- Adamantylated organosilatranes: Design, synthesis, and potential appraisal in surface modification and anti-protozoal activity
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The present investigation evaluates the design and facile synthesis of a series of organosilatranes (1-7) tethered with the privileged adamantane motif, labelled as a 'lipophilic bullet', via numerous biocompatible linkages i.e. amide, ester, thioester, urea, thiourea, and thiocarbamate groups. The assembled silatranes have been scrupulously characterized by elemental analysis, FT-IR and NMR (1H and 13C) spectroscopy, and mass spectrometry. The parasitic diseases caused by unicellular protozoa, Giardia lamblia (G. lamblia) and Trichomonas vaginalis (T. vaginalis), represent a major health burden, therefore the synthesized compounds were probed for in vitro giardicidal and trichomonacidal activities. With this aim, firstly the pharmacokinetic profiles of the compounds were scrutinized using absorption, distribution, metabolism, excretion, and toxicity (ADMET) tools and on the whole, all compounds showed good oral bioavailability. The anti-parasitic activity of the newly synthesized compounds was evaluated in comparison to a standard drug (metronidazole) by 3-(4,5-dimethylthiazol-yl)-diphenyl tetrazolium bromide (MTT) assay. All the compounds displayed significant activity against G. lamblia and T. vaginalis with IC50 values ranging from 10.9-127.4 μM and 6.2-128.9 μM, respectively. To improve the aqueous solubility of the synthesized compounds, the enticing feature of the adamantane moiety to undergo inclusion binding with the β-cyclodextrin cavity is explored. Furthermore, a simplistic methodology is proposed to covalently anchor adamantylated silatrane onto the surface of magnetic silica nanoparticles. This material promises to be a non-invasive and externally controlled drug delivery system with enormous anti-protozoal potential.
- Singh, Gurjaspreet,Rani, Sunita,Gawri, Sanchita,Sinha, Shweta,Sehgal, Rakesh
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- The Synthesis of Adamantane Ring Containing Benzimidazole, Benzoxazole, and Imidazo[4,5-e]benzoxazole Derivatives from 3-Aminophenol
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Adamantane derivatives containing heterocycles such as benzimidazoles, benzoxazoles, and fused imidazo[4,5-e]benzoxazoles were synthesized from 3-aminophenol. The route started with amidation of adamantane-1-carboxylic acid chloride with 3-aminophenol fur
- Soselia, Marina,Geibel, Irina,Zurabishvili, Davit,Samsoniya, Shota
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- Intermolecular interactions in crystalline 1-(adamantane-1-carbonyl)-3-substituted thioureas with Hirshfeld surface analysis
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The conformationally congested species 1-(adamantane-1-carbonyl)-3-(2,4,6-trimethylphenyl)thiourea has been prepared and fully characterized by elemental analyses, FTIR, 1H NMR, 13C NMR and mass spectrometry. Its crystal structure was determined by single-crystal X-ray diffraction. The dihedral angle between the plane of the 2,4,6-trimethylphenyl group and the plane of the thiourea fragment was optimized by theoretical calculations applying the B3LYP/6-311++G(d,p) level for the purpose of investigating the conformational effects on the stabilization of the crystal packing. A detailed analysis of the intermolecular interactions in a series of six closely related phenylthiourea species bearing the 1-(adamantane-1-carbonyl) group has been performed based on the Hirshfeld surfaces and their associated two-dimensional fingerprint plots. The relative contributions of the main intermolecular contacts as well as the enrichment ratios derived from the Hirshfeld surface analysis establish the 1-acyl thiourea synthon to be a widespread contributor.
- Saeed, Aamer,Bolte, Michael,Erben, Mauricio F.,Pérez, Hiram
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- A novel self-healing power cable insulating material based on host-guest interactions
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The insulating materials used in power cables are susceptible to damage and cracks during installation and operation. To solve this problem, we have prepared a self-healing material PVP/p(HEMA-co-BA), which is synthesized by radical polymerization using HEMA, BA, PVP and a host-guest assembly. The host-guest assembly is constructed through interactions between host and guest molecules (CD-Al2O3 NPs act as the host, and HEMA-Ad acts as the guest). The characterization results of the materials show that there are two kinds of supramolecular interactions, namely, the host-guest interaction and the hydrogen bonding. The material possesses good thermal stability (heat-resisting temperature can reach 200 °C) and good electrical performance. The storage modulus of the material can be increased up to 432 MPa using a cross-linking agent at 20 °C. Furthermore, the material exhibits self-healing property, and it can self-heal several times; its self-healing efficiency is relative to the dosage of the cross-linking agent.
- Peng, Lei,Zhang, Manjun,Lin, Musong,Fu, Qiang
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- Noncovalent binding of sensitizers for lanthanide(III) luminescence in an EDTA-bis(β-cyclodextrin) ligand
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EDTA-linked β-cyclodextrin dimer 3 was synthesized from EDTA bis(anhydride) 1 and mono-(propylamino)-appended β-cyclodextrin 2. p-tert-Butylbenzoate 5, bound by the β-cyclodextrin cavities of 3 with an association constant of 104 M-1 in water, acts as a sensitizer for the EuIII and TbIII complexes of 3. Luminescence spectroscopy, microcalorimetry, and GdIII-induced NMR relaxation rate measurements prove that 3 forms a 1:2 complex with 5 and that one of the β-cyclodextrin-bound sensitizers coordinates to the EDTA-encapsulated LnIII ion. The EuIII complex of 3 forms strong 1:1 complexes (K ≈ 107 M-1) with bis(propylamido adamantyl)-functionalized biphenyl sensitizers 7 and 8 in water. Both β-cyclodextrins of 3 are involved in the binding of these guests. The amide functionality adjacent to the biphenyl unit in 7 and 8 coordinates to the EDTA-encapsulated LnIII ion. For these biphenyl-based antennae both binding to β-cyclodextrin and coordination to the LnIII center are crucial for efficient sensitization.
- Michels, Jasper J.,Huskens, Jurriaan.,Reinhoudt, David N.
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- Mannich bases of 1,2,4-triazole-3-thione containing adamantane moiety: Synthesis, preliminary anticancer evaluation, and molecular modeling studies
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A series of 18 novel N-Mannich bases derived from 5-adamantyl-1,2,4-triazole-3-thione was synthesized and characterized using NMR spectroscopy and X-ray diffraction technique. All derivatives were evaluated for their anticancer potential against four human cancer cell lines. Several tested compounds exerted good cytotoxic activities on K562 and HL-60 cell lines, along with pronounced selectivity, showing lower cytotoxicity against normal fibroblasts MRC-5 compared to cancer cells. The effects of compounds 5b, 5e, and 5j on the cell cycle were investigated by flow cytometric analysis. It was found that these compounds cause the accumulation of cells in the subG1 and G1 phases of the cell cycle and induce caspase-dependent apoptosis, while the anti-angiogenic effects of 5b, 5e, and 5j have been confirmed in EA.hy926 cells using a tube formation assay. Further, the interaction of Bax protein with compound 5b was investigated by means of molecular modeling, applying the combined molecular docking/molecular dynamics approach.
