- A green emitting phosphorescent copper(I) complex with tetrazole derived ligand for electroluminescence application
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In this paper, a tetrazole derived diamine ligand of 2-(1H-tetrazol-5-yl) pyridine (TP) owing electron-donors and short conjugation chain was synthesized to increase the band gap of its corresponding phosphorescent Cu(I) complex. This Cu(I) complex was ch
- Tong, Senmiao,Yuan, Donglin,Yi, Lita
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- Thiocyanate-free ruthenium(II) sensitizer with a pyrid-2-yltetrazolate ligand for dye-sensitized solar cells
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The synthesis of the new complex [Ru(Tetrazpy)(dcbpy)2]Cl is reported, along with its spectroscopical, electrochemical, and theoretical characterization. The first dye-sensitized solar cell device with this complex has been prepared, leading to a 3% of conversion efficiency, promising data considering the simplicity of the Tetrazpy ligand.
- Dragonetti, Claudia,Colombo, Alessia,Magni, Mirko,Mussini, Patrizia,Nisic, Filippo,Roberto, Dominique,Ugo, Renato,Valore, Adriana,Valsecchi, Arianna,Salvatori, Paolo,Lobello, Maria Grazia,Angelis, Filippo De
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- Metal-Binding Isosteres as New Scaffolds for Metalloenzyme Inhibitors
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The principle of isosteres or bioisosteres in medicinal chemistry is a central and essential concept in modern drug discovery. For example, carboxylic acids are often replaced by bioisosteres to mitigate issues related to lipophilicity or acidity while retaining acidic characteristics in addition to hydrogen bond donor/acceptor abilities. Separately, the development of metal-binding pharmacophores (MBPs) for binding to the active site metal ion in metalloenzymes of therapeutic interest is an emerging area in the realm of fragment-based drug discovery (FBDD). The direct application of the bioisostere concept to MBPs has not been well-described or systematically investigated. Herein, the picolinic acid MBP is used as a case study for the development of MBP isosteres (so-called MBIs). Many of these isosteres are novel compounds, and data on their physicochemical properties, metal binding capacity, and metalloenzyme inhibition characteristics are presented. The results show that MBIs of picolinic acid generally retain metal coordinating properties and exhibit predictable metalloenzyme inhibitory activity while possessing a broad range of physicochemical properties (e.g., pKa, logP). These findings demonstrate the use of bioisosteres results in an untapped source of metal binding functional groups suitable for metalloenzyme FBDD. These MBIs provide a previously unexplored route for modulating the physicochemical properties of metalloenzyme inhibitors and improving their drug-likeness.
- Dick, Benjamin L.,Cohen, Seth M.
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- Synthesis and Characterization of New Phosphorescent Heteroleptic Iridium (III) Complex by Using Tetrazole as an Ancillary Ligand for Organic Light-Emitting Diodes
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The yellow emitting tetrazole based heteroleptic iridium(III) complex, bis(diphenylquinoline)iridium(pyridyltetrazole)[(DPQ)2Ir(PyTz)], was synthesized and conformed by 1H-,13C NMR spectral techniques. The purity was also
- Giridhar, Thota,Cho, Woosum,Gal, Yeong-Soon,Lee, Jae Wook,Jin, Sung-Ho
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- Synthesis and photophysical investigations of novel transition metal complexes of pyridine tetrazole ligands
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Two bidentate pyridine-tetrazole ligands viz. pyridine tetrazole (Hpytz) and pyridine tetrazole-N-oxide (Hpytzo), which are integrated in vitro from pyridine carbonitrile by thermal cycloaddition reaction with sodium azide for complexation with transition metals (Fe3+, Co2+, Ni2+, Zn2+ and Ru3+) to improve sophisticated photonic appliances in them as perceived in Ln (III) complexes. The configuration investigation of bis and tris-complexes was studied in solution by UV, FTIR and1H NMR techniques. The hetero-nuclear pyridine tetrazole metal complexes display a close performance concerning the photo-physical properties as displayed by lanthanide(III) complexes and conventional carboxylate analogous.
- Malik, Rayees Ahmad,Bhat, Nawaz Gulzar,Yadav, Renu,Singh, Navjot,Kumar, Gulshan,Mal, Suraj
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- Design, Synthesis, Single X-Ray Crystal Structure, DFT and Molecular Docking Studies of Novel Clip Type-Pyridyltetrazole Analogues
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Novel clip type-pyridyltetrazole analogs of 1,3-bis(5-(pyridin-2-yl)-1H-tetrazol-1-yl)propan-2-ol (3A) and 1,3-bis(5-(pyridin-2-yl)-2H-tetrazol-2-yl) propan-2-ol (3B) have been synthesized by the reaction of 2-(1H-tetrazol-5-yl)pyridine (2) with 0.5 equivalent of epichlorohydrine in DMF using K2CO3 as a base. Relevant monomers of 1-chloro-3-(5-(pyridin-2-yl)-1H-tetrazol-1-yl)propan-2-ol (3C) and 1-chloro-3-(5-(pyridin-2-yl)-2H-tetrazol-2-yl)propan-2-ol (3D) have been synthesized by reaction of compound 2 with one equivalent of epichlorohydrine in DMF using K2CO3 as a base. The compounds 3C and 3D are further modified by the reaction sequences to obtain the ligands 1-(2-(hydroxymethyl)phenoxy)-3-(5-(pyridin-2-yl)-1H-tetrazol-1-yl)propan-2-ol (3G) and 1-(2-(hydroxymethyl)phenoxy)-3-(5-(pyridin-2-yl)-2H-tetrazol-2-yl)propan-2-ol (3H) respectively. The eight synthesized compounds (3A-3H) were characterized by 1H NMR, 13C NMR, IR and Mass spectroscopy. The compound 3A, was crystallized in triclinic primitive system space group P2(1)/c with a = 8.9442 ?, b = 9.2097 ?, c = 11.3558 ?, V = 814.68 ?, R1 = 0.0213 at 298 K. The compounds 3A and 3B were optimized, HOMO/ LUMO and molecular electrostatic potential studies were carried by DFT calculations with B3LYP/6.311G** method. The molecular docking studies were performed on 3A, 3B, 3G and 3H and the studies reveal that all the compounds exist in crescent shapes.
- Surendra Babu,Santhosh Reddy,Ghosh, Kalyan Sundar,Sahoo, Bijaya Ketan,Himasekar,Mustafa, Shaik
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- Two novel bipolar Ir(III) complexes based on 9-(4-(pyridin-2-yl)phenyl)-9H-carbazole and N-heterocyclic ligand
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Two novel bipolar Ir(III) complexes named (Czppy)2Ir(tfmptz) and (Czppy)2Ir(pptz) were synthesized and characterized, where the Czppy is 9-(4-(pyridin-2-yl)phenyl)-9H-carbazole, tfmptz refers to 2-(3-(trifluoromethyl)-1H-1,2,4-triazol-5-yl)pyridine and Hpptz represents 2-(1H-tetrazol-5-yl)pyridine, respectively. Their molecular structures were confirmed by 1H NMR and photophysical were investigated. The performances in phosphorescent organic light emitting devices (PhOLEDs) were characterized by a heavy doping concentration of 20 wt% in host as emitting layer. The results suggest that the number of nitrogen atoms in ancillary has no obvious effects on their photophysical properties. Both (Czppy)2Ir(tfmptz) and (Czppy)2Ir(pptz) display the blue-green emission with the peaks at 492, 526 nm. The performances of complexes (Czppy)2Ir(tfmptz) in PhOLEDs superior to that of the (Czppy)2Ir(pptz) due to the poor thermal stability.
- Huixia, Xu,Fang, Wang,Kexiang, Wang,Peng, Sun,Jie, Li,Tingting, Yang,Hua, Wang,Bingshe, Xu
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- Synthesis, Characterization, and Biological Activities of Pendant Arm-Pyridyltetrazole Copper(II) Complexes: DNA Binding/Cleavage Activity and Cytotoxic Studies
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2-(1H-Tetrazol-5-yl)pyridine (L) has been reacted separately with Me2NCH2CH2Cl·HCl and ClCH2CH2OH to yield two regioisomers in each case, N,N-dimethyl-2-[5-(pyridin-2-yl)-1H-tetrazol-1-yl]ethanamine (L1)/N,N-dimethyl-2-[5-(pyridin-2-yl)-2H-tetrazol-2-yl]ethanamine (L2) and 2-[5-(pyridin-2-yl)-1H-tetrazol-1-yl]ethanol (L3)/2-[5-(pyridin-2-yl)-2H-tetrazol-2-yl]ethanol (L4), respectively. These ligands, L1-L4, have been coordinated with CuCl2·H2O in 1:1 composition to furnish the corresponding complexes 1-4. EPR Spectra of Cu complexes 1 and 3 were characteristic of square planar geometry, with nuclear hyperfine spin 3/2. Single X-ray crystallographic studies of 3 revealed that the Cu center has a square planar structure. DNA binding studies were carried out by UV/VIS absorption; viscosity and thermal denaturation studies revealed that each of these complexes are avid binders of calf thymus DNA. Investigation of nucleolytic cleavage activities of the complexes was carried out on double-stranded pBR322 circular plasmid DNA by using a gel electrophoresis experiment under various conditions, where cleavage of DNA takes place by oxidative free-radical mechanism (OH·). In vitro anticancer activities of the complexes against MCF-7 (human breast adenocarcinoma) cells revealed that the complexes inhibit the growth of cancer cells. The IC50 values of the complexes showed that Cu complexes exhibit comparable cytotoxic activities compared to the standard drug cisplatin.
