated porphyrins
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A general and efficient synthesis of fused five-membered porphyrins from the readily available β-brominated porphyrins via palladium-catalyzed intramolecular cyclization has been developed, which can be applied for various metal complexes of β-brominated
- Shen, Dong-Mei,Liu, Chao,Chen, Qing-Yun
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p. 6508 - 6511
(2007/10/03)
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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)
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- Novel synthesis of meso-tetraarylporphyrins using CF3SO 2Cl under aerobic oxidation
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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)
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- Synthesis of meso-tetraarylporphyrins in air with silica chloride as catalyst
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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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- Facile synthesis of meso-substituted dipyrromethanes and porphyrins using cation exchange resins
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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)
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- Phosphorus pentachloride (PCl5) mediated synthesis of tetraarylporphyrins
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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)
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- Further Studies on the Synthesis of meso-Tetraarylazuliporphyrins under Lindsey-Rothemund Reaction Conditions and Their Conversion into Benzocarbaporphyrins
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Azulene has been shown to react with pyrrole and a series of aromatic aldehydes in the presence of boron trifluoride etherate to give meso-tetraarylazuliporphyrins 6. Good yields of azuliporphyrins were obtained for benzaldehyde, 4-chlorobenzaldehyde, 4-bromobenzaldehyde, and 4-iodobenzaldehyde, and under dilute conditions p-tolualdehyde gave respectable yields. In each case, substantial amounts of meso-tetraarylporphyrins were also formed and a minor fraction of carbaporphyrin by-products could be detected, but otherwise no other macrocyclic products could be identified. 4-Nitrobenzaldehyde gave relatively poor yields of the corresponding azuliporphyrin, while p-anisaldehyde only gave trace amounts of product. Pentafluorobenzaldehyde gave variable results, although in this case a large number of additional by-products were identified including N-fused pentaphyrin, hexaphyrin, and higher order porphyrinoids, but no expanded azulene-containing macrocycles could be detected. Azuliporphyrins undergo reversible nucleophilic substitution on the seven-membered ring with pyrrolidine, benzenethiol, hydrazine, or benzylamine to give carbaporphyrin adducts. This property appears to facilitate an oxidative ring contraction of azuliporphyrins 6 with tert-butyl hydroperoxide in the presence of potassium hydroxide to produce mixtures of benzocarbaporphyrins 19 and 20. Tetraaryl-benzocarbaporphyrins exhibit slightly reduced diatropic ring currents compared to their meso-unsubstituted counterparts, although their UV/Vis spectra are very porphyrin-like and exhibit strong Soret bands near 450 nm. The benzocarbaporphyrins undergo reversible protonation to give monocationic and dicationic species. The latter involves C-protonation to generate an internal CH2 within the macrocyclic cavity. X-ray crystallography of tetraphenylbenzocarbaporphyrin 19a confirms that the preferred tautomer has the two NHs on either side of the indene subunit, in agreement with previous theoretical and spectroscopic studies. In addition, the presence of phenyl substituents at the 5,20-positions was found to tilt the indene moiety substantially by 27.4(1)° relative to the [18]annulene substructure. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
- Lash, Timothy D.,Colby, Denise A.,Ferrence, Gregory M.
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p. 4533 - 4548
(2007/10/03)
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- Synthesis, characterisation and spectral studies of some molecular adducts of organotin(IV) chlorides with free base meso-tetraarylporphyrins
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Some molecular complexes of diethyltin(IV) dichloride and methyltin(IV) trichloride with para-substituted mesotetraphenylporphyrins of the general formula [(Et2SnCl2)2H2T(4-X)PP] and [(MeSnCl3)2
- Asadi, Mozaffar,Zabardasti, Abedien
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p. 611 - 613
(2007/10/03)
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- Microwave-assisted synthesis of 5,10,15,20-tetraaryl porphyrins
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Clean and eco-friendly microwave-assisted cyclocondensation of different aryl aldehydes with pyrrole forms 5,10,15,20 tetraaryl porphyrins in 20 to 43% yields in very low amount of propionic acid in one step is presented.
- Chauhan,Sahoo,Srinivas
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-
- Synthesis and Characterization of Three New Unsymmetrical Porphyrins
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The synthesis and characterization of three new unsymmetrical porphyrins is reported. These porphyrins are isomers and have not been reported previously. A new method was used to synthesize the porphyrins which is different from the general synthetic porcedure which was developed by Adler. The structural assignment of the three isomers was based on the elemental analyses, UV-Vis, IR, and 1H NMR spectra.
- Xiaoquan, Lu,Zaixin, Geng,Jingwan, Kang,Zhihua, Wang,Jinzhang, Gao
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p. 2213 - 2222
(2007/10/03)
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- Exclusive 2:1 molecular complexation of 2,3-dichloro-5,6-dicyano-benzoquinone and para-substituted meso-tetraphenylporphyrins: Spectral analogues for diprotonated meso-tetraphenylporphyrin
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Various molar ratios of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) and para-substituted meso-tetraphenyl-porphyrins (H2T(4-X)PP, X = H, Cl, CH3, CH(CH3)2, OCH3) in dichloromethane at room temperature
- Mohajer, Daryoush,Dehghani, Hossein
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p. 199 - 205
(2007/10/03)
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