- Milo?ev, Milorad Z.,Jakovljevi?, Katarina,Joksovi?, Milan D.,Stanojkovi?, Tatjana,Mati?, Ivana Z.,Perovi?, Milka,Te?i?, Vesna,Kanazir, Selma,Mladenovi?, Milan,Rodi?, Marko V.,Leovac, Vukadin M.,Trifunovi?, Sne?ana,Markovi?, Violeta
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- Construction and DNA condensation of cyclodextrin-coated gold nanoparticles with anthryl grafts
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The condensation of DNA in a controlled manner is one of the key steps in gene delivery and gene therapy. For this purpose, a water-soluble supramolecular nanostructure is constructed by coating 14 β-cyclodextrins onto the surface of a gold nanoparticle, followed by the noncovalent association of different amounts of anthryl-modified adamantanes with coated β-cyclodextrins. The strong binding of β-cyclodextrins with anthryl adamantanes (KS=8.61×104 M-1) efficiently stabilizes the supramolecular nanostructure. Spectrophotometric fluorescence spectra and microscopic studies demonstrated that, with many anthryl grafts that can intercalate in the outer space of the DNA double helix, this supramolecular nanostructure showed good condensation abilities to calf thymus DNA. Significantly, the condensation efficiency of supramolecular nanostructure towards DNA could be conveniently controlled by adjusting the ratio between gold nanoparticles and anthryl adamantane grafts, leading to the formation of DNA condensates of a size that are suitable for the endocytosis of hepatoma cells, which will make it potentially applicable in many fields of medicinal science and biotechnology. Congenial host: A supramolecular DNA condenser containing gold nanoparticles (AuNPs; see picture), β-cyclodextrins (CDs), and anthryl adamantanes exhibits good DNA condensation efficiency and low toxicity; thus making it potentially applicable in medicinal science and biotechnology.
- Zhao, Di,Chen, Yong,Liu, Yu
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- Synthesis, X-ray, Hirshfeld surface analysis, exploration of DNA binding, urease enzyme inhibition and anticancer activities of novel adamantane-naphthyl thiourea conjugate
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1-(adamantane-1-carbonyl-3-(1-naphthyl)) thiourea (C22H24N2OS (4), was synthesized by the reaction of freshly prepared adamantane-1-carbonyl chloride from corresponding acid (3) with ammonium thiocyanate in 1:1 M ratio in dry acetone to afford the adamantane-1-carbonyl isothiocyanate (2) in situ followed by treatment with 1-naphthyl amine (3). The structure was established by elemental analyses, FTIR, 1H, 13C NMR and mass spectroscopy. The molecular and crystal structure were determined by single crystal X-ray analysis. It belongs to triclinic system P ? 1 space group with a = 6.7832(5) ?, b = 11.1810(8) ?, c = 13.6660(10) ?, α = 105.941(6)°, β = 103.730(6)°, γ = 104.562(6)°, Z = 2, V = 910.82(11) ?3. The naphthyl group is almost planar. In the crystal structure, intermolecular C[sbnd]H···O hydrogen bonds link the molecules into centrosymmetric dimers, enclosing R22(14) ring motifs, while the intramolecular N[sbnd]H···O hydrogen bonds enclose S(6) ring motifs, in which they may be effective in the stabilization of the structure. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H … H (59.3%), H … C/C … H (19.8%) and H … S/S … H (10.1%) interactions. Hydrogen bonding and van der Waals interactions are the dominant interactions in the crystal packing. DFT, molecular docking and urease inhibition studies revealed stability and electron withdrawing nature of 4 as compared to DNA base pairs and residues of urease. The DNA binding results from docking, UV– visible spectroscopy, and viscosity studies indicated significant binding of 4 with the DNA via intercalation and groove binding. Further investigation of the compound was done on hepatocellular carcinoma; Huh-7 cell line as well as normal human embryonic kidney; Hek-293 cell line. The compound showed significant cytotoxic activity against Huh-7 cells in comparison to normal Hek-293 cells indicating selective cytotoxicity towards cancer cells.
- Arshad, Nasima,Saeed, Aamer,Perveen, Fouzia,Ujan, Rabail,Farooqi, Shahid I.,Ali Channar, Pervaiz,Shabir, Ghulam,El-Seedi, Hesham R.,Javed, Aneela,Yamin, Maham,Bolte, Michael,H?kelek, Tuncer
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- Construction of a novel INHIBIT logic gate through a fine-tuned assembly of anthryl fluorophores via selective anion recognition and host-guest interactions
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A novel ligand (AAP) based on an anthryl fluorophore was rationally designed and synthesized. The presence of H2PO4- (Pi) could induce the effective assembly of the ligand which leads to a strong excimer emission, while β-cyclodextrin (β-CD) disassembled the Pi-ligand complex through a host-guest interaction with terminal adamantane groups. This disassembly causes a considerable decrement in emissive intensity as well as a clear blue-shift in emissive wavelength. By manipulating the assembly and disassembly of anthryl fluorophores with Pi and β-CD, a novel INHIBIT logic gate was constructed using Pi and β-CD as the chemical inputs and fluorescence emission as the output.
- Zhang, Lei,He, Yilong,Zhang, Na,Liu, Daosheng,Han, Jiao,Gong, Weitao
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- Conductive Elastomers with Autonomic Self-Healing Properties
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Healable, electrically conductive materials are highly desirable and valuable for the development of various modern electronics. But the preparation of a material combining good mechanical elasticity, functional properties, and intrinsic self-healing ability remains a great challenge. Here, we design composites by connecting a polymer network and single-walled carbon nanotubes (SWCNTs) through host-guest interactions. The resulting materials show bulk electrical conductivity, proximity sensitivity, humidity sensitivity and are able to self-heal without external stimulus under ambient conditions rapidly. Furthermore, they also possess elasticity comparable to commercial rubbers.
- Guo, Kun,Zhang, Da-Li,Zhang, Xiao-Mei,Zhang, Jian,Ding, Li-Sheng,Li, Bang-Jing,Zhang, Sheng
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- Preparation of 2-(1-adamantyl)-1H-benzimidazole and novel derivatives thereof
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[MediaObject not available: see fulltext.]2-(1-Adamantyl)-1H-benzimidazole has been synthesized, its nitration and reduction of the nitro derivative have been carried out. By condensation of the obtained 2-(1-adamantyl)-1H-benzimidazol-5(6)-amine with aromatic aldehydes and acyl chlorides, the corresponding novel Schiff bases and amides have been accessed.