- Mustafa, Shaik,Rao, Bommuluri Umamaheswara,SurendraBabu, Manubolu Surya,Raju, Kalidindi Krishnam,Rao, Gollapalli Nageswara
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- Synthesis and structures of 5-(pyridyl)tetrazole complexes of Mn(II)
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New MnII complexes containing 5-(2-pyridyl)tetrazole, 5-(3-cyano-4-pyridyl)tetrazole or 5-(4-pyridyl)tetrazole ligands are described. The complexes are prepared by reaction of the corresponding cyanopyridines with sodium azide in the presence of MnII salts. All the complexes have been characterized by X-ray crystallography, which reveals that 5-(pyridyl)tetrazole ligands can coordinate to Mn through either type of nitrogen atom in the tetrazole residue or via the pyridyl group. In the solid state, extended 2D and 3D structures are produced through networks of hydrogen bonding (involving water molecules and the tetrazolate residue). Acidification of the complexes produces the corresponding free 5-(pyridyl)-1H-tetrazole. The Royal Society of Chemistry 2005.
- Lin, Ping,Clegg, William,Harrington, Ross W.,Henderson, Richard A.
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- Strongly photoluminescent Eu(III) tetrazolate ternary complexes with phosphine oxides as powerful sensitizers
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The Eu(III) cation forms electrically neutral photoluminescent complex with 5-(2-pyridyl-1-oxide)tetrazolate (PTO) anion. Although the photoluminescence properties of such tertiary Eu(III) and Tb(III) complexes were not as high (13 and 31% photoluminescence quantum yield, respectively) as reported for other diketonate lanthanide complexes probably because of high number of nitrogen atoms involved in PTO which leads to attachment of water molecules, reducing the luminescence quantum yield with vibrational and rotational quenching. Here, we report the removal of quencher molecules from the coordination sphere of tris-europium tetrazolate oxide complex by replacing them with various phosphine oxides which leads to improved photoluminescence quantum yield for the complexes by acting as auxiliary co-ligands with that of the main antenna 5-(2-pyridyl-1-oxide)tetrazolate. The coordination sphere in these complexes can be complemented by aromatic phosphine oxides to provide highly photoluminescent Eu(III) complexes. The highest quantum yield was 38% in 3 [Eu(PTO)3·DPEPO](H2O)5 containing bis(2-(diphenylphosphino)phenyl) ether oxide (DPEPO) as compared to tris-europium complex with 5-(2-pyridyl-1-oxide)tetrazolate.
- Mal, Suraj,Pietraszkiewicz, Marek,Pietraszkiewicz, Oksana
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- Going from green to red electroluminescence through ancillary ligand substitution in ruthenium(ii) tetrazole benzoic acid emitters
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The synthesis, characterization, photoluminescence (PL) and electroluminescence (EL) properties of novel ruthenium(ii) emitters with 4-(1H-tetrazole-5-yl)benzoic acid (TzBA) as a novel basic ligand and 2,2-bipyridine (bpy), 1,10-phenanthroline (phen) and pyridine tetrazole (pyTz) as ancillary ligands have been reported. The EL results show that the luminescence of Ru(TzBA) depends on the ancillary ligands, which can be used to tune the EL color of the Ru(TzBA) complexes from green to red emission. The role of ancillary ligands in EL devices of the Ru(TzBA) complexes was investigated by DFT calculations. The device [Ru(TzBA)(bpy)(pyTz)(SCN)] (5) has a luminance of 480 cd m-2 and a maximum efficiency of 1.2 cd A-1 at 16 V, which are the highest values among the five devices studied. The turn-on voltage of this device is approximately 6 V. We suggest that an electroplex occured at the PVK-Ru complex interface when pyTz was incorporated as an ancillary ligand into Ru(TzBA). OLED studies reveal that pyTz as an ancillary ligand exhibits better current generating capacity than bpy and phen ligands, which are introduced by an emitter (5).
- Shahroosvand, Hashem,Najafi, Leyla,Sousaraei, Ahmad,Mohajerani, Ezeddin,Janghouri, Mohammad
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- Polymer immobilization effect on excited state of emitting copper complex: Synthesis, characterization and performance improvement
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In this effort, the correlation between polymer immobilization effect and excited state of emitting copper complex was discussed. An electron-pulling diamine ligand having an oxadiazole ring and a fluorine atom was synthesized. Its corresponding Cu(I) com
- Zhao, Yuqing,Van, Yilei,Wang, Di,Li, Lihua,Qiu, Pan
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- Synthesis of novel tetrazole transition metal complexes for advanced photonic applications
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As tetrazole themselves revealed a rich photochemistry and are piquantly affected by the presence of substituents on tetrazole ring. This exertion explores the harmony of two bidentate ligands-pyridine tetrazole (Hpytz) and pyridine tetrazole-N-oxide (Hpytzo) as "antennae" and their complexes with transition metals (Fe3+, Co2+, Ni2+, Zn2+ and Ru3+). The erections of these pyridine tetrazole metal complexes were elucidated by UV, IR and 1H NMR by using DMSO, acetonitrile as solvents in which these metal complexes persist in undissociated form and also show high melting point >360 °C. These pyridine tetrazole ligands ("antennae") sensitize efficiently the metal centre and stimulus the absorption window of pyridine tetrazole transition metal complexes, which was appreciably stretched towards the UV-visible region of 400-800 nm. The wavelength of these ligands λemission was found to be amplified upto 522-540 nm (λexcitation = 270 nm) that might enlightens the extremely conjugated unsaturated system which triggers the UV-region and for metal complexes (λexcitation, Fe3+ = 270 nm, Co2+ = 280 nm, Ni2+ = 285 nm, Zn2+ = 270 nm and Ru3+ = 260 nm (λemission, Fe3+ = 522.5 nm, Co2+ = 576 nm, Ni2+ = 554 nm, Zn2+ = 521 nm and Ru3+ = 522 nm). The escalation in λemission of the metal complexes with novel designed tetrazole ligands spectacles a drift on complex formation due to the augmented conjugation and conformation, which might sensitizes luminescence properties as reported with La(III) complexes more proficiently. The fluorescent property revealed with these neutral pyridine tetrazole derivatives stipulate an efficient alternative to that of usual dipicolinate analogues.
- Malik, Rayees Ahmad,Bhat, Nawaz Gulzar,Yadav, Renu,Singh, Navjot,Kumar, Gulshan,Mal, Suraj
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- Coordination studies of copper(II), cobalt(II) and iron(II) with isomeric pyridyl-tetrazole ligands
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The reaction of 2-(2H-tetrazol-5-yl)pyridine (L1) with 1,6-dibromohexane results in formation of the isomers 2-(6″-bromohexyl)-(1-tetrazol-5-yl) pyridine (L2) and 2-(6″-bromohexyl)-(2-tetrazol-5-yl)pyridine (L3). Coordination reactions of L2 and L3 with CuCl2·2H 2O, Co(SCN)2 and Fe(ClO4)2· H2O yielded the strongly coloured solids [Cu(II)(L2)Cl 2]2 (1), [Cu(II)(L3)Cl2]2 (2), [Co(II)(L2)2(NCS)2] (3), [Co(II)(L3)2(NCS) 2] (4), [Fe(II)(L2)2(H2O)2](ClO 4)2 (5) and [Fe(II)(L3)2(H2O) 2](ClO4)2 (6), containing high-spin metal centres for the Co(II) and Fe(II) compounds. X-ray crystal structures were obtained for complexes 1-5. In each complex, ligands L2 and L3 coordinate to the metal centre through the pyridyl N atom and the 1-N site of the tetrazole ring, and the pyridyl-tetrazole ligand remains planar in all cases except 3. Complexes 1 and 2 comprise a central Cu2Cl2 dimeric core with Cu(II) in an essentially square-pyramidal coordination environment. Complexes 3 and 4 contain Co(II) in a distorted octahedral coordination environment. In 3, the pyridyl and tetrazole rings of L2 are twisted with respect to each other and the complex adopts a puckered conformation in its equatorial plane. Complex 5 contains water molecules coordinated to Fe(II) in the axial sites, which form hydrogen bonds to the perchlorate counter anions.
