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The oxidation of white phosphorus by hydrogen peroxide or different organic peroxides (such as tert-butyl hydroperoxide, dibenzoylperoxide, 3-chloroperoxybenzoic acid) has been studied in both aqueous and alcoholic solutions under anaerobic conditions. Depending on the reaction conditions, P(I) (hypophosphorous acid), P(III) [phosphorous acid, mono- and dialkyl (or diaryl) hydrogen phosphonates] and P(V) [phosphoric acid or trialkyl (or triaryl) phosphates] derivatives are produced. The catalytic oxidative P-O coupling of P4 to water, aliphatic alcohols and phenol under mild reaction conditions is accomplished by using copper(I), copper(II) and vanadium(IV) complexes. Catalytic conversion of white phosphorus with complete efficiency and high selectivity for monoalkyl hydrogen phosphonates (>95%) may be achieved using 3-ClC6H4C(O)OOH as oxidant under optimized conditions. An identical radical mechanism is suggested to account for both the stoichiometric and the catalytic oxidative hydroxydation, alkoxydation and phenoxydation of white phosphorus promoted by peroxides in both aqueous biphasic conditions and organic solutions.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Co(II), Ni(II), Cu(II) and Zn(II) complexes of bidentate Schiff bases derived from the condensation of 4-amino-5-mercapto-3-methyl/ethyl-1,2,4-triazole with 5-nitrofurfuraldehyde were synthesized and tested as antimicrobial agents. The Schiff bases and their metal complexes were characterized by elemental analyses, magnetic moment measurements, spectroscopic (IR, Electronic, 1H NMR, ESR) and thermogravimetric analyses. A square planar geometry for Cu(II) and octahedral geometry for Co(II), Ni(II) and Zn(II) complexes have been proposed. The presence of coordinated water in metal complexes was confirmed by thermal and IR data of the complexes. The Schiff bases and their metal complexes have been screened for antibacterial [Pseudomonas aeruginosa, Bacillus subtilis, Escherichia coli, Staphylococcus aureus] and antifungal activities [Aspergillus niger, A. flavus].

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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A reaction of acetylacetone with the framework sandwich-type metallosiloxanes (MOS) of general formula [PhSiO2]6M 6[PhSiO2]6, where M = Cu, Ni, Mn, was studied by GPC, 1H and 29Si NMR spectroscopy, X-ray diffraction, elemental and functional analysis. The reaction involved replacement of the metal atoms with the hydrogen atoms and is accompanied by the formation of the corresponding chelate complexes M(acac)2. Displacement of the metal from the framework MOS leads to the destruction of molecular skeleton and formation of phenylsiloxanes containing Si-OH groups. The yield and composition of the reaction products considerably depend on the nature of the metal in [PhSiO2]6M6[ThSiO2]6. A selective substitution of the metal leads to the stereoregular hexahydroxyhexaphenylcyclohexasiloxane, [PhSiO(PH)]6, cis-isomer. The structure and composition of the crystalline hexahydroxyhexaphenylcyclohexasiloxane obtained were confirmed by 29Si NMR spectroscopy, X-ray diffraction study, and functional analysis, while its TMS derivative was studied with 1H NMR spectroscopy and GPC. Using a framework manganese phenylsiloxane as an example, a reversible character of the process has been established and an alternative synthesis of this compound from hexahydroxyhexaphenylcyclohexasiloxane and Mn(acac)2 has been accomplished for the first time.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Abstract: Nanostructured inorganic?organic hybrid thin films of copper(I) thiocyanate (CuSCN) and 4-(N,N-dimethylamino)-4?-(N?-methyl)stilbazolium tosylate (DAST) were electrochemically self-assembled by adding DAST into methanolic bath containing Cu2+ and SCN? ions. Loading of the stilbazolium organic chromophore (DAS+) increased linearly on increasing DAST concentration, accompanied with changes of the film morphology, crystallographic orientation of CuSCN and transition from beta- to alpha-CuSCN. At low DAST concentrations, transport limited passive occlusion of DAS+ has been suggested with its diffusion coefficient of 1.25 × 10?6 cm2 s?1 in methanol at 298 K, while the loading receives kinetic limitation by the surface chemical reaction to yield definitive hybrid structures, resulting in unique ?hair comb? shape beta-CuSCN-DAST and ?nano-platelets? shape alpha-CuSCN-DAST hybrid structures. Both the inorganic and organic components are interconnected and bi-continuous, as the loaded DAS+ could be totally extracted by dimethylacetamide to leave porous skeleton of crystalline CuSCN, making them highly interesting for device applications. Graphical abstract: [Figure not available: see fulltext.]