- Zurabishvili, Davit S.,Bukia, Tinatin J.,Lomidze, Medea O.,Trapaidze, Marina V.,Elizbarashvili, Elizbar N.,Samsoniya, Shota A.,Doroshenko, Tamara V.,Kazmaier, Uli
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- Directed C?H Bond Oxidation of Bridged Cycloalkanes Catalyzed by Palladium(II) Acetate
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We have developed a synthesis of 1,2-substituted adamantane carboxylic acids and further bridged cycloalkanes (cage compounds) by palladium acetate-catalyzed C?H bond oxidation. Acetoxylation of cycloalkane framework was performed using picolylamide as a directing group. Modification of the substrate, ligand design and variation of reaction conditions enabled us to study the mechanism of acetoxylation of aliphatic compounds. Post-functionalization reactions and cleavage of the directing group were developed. For the first time the synthesis and characterization of a β-C3-tri-substituted adamantane derivatives was achieved.
- Larrosa, Marta,Zonker, Benjamin,Volkmann, Jannis,Wech, Felix,Logemann, Christian,Hausmann, Heike,Hrdina, Radim
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- Highly disordered crystalline-phase transition of tetrakis(1- adamantanecarboxymethyl)methane
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Tetrakis(1-adamantanecarboxymethyl)methane was prepared by indirect esterification. DSC traces of tetrakis(1-adamantanecarboxymethyl) methane showed two endothermic peaks. Entropy ratio of these two peaks is: ΔS trs/ΔSfus = 1.58 > 1. XRD confirmed the solidsolid transition and analysis of XRD by DICVOL demonstrated tetrakis(1-adamantanecarboxymethyl) methane is a new compound with a highly disordered crystalline phase. Analysis of entropy changes at transitions showed why fusion entropy (ΔSfus = 70.07 Jmol-1K -1) of tetrakis(1-adamantanecarboxymethyl)- methane is much larger than Timmermans' criterion.
- Li, Rong,Pan, Chunyue,Xiong, Shaohui,Yu, Guipeng,Wang, Pingshan,Zou, Yingping,Zhang, Aiqing
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- Activation of Sirtuin 2 Inhibitors Employing Photoswitchable Geometry and Aqueous Solubility
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Because isoenzymes of the experimentally and therapeutically extremely relevant sirtuin family show high similarity, addressing the unique selectivity pocket of sirtuin 2 is a promising strategy towards selective inhibitors. An unrelated approach towards selective inhibition of isoenzymes with varied tissue distribution is targeted drug delivery or spatiotemporal activation by photochemical activation. Azologization of two nicotinamide-mimicking lead structures was undertaken to combine both approaches and yielded a set of 33 azobenzenes and azopyridines that have been evaluated for their photochemical behaviour and bioactivity. For some compounds, inhibitory activity reached the sub-micromolar range in their thermodynamically favoured E form and could be decreased by photoisomerization to the metastable Z form. Besides, derivatization with long-chain fatty acids yielded potent sirtuin 2 inhibitors, featuring another intriguing aspect of azo-based photoswitches. In these compounds, switching to the Z isomer increased aqueous solubility and thereby enhanced biological activity by up to a factor of 21. The biological activity of two compounds was confirmed by hyperacetylation of sirtuin specific histone proteins in a cell-based activity assay.
- Grathwol, Christoph W.,W?ssner, Nathalie,Behnisch-Cornwell, Steven,Schulig, Lukas,Zhang, Lin,Einsle, Oliver,Jung, Manfred,Link, Andreas
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- Self-assembled nanostructures from C60-containing supramolecular complex: Its stimuli-responsive reversible transition and biological antioxidative capacity
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A thermo-responsive copolymer, P(NIPAM-co-CD), containing β-cyclodextrin as classical host molecule to form highly stable host-guest complexes with 1-adamantane derivatives, was designed and synthesized. The compound tetra-Ad-C60 with a fullerene[60] moiety and four adamantyl heads was designed as a hydrophobic guest molecule. In aqueous solution, P(NIPAM-co-CD) and tetra-Ad-C60 could easily form supramolecular complex by self-assembly of β-cyclodextrin and adamantane, and the supramolecular complex could exist stably as vesicles in ambient environment. Furthermore, the morphology of the supramolecular complex could also be switched reversibly by the change of temperature around the lower critical solution temperature (LCST) of P(NIPAM-co-CD). When temperature was changed around the LCST, vesicles and nano-spheres formed by supramolecular complex could transform reversibly. Due to the presence of the fullerene moieties, the supramolecular complex exhibited excellent ability to scavenge hydroxyl radicals of biological system; furthermore, the antioxidative property could be affected obviously by the change of temperature owing to the thermo-response property of P(NIPAM-co-CD) moiety.
- Wang, Haoyu,Wang, Liang,Wang, Xiaoguang,Xu, Jiayun,Luo, Quan,Liu, Junqiu
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- Fluorous 1,2,3-Triazol-4-ylmethyl Amines and Amine Derivatives for Novel Surfactant Applications
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A series of fluorous surfactants with additional functionality were generated through the attachment of substituents at the amino nitrogen atom of the surfactant moiety. Examples of molecules containing one and two triazole ring systems were synthesized through N-alkylation and N-acylation strategies.
- Francis, Dominic V.,Harper, Jason B.,Read, Roger W.
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- Metal-free approach for hindered amide-bond formation with hypervalent iodine(iii) reagents: application to hindered peptide synthesis
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A new bio-inspired approach is reported for amide and peptide synthesis using α-amino esters that possess a potential activating group (PAG) at the ester residue. To activate the ester functionality under mild metal-free conditions, we exploited the facile dearomatization of phenols with hypervalent iodine(iii) reagents. Using a pyridine-hydrogen fluoride complex, highly reactive acyl fluoride intermediates can be successfully generated, thereby allowing for the smooth formation of sterically hindered amides and peptides from bulky amines and α-amino esters, respectively.
- Lee, Hyo-Jun,Huang, Xiao,Sakaki, Shigeyoshi,Maruoka, Keiji
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supporting information
p. 848 - 855
(2021/02/09)
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- Structural Basis of Nanomolar Inhibition of Tumor-Associated Carbonic Anhydrase IX: X-Ray Crystallographic and Inhibition Study of Lipophilic Inhibitors with Acetazolamide Backbone
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This study provides a structure-Activity relationship study of a series of lipophilic carbonic anhydrase (CA) inhibitors with an acetazolamide backbone. The inhibitors were tested against the tumor-expressed CA isozyme IX (CA IX), and the cytosolic CA I, CA II, and membrane-bound CA IV. The study identified several low nanomolar potent inhibitors against CA IX, with lipophilicities spanning two log units. Very potent pan-inhibitors with nanomolar potency against CA IX and sub-nanomolar potency against CA II and CA IV, and with potency against CA I one order of magnitude better than the parent acetazolamide 1 were also identified in this study, together with compounds that displayed selectivity against membrane-bound CA IV. A comprehensive X-ray crystallographic study (12 crystal structures), involving both CA II and a soluble CA IX mimetic (CA IX-mimic), revealed the structural basis of this particular inhibition profile and laid the foundation for further developments toward more potent and selective inhibitors for the tumor-expressed CA IX.