- Bond, Andrew D.,Fleming, Adrienne,Gaire, Jackie,Kelleher, Fintan,McGinley, John,McKee, Vickie,Sheridan, Ursula
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- Selective Synthesis and Complexation of Novel N,N′-Alkylene-Bridged Bis(5-pyridyltetrazole)
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A novel N,N′-alkylene-bridged bis(5-pyridyltetrazole) ligand, namely 2,5-bis[5-(2-pyridyl)-tetrazol-2-yl]-2,5-dimethylhexane (bpt), was prepared by regioselective N2-alkylation of 5-(2-pyridyl)tetrazole with 2,5-dimethylhexane-2,5-diol in perchloric acid. The ligand bpt was found to react with copper(II) chloride to give the dinuclear complex [Cu2(bpt)Cl4]. According to single-crystal X-ray analysis of the complex, bpt acts as a chelating ligand, coordinated by the metal through the tetrazole ring N4 and the pyridine ring nitrogen atoms. In the complex molecule, two copper atoms are linked by double chlorido bridges, and ligand bpt plays the role of the third bridge. The temperature-dependent magnetic susceptibility measurements of the complex revealed that the copper(II) ions were weakly antiferromagnetically coupled showing a coupling constant J of –1.04 cm–1.
- Voitekhovich, Sergei V.,Mosalkova, Anastasiya P.,Lyakhov, Alexander S.,Ivashkevich, Ludmila S.,Schmorl, Sara,Kersting, Berthold,Ivashkevich, Oleg A.
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- Synthesis, characterization and antimicrobial activity of isomeric pyridyl-tetrazole derivative ligands and their bivalent metal complexes
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Nickel(II) and zinc(II) complexes were synthesized from bidentate isomeric pyridyl tetrazole ligands such as 2-(1-vinyl-1H-tetrazol-5-yl)pyridine (L1), N,N-dimethyl-3-(5-(pyridin-2-yl)-1H-tetrazol-1-yl)propan-1-amine (L2), 2-(2-vinyl-2H-tetrazol-5-yl)pyridine (L3), N,Ndimethyl-3-(5-(pyridin-2-yl)-2H-tetrazol-2-yl)propan-1-amine (L4). All the complexes were characterized in the light of elemental analysis, FTIR, UV-visible and magnetic studies. The spectroscopic data suggested that, the ligands act as neutral and monobasic bidentate ligands and form octahedral complexes with general formula [M(L1-4)2Cl2] (M = Ni(II) and Zn(II). The isomeric pyridyl-tetrazole derivative ligands and their Ni(II) and Zn(II) complexes have also been screened for their antibacterial (Bacillus subtilis, Staphylococcus aureus, Proteus vulgaris) and antifungal activities (Aspergillus Niger, Candida albicans) by MIC method.
- Rao, B. Umamaheswara,Krishna,Rao, G. Nageswara
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- A Ratiometric Tetrazolylpyridine-Based "turn-On" Fluorescent Chemosensor for Zinc(II) Ion in Aqueous Media
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The highly selective ratiometric "turn-on" fluorescent sensing of Zn2+ ion involving 2-(1H-tetrazole-5-yl)pyridine (2PT) in aqueous medium is reported, which is not observed when other metal ions are present. Upon 2PT binding selectively with Zn2+ ion, a fluorescence enhancement is observed that is attributed to an enhancement of localized emission and suppression of excited-state intramolecular proton transfer. The described sensing system involving 2PT is also successfully applied to the detection of Zn2+ ion in real samples with a detection limit of 7.5×10-7 M.
- Kaleeswaran, Palanichamy,Azath, Ismail Abulkalam,Tharmaraj, Vairaperumal,Pitchumani, Kasi
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- Iridium and Palladium CO2Hydrogenation in Water by Catalyst Precursors with Electron-Rich Tetrazole Ligands
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Hydrogenation of CO2 to formate serves as a means of H2 storage. By utilizing robust, electron-rich and bulky N∧N bidentate tetrazolylpyridyl ligands, we have prepared CO2 hydrogenation iridium(III) and palladium(II) catalyst precursors (3-7) that operate in water as a solvent. In situ 1H NMR spectroscopic data obtained when the hydrogenation catalyst is 5 detect that a hydrido-bridged binuclear iridium intermediate compound is formed prior to the formation of the catalytically active iridium hydride species. This hydrido-bridged iridium intermediate is observable by in situ 1H NMR spectroscopy even after extended periods of storage. In addition, we demonstrate that product formation in the CO2 hydrogenation, catalyzed by these tetrazolylpyridyl iridium catalysts, proceeds via either CO2 hydrogenation or NaHCO3 reduction.
- Darkwa, James,Makhubela, Banothile C. E.,Ocansey, Edward
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- CuO–NiO bimetallic nanoparticles supported on graphitic carbon nitride with enhanced catalytic performance for the synthesis of 1,2,3-triazoles, bis-1,2,3-triazoles, and tetrazoles in parts per million level
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The unification of CuCl2·2H2O and NiCl2·6H2O with the support of graphitic carbon nitride yielded to form an efficient, synergistic, bimetallic nano-catalyst CuO–NiO@g-C3N4. FT-IR, SEM, TEM
- Gajurel, Sushmita,Dam, Binoyargha,Bhushan, Mayank,Singh, L. Robindro,Pal, Amarta Kumar
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- Magnetic nitrogen-doped carbon derived from silk cocoon biomass: a promising and sustainable support for copper
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In this study, a magnetic nitrogen-doped carbon-based copper (MNC-Cu) catalyst was fabricated so that natural silk cocoons undergo thermal processes and then activate by combining with Fe3O4 MNPs as a suitable substrate for placement copper metal. The efficiency of the generated catalyst in the synthesis of 5-substituted 1H-tetrazole derivatives was evaluated by the [3 + 2] cycloaddition reaction of aromatic aldehydes, azide ions, and hydroxylamines. FT-IR, FE-SEM, EDS, TEM, XRD, TGA, and VSM techniques have been adopted to identify and validate this heterogeneous catalyst. The observation from EDS, elemental mapping, XRD, and FT-IR analysis confirms the immobilization of Cu metals on the MNC surface and uniform distribution of species and then no aggregation occurs during functionalization. VSM results show the magnetic feature of fabricated catalyst, and based on the leaching test, the amount of catalyst leaching was negligible. Moreover, this reaction is a one-pot multicomponent reaction (MCRs) or more precisely a one-pot, three-component reaction, which is one of the advantages of this work. The fabricated catalyst shows high efficiency, good stability, and considerable reactivity in synthesizing 5-substituted 1H-tetrazole derivatives. So it can be seen that the fabricated magnetic catalyst is a useful and practical catalyst for synthesizing [3 + 2] cycloaddition reactions. Reusability and recyclability for five sequential runs without notable increase and reduction in activity are other advantages. In addition, the magnetic properties of this heterogeneous catalyst led to easy and quickly recovered and striking copper leaching. Graphical abstract: [Figure not available: see fulltext.]
- Tahmasbi, Marzieh,Akbarzadeh, Parisa,Koukabi, Nadiya
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p. 1383 - 1401
(2021/12/01)
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- Oxidation/ MCR domino protocol for direct transformation of methyl benzene, alcohol, and nitro compounds to the corresponding tetrazole using a three-functional redox catalytic system bearing TEMPO/Co(III)-porphyrin/ Ni(II) complex
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A redox catalytic system for oxidation-reduction reactions and the domino preparation of tetrazole compounds from nitro and alcohol precursors was designed, prepared and characterized by UV–vis, GPC, TGA, XRD, EDX, XPS, VSM, FE-SEM, TEM, DLS, BET, NMR, and ICP analyses. The catalyst was prepared via several successive steps by demetalation of chlorophyll b, copolymerization with acrylated TEMPO monomers, complexation with Ni and Co metals (In two different steps), then immobilized on magnetic nanoparticles. The presence of three functional groups including TEMPO, coordinated cobalt, and coordinated nickel in the catalyst, allowed the oxidation of various types of alcohols, alkyl benzenes as well as the reduction of nitro compounds by a single catalyst. All reactions yielded up to 97 % selectivity for oxidation and reduction reactions. Next, the ability of the catalyst to successfully convert alcohol, methyl benzenes and nitro to their corresponding tetrazoles was studied.
