576 resultados para STEREOSELECTIVE-SYNTHESIS


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Total synthesis of the dimethyl ether of marsupsin, in seven steps starting from phloroglucinol, is described.

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First enantiospecific total synthesis of optical antipode of the sesquiterpene 10,11-epoxythapsan-10-ol has been described. (R)-Carvone has been employed as the chiral starting material and a combination of intramolecular alkylation and Criegee fragmentation are employed for intramolecular stereospecific transfer of the chirality. An intramolecular diazoketone cyclopropanation and regioselective cyclopropane ring cleavage reactions have been employed for the creation of the three requisite contiguous quaternary carbon atoms.

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Hydroxo-bridged homo- and hetero-trinuclear cobalt(III) complexes of the type [MII(H2O)2{(OH)2CoIII(N4)}2]X2·nH2O [MII= a divalent metal ion such as CoII, NiII or ZnII; N4=(en)2(en = ethane-1,2-diamine) or (NH3)4; X = SO4 or (ClO4)2; n= 3 or 5] have been prepared and spectroscopically characterized. The structure of [Cu{(OH)2Co(en)2}2][SO4]2·2H2O 1 has been determined. The geometry around copper atom is a pseudo-square-based pyramid, with the basal sites occupied by four bridging hydroxide oxygens and the apical site is occupied by a weakly co-ordinated sulfate anion [Cu–O 2.516(4)Å]. The hydroxo groups bridge pairs of cobalt(III) ions which are in near-octahedral environments. The ethylenediamine chelate rings have the twist conformation. In the crystal structure of [Cu{(OH)2Co(en)2}2][ClO4]4·2H2O 2 the perchlorate ion is not co-ordinated and the en ligands have envelope conformations. The sulfate ion in [Cu{(OH)2Co(NH3)4}2][SO4]2·4H2O 3 is not co-ordinated to the central copper ion. Electronic, infrared and variable-temperature EPR spectral data are discussed.

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Fine particle FeVO4, AIVO4, YVO4 and Yo.95Eu0.05VO4 have been prepared by the combustion of aqueous solutions containing corresponding metal nitrate, ammonium metavanadate, ammonium nitrate and 3-methyl-5-pyrazolone.The solutions containing the redox mixtures, when rapidly heated at 370 °C, ignite and undergo self-propagating,gas-producing, exothermic reactions to yield fine particle metal vanadates. Formation of crystalline vanadates was confirmed by powder X-ray diffraction patterns,27A1 nuclear magnetic resonance, IR and fluorescence spectra.

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A complex oxalate precursor, CaCu3(TiO)(4)(C2O4)(8)center dot 9H(2)O, (CCT-OX), was synthesized and the precipitate that obtained was confirmed to be monophasic by the wet chemical analyses, X-ray diffraction, FTIR absorption and TG/DTA analyses. The thermal decomposition of this oxalate precursor led to the formation of phase-pure calcium copper titanate, CaCu3Ti4O12, (CCTO) at a parts per thousand yen680A degrees C. The bright-field TEM micrographs revealed that the size of the as synthesized crystallites to be in the 30-80 nm range. The powders so obtained had excellent sinterability resulting in high density ceramics which exhibited giant dielectric constants upto 40000 (1 kHz) at 25A degrees C, accompanied by low dielectric losses.

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New diacylglycerols (2-4) containing intramolecular disulfide linkages between pendant acyl chains were synthesized. Due to the differences in the location of disulfide units, the present method allows synthesis of macrocycles that vary in sizes. Copyright.

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The synthesis of three new Troger's base analogues, each functionalized with two carboxyl groups, is described. Copyright.

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Flower-like nickel nanocone structures are synthesized by a simple chemical reduction method using hydrazine hydrate as the reducing agent. The structure, morphology and magnetic properties of as synthesized products are studied by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and SQUID magnetometer. The morphology evolution is studied by varying the reaction temperature and concentration of nickel chloride keeping other conditions unchanged.

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The coordination driven self-assembly of discrete molecular triangles from a non-symmetric ambidentate linker 5-pyrimidinecarboxylate (5-pmc) and Pd(II)/Pt(II) based 90◦ acceptors is presented. Despite the possibility of formation of a mixture of isomeric macrocycles (linkage isomers) due to different connectivity of the ambidentate linker, formation of a single and symmetrical linkage somer in both the cases is an interesting observation. Moreover, the reported macrocycles represent the first example of discrete metallamacrocycles of bridging 5-pmc. While solution composition in both the cases was characterised by multinuclear NMR study and electrospray ionization mass spectrometry (ESI-MS), the identity of the assemblies in the solid state was established by X-ray single crystals structure analysis. Variable temperature NMR study clearly ruled out the formation of any other macrocycles by [4 + 4] or [2 + 2] self-assembly of the reacting components.