- Andring, Jacob T.,Fouch, Mallorie,Akocak, Suleyman,Angeli, Andrea,Supuran, Claudiu T.,Ilies, Marc A.,McKenna, Robert
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p. 13064 - 13075
(2020/11/20)
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- Design, synthesis, and biological evaluation of novel arylcarboxamide derivatives as anti-tubercular agents
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Our group has previously reported several indolecarboxamides exhibiting potent antitubercular activity. Herein, we rationally designed several arylcarboxamides based on our previously reported homology model and the recently published crystal structure of the mycobacterial membrane protein large 3 (MmpL3). Many analogues showed considerable anti-TB activity against drug-sensitive (DS) Mycobacterium tuberculosis (M. tb) strain. Naphthamide derivatives 13c and 13d were the most active compounds in our study (MIC: 6.55, 7.11 μM, respectively), showing comparable potency to the first line anti-tuberculosis (anti-TB) drug ethambutol (MIC: 4.89 μM). In addition to the naphthamide derivatives, we also identified the quinolone-2-carboxamides and 4-arylthiazole-2-carboxamides as potential MmpL3 inhibitors in which compounds 8i and 18b had MIC values of 9.97 and 9.82 μM, respectively. All four compounds retained their high activity against multidrug-resistant (MDR) and extensively drug-resistant (XDR) M. tb strains. It is worth noting that the two most active compounds 13c and 13d also exhibited the highest selective activity towards DS, MDR and XDR M. tb strains over mammalian cells [IC50 (Vero cells) ≥ 227 μM], indicating their potential lack of cytotoxicity. The four compounds were docked into the MmpL3 active site and were studied for their drug-likeness using Lipinski's rule of five.
- Alsayed, Shahinda S. R.,Beh, Chau Chun,Bishai, William R.,Foster, Neil,Gunosewoyo, Hendra,Lun, Shichun,Luna, Giuseppe,Payne, Alan D.
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p. 7523 - 7540
(2020/03/13)
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- Photoelimination of Nitrogen from Diazoalkanes: Involvement of Higher Excited Singlet States in the Carbene Formation
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Although diazoalkanes are important carbene precursors in organic synthesis, a comprehensive mechanism of photochemical formation of carbenes from diazoalkanes has not been proposed. Synergies of experiments and computations demonstrate the involvement of higher excited singlet states in the photochemistry of diazoalkanes. In all investigated diazoalkanes, excitation to S1 results in nonreactive internal conversion to S0. On the contrary, excitation to higher-lying singlet states (Sn, n > 1) drives the reaction toward a different segment of the S1/S0 conical intersection seam and results in nitrogen elimination and formation of carbenes.
- Pite?a, Tomislav,Ale?kovi?, Marija,Becker, Kristin,Basari?, Nikola,Do?li?, Nada
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supporting information
p. 9718 - 9724
(2020/07/02)
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- Metal-Free Photoinduced Hydroalkylation Cascade Enabled by an Electron-Donor-Acceptor Complex
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A metal- A nd photocatalyst-free photoinduced radical cascade hydroalkylation of 1,7-enynes has been disclosed. The process is triggered by a single electron transfer (SET) event involving a photoexcited electron-donor-acceptor complex between an NHPI ester and a Hantzsch ester, which decomposes to afford a tertiary radical that is readily trapped by the enyne. The method provides an operationally simple, robust, and step-economical approach toward the construction of diversely functionalized dihydroquinolinones bearing quaternary centers. A sequential one-pot hydroalkylation-isomerization approach is also offered, giving access to a family of quinolinones. A wide substrate scope and high functional group tolerance were observed in both approaches.
- Correia, José Tiago M.,Piva Da Silva, Gustavo,Kisukuri, Camila M.,André, Elias,Pires, Bruno,Carneiro, Pablo S.,Paixa?, Márcio W.
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p. 9820 - 9834
(2020/09/03)
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- Preparation method of rimantadine hydrochloride preparation
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The invention discloses a preparation method of a rimantadine hydrochloride preparation. The preparation method comprises the following steps: preparation of 1-bromoadamantane, preparation of amantadecanoic acid, preparation of adamantanecarbonyl chloride, preparation of adamantyl methy ketone, preparation of 1-amantadine methyl ketone oxime, preparation of rimantadine hydrochloride, and preparation of the rimantadine hydrochloride preparation. The preparation of adamantyl methy ketone comprises the following steps: adding (CH3)3Sb and nickelous formate into a flask; dropwise adding an acetonitrile solution of adamantanecarbonyl chloride, wherein adamantanecarbonyl chloride reacts with (CH3)3Sb to generate adamantyl methy ketone; after reaction, pouring a reaction liquid into ice water; and filtering and drying the mixture to obtain a light yellow precipitate, thereby obtaining the adamantyl methy ketone. The preparation method has the beneficial effects that the preparation method ofrimantadine hydrochloride preparation is good in environmental protection, mild in condition of a synthetic method, simple and feasible in process and high in product yield.
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- Synthesizing method of rimantadine hydrochloride
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The invention discloses a synthesizing method of rimantadine hydrochloride. The synthesizing method comprises the following steps of preparing of 1-bromoadamantane, preparing of adamantane carboxylicacid, preparing of adamantanecarbonyl chloride, preparing of adamantyl methyl ketone, preparing of 1-amantadine methyl ketone oxime, preparing of rimantadine hydrochloride, and preparing of a rimantadine hydrochloride preparation; in the preparing process of adamantyl methyl ketone: adding trimethylaluminum and cerium formate into a flask, then dripping a benzene solution of adamantanecarbonyl chloride, and enabling the adamantanecarbonyl chloride and the trimethylaluminum to react and generate adamantyl methyl ketone; after reaction is finished, pouring a reaction solution into ice water, filtering and drying, so as to obtain a light yellow precipitate, namely the adamantyl methyl ketone. The synthesizing method has the beneficial effects that the conditions are mild, and the technology is simple and feasible; the usage amount of catalyst is small, the environment-friendly effect is realized, and the yield of product is high.