- Mahmoudi, Boshra,Rostami, Amin,Kazemnejadi, Milad,Hamah-Ameen, Baram Ahmed
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- Fe3O4@L-lysine-Pd(0) organic–inorganic hybrid: As a novel heterogeneous magnetic nanocatalyst for chemo and homoselective [2 + 3] cycloaddition synthesis of 5-substituted 1H-tetrazoles
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An efficient and sustainable synthetic protocol has been presented to synthesis and 5-substituted 1H-tetrazole privileged heterocyclic substructures. The synthetic protocol involves two-component reaction between aryl nitriles and NaN3 in water using complex of L-lysine-palladium nanoparticles (NPs) modified Fe3O4 nanoparticles as magnetically separable, recyclable, and reusable heterogeneous catalyst. Magnetically retrievable L-lysine-Pd(0) modified Fe3O4 nanoparticles were applied in [2 + 3] cycloaddition synthesis of 5-substituted 1H-tetrazoles. The advantages of this strategy include easy recovery and efficient reusability of the expensive Pd NPs, obtaining high yields of [2 + 3] cycloaddition, short reaction times, and all of the reported synthetic strategies are being performed in water as green solvent for a wide range of substrates.
- Ashraf, Muhammad Aqeel,Liu, Zhenling,Li, Cheng,Zhang, Dangquan
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- Evaluating Metal-Ligand Interactions of Metal-Binding Isosteres Using Model Complexes
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Bioisosteres are a useful approach to address pharmacokinetic liabilities and improve drug-like properties. Specific to developing metalloenzyme inhibitors, metal-binding pharmacophores (MBPs) have been combined with bioisosteres, to produce metal-binding isosteres (MBIs) as alternative scaffolds for use in fragment-based drug discovery (FBDD). Picolinic acid MBIs have been reported and evaluated for their metal-binding ability, pharmacokinetic properties, and enzyme inhibitory activity. However, their structural, electronic, and spectroscopic properties with metal ions other than Zn(II) have not been reported, which might reveal similarities and differences between MBIs and the parent MBPs. To this end, [M(TPA)(MBI)]+ (M = Ni(II) and Co(II), TPA = tris(2-pyridylmethyl)amine) is presented as a bioinorganic model system for investigating picolinic acid, four heterocyclic MBIs, and 2,2′-bipyridine. These complexes were characterized by X-ray crystallography as well as NMR, IR, and UV-vis spectroscopies, and their magnetic moments were accessed. In addition, [(TpPh,Me)Co(MBI)] (TpPh,Me = hydrotris(3,5-phenylmethylpyrazolyl)borate) was used as a second model compound, and the limitations and attributes of the two model systems are discussed. These results demonstrate that bioinorganic model complexes are versatile tools for metalloenzyme inhibitor design and can provide insights into the broader use of MBIs.
- Cohen, Seth M.,Dick, Benjamin L.,Kalaj, Mark,Karges, Johannes,Prosser, Kathleen E.,Seo, Hyeonglim
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p. 17161 - 17172
(2021/11/17)
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- Synthesis of tetranuclear rhenium(i) tricarbonyl metallacycles
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Re(i) tricarbonyl complexes have received much attention due to their attractive photochemical, electrochemical, and biological properties. Beyond simple mononuclear complexes, multinuclear assemblies offer greater structural diversity and properties. Despite previous reports on the preparation of di-, tri-, or tetranuclear Re(i) tricarbonyl assemblies, the synthesis of these supramolecular structures remains challenging due to overall low yields or tedious purification protocols. Herein, the facile preparation and characterization of tetranuclear Re(i) tricarbonyl metallacycles with a square geometry is reported using a tetrazole-based ligand. The synthesis of the metallacycle was optimized using different metal precursors, solvents, temperatures, and reagent concentrations. Finally, the scope of suitable tetrazole-based ligands was explored to produce several tetranuclear Re(i) tricarbonyl-based metallacycles. This journal is
- Cohen, Seth M.,Karges, Johannes,Seo, Hyeonglim
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supporting information
p. 16147 - 16155
(2021/11/27)
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- A silicododecamolybdate/pyridinium-tetrazole hybrid molecular salt as a catalyst for the epoxidation of bio-derived olefins
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The hybrid polyoxometalate (POM) salt (Hptz)4[SiMo12O40]?nH2O (1) (ptz = 5-(2-pyridyl)tetrazole) has been prepared, characterized by X-ray crystallography, and examined as a catalyst for the epoxidation of cis-cyclooctene (Cy) and bio-derived olefins, namely dl-limonene (Lim; a naturally occurring monoterpene found in the rinds of citrus fruits), methyl oleate and methyl linoleate (fatty acid methyl esters (FAMEs) obtained by transesterification of vegetable oils). The crystal structure of 1 consists of α-Keggin-type heteropolyanions, [SiMo12O40]4-, surrounded by space-filling and charge-balancing 2-(tetrazol-5-yl)pyridinium (Hptz+) cations, as well as by a large number of water molecules of crystallization (n = 9). The water molecules mediate an extensive three-dimensional (3D) hydrogen-bonding network involving the inorganic anions and organic cations. For the epoxidation of the model substrate Cy in a nonaqueous system (tert-butylhydroperoxide as oxidant), the catalytic performance of 1 (100% epoxide yield at 24 h, 70 °C) was superior to that of the tetrabutylammonium salt (Bu4N)4[SiMo12O40] (2) (63% epoxide yield at 24 h), illustrating the role of the counterion Hptz+ in enhancing catalytic activity. The hybrid salt 1 was effective for the epoxidation of Lim (69%/85% conversion at 6 h/24 h) and the FAMEs (87–88%/100% conversion at 6 h/24 h), leading to useful bio-based products (epoxides, diepoxides and diol products).
- Nunes, Martinique S.,Neves, Patrícia,Gomes, Ana C.,Cunha-Silva, Luís,Lopes, André D.,Valente, Anabela A.,Pillinger, Martyn,Gon?alves, Isabel S.
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supporting information
(2020/11/27)
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- Catalytic conversion of 2,4,5-trisubstituted imidazole and 5-substituted 1H-tetrazole derivatives using a new series of half-sandwich (η6-p-cymene)Ruthenium(II) complexes with thiophene-2-carboxylic acid hydrazone ligands
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A new series of half-sandwich (η6-p-cymene) ruthenium(II) complexes with thiophene-2-carboxylic acid hydrazide derivatives [Ru(η6-p-cymene)(Cl)(L)] [L = N'-(naphthalen-1-ylmethylene)thiophene-2-carbohydrazide (L1), N'-(anthracen-9-ylmethylene)thiophene-2-carbohydrazide (L2) and N'-(pyren-1-ylmethylene)thiophene-2-carbohydrazide (L3)] were synthesized. The ligand precursors and their Ru(II) complexes (1–3) were structurally characterized by spectral (IR, UV–Vis, NMR and mass spectrometry) and elemental analysis. The molecular structures of the ruthenium(II) complexes 1–3 were determined by single-crystal X-ray diffraction. All complexes were used as catalysts for the one-pot three-component syntheses of 2,4,5-trisubstitued imidazole and 5-substituted 1H-tetrazole derivatives. The catalytic studies optimized parameters as solvent, temperature and catalyst. The catalysts revealed very active for a broad range of aromatic aldehydes presenting either electron attractor or electron donor substituents and, although less active, moderate to high activities were observed for alkyl aldehydes.
- Vinoth, Govindasamy,Indira, Sekar,Bharathi, Madheswaran,Archana, Govindhasamy,Alves, Luis G.,Martins, Ana M.,Shanmuga Bharathi, Kuppannan
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- Sustainable and recyclable magnetic nanocatalyst of 1,10-phenanthroline Pd(0) complex in green synthesis of biaryls and tetrazoles using arylboronic acids as versatile substrates
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A magnetic nanocatalyst was purveyed as a heterogeneous recoverable palladium-based catalyst anchored on green, sustainable and phosphine free support. Resulted Fe3O4@SiO2-Phen-Pd(0) nanocatalyst bearing powerful phenanthroline ligand was thoroughly characterized by physicochemical approaches like UV–vis, FT-IR, EDX, XRD, TGA, ICP, VSM, DLS, FESEM, and TEM analyses. After finding trustable data, the obtained magnetic catalyst was considered to be applied in the Suzuki-Miyaura type C-C couplings and getting corresponding tetrazoles using arylboronic acid derivatives as alternate precursors of aromatic halides and stupendous data were observed.