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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During our research looking for novel inverse agonists of RORgammat, we identified a potent sulfoximine-based modulator as one of our pre-clinical candidates for the topical treatment for psoriasis. Herein, we describe the various routes we evaluated during the lead generation and optimization phases and the final route chosen for scale-up to deliver the first 100 g of API.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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The thermal decomposition of Cu2L2Cl4, Cu2L2Cl2, Cu2L2Br 2 and Co2L2Cl4 complexes (L=3,5-dimethyl-1-thiocarboxamidepyrazole) is described. The influence of the central ion to ligand mole ratio on the course of complex formation is examined in reaction of L with copper(II) chloride. In Cu(II):L mole ratio of 1:1, in methanolic solution the reaction yields to yellow-green Cu2L 2Cl4 crystals. In the filtrate a thermodynamically more stable orange Cu2L2Cl2 copper(I) complex is forming. With a Cu(II):L mole ratio of 1:2 only the latter compound is obtained. The composition and the structure of the compounds have been determined on the basis of customary methods. On the basis of FTIR spectrum of the intermediate which is forming during the thermal decomposition of Cu2L 2Cl2 a decomposition mechanism is proposed.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Numerous artificial salivas have been used during studies in odontology. These salivas have compositions, which are more or less the same as that of natural saliva. In this article, we are presenting a discussion about the various media described in the related literature. A review of nearly 60 artificial salivas was carried out to clarify the role of some of the compounds most frequently met in the proposed formulae. The study focused on the buffer effect, the role played by CO2 gas and the presence of calcium ions, hydrogenocarbonates, hydrogenophosphates and thiocyanates. The SAGF medium, which we proposed some years ago, was used as a reference and some in vitro behavioral tests of dental biomaterials were studied in a comparative way. Using the SAGF medium allowed us to specify the mode of fluoride ions release from glass ionomer cements and the corrosion behavior of the dental amalgams.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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The authors present a novel compound [Cu(Pcba)2]n synthesized from the reaction between copper(I) thiocyanate and the ligand Pcba (Pcba = 2-pyrazine carboxylic acid), which exhibits a one-dimensional structure and has been characterized by Xray crystallography. In the process of synthesis, copper(I) ion has been oxidized into copper(II). This compound crystallizes in monoclinic, space group P2 (1)/c with cell parameters of a = 5.0387(4) A, b = 15.3317(13) A, c = 7.0720(6) A, beta = 106.63(0). The central ion Cu(II) is six-coordinated in a typical hexahedral geometry by four oxygen atoms and two nitrogen atoms in Pcba. Except chelating with two Pcbas, each central ion Cu(II) is extended to form one-dimensional linear structure through Pcba as the bridge. This compound was further characterized with IR spectra, fluorescence properties, UV-vis properties, and thermal analysis. Copyright Taylor & Francis Group, LLC 2013.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Multi-crystalline Si (mcSi) and CdTe solar photovoltaic technologies have gained significant improvement. Shockley?Queisser (S?Q) limit consideration further progress of open-circuit voltage (Voc), fill factor (FF) and the efficiency of CdTe cell are anticipated. Sub-bandgap parasitic absorption, grain boundaries and back contacts recombination lessening are vital to minimize these opto-electrical losses. mcSi and CdTe heterojunction (HJ) cells? intrinsic thermal co-efficient to optical (bandgap) loss, interface and bulk defects and related thermal diffusion are possible opto-electrical limitations. Wafer based mcSi passivated emitter rear contact (PERC) and tunnel oxide passivated contact (TOPCon) over Al back surface field (Al-BSF) contact have incredibly progressed in current decades. Similar as mcSi cell, advancement of commercial CdTe cell is desired. Reviewing CdTe and mcSi/cSi (photo-physical similarity) based one hundred and fifty research papers it is comprehended that not only band aligned but also thin, transparent passivation window and electron reflector as barrier are central to minimize the shortcomings. CdTe absorber thickness-dependent Voc and fill factor trade-off while diverse window and barrier layer performance review are realized optical transparencies to electrical loss outcome. Stated opto-electrical development purpose thin absorber supportive band and lattice matching double HJ or graded CdSexTe1-x/CdTe HJ is possible realistic pathways. mcSi thin wafer is exposed to minimize bulk degradation that is caring for a stable and cost-effective PV. Finally, CdTe solar cells present limitations to laboratory design towards the best progression trails are focused. It is anticipated to limit the levelized cost of energy (LCOE).

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Enzymes are biological catalysts that produce large increases in reaction rates and tend to be specific for certain reactants and products. I hope my blog about 1111-67-7 is helpful to your research.

Chemistry graduates have much scope to use their knowledge in a range of research sectors, including roles within chemical engineering, chemical and related industries, healthcare and more. Application In Synthesis of Cuprous thiocyanate. Introducing a new discovery about 1111-67-7, Name is Cuprous thiocyanate, The appropriate choice of redox mediator can avoid electrode passivation and overpotential, which strongly inhibit the efficient activation of substrates in electrolysis.

Under different situations, solvothermal reactions of 3,5-diethyl-4-(4- pyridyl)-pyrazole (HL) with CuX or CuX2 (X = Cl, Br, I, and SCN) afforded five copper(I) coordination polymers, {CuX[CuL]3· solvent}n (X = Cl, 1; Br, 2; I, 3; X = SCN and solvent = MeCN, 4) and {Cu2I2[CuL]3}n (5). X-ray diffraction analyses show that all the complexes have trinuclear [CuL] 3 (referred as Cu3) secondary building units featuring planar nine-membered Cu3N6 metallocycles with three peripheral pyridyl groups as connectors, which are further linked by CuX or Cu2X2 motifs to generate single- or double-strand chains. Interestingly, the Cu(I) atoms within the Cu3 units in 1-5 behave as coordinatively unsaturated pi-acid centers to contact soft halide/pseudohalide X atoms of CuX and Cu2X2 motifs, which lead to novel sandwich substructures of [(Cu3)(Cu2X2)(Cu 3)] (X = Br, I, and SCN) in 2-4. In addition, both the pi-acid [Cu3]···X contacts and intertrimer Cu···Cu interactions contribute to the one-dimensional (1D) double-strand and 2D/3D supramolecular structures of 1-5. All of these complexes exhibit high thermostability and bright solid-state phosphorescence upon exposure to UV radiation at room temperature. The emissions arise from the mixtures of metal-centered charge transfer, metal to ligand charge transfer, and halide-to-ligand charge transfer excited states, and can be tuned by intermolecular pi-acid [Cu3]···halide/ pseudohalide contacts.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”