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- Novel rimantadine analog and synthetic method thereof
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The invention provides a novel rimantadine analog. The novel rimantadine analog has a structure shown in formula (I). The rimantadine analog has high activity and is more beneficial to clinical use and further development and research of drugs.
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- A kind of anti-influenza virus preparation
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The present invention discloses an anti-influenza virus preparation, including 1 - bromo adamantane preparation, adamantane formic acid preparation, adamantane chloride preparation, adamantane methyl preparation, 1 - adamantane methyl oxime preparation, hydrochloric acid rimantadine preparation, anti-influenza virus preparation, wherein the adamantane methyl preparation steps are as follows: in the flask to join the three trimethylaluminum, formic acid cerium, then dropwise adamantane formyl chloride [...], the adamantane chloride with three methyl aluminum reaction generating adamantane methyl ketone, after the reaction is completed in the reaction liquid into ice water, then filtering, drying, the resulting pale yellow precipitate adamantane methyl ketone. The beneficial effects: preparation method of this invention mild condition, the process is simple and feasible, high product yield, the system anti- influenza virus preparation can be effective prevention and treatment of type a/b influenza virus infection, also can effectively alleviate the symptoms of the common cold.
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- Preparation method of 1-adamantyl methy ketone
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The invention belongs to the field of preparation of chemical intermediates, and particularly relates to a preparation method of 1-adamantyl methy ketone. The preparation method comprises the following steps of step 1, enabling adamantane and liquid bromine to react, so as to obtain 1-bromoadamantane; step 2, using concentrated sulfuric acid as a catalyst, adding the 1-bromoadamantane and n-hexane, and dripping formic acid, so as to obtain 1-adamantanecarboxylic acid; step 3, enabling the 1-adamantanecarboxylic acid and thionyl chloride to react, heating and refluxing, extracting by benzene, and directly applying the extracting liquid for the reaction in next step; step 4, dripping a mixed solution of benzene, diethyl malonate and anhydrous ethyl alcohol into a mixed solution of magnesiumpowder, iodine, anhydrous ethyl alcohol and benzene, dripping a benzene solution of 1-adamantanecarbonyl chloride, extracting by benzene, drying and distilling, so as to obtain 2- adamantanecarbonyl diethyl malonate; step 5, adding glacial acetic acid, water and concentrated sulfuric acid into the residue. The preparation method has the advantage that the yield rate is high.
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- Tandem double acylation/[3,3]-rearrangement of aliphatic nitro compounds: A route to α-oxygenated oxime derivatives
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A new tandem double acylation/rearrangement reaction of nitro compounds is described. It has a broad substrate scope allowing the mild and efficient synthesis of α-acyloxy oxime esters in high yields and regioselectivity. According to the obtained data, the mechanism for transformation was proposed. The utility of the obtained α-hydroxy oxime esters was demonstrated.
- Antonova, Yulia A.,Nelyubina, Yulia V.,Sukhorukov, Alexey Yu.,Ioffe, Sema L.,Tabolin, Andrey A.
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supporting information
p. 5997 - 6006
(2019/06/24)
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- A 5 - (1 - adamantane amido) isophthalic acid synthetic method
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The invention of formula (I) of the 5 - (1 - adamantane amido) isophthalic acid synthetic method. Characterized in that in order to 1 - adamantane formic acid as the raw material, after the chlorization with 5 - amino isophthalic acid dimethyl ester carri
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Paragraph 020; 0021; 0024; 0025; 0028; 0029
(2019/06/30)
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- A Gemini surfactant containing adamantane and its synthetic method
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The invention belongs to the technical field of organic chemical surface activity, in particular to a Gemini surfactant containing adamantane of synthesis, the invention designed and prepared containing adamantane Gemini surfactants of the structural formula is: , Wherein: C R is expressed asn H2 N + 1 , N=12, 16 or 18. The Gemini surfactant of the invention is to 1 - adamantane formic acid as raw materials, through a three-step reaction: first of all by the 1 - adamantane carboxylic acid with thionyl chloride synthesized by the reaction of acyl 1 - adamantane chloride, then with the 3, 3' - bis-imine (N, N - dimethyl propylamine) carries out amidation reaction, to prepare the key intermediate double-(N, N - dimethyl propylamine) adamantane - 1 - carboxamide, finally the intermediate and long-chain bromo alkane by quaternary amine form of the Gemini surfactant containing adamantane. The present invention provides a Gemini surfactant containing adamantane of mild reaction conditions, raw materials are easy, simple and easy operation, in supramolecular chemistry, nano material, special washing fields has potential application prospect.
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Paragraph 0016; 0024-0025; 0028-0029; 0032-0033
(2019/07/01)
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- METHOD FOR PRODUCING ADAMANTANE CARBOXYLIC ACID HALIDE, AND ADAMANTANE CARBOXYLIC ACID HALIDE
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PROBLEM TO BE SOLVED: To provide a method for producing an adamantane carboxylic acid halide, and a high-purity adamantane carboxylic acid halide. SOLUTION: A method for producing an adamantane carboxylic acid halide has a reaction step for reacting a compound represented by formula (II) with a halogenating agent, and a distillation step for purifying an obtained reaction product by distillation operation, where, a Lewis base is added in the reaction step before the distillation step or the distillation operation [R1 and R2 independently represent H, halogen, an alkyl group, an aryl group or a hydroxyl group]. SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
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Paragraph 0049-0062
(2019/02/27)
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- A rimantadine Schiff base synthetic method (by machine translation)
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The invention discloses a rimantadine Schiff base synthetic method, including adamantane chloride preparation, adamantane methyl preparation, 1 - adamantane methyl oxime preparation, rimantadine preparation, rimantadine Schiff base preparation, wherein the adamantane methyl preparation steps are as follows: in the flask to join the three trimethylaluminum, formic acid cerium, then dropwise adamantane formyl chloride [...], the adamantane chloride with three methyl aluminum reaction generating adamantane methyl ketone, after the reaction is completed in the reaction liquid into ice water, then filtering, drying, the resulting pale yellow precipitate adamantane methyl ketone. The beneficial effects: the reaction of this invention route changes before the adamantane methyl ketone synthesis route, the use of formic acid cerium auxiliary trimethyl aluminum reaction, mild reaction conditions, few by-products. The invention synthetic method mild condition, the process is simple and feasible, less catalyst levels, environmental protection, high product yield. (by machine translation)
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Paragraph 0021; 0023; 0028; 0030; 0035; 0037; 0044-0047
(2019/01/16)
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- Compounding agent of rimantadine hydrochloride and camphor tree essential oil and application thereof
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The invention discloses a compounding agent of rimantadine hydrochloride and camphor tree essential oil and application thereof, wherein the weight ratio of the amantadine hydrochloride to the camphortree essential oil in the compounding agent is 1: 50-50: 1, Adamantanecarbonyl chloride as a raw material, trimethylaluminum as a reagent and cerium formate as an auxiliary agent are reacted to formadamantane methyl ketone, and the rimantadine hydrochloride is prepared by oximation and platinum-carbon hydrogenation reduction of the adamantane methyl ketone; and the camphor tree essential oil isprepared by crushing camphor tree seeds, leaves, bark and the like as raw materials, using sodium glycinate and citric acid to assist breaking of cell walls and using a distillation technique; and thebeneficial effects are that: high purity and high yield of the rimantadine hydrochloride and the camphor tree essential oil. The compound composition of the rimantadine hydrochloride and the camphortree essential oil has synergistic effect, can effectively reduce the application amount of single agents, expands the sterilization spectrum, reduces the phytotoxicity, significantly improves the control effect against pathogens and viruses, alleviates the resistance problem of pathogenic bacteria, and reduces the cost of prevention.