- Bagherzadeh, Nastaran,Sardarian, Ali Reza,Eslahi, Hassan
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- Synthesis of 5-Substituted 1 H-Tetrazoles from Nitriles by Continuous Flow: Application to the Synthesis of Valsartan
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An efficient continuous flow process for the synthesis of 5-substituted 1H-tetrazoles is described. The process involves the reaction between a polymer-supported triorganotin azide and organic nitriles. The polymer-supported organotin azide, which is in situ generated with a polystyrene-supported triorganotin alkoxide and trimethylsilylazide, is immobilized in a packed bed reactor. This approach is simple, fast (it takes from 7.5 to 15 min), and guarantees a low concentration of tin residues in the products (5 ppm). The process was developed to aryl-, heteroaryl-, and also alkylnitriles and was applied for the synthesis of valsartan, an angiotensin II receptor antagonist.
- Carpentier, Florian,Felpin, Fran?ois-Xavier,Zammattio, Fran?oise,Le Grognec, Erwan
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p. 752 - 761
(2020/03/13)
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- Novel Benzohydroxamate-Based Potent and Selective Histone Deacetylase 6 (HDAC6) Inhibitors Bearing a Pentaheterocyclic Scaffold: Design, Synthesis, and Biological Evaluation
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Histone deacetylase 6 (HDAC6) is a peculiar HDAC isoform whose expression and functional alterations have been correlated with a variety of pathologies such as autoimmune disorders, neurodegenerative diseases, and cancer. It is primarily a cytoplasmic protein, and its deacetylase activity is focused mainly on nonhistone substrates such as tubulin, heat shock protein (HSP)90, Foxp3, and cortactin, to name a few. Selective inhibition of HDAC6 does not show cytotoxic effects in healthy cells, normally associated with the inhibition of Class I HDAC isoforms. Here, we describe the design and synthesis of a new class of potent and selective HDAC6 inhibitors that bear a pentaheterocyclic central core. These compounds show a remarkably low toxicity both in vitro and in vivo and are able to increase the function of regulatory T cells (Tregs) at well-tolerated concentrations, suggesting a potential clinical use for the treatment of degenerative, autoimmune diseases and for organ transplantation.
- Vergani, Barbara,Sandrone, Giovanni,Marchini, Mattia,Ripamonti, Chiara,Cellupica, Edoardo,Galbiati, Elisabetta,Caprini, Gianluca,Pavich, Gianfranco,Porro, Giulia,Rocchio, Ilaria,Lattanzio, Maria,Pezzuto, Marcello,Skorupska, Malgorzata,Cordella, Paola,Pagani, Paolo,Pozzi, Pietro,Pomarico, Roberta,Modena, Daniela,Leoni, Flavio,Perego, Raffaella,Fossati, Gianluca,Steinkühler, Christian,Stevenazzi, Andrea
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p. 10711 - 10739
(2019/12/02)
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- Synthesis of α-Aminonitriles and 5-Substituted 1H-Tetrazoles Using an Efficient Nanocatalyst of Fe3O4@SiO2–APTES-supported Trifluoroacetic Acid
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Fe3O4@SiO2–APTES-supported trifluoroacetic acid nanocatalyst was used for the one-pot synthesis of α-aminonitriles via a three-component reaction of aldehydes (or ketones), amines, and sodium cyanide. This method produced a high yield of 75–96% using only a small amount of the catalyst (0.05?g) in EtOH at room temperature. The catalyst was also employed for the synthesis of 5-substituted 1H-tetrazoles from nitriles and sodium azide in EtOH at 80°C. The tetrazoles were produced with good-to-excellent yields in a short reaction time of 4?h. Both synthetic methods were carried out in the absence of an organic volatile solvent. Because the supported trifluoroacetic acid generated a solid acid on the surface, thus the acid corrosiveness was not a serious challenge. This heterogeneous nanocatalyst was magnetically recovered and reused several times without significant loss of catalytic activity.
- Fatahi, Hosna,Jafarzadeh, Mohammad,Pourmanouchehri, Zahra
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p. 2090 - 2098
(2019/07/05)
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- Iron (III)-porphyrin Complex FeTSPP as an efficient catalyst for synthesis of tetrazole derivatives via [2?+?3]cycloaddition reaction in aqueous medium
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The metal complex (5,10,15,20-tetrakis-(4-sulfonatophenyl)-porphyrin-iron (III) chloride (FeTSPP) was new employed in an environmentally benign protocol as an efficient catalyst for a “click” chemistry approach for the synthesis of tetrazole and guanindinyltetrazole derivatives via [2?+?3] cycloaddition reaction of nitriles and azide derivatives in aqueous medium. The synthesized compounds were obtained in excellent yield, short reaction times and a recoverable catalyst.
- El-Remaily, Mahmoud Abd El Aleem Ali Ali,Elhady
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- Enhanced Thermocatalytic Activity of Porous Yellow ZnO Nanoflakes: Defect- and Morphology-Induced Perspectives
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Herein, we report a simple and effective strategy for the synthesis of yellow ZnO (Y-ZnO) nanostructures with abundant oxygen vacancies on a large scale, through the sulfidation of ZnO followed by calcination. The developed strategy allows retention of the overall morphology of Y-ZnO compared with pristine ZnO and the extent of oxygen vacancies can be tuned. The influence of oxygen deficiencies, the extent of defect sites, and the morphology of ZnO on its solution-phase thermocatalytic activity has been evaluated in the synthesis of 5-substituted-1H-tetrazoles with different nitriles and sodium azide. A reasonable enhancement in the reaction rate was achieved by using Y-ZnO nanoflakes (Y-ZnO NFs) as a catalyst in place of pristine ZnO NFs. The reaction was complete within 6 h at 110 °C with Y-ZnO NFs, whereas it took 14 h at 120 °C with pristine ZnO NFs. The catalyst is easy to recycle without a significant loss in catalytic activity.
- Galani, Sunil M.,Panda, Asit Baran
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p. 612 - 620
(2019/02/14)
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- A series of blue-green-yellow-red emitting Cu(I) complexes: Molecular structure and photophysical performance
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In this work, we designed a series of [Cu(N–N)(PPh3)2]BF4 complexes with different optical edge values and emission colors from blue to red, where N–N and PPh3 denoted a diamine ligand and triphenylphosphine, respectively. Six N–N ligands with various conjugation chains (short π chain, modest π chain and long π chain) were selected. A systematical comparison between these Cu(I) complexes was performed, so that the correlation between N–N structure and [Cu(N–N)(PPh3)2] photophysical performance was tentatively discussed. Their single crystal structure was found consistent with literature ones, forming a typical tetrahedral coordination geometry. Density functional theory calculation indicated that their onset electronic transition showed a mixed character of metal-to-ligand-charge-transfer and ligand-to-ligand-charge-transfer. Detailed analysis on photophysical parameters suggested that the absorption edge of [Cu(N–N)(PPh3)2]BF4 complex was controlled by conjugation length in diamine ligand. A wide absorption edge needed a short conjugation chain in diamine ligand. Similar tendency was found for their emission spectra. In addition, a long conjugation chain in diamine ligand widened emission spectra obviously. Emission dynamics showed slim correlation with diamine ligand conjugation length since the excited state was controlled mainly by dynamic procedure and steric factor of diamine ligands.
- Zhang, Liming,Zuo, Qinghui
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- Cationic organotin cluster [t-Bu2Sn(OH)(H2O)]2 2+2OTf?-catalyzed one-pot three-component syntheses of 5-substituted 1H-tetrazoles and 2,4,6-triarylpyridines in water
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The cationic organotin cluster [t-Bu2Sn(OH)(H2O)]2 2+2OTf? is easy to prepare and stable in air. The catalytic activity of [t-Bu2Sn(OH)(H2O)]2 2+2OTf? as a neutral organotin Lewis acid catalyst is probed through the one-pot three-component syntheses of 5-substituted 1H-tetrazoles from aldehydes, hydroxylamine hydrochloride and sodium azide, and of 2,4,6-triarylpyridines from aromatic aldehydes, substituted acetophenones and ammonium acetate. The reactions proceed well in the presence of 1?mol% of [t-Bu2Sn(OH)(H2O)]2 2+2OTf? in water and provide the corresponding 5-substituted 1H-tetrazoles and 2,4,6-triarylpyridines in good to excellent yields. The method reported has several advantages such as the catalyst being neutral, low catalyst loading and use of water as a green solvent.