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Reaction between PdCl2 and 1-alkyl-2-(arylazo)imidazole (RaaiR') or 1-alkyl-2-(naphthyl-alpha/beta-azo)imidazole (alpha/beta-NaiR') under reflux in ethanol has isolated complexes of compositions Pd(RaaiR')(2)Cl-2 (5, 6) and Pd(alpha/beta-NaiR')(2)Cl-2 (7, 8). The X-ray structure determination of one of the molecules, Pd(alpha-NaiBz)(2)Cl-2 (7c), has reported a trans-PdCl2 configuration, and alpha-NaiBz acts as monodentate N(imidazole) donor ligand. The spectral (IR, UV-vis, H-1 NMR) data support the structure. UV light irradiation (light source: Perkin-Elmer LS 55 spectrofluorimeter, Xenon discharge lamp, lambda = 360-396 nm) in a MeCN solution of the complexes shows E-to-Z isomerization of the coordinated azoimidazole unit. The reverse transformation, Z-to-E, is very slow with visible light irradiation. Quantum yields (phi(E-Z)) of E-to-Z isomerization are calculated, and phi is lower than that of the free ligand but comparable with those of Cd(II) and Hg(II) complexes of the same ligand. The Z-to-E isomerization is a thermally induced process. The activation energy (E-a) of Z-to-E isomerization is calculated by controlled-temperature experimentation. cis-Pd(azoimidazole)Cl-2 complexes (azomidazole acts as N(imidazole) and N(azo) Chelating ligand) do not respond upon light irradiation, which supports the idea that the presence of noncoordinated azo-N to make free azo (-N=N-) function is important to reveal photochromic activity. DFT calculation of Pd(alpha-NaiBz)(2)Cl-2 (7c) has suggested that the HOMO of the molecule is constituted of Pd (32%) and Cl (66%), and hence photo excitation may use the energy of Pd and Cl instead of that of the photofunctional -N=N-Ar motif; thus, the rate of photoisomerization and quantum yield decrease versus the free ligand values.

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We report the first-time experimental realization of rocksalt AuCl crystals. Our approach involves Au(III) complexing and reduction to Au(I) using an amine-terminated surfactant in a low dielectric permittivity solvent. The low charge screening in nonpolar solvents promotes crystallization of rocksalt AuCl, in which the bonding is predominantly ionic, in preference over tetragonal AuCl. The rocksalt AuCl crystals obtained here will facilitate studies to unveil the nexus between electronic structure and crystal structure in AuCl polymorphs, and provide insights on these relationships in other polymorphic crystal systems. Our approach provides a new means for crystallizing selective polymorphs of inorganic compounds by subtly influencing the cation electronic structure by varying the dielectric permittivity of the synthesis medium. In addition, the AuCl crystals can serve as inexpensive Au(I) precursors for forming a variety of Au nanostructures.

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Flower-like nickel nanocone structures are synthesized by a simple chemical reduction method using hydrazine hydrate as the reducing agent. The structure, morphology and magnetic properties of as synthesized products are studied by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and SQUID magnetometer. The morphology evolution is studied by varying the reaction temperature and concentration of nickel chloride keeping other conditions unchanged.

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Iron(III) complexes, (NHEt3)[Fe(III)(sal-met)(2)] and (NHEt3)[Fe(III)(sal-phe)(2)], of amino acid Schiffbase ligands, viz., N-salicylidene-L-methionine and N-salicylidene L-phenylalanine, have been prepared and their binding to bovine serum albumin (BSA) and photo-induced BSA cleavage activity have been investigated. The complexes are structurally characterized by single crystal X-ray crystallography. The crystal Structures of the discrete mononuclear rnonoanionic complexes show FeN2O4 octahedral coordination geometry in which the tridentate dianionic amino acid Schiff base ligand binds through phenolate and carboxylate oxygen and imine nitrogen atoms. The imine nitrogen atoms are trans to each other. The Fe-O and Fe-N bond distances range between 1.9 and 2.1 angstrom. The sal-met complex has two pendant thiomethyl groups. The high-spin iron(III) complexes (mu(eff) similar to 5.9 mu(B)) exhibit quasi-reversible Fe(III)/Fe(II) redox process near -0.6 V vs. SCE in water. These complexes display a visible electronic hand near 480 nm in tris-HCl buffer assignable to the phenolate-to-iron(III) charge transfer transition. The water soluble complexes bind to BSA giving binding constant values of similar to 10(5) M-1. The Complexes show non-specific oxidative cleavage of BSA protein on photo-irradiation with UV-A light of 365 nm.

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A new class of 1,3,4-oxadiazoles were prepared from acid hydrazides on treatment with different carboxylic acids in the presence of phosphorus oxychloride. Interconversion of oxadiazoles to thiadiazoles and triazoles was carried out with appropriate reagents. The antimicrobial and cytotoxic activities of compounds 7a-d to 12a-d were tested. Compounds 10d and 12d showed pronounced antimicrobial activity. Further, compound 10d exhibited maximum cytotoxicity. (C) 2008 Elsevier Masson SAS. All rights reserved.

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New complexes of Lanthanide nitrates with N-(4-methyl-2-pyridyl)-acetamide (4-me-aapH) of the general formulae. [Ln(4-me-aapH)2] [NO3] (where Ln=La=La-Yb and Y)have been synthesized and haracterised by chemical analysis, molar conductivity and physical methods such as infrared, 13C NMR an electronic spectra in the visible region. Molar conductance and infrared data point to the presence to the coordinated nitrates groups. Infrared and 13C NMR data have been interpreted in terms of the coordination of the legand to the metal ion through the oxygen of the secondary amide and nitrogen of the hetrocyclic ring, in a bidentate fashion. Coordination number of ten seems probable for the complexes.