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Page/Page column 5-9
(2019/01/24)
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- Electrochemical [4+2] Annulation-Rearrangement-Aromatization of Styrenes: Synthesis of Naphthalene Derivatives
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We report the first electrochemical strategy to synthesize functionalized naphthalene derivatives through [4+2] annulation—rearrangement–aromatization from styrenes under mild conditions. The electrolysis does not require metals, oxidants and high valence substrates, indicating the atom and step-economy ideals. The dehydrodimer produced through [4+2] cycloaddition of 4-methoxy α-methyl styrene is isolated and proved to be the key intermediate for the following oxydehydrogenation to form carbon cation, which undergoes rearrangement–aromatization to afford the final products. This reaction represents a powerful access to construct multi-substituted naphthalene blocks in a single step.
- Ma, Yueyue,Lv, Jufeng,Liu, Chengyu,Yao, Xiantong,Yan, Guoming,Yu, Wei,Ye, Jinxing
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supporting information
p. 6756 - 6760
(2019/04/17)
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- Aniline-Based Inhibitors of Influenza H1N1 Virus Acting on Hemagglutinin-Mediated Fusion
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Two series of easily accessible anilines were identified as inhibitors of influenza A virus subtype H1N1, and extensive chemical synthesis and analysis of the structure-activity relationship were performed. The compounds were shown to interfere with low pH-induced membrane fusion mediated by the H1 and H5 (group 1) hemagglutinin (HA) subtypes. A combination of virus resistance, HA interaction, and molecular dynamics simulation studies elucidated the binding site of these aniline-based influenza fusion inhibitors, which significantly overlaps with the pocket occupied by some H3 HA-specific inhibitors, indicating the high relevance of this cavity for drug design.
- Leiva, Rosana,Barniol-Xicota, Marta,Codony, Sandra,Ginex, Tiziana,Vanderlinden, Evelien,Montes, Marta,Caffrey, Michael,Luque, F. Javier,Naesens, Lieve,Vázquez, Santiago
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supporting information
p. 98 - 118
(2018/02/10)
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- Systematic structure-activity relationship (SAR) exploration of diarylmethane backbone and discovery of a highly potent novel uric acid transporter 1 (URAT1) inhibitor
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In order to systematically explore and better understand the structure-activity relationship (SAR) of a diarylmethane backbone in the design of potent uric acid transporter 1 (URAT1) inhibitors, 33 compounds (1a-1x and 1ha-1hi) were designed and synthesized, and their in vitro URAT1 inhibitory activities (IC50) were determined. The three-round systematic SAR exploration led to the discovery of a highly potent novel URAT1 inhibitor, 1h, which was 200-and 8-fold more potent than parent lesinurad and benzbromarone, respectively (IC50 = 0.035 μM against human URAT1 for 1h vs. 7.18 μM and 0.28 μM for lesinurad and benzbromarone, respectively). Compound 1h is the most potent URAT1 inhibitor discovered in our laboratories so far and also comparable to the most potent ones currently under development in clinical trials. The present study demonstrates that the diarylmethane backbone represents a very promising molecular scaffold for the design of potent URAT1 inhibitors.
- Cai, Wenqing,Wu, Jingwei,Liu, Wei,Xie, Yafei,Liu, Yuqiang,Zhang, Shuo,Xu, Weiren,Tang, Lida,Wang, Jianwu,Zhao, Guilong
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- Novel guanidine compound against multidrug-resistant cystic fibrosis-associated bacterial species
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Chronic pulmonary infection is a hallmark of lung disease in cystic fibrosis (CF). Infections dominated by non-fermentative Gram-negative bacilli are particularly difficult to treat and highlight an urgent need for the development of new class of agents to combat these infections. In this work, a small library comprising thiourea and guanidine derivatives with low molecular weight was designed; these derivatives were studied as antimicrobial agents against Gram-positive, Gram-negative, and a panel of drug-resistant clinical isolates recovered from patients with CF. One novel compound, a guanidine derivative bearing adamantane-1-carbonyl and 2-bromo-4,6-difluouro-phenyl substituents (H-BDF), showed potent bactericidal activity against the strains tested, at levels generally higher than those exhibited by tobramycin, ceftazimide and meropenem. The role that different substituents exert in the antimicrobial activity has been determined, highlighting the importance of the halo-phenyl group in the guanidine moiety. The new compound displays low levels of cytotoxicity against THP-1 and A549 cells with a selective index (SI) > 8 (patent application PCT/IB2017/054870, August 2017). Taken together, our results indicate that H-BDF can be considered as a promising antimicrobial agent.
- Saeed, Aamer,Bosch, Alejandra,Bettiol, Marisa,Nossa González, Diana L,Erben, Mauricio Federico,Lamberti, Yanina
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- Visible Light-Mediated Decarboxylative Alkylation of Pharmaceutically Relevant Heterocycles
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A net redox-neutral method for the decarboxylative alkylation of heteroarenes using photoredox catalysis is reported. Additionally, this method features the use of simple, commercially available carboxylic acid derivatives as alkylating agents, enabling the facile alkylation of a variety of biologically relevant heterocyclic scaffolds under mild conditions.
- Sun, Alexandra C.,McClain, Edward J.,Beatty, Joel W.,Stephenson, Corey R. J.
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supporting information
p. 3487 - 3490
(2018/06/26)
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- Domino Pd0-Catalyzed C(sp3)–H Arylation/Electrocyclic Reactions via Benzazetidine Intermediates
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The Pd0-catalyzed C(sp3)-H arylation of 2-bromo-N-methylanilides leads to unstable benzazetidine intermediates that rearrange to benzoxazines through 4π electrocyclic ring-opening and 6π electrocyclization. The introduction of a bulky, non-activatable amide group on the nitrogen atom was key to favor the challenging reductive elimination step and disfavor undesired reaction pathways.