- Wang, Hongshe,Zhao, Weixing,Du, Juan,Wei, Fenyan,Chen, Qi,Wang, Xiaomei
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- Humic acid as an efficient and reusable catalyst for one pot three-component green synthesis of 5-substituted 1: H -tetrazoles in water
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Humic acid is a non toxic, inexpensive, easily available high-molecular weight polymer. A simple and facile one pot three-component synthesis of 5-substituted 1H-tetrazoles from aldehydes, hydroxyamine hydrochloride and sodium azide using humic acid as an efficient catalyst in water is described. The method reported has several advantages such as high to excellent yields, easy work-up, mild reaction conditions, use of water as a green solvent, and a commercially available, nontoxic and reusable catalyst.
- Wang, Hongshe,Wang, Yichun,Han, Yinfeng,Zhao, Weixing,Wang, Xiaomei
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p. 784 - 789
(2020/01/23)
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- A practical multigram-scale method for the green synthesis of 5-substituted-1H-tetrazoles in deep eutectic solvent
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A series of 5-substituted-1H-tetrazoles have been efficiently synthesized in moderate to excellent yields (68–90%) under mild reaction conditions by combining aryl aldehydes, hydroxylamine hydrochloride with sodium azide in the presence of catalytic amoun
- Xiong, Xingquan,Yi, Chao,Liao, Xu,Lai, Shilin
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p. 402 - 406
(2019/01/05)
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- [3 + 2] Cycloaddition promoted by zinc oxide nanoparticles anchored on reduced graphene oxide using green solvent
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ZnO anchored on RGO-catalyzed [3 + 2] cycloaddition of nitriles and sodium azide in the synthesis of 5-substituted 1H-tetrazoles in water is an efficient and simple protocol with low catalyst loading under reflux condition. It is applied to a wide range of substrates with an excellent yield, simple workup procedure, recovery, and reusability of catalyst with consistent activity and high turnover number. It is proposed that the functional groups present in RGO surface are effective for preventing the aggregation of catalytically active ZnO species during the reaction. Moreover, the excellent performance of ZnO–RGO nanocomposite is ascribed to the excellent dispersity of catalyst in water, hydrophilic nature of the RGO for the accumulation of organic substrates in water, and the “Breslow effect.”.
- Clarina, Thanaraj,Rama, Velladurai
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supporting information
p. 175 - 187
(2018/01/01)
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- L -Proline: An Efficient Organocatalyst for the Synthesis of 5-Substituted 1 H -Tetrazoles via [3+2] Cycloaddition of Nitriles and Sodium Azide
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A simple and efficient route for the synthesis of a series of 5-substituted 1 H -tetrazoles using l -proline as a catalyst from structurally diverse organic nitriles and sodium azide is reported. The prominent features of this environmentally benign, cost effective, and high-yielding l -proline-catalyzed protocol includes simple experimental procedure, short reaction time, simple workup, and excellent yields making it a safer and economical alternative to hazardous Lewis acid catalyzed methods. The protocol was successfully applied to a broad range of substrates, including aliphatic and aryl nitriles, organic thiocyanates, and cyanamides.
- Bhagat, Saket B.,Telvekar, Vikas N.
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supporting information
p. 874 - 879
(2018/02/16)
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- Preparation of Ag-doped g-C3N4 Nano Sheet Decorated Magnetic γ-Fe2O3@SiO2 Core–Shell Hollow Spheres through a Novel Hydrothermal Procedure: Investigation of the Catalytic activity for A3, KA2 Coupling Reactions and [3?+?2] Cycloaddition
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Taking advantageous of both g-C3N4 and magnetic core-shell hollow spheres, for the first time a heterogeneous and magnetically separable hybrid system was prepared through a novel and simple hydrothermal procedure and used for immobilization of bio-synthesized Ag(0) nanoparticles. The hybrid system was fully characterized by using SEM/EDS, FTIR, VSM, TEM, XRD, TGA, DTGA, ICP-AES, BET and elemental mapping analysis. The catalytic utility of the obtained system, h-Fe2O3@SiO2/g-C3N4/Ag, for promoting ultrasonic-assisted A3, KA2 coupling reactions and [3?+?2] cycloaddition has been confirmed. The results established that the catalyst could efficiently catalyze the reaction to afford the corresponding products in high yields in short reaction times. The reusability study confirmed that the catalyst could be recovered and reused for at least five reaction runs with only slight loss of the catalytic activity. The hot filtration test also proved low silver leaching, indicating the heterogeneous nature of the catalysis.
- Sadjadi, Samahe,Malmir, Masoumeh,Heravi, Majid M.
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- KIT-6-anchored sulfonic acid groups as a heterogeneous solid acid catalyst for the synthesis of aryl tetrazoles
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In the current study, a simple, environmentally benign and cost-effective method is presented for the preparation of 5-substituted-1H-aryltetrazoles. To this goal, mesoporous KIT-6 silica anchored with sulfonic acid (–SO3H) groups via post-grafting modification was synthesized using the sol–gel method and characterized by XRD, TGA, FTIR, BET, TEM and SEM techniques. For the preparation of tetrazole derivatives, the effect of various parameters such as catalyst amount, aryl nitrile:azide ratio, temperature and reaction time was tested. The hybrid organic/inorganic catalyst could be recovered easily through a simple filtration and reused multiple times without significant loss in activity.
- Najafi Chermahini, Alireza,Andisheh, Nikzad,Teimouri, Abbas
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p. 831 - 838
(2018/03/01)
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- Cytotoxicity of η6-areneruthenium-based molecules to glioblastoma cells and their recognition by multidrug ABC transporters
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A new series of amphiphilic η6-areneruthenium(II) compounds containing phenylazo ligands (group I: compounds 1a, 1b, 2a and 2b) and phenyloxadiazole ligands (group II: compounds 3a, 3b, 4a and 4b) were synthesized and characterized for their anti-glioblastoma activity. The effects of the amphiphilic η6-areneruthenium(II) complexes on the viability of three human glioblastoma cell lines, U251, U87MG and T98G, were evaluated. The azo-derivative ruthenium complexes (group I) showed high cytotoxicity to all cell lines, whilst most oxadiazole-derivative complexes (group II) were less cytotoxic, except for compound 4a. The cationic complexes 2a, 2b and 4b were more cytotoxic than the neutral complexes. Compounds 2a and 2b caused a significant reduction in the percentage of cells in the G0/G1 phase, with concomitant increases in the G2/M phase and fragmented DNA in the T98G cell line. The η6-areneruthenium(II) compounds were also tested in cell lines that overexpress the multidrug ABC transporters P-gp, MRP1 and ABCG2. Compounds 2b and 4a were substrates for the P-gp protein, with resistance indexes of 8.6 and 1.9, respectively. Compound 2b was also a substrate for ABCG2 and MRP1 proteins, with lower resistance indexes (1.8 and 1.6, respectively). The contribution of multidrug ABC transporters to the cytotoxicity of compound 2b in T98G cells was evidenced, since verapamil (a characteristic inhibitor of MRP1) increased the cytotoxicity of compound 2b at concentrations up to 20 μmol L?1, whilst GF120918 and Ko143 (specific inhibitors of P-gp and ABCG2, respectively) had no significant effect. In addition, we showed that compound 2b interacts with glutathione (GSH), which could explain its cellular efflux by MRP1. Our results showed that the amphiphilic η6-areneruthenium(II) complexes are promising anti-glioblastoma compounds, especially compound 2b, which was cytotoxic for all three cell lines, although it is transported by the three main multidrug ABC transporters.
- Pazinato, Jaqueline,Cruz, Otávio M.,Naidek, Karine P.,Pires, Amanda R.A.,Westphal, Eduard,Gallardo, Hugo,Baubichon-Cortay, Hélène,Rocha, Maria E.M.,Martinez, Glaucia R.,Winnischofer, Sheila M.B.,Di Pietro, Attilio,Winnischofer, Herbert
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p. 165 - 177
(2018/02/20)
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- Synthesis, molecular docking and xanthine oxidase inhibitory activity of 5-aryl-1H-tetrazoles
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5-Aryl-1H-tetrazoles (1–24) were synthesized and screened for their xanthine oxidase (XO) inhibitory activity using allopurinol as standard inhibitor (IC50 = 2.0 ± 0.01 μM). Six compounds 3, 4, 5, 9, 21, and 24 exhibited significant to weak act
- Fatima, Itrat,Zafar, Humaira,Khan, Khalid Mohammed,Saad, Syed Muhammad,Javaid, Sumaira,Perveen, Shahnaz,Choudhary, M. Iqbal
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p. 201 - 211
(2018/05/24)
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- Indium-, Magnesium-, and Zinc-Mediated Debenzylation of Protected 1 H -Tetrazoles: A Comparative Study
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5-Substituted 1-benzyltetrazoles are easily debenzylated to give the corresponding deprotected tetrazoles using dissolved metals under protic conditions: Mg/MeOH, In/MeOH, or Zn/MeCO 2 H are the procedures of choice for this transformation.
