SiO2-NHC-CuI–Catalyzed N-Arylation of Imidazoles with Arylboronic Acids Under Base-Free Reaction Conditions

N-Arylation of imidazoles with arylboronic acids was efficiently carried out in the presence of a catalytic amount of SiO₂-NHC-Cu^I in methanol at room temperature under base-free reaction conditions. The reactions of a variety of arylboronic acids with imidazoles generated the corresponding products N-arylimidazoles in good to excellent yields. In addition, SiO₂-NHC-Cu^I could be recovered and recycled for six consecutive trials without significant loss of its reactivity.     

Sonochemical Synthesis of 1,4‐Disubstituted 1,2,3‐Triazoles in Aqueous Medium

An ultrasound‐accelerated fast and efficient three‐component reaction for the regioselective synthesis of l,4‐disubstituted 1,2,3‐triazoles using different alkyl and allyl halides, terminal alkynes, and sodium azide in water at room temperature has been developed using CuI as catalyst. Ultrasonication dramatically decreases the reaction times.     

Protection of Copper Surface Against Corrosion by Cationic Surfactant in Seawater

The protection power of the cationic surfactant decylammonium acetate (DAA) in seawater has been studied to define the perfect conditions have to be found for using it as a corrosion inhibitor for copper surface. The adsorption isotherm of this surfactant on copper surface has been determined at different interval times at 30°C. The given isotherms have, in general, similar shapes exhibiting a Languimirian L-shape. The corrosion measurement has been determined according to weight loss method. The study declines that cationic DAA, in seawater, protects well the copper surface against corrosion when added with low concentrations, while high concentrations show bad inhibition efficiency. ICP spectroscopic analysis assures this result where high Cu% has been obtained in the presence of high DAA concentration.     

Synthesis of Thermally Stable Energetic 1,2,3‐Triazole Derivatives

Various thermally stable energetic polynitro‐aryl‐1,2,3‐triazoles have been synthesized through Cu‐catalyzed [3+2] cycloaddition reactions between their corresponding azides and alkynes, followed by nitration. These compounds were characterized by analytical and spectroscopic methods and the solid‐state structures of most of these compounds have been determined by using X‐ray diffraction techniques. Most of the polynitro‐bearing triazole derivatives decomposed within the range 142–319 °C and their heats of formation and crystal densities were determined from computational studies. By using the Kamlet–Jacobs empirical relation, their detonation velocities and pressures were calculated from their heats of formation and crystal densities. Most of these newly synthesized compounds exhibited high positive heats of formation, good thermal stabilities, reasonable densities, and acceptable detonation properties that were comparable to those of TNT.     

Mechanism of Copper(I)‐Catalyzed Allylic Alkylation of Phosphorothioate Esters: Influence of the Leaving Group on α Regioselectivity

The mechanism of Cu^I‐catalyzed allylic alkylation and the influence of the leaving groups (OPiv, SPiv, Cl, SPO(OiPr)₂; Piv: pivavloyl) on the regioselectivity of the reaction have been explored by using density functional theory (DFT). A comprehensive comparison of many possible reaction pathways shows that [(iPr)₂Cu]^? prefers to bind first oxidatively to the double bond of the allylic substrate at the anti position with respect to the leaving group, and this is followed by dissociation of the leaving group. If the leaving group is not taken into account, the reaction then undergoes an isomerization and a reductive elimination process to give the α‐ or γ‐selective product. If OPiv, SPiv, Cl, or SPO(OiPr)₂ groups are present, the optimal route for the formation of both α‐ and γ‐substituted products changes from the stepwise elimination to the direct process, in which the leaving group plays a stabilizing role for the reactant and destabilizes the transition state. The differences to the energy barrier for the α‐ and γ‐substituted products are 2.75 kcal mol^?1 with SPO(OiPr)₂, 2.44 kcal mol^?1 with SPiv, 2.33 kcal mol^?1 with OPiv, and 1.98 kcal mol^?1 with Cl, respectively; these values show that α regioselectivity in the allylic alkylation follows a SPO(OiPr)₂>SPiv>OPiv>Cl trend, which is in satisfactory agreement with the experimental findings. This trend mainly originates in the differences between the attractive electrostatic forces and the repelling steric interactions of the SPO(OiPr)₂, SPiv, OPiv, and Cl groups on the Cu group.     