- Rocaboy, Ronan,Dailler, David,Zellweger, Florian,Neuburger, Markus,Salomé, Christophe,Clot, Eric,Baudoin, Olivier
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supporting information
p. 12131 - 12135
(2018/09/11)
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- Ligand-Enabled Alkynylation of C(sp3)?H Bonds with Palladium(II) Catalysts
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The palladium(II)-catalyzed β- and γ-alkynylation of amide C(sp3)?H bonds is enabled by pyridine-based ligands. This alkynylation reaction is compatible with substrates containing α-tertiary or α-quaternary carbon centers. The β-methylene C(sp
- Fu, Haiyan,Shen, Peng-Xiang,He, Jian,Zhang, Fanglin,Li, Suhua,Wang, Peng,Liu, Tao,Yu, Jin-Quan
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supporting information
p. 1873 - 1876
(2017/02/05)
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- C3-Selective alkenylation of N-acylindoles with unactivated internal alkynes by cooperative nickel/aluminium catalysis
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Highly regio- and stereoselective alkenylation of N-acylindoles with unactivated internal alkynes has been accomplished by cooperative nickel/aluminium catalysis to afford C3-alkenylated indoles. Coordination of the acyl moiety to a bulky aluminium-based Lewis acid plays a crucial role in the selective functionalization at the C3-position by electron-rich nickel(0) catalysis.
- Inoue, Fumiyoshi,Saito, Teruhiko,Semba, Kazuhiko,Nakao, Yoshiaki
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supporting information
p. 4497 - 4500
(2017/04/26)
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- Synergistic Visible-Light Photoredox/Nickel-Catalyzed Synthesis of Aliphatic Ketones via N-C Cleavage of Imides
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An electrophilic, imide-based, visible-light-promoted photoredox/Ni-catalyzed cross-coupling reaction for the synthesis of aliphatic ketones has been developed. This protocol proceeds through N-C(O) bond activation, made possible through the lower activation energy for metal insertion into this bond due to delocalization of the lone pair of electrons on the nitrogen by electron-withdrawing groups. The operationally simple and mild cross-coupling reaction is performed at ambient temperature and exhibits tolerance for a variety of functional groups.
- Amani, Javad,Alam, Rauful,Badir, Shorouk,Molander, Gary A.
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supporting information
p. 2426 - 2429
(2017/05/12)
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- Tunable Supramolecular Assembly and Photoswitchable Conversion of Cyclodextrin/Diphenylalanine-Based 1D and 2D Nanostructures
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A photocontrolled, interconvertible supramolecular 2D-nanosheet/1D-nanotube system was constructed through the supramolecular assembly of adamantanyl-modified diphenylalanine with azobenzene-bridged bis(β-cyclodextrin). The nanosheet exhibited a greater f
- Sun, He-Lue,Chen, Yong,Han, Xu,Liu, Yu
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supporting information
p. 7062 - 7065
(2017/06/13)
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- Merging gold catalysis, organocatalytic oxidation, and Lewis acid catalysis for chemodivergent synthesis of functionalized oxazoles from: N -propargylamides
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Novel catalytic systems consisting of cationic gold complexes, N-hydroxyphthalimide (NHPI), and transition-metal-based Lewis acids have been developed for the one-pot synthesis of functionalized oxazoles from N-propargylamides with excellent functional group tolerance. These transformations demonstrated the excellent compatibility of homogeneous gold catalysis with organocatalytic oxidative carbon-nitrogen bond formations using tert-butyl nitrite as the terminal oxidant. Moreover, oxazolecarbonitriles or carboxamides can be easily synthesized in a one-pot protocol according to the different synthetic requirements.
- Mai, Shaoyu,Rao, Changqing,Chen, Ming,Su, Jihu,Du, Jiangfeng,Song, Qiuling
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supporting information
p. 10366 - 10369
(2017/09/25)
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- Difluoromethylation of carboxylic acids via the addition of difluorinated phosphorus ylide to acyl chlorides
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A one-step protocol for the difluoromethylation of carboxylic acids is described. The reaction involves the interaction of intermediate acyl chlorides with in situ generated difluorinated phosphorus ylide Ph3P=CF2. Aromatic acids can be selectively transformed within one step either to bis-difluoromethylated alcohols or to difluorinated ketones depending on the particular reaction conditions. For bulky α-branched carboxylic acids, only ketones are produced.
- Trifonov, Alexey L.,Levin, Vitalij V.,Struchkova, Marina I.,Dilman, Alexander D.
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supporting information
p. 5304 - 5307
(2017/11/06)
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- A method for synthesizing diamond ethylamine
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The invention discloses a synthetic method for rimantadine. The synthetic method is characterized by comprising the following steps: firstly, obtaining 1-bromoadamantane by reacting adamantine with liquid bromine; then, acidifying to obtain adamantanecarboxylic acid after reacting 1-bromoadamantane with magnesium and anhydrous ether; obtaining adamantine carbonyl chloride by performing reflux reaction on tehadamantanecarboxylic acid with thionyl chloride; obtaining adamantane methyl ketone by reacting the adamantine carbonyl chloride with (CH3)2CdCu; and finally, obtaining the rimantadine by hydriding and reacting adamantane methyl ketone with hydrochloric acid and ammonia water in the presence of sodium borohydride. The synthetic method disclosed by the invention is gentle in condition, simple in follow-up processing, high in yield, cheap in raw material and low in synthesis cost.
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- Metal-Free Oxidation of Primary Amines to Nitriles through Coupled Catalytic Cycles
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Synergism among several intertwined catalytic cycles allows for selective, room temperature oxidation of primary amines to the corresponding nitriles in 85-98 % isolated yield. This metal-free, scalable, operationally simple method employs a catalytic quantity of 4-acetamido-TEMPO (ACT; TEMPO=2,2,6,6-tetramethylpiperidine N-oxide) radical and the inexpensive, environmentally benign triple salt oxone as the terminal oxidant under mild conditions. Simple filtration of the reaction mixture through silica gel affords pure nitrile products.
- Lambert, Kyle M.,Bobbitt, James M.,Eldirany, Sherif A.,Kissane, Liam E.,Sheridan, Rose K.,Stempel, Zachary D.,Sternberg, Francis H.,Bailey, William F.