- Behloul, Cherif,Benlahrech, Meriem,Foubelo, Francisco,Nájera, Carmen,Yus, Miguel
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supporting information
p. 3430 - 3435
(2018/07/02)
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- Synthesis, Structure, and Anti-influenza Activity of 2-(Adamantan-1-yl)-5-aryl-1,3,4-oxadiazoles and 2-(Adamantan-1-yl)-5-aryltetrazoles
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Two series of new adamantyl derivatives of polynitrogen heterocycles, 2-(adamantan-1-yl)-5-aryl- 1,3,4-oxadiazoles and 2-(adamantan-1-yl)-5-aryl-2H-tetrazoles, have been synthesized, and their structure has been determined by NMR spectroscopy, mass spectr
- Seliverstova,Suslonov,Zarubaev,Trifonov
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p. 633 - 638
(2018/06/12)
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- Dendrimer-encapsulated Cu(Π) nanoparticles immobilized on superparamagnetic Fe3O4@SiO2 nanoparticles as a novel recyclable catalyst for N-arylation of nitrogen heterocycles and green synthesis of 5-substituted 1H-tetrazoles
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In this study, dendrimer-encapsulated Cu(Π) nanoparticles immobilized on superparamagnetic Fe3O4@SiO2 nanoparticles were prepared via a multistep-synthesis. Then, the synthesized composite was fully characterized by various techniques such as fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), dynamic light scattering (DLS), UV-vis spectroscopy, energy dispersive X-ray analysis (EDX), thermogravimetric analysis (TGA) and vibration sample magnetometer (VSM). From the information gained by. FE-SEM and TEM studies it can be inferred that the particles are mostly spherical in shape and have an average size of 50?nm. Also, the amount of Cu is determined to be 0.51?mmol/g in the catalyst by inductively coupled plasma (ICP) analyzer. This magnetic nano-compound has been successfully applied as a highly efficient, magnetically recoverable and stable catalyst for N-arylation of nitrogen heterocycles with aryl halides (I, Br) and arylboronic acids without using external ligands or additives. The catalyst was also employed in a one-pot, three-component reaction for the efficient and green synthesis of 5-substituted 1H-tetrazoles using various aldehydes, hydroxylamine hydrochloride and sodium azide in water. The magnetic catalyst can be easily separated by an external magnet bar and is recycled seven times without significant loss of its activity.
- Esmaeilpour, Mohsen,Sardarian, Ali Reza,Firouzabadi, Habib
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- Development and Demonstration of a Safer Protocol for the Synthesis of 5-Aryltetrazoles from Aryl Nitriles
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The search for a faster, safer protocol for the direct synthesis of 5-aryltetrazoles from aryl nitriles in the presence of sodium azide and an amine hydrochloride salt led to the discovery of a buffered system comprised of BnNH2, BnNH2·HCl, and NaN3. After optimization of reaction conditions and a thorough investigation of reaction safety, the procedure was demonstrated for the synthesis of several hundred grams of 4-chloro-2-(2H-tetrazol-5-yl)phenol. The generality of the developed reaction conditions was established by a small-scale reactivity screen using 16 additional aryl and heteroaryl nitrile substrates.
- Treitler, Daniel S.,Leung, Simon,Lindrud, Mark
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p. 460 - 467
(2017/03/24)
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- Cu(II) immobilized on Fe3O4@APTMS-DFX nanoparticles: An efficient catalyst for the synthesis of 5-substituted 1: H -tetrazoles with cytotoxic activity
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Cu(ii) immobilized on deferasirox loaded amine functionalized magnetic nanoparticles (Cu(ii)/Fe3O4@APTMS-DFX) as a novel magnetically recyclable heterogeneous catalyst is able to catalyze the [3 + 2] cycloaddition reactions of various organic nitriles with sodium azide. Using this method, a series of 5-substituted-1H-tetrazoles under mild conditions in DMSO were prepared. The reaction involves mild reaction conditions with efficient transformation capability. The developed catalyst could be easily separated by applying an external magnetic field. Furthermore, it could be recycled for 5 runs with negligible leaching of copper from the surface of the catalyst. The catalyst was characterized by various techniques such as FT-IR, TGA, VSM, SEM-EDX, and ICP-OES. Several derivatives of 1H-tetrazoles were prepared using this catalyst, and their structures were confirmed using different techniques. Then, the synthesized anthraquinones were evaluated for their cytotoxicity against several cell lines including MCF-7, MAD-MD-231, HT-29, HeLa, neuro-2a and L-929. The results obtained from the MTT assay revealed that the 6 derivatives exhibited a high level of cytotoxicity. In order to determine the cytotoxicity mechanism, 2 derivatives with the highest cytotoxic activity were selected, and an apoptosis assay was carried out by flow cytometry, which supported that apoptosis is the major mechanism.
- Taghavi, Faezeh,Gholizadeh, Mostafa,Saljooghi, Amir Sh.,Ramezani, Mohammad
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p. 1953 - 1964
(2017/10/27)
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- Thermally Activated Delayed Fluorescence in CuI Complexes Originating from Restricted Molecular Vibrations
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The mechanism of thermally activated delayed fluorescence (TADF) in molecules in aggregated or condensed solid states has been rarely studied and is not well understood. Nevertheless, many applications of TADF emitters are strongly affected by their lumin
- Li, Guangfu,Nobuyasu, Roberto S.,Zhang, Baohua,Geng, Yun,Yao, Bing,Xie, Zhiyuan,Zhu, Dongxia,Shan, Guogang,Che, Weilong,Yan, Likai,Su, Zhongmin,Dias, Fernando B.,Bryce, Martin R.
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supporting information
p. 11761 - 11766
(2017/09/07)
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- Photophysical performance comparison between bulk Cu(I) complex and its electrospinning fibers: Synthesis and characterization
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In this report, a diamine ligand having an electron-pulling group in its conjugation plane was designed. A methyl group was connected with this diamine ligand, hoping to further increase its steric hindrance. Its Cu(I) complex was synthesized and characte
- Pu, Wan,Yuqing, Zhao,Lisha, Wang
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- One-pot synthesis of 1- and 5-substituted 1H-tetrazoles using 1,4-dihydroxyanthraquinone–copper(II) supported on superparamagnetic Fe3O4@SiO2 magnetic porous nanospheres as a recyclable catalyst
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An effective one-pot, convenient process for the synthesis of 1- and 5-substituted 1H-tetrazoles from nitriles and amines is described using1,4-dihydroxyanthraquinone–copper(II) supported on Fe3O4@SiO2 magnetic porous nanospheres as a novel recyclable catalyst. The application of this catalyst allows the synthesis of a variety of tetrazoles in good to excellent yields. The preparation of the magnetic nanocatalyst with core–shell structure is presented by using nano-Fe3O4 as the core, tetraethoxysilane as the silica source and poly(vinyl alcohol) as the surfactant, and then Fe3O4@SiO2 was coated with 1,4-dihydroxyanthraquinone–copper(II) nanoparticles. The new catalyst was characterized using Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, field emission scanning electron microscopy, dynamic light scattering, thermogravimetric analysis, vibration sample magnetometry, X-ray photoelectron spectroscopy, nitrogen adsorption–desorption isotherm analysis and inductively coupled plasma analysis. This new procedure offers several advantages such as short reaction times, excellent yields, operational simplicity, practicability and applicability to various substrates and absence of any tedious workup or purification. In addition, the excellent catalytic performance, thermal stability and separation of the catalyst make it a good heterogeneous system and a useful alternative to other heterogeneous catalysts. Also, the catalyst could be magnetically separated and reused six times without significant loss of catalytic activity. Copyright
- Esmaeilpour, Mohsen,Javidi, Jaber,Zahmatkesh, Saeed
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p. 897 - 904
(2016/10/18)
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- Cu-MCM-41 nanoparticles: An efficient catalyst for the synthesis of 5-substituted 1H-tetrazoles via [3+2] cycloaddition reaction of nitriles and sodium azide
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[3 + 2] cycloaddition reaction of various types of nitriles and sodium azide (NaN 3) were studied in the presence of nano-sized Cu-MCM-41 as an efficient recoverable heterogeneous catalyst. Nano-sized Cu-MCM-41 mesoporous molecular sieves with various Si/Cu molar ratios were synthesized by direct insertion of metal ions at room temperature. The textural properties of the materials have been studied by means of XRD, FTIR, SEM and TEM techniques. Catalytic behavior of Cu-MCM-41 was also investigated by pyridine absorption and potentiometric titration. The reactions data verified characterization results and show that Cu-MCM-41 with Si/Cu molar ratio of 20 has considerably better catalytic activity compared to the other molar ratios. To investigate reusability, the catalyst was recovered by simple filtration and reused for several cycles with consistent activity.