Synthesis,spectroscopy, electrochemistry,and methylation reaction of the dithiolate-based cobalt(II) complex derived from tert-butyl N-(2-mercaptoethyl)carbamate

A dithiolate-containing a carbamate mononuclear cobalt(II) complex namely, [Co(Boc-S)₂] (1), was obtained by the reaction of a methanolic solution of cobalt(II) nitrate hexahydrate with two equimolar amounts of the deprotonated form of tert-butyl N-(2-mercaptoethyl)carbamate (Boc-SH). The cobalt(II) complex (1) was characterized in the solid state and in solution by using FT–IR, Raman, UV–visible, and EI–mass spectroscopies, as well as thermal and X-ray diffraction studies. Spectral data showed that the carbamate (Boc-SH) acts as a mono-anionic bidentate ligand coordinating the cobalt(II) ion through two imine nitrogen and two deprotonated thiolate sulfur donor atoms in a distorted tetrahedral geometry. The thermoanalytical data evidence that the complex is stable up to 165 °C and undergoes complete decomposition, resulting in CoO. TEM imaging of the oxide residue shows its nano size clusters, suggesting that the complex (1) may be used as a precursor for nano-oxides. X-ray powder diffraction patterns evidence an isomorphism among the complex. The redox behavior of the cobalt(II) complex was also investigated by cyclic voltammetry. The reaction of the dithiolate cobalt(II) complex (1) with methyl iodide appears to occur intramolecularly with the cobalt-bound dithiolate, forming the cobalt(II)-bound dithioether complex [Co(Boc–SCH₃)₂]I₂ (2), as a dication complex with a clean second-order reaction of 13.24 × 10⁻² M⁻¹·s⁻¹.     

An innovative SiO2-pyrazole nanocomposite for Zn(II) and Cr(III) ions effective adsorption and anti-sulfate-reducing bacteria from the produced oilfield water

Novel SiO₂-pyrazole (SiO₂-PYZ) nanocomposite was introduced for the elimination of Zn(II) and Cr(III) from oil reservoir water. Characterization analysis of prepared SiO₂-PYZ nanocomposite was investigated using SEM, FTIR, TGA, XRD, TEM, and BET. Studying the effects and optimization of the parameters such as retention time, pH, initial Cr(III) and Zn(II) ions concentrations, adsorbent dosage, and temperature were examined. For kinetics investigation, the pseudo-second-order (PSO) model matches the adsorption process effectively under different operating conditions. After applying two other isotherm models (Langmuir and Freundlich), the experimental data was adequately equipped with Langmuir, R² = 1. The thermodynamic results pointed that the adsorption of Zn(II) and Cr(III) ions was spontaneous, endothermic, and physisorption reaction. At pH 12, the influence of more than one ion, such as Ca(II) and Na(I), was checked, and the results revealed that this conjugate substance was highly selective to Cr(III). After washing with water in multiple cycles, the adsorbed material was regenerated with 0.1 M HCl and subsequently reused without deterioration in its case cavities. Interestingly, SiO₂-PYZ was highly effective against sulfate-reducing bacteria (SRB) in the petroleum field.     

Speciation of Copper(II)-Betaine Complexes as Starting Point for Electrochemical Copper Deposition from Ionic Liquids

The application of ionic liquids for the dissolution of metal oxides is a promising field for the development of more energy- and resource-efficient metallurgical processes. Using such solutions for the production of valuable chemicals or electrochemical metal deposition requires a detailed understanding of the chemical system and the factors influencing it. In the present work, several compounds are reported that crystallize after the dissolution of copper(II) oxide in the ionic liquid [Hbet][NTf₂]. Dependent on the initial amount of chloride, the reaction temperature and the purity of the reagent, copper crystallizes in complexes with varying coordination geometries and ligands. Subsequently, the influence of these different complex species on electrochemical properties is shown. For the first time, copper is deposited from the ionic liquid [Hbet][NTf₂], giving promising opportunities for more resource-efficient copper plating. The copper coatings were analyzed by SEM and EDX measurements. Furthermore, a mechanism for the decomposition of [Hbet][NTf₂] in the presence of chloride is suggested and supported by experimental evidence.     

Exceedingly Fast Copper(II)‐Promoted ortho CH Trifluoromethylation of Arenes using TMSCF3

The direct ortho‐trifluoromethylation of arenes, including heteroarenes, with TMSCF₃ has been accomplished by a copper(II)‐promoted C? H activation reaction which completes within 30 minutes. Mechanistic investigations are consistent with the involvement of C? H activation, rather than a simple electrophilic aromatic substitution (S_EAr), as the key step.     

高效可回收多相催化剂SiO_2-Cu_2O催化伯胺和仲胺苄基化反应(英文)

A mild,effective,and selective procedure is reported for the mono N-benzylation and N,N-dibenzylation of primary amines as well as mono N-benzylation of secondary amines using silicasupported copper(I) oxide in water.The silica-supported Cu2O was generated in situ by the reaction of Fehling solution and glucose at 100 °C onto activated silica.The catalyst was filtered,washed with water,and oven-dried,and was characterized by Fourier transform infrared spectroscopy,thermogravimetric analysis,scanning electron microscopy,transmission electron microscopy,and atomic absorption spectroscopy.The prepared Cu2O-SiO2 was found to be thermally stable up to 325 °C.The copper was uniformly distributed onto the surface of the silica,and the mean particle diameter was 7 nm.The catalyst served as a selective heterogenous catalyst for the N-benzylation of primary and secondary amines.The catalyst is recyclable and was used effectively upto fifth run without a significant loss of catalytic activity.Various reaction solvents including water,acetonitrile,and toluene were screened for N-benzylation of amines,and the success of the aqueous system highlights the low environmental impact of the procedure.