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supporting information
p. 5156 - 5159
(2016/04/09)
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- Asymmetric tertiary alcohol and (meth) acrylic ester production method (by machine translation)
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The invention provides a method for easily preparing an asymmetric tertiary alcohol having a ring-shaped framework with a high yield even if a metallic compound with high toxicity is not used. In addition, the invention provides a method for obtaining a (methyl) acrylic ester which contains the tertiary alcohol having the ring-shaped framework with a high yield. The method for preparing the asymmetric tertiary alcohol at least contains a process (A) and a process (B). Process (A): adding liquid containing a specific organometallic compound into liquid containing a compound represented by Formula (1) at the speed of 0.01-05 equivalent/h to generate a ketone represented by Formula (3). Process (B): reacting the specific organometallic compound with the ketone to generate the asymmetric tertiary alcohol expressed by Formula (5). [Formula 1][In the formula, ring Z1 represents a monocyclic or polycyclic non-aromatic group or aromatic ring, and X1 represents halogen atoms, etc.][Formula 2][Formula 3]
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Paragraph 0207-0208
(2016/10/08)
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- Generation of liquid crystallinity from a Td-symmetry central unit
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A series of new columnar liquid crystals containing an adamantane central unit with its four bridgehead positions partially or fully decorated with different numbers (1-4) of 3,4,5-tris(dodecyloxy)phenyl carbamoyl groups were designed and investigated carefully to explore the structure-property correlations. The molecular structures and mesomorphic properties of the DLCs were characterized by 1H-NMR, 13C-NMR, IR, UV-vis, POM, DSC and XRD. It was found that the mesophase symmetry and thermal stability were extremely dependent on the structures of the adamantane derivatives. No mesophase was observed for the 1-adamantanecarboxylic acid derivative ADLC1, while two different mesophases were observed for ADLC2, a 1,3-disubstituted derivative functionalized with two 3,4,5-tris(dodecyloxy)phenyl carbamoyl groups at two symmetric bridgehead positions. At lower temperature ADLC2 exhibited a rectangular columnar phase, which switched to a square columnar phase possessing a wide temperature range. Similarly, a hexagonal columnar mesophase was observed for the bridgehead trisubstituted adamantane molecule ADLC3. Interestingly, the fully bridgehead-functionalized 1,3,5,7-tetrasubstituted adamantane compound ADLC4 completely lost liquid crystallinity.
- Sayed, Sayed Mir,Lin, Bao-Ping,Yang, Hong
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p. 6148 - 6156
(2016/07/26)
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- C H Bond Arylation of Diamondoids Catalyzed by Palladium(II) Acetate
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We have developed an effective approach to 1,2-disubstituted diamondoids by palladium(II) acetate catalyzed functionalization of C H bond. Selective mono-arylation of the adamantane framework was achieved using picolylamide as a directing group in yields up to 87 %. Kinetic studies in combination with deuterium labeling experiments, competitive experiments and mass spectrometry contribute to the mechanistic understanding of the arylation process of alkanes with number of C H bonds neighboring the directing group. Triflic anhydride promoted cyclization of the directing group generates imidazo[1,5-a]pyridine derivatives. Acid-mediated removal of the directing group provides access to 2-aryl diamondoid carboxylic acids, which are common precursors for the synthesis of various bioactive compounds (drug candidates). (Figure presented.) .
- Larrosa, Marta,Heiles, Sven,Becker, Jonathan,Spengler, Bernhard,Hrdina, Radim
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supporting information
p. 2163 - 2171
(2016/07/16)
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- Kongo alkyl pyridine double-nuclear complex, intermediate and its preparation method and application
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The invention discloses an adamantly pyridine binuclear complex, an intermediate as well as preparation methods and applications of the complex and the intermediate. The complex has a structural formula shown in a formula (I) in which M is divalent metal cation; the complex provided by the invention or the complex prepared by adopting the method provided by the invention is excellent in catalytic activity of super oxygen anion disproportionation.
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Paragraph 0062-0064
(2017/02/17)
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- Kongo alkyl pyridine amide complex, intermediate and its preparation method and application
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The invention discloses an adamantyl picolinamide complex, an intermediate of the complex, and preparation methods of the complex and the intermediate of the complex and an application of the complex. The structure of the complex is represented by a formula (I) or formula (II); in the formula (I), M is a divalent metal cation, and each of N1 and N2 is a halogen anion independently; and in the formula (II), M is a divalent metal cation, and N3 is an ion selected from perchlorate ions, hexafluorophosphate ions or tetrafluoroborate ions. The complex disclosed by the invention or the complex prepared by the method disclosed by the invention has excellent activity for catalyzing the dismutation of superoxide anions.
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Paragraph 0069-0071
(2017/03/18)
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- Kongo alkyl pyridine carboxamide complexes, intermediate and its preparation method and application
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The invention discloses an adamantyl pyridinecarboxamide complex as well as intermediate, a preparation method and application thereof. The structure of the complex is as shown in the formula (I), wherein n is 1-3, M is a divalent metal cation, N is one of perchlorate ions, hexafluoro-phosphate radicals or tetrafluoroborate radicals. The complex provided by the invention or the complex prepared by the method has an excellent activity of catalyzing superoxide disproportionation. The formula (I) is as shown in the specification.
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Paragraph 0071-0073
(2017/03/21)
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- Synthesis of oxazolines from amides via palladium-catalyzed functionalization of unactivated C(sp3)-H bond
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A complementary method that enables the expeditious synthesis of oxazolines from amides via Pd-catalyzed C(sp3)-H functionalization has been described. Preliminary studies indicate that the reaction might go through a chlorination/nucleophilic cyclization sequence, and the high efficiency of this sequence is enhanced by the in situ cyclative capture of the chlorinated intermediate. The resulting oxazolines can be further converted into the corresponding β-amino alcohols without chromatography.
- Li, Bo,Wang, Si-Qing,Liu, Bin,Shi, Bing-Feng
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supporting information
p. 1200 - 1203
(2015/03/14)
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- Acylative Suzuki coupling of amides: Acyl-nitrogen activation via synergy of independently modifiable activating groups
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A highly efficient palladium-catalyzed acylative cross-coupling of carboxylic amides with arylboronic acids has been achieved via synergistic activation of the Cacyl-N bond by independently modifiable activating groups. Coupling of amides features not only good functional group tolerance but also modifiable reactivities to overcome steric hindrance. This journal is
- Li, Xijing,Zou, Gang
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supporting information
p. 5089 - 5092
(2015/03/30)
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- Palladium-catalyzed acylative cross-coupling of amides with diarylborinic acids and sodium tetraarylborates
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Abstract A general and efficient acylative Suzuki coupling of active amides with diarylborinic acids has been achieved by using 1 mol% Pd(PCy3)2Cl2/0.6 mol% PCy3 as catalyst system taking advantage of modifiable reactivities of acyl-nitrogen bonds of amides. Both electronic and steric influences from either aryl or acyl counterparts on the coupling proved to be negligible or small. A variety of aryl ketones including sterically hindered ones could be synthesized by the coupling of diarylborinic acids in good to excellent yields. Sodium tetraarylborates could also be used as high atom-economy aryl source in the palladium-catalyzed cross-coupling with active amides.
- Li, Xijing,Zou, Gang
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p. 136 - 145
(2015/07/27)
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