- Abdollahi-Alibeik, Mohammad,Moaddeli, Ali
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- Magnetically separable Fe3O4@chitin as an eco-friendly nanocatalyst with high efficiency for green synthesis of 5-substituted-1H-tetrazoles under solvent-free conditions
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The present study describes an efficient, eco-friendly and simple method for the synthesis of 5-substituted-1H-tetrazoles catalyzed by magnetite-chitin (Fe3O4@chitin) as a green and recyclable catalyst. Fe3O4@chitin was initially prepared using hydrothermal synthesis. Subsequently, the structure, morphology, and magnetic properties of the prepared nanocatalyst were studied with some different spectroscopic, microscopic and thermogravimetric techniques such as FT-IR, XRD, SEM, TEM, VSM and TGA. Obtained results showed that Fe3O4@chitin nanoparticles exhibited uniform cubic shape and were well monodispersed. Also, magnetic measurement revealed that the synthesized nanocatalyst had superparamagnetic features. The application of this new nanocatalyst allows the synthesis of a variety of tetrazoles through the reaction of nitriles with 1-butyl-3-methylimidazolium azide ([bmim][N3]) under solvent-free conditions. This synthetic pathway is a green protocol offering significant advantages, such as excellent yield of products in short reaction times, mild reaction conditions, minimization of chemical waste, easy preparation of the catalyst and its recyclability up to six cycles without any considerable loss of efficiency.
- Zarghani, Monireh,Akhlaghinia, Batool
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p. 31850 - 31860
(2016/04/26)
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- Zn/MeOH-Mediated Practical and Easy Detritylation of Protected 1-Trityltetrazoles
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A practical and low-cost method for the detritylation of 1-titryltetrazoles using zinc and methanol is described. This procedure is versatile and efficient in the deprotection of several protected tetrazoles bearing aliphatic, aromatic, and heteroaromatic substituents, as well as some functional groups, without decomposition of the tetrazole ring.
- Behloul, Cherif,Bouchelouche, Kenza,Hadji, Yasmine,Benseghir, Saadia,Guijarro, David,Nájera, Carmen,Yus, Miguel
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supporting information
p. 2455 - 2460
(2016/07/28)
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- Ag-doped nano magnetic γ-Fe2O3@DA core-shell hollow spheres: An efficient and recoverable heterogeneous catalyst for A3 and KA2 coupling reactions and [3 + 2] cycloaddition
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An effective protocol for the fabrication of Ag-doped nano magnetic γ-Fe2O3@DA core-shell hollow spheres (h-Fe2O3@DA/Ag) by a simple hydrothermal method is demonstrated without any templates in the reaction system. The synthesized core-shell structure was successfully characterized in terms of the chemical composition, surface morphology, and magnetic properties using FT-IR, VSM, TGA, TEM, FE-SEM, EDS, and XRD patterns. The possible formation mechanism of this magnetic γ-Fe2O3@DA/Ag hollow sphere structure is described based on the experimental results. In addition, as a physical property, the apparent shell density was determined using the specific surface area (BET) and shell thickness (BJH). The important, novel and unique catalyst with a hollow structural character and strong magnetic behavior exhibited a high catalytic activity in the A3 and KA2 coupling reactions and [3 + 2] cycloaddition for the synthesis of 1H-tetrazoles. Furthermore, the recovered catalyst of the reaction mixture was facilitated by a magnetic field and multiple recycling was carried out without any significant loss in the catalytic activity.
- Elhampour,Malmir,Kowsari,Boorboor Ajdari,Nemati
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p. 96623 - 96634
(2016/10/25)
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- Copper complexes of pyridyl–tetrazole ligands with pendant amide and hydrazide arms: synthesis, characterization, DNA-binding and antioxidant properties
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Pyridyl–tetrazole ligands 2-(5-(pyridin-2-yl)-1H-tetrazol-1-yl)acetamide (L1), 2-(5-(pyridin-2-yl)-2H-tetrazol-2-yl)acetamide (L2), 2-(5-(pyridin-2-yl)-1H-tetrazol-1-yl)acetohydrazide (L3) and 2-(5-(pyridin-2-yl)-2H-tetrazol-2-yl)acetohydrazide (L4) have been prepared and coordinated with CuCl2·2H2O to furnish the corresponding complexes [Cu(L1)2]–[Cu(L4)2]. EPR spectra of the complexes are characteristic of square planar geometries, with nuclear hyperfine spin 3/2. DNA-binding studies using UV–Vis absorption spectroscopy, viscosity and thermal denature studies revealed that all of these complexes are avid binders of calf thymus DNA. The antioxidant properties of the free ligands and the Cu(II) complexes were investigated using the p-nitrosodimethyl aniline hydroxyl radical scavenging method, and [Cu(L4)2] was found to show the highest activity.
- Kasi Reddy, Santhosh Reddy,Manabolu Surya, Surendrababu,Shaik, Mustafa,Kanuparthy, Phani Raja
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p. 517 - 523
(2016/07/20)
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- ALIPHATIC-AROMATIC HETEROCYCLIC COMPOUNDS AND USES THEREOF IN METAL EXTRACTANT COMPOSITIONS
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The invention relates to an aliphatic-aromatic heterocyclic compound A which comprises at least two heterocyclic rings B and C, to a metal extractant composition E comprising this aliphatic-aromatic heterocyclic compound A and an organic acid D having at least one carboxylic, sulfonic, sulfuric, phosphinic, phosphonic, or phosphoric acid group, and to a process to extract one or more metals M selected from the group consisting of Ni and Co from an aqueous acidic leach solution PL comprising ions of at least one of the metals M, and further, at least one kind of further ions selected from the group consisting of Fe ions, Al ions, Cu ions, Mg ions, Mn ions, and also silicate anions, by mixing the solution PL with an extractant composition E, separating the organic and aqueous phases, and recovering the metal M from the separated organic phase.
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Paragraph 0183
(2016/09/26)
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- A rapid metal free synthesis of 5-substituted-1H-tetrazoles using cuttlebone as a natural high effective and low cost heterogeneous catalyst
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A convenient, rapid and metal free synthesis of 5-substituted-1H-tetrazoles is described by [3 + 2] cycloaddition reaction of nitriles with sodium azide. The reaction was catalyzed by cuttlebone in DMSO at 110°C. Cycloaddition reaction of nitriles with sodium azide happened in the presence of mesoporous cuttlebone by "electrophilic activation" of nitriles through hydrogen bond formation between the cuttlebone and nitrile. Cuttlebone as a natural low cost heterogeneous catalyst with high porosity, high flexural stiffness, high compressive strength and high thermal stability affords 5-substituted-1H-tetrazoles rapidly with high efficiency.
- Ghodsinia, Sara S. E.,Akhlaghinia, Batool
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p. 49849 - 49860
(2015/06/25)
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- Expanded perlite: An inexpensive natural efficient heterogeneous catalyst for the green and highly accelerated solvent-free synthesis of 5-substituted-1H-tetrazoles using [bmim]N3 and nitriles
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A versatile, green and highly accelerated protocol for preparing 5-substituted-1H-tetrazoles is reported. In this method, 5-substituted-1H-tetrazoles are synthesized from nitriles and [bmim]N3, in the presence of the expanded perlite as an inexpensive natural efficient heterogeneous catalyst, under solvent-free condition. A wide variety of aryl nitriles underwent [3 + 2] cycloaddition to afford the desired tetrazoles in good to excellent yields, rapidly. This method has the advantages of high yields, short reaction times, simple methodology, and easy work-up. The catalyst can be recovered by simple filtration and reused delivering good yields.
- Jahanshahi, Roya,Akhlaghinia, Batool
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p. 104087 - 104094
(2015/12/24)
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- Indium-Mediated Cleavage of the Trityl Group from Protected 1 H -Tetrazoles
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On treatment with indium metal in MeOH-THF, trityl groups undergo reductive removal from 1H-protected tetrazoles (including aliphatic, aromatic, and heteroaromatic substituents), affording the corresponding free tetrazoles in excellent yields, without any decomposition of the tetrazole ring or reduction of any other group.
- Behloul, Cherif,Bouchelouche, Kenza,Guijarro, David,Foubelo, Francisco,Nájera, Carmen,Yus, Miguel
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supporting information
p. 2399 - 2402
(2015/10/19)
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