Reactivities of mixed organozinc and mixed organocopper reagents. Part 13 Kinetic study for phosphine‐catalyzed acylation of alkylarylzincs and effect of residual group on the transfer rate of alkyl group

Kinetics of reactions of di‐n‐butylzinc, n‐Bu₂Zn, and mixed n‐butyl(substituted phenyl)zinc reagents and n‐Bu(functional group (FG)?C₆H₄)Zn with benzoyl chloride in the presence of tri‐n‐butylphosphine have been investigated. Reaction rates of transferable n‐butyl group have been determined in tetrahydrofuran at 0 °C to compare the transfer rate of n‐butyl group in homo and mixed diorganozincs. Rate law is consistent with a third‐order reaction, which is first order in diorganozinc, benzoyl chloride, and n‐Bu₃P, and a mechanism was proposed. The lower reaction rate of n‐BuPhZn than that of n‐Bu₂Zn and negative reaction constant in Hammett plot are in accordance with the carbanionic charge of transferable n‐butyl group in the acylation reaction. These findings support the hypothesis that the reaction rate of transferable group, R_T, changes depending upon the residual group, R_R, in R_RR_TZn reagents. Copyright © 2016 John Wiley & Sons, Ltd.     

Cyanines comprising barbiturate group facilitate NIR-light assisted ATRP under anaerobic and aerobic conditions at two wavelengths using Fe(III) catalyst

Cyanines with heptamethine pattern namely 5-(6-(2-(3-ethyl-1,1-dimethyl-1H-benzo[e]indol-2(3H)-ylidene)ethylidene)-2-(2-(3-ethyl-1,1-dimethyl-1H-benzo[e]indol-3-ium-2yl) vinyl) cyclo-hex-1-en-1-yl)-1,3-dimethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-olate comprising a barbiturate group facilitate controlled radical polymerization using FeBr₃ in the ppm range applying radiation at 790 nm. Tris(4-methoylphenyl)phosphine, Tris(2-pyridylmethyl)amine or tetrabutylammonium bromide served as ligand. The latter showed the best performance resulting in a system needing no amino nitrogen for photo-ATRP. Ethyl α-bromophenylacetate worked as initiator. The cyanine interacts with FeBr₃ resulting in a new absorption band at 877 nm that also resulted in formation of polymer exhibiting similar molecular weight but higher dispersity compared to that obtained by 790 nm radiation by exposure with a light-emitting diode (LED) emitting at 870 nm. This explains the reactivity of the system while other cyanines such as 2-[2-[3-[2-(1,3-Dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)-ethylidene]-2-(1-phenyl- 1H-tetrazol-5-ylsulfanyl)-1-cyclohexen-1-yl]-ethenyl]-1,3,3-trimethyl-3H-indolium chloride showed no activity by exposure at 790 nm in combination with FeBr₃/Br⁻. Controlled radical polymerization was confirmed by successful chain extension and block copolymerization experiments resulting in polymers, which exhibit a dispersity of about 1.3. Interestingly, the new system comprising the aforementioned barbiturate substituted cyanine, FeBr₃/Br⁻ and ethyl α-bromophenylacetate showed a certain oxygen tolerance. Polymers obtained exhibited similar dispersity as those made under inert conditions.     

Novel utilization of waste marine sponge (Demospongiae) as a catalyst in ultrasound-assisted transesterification of waste cooking oil

This study demonstrates the potential of Na-silica waste sponge as a source of low cost catalyst in the transesterification of waste cooking oil aided by ultrasound. In this work an environmentally friendly and efficient transesterification process using Na-loaded SiO₂ from waste sponge skeletons as a solid catalyst is presented. The results showed that the methyl esters content of 98.4 ± 0.4 wt.% was obtainable in less than an hour (h) of reaction time at 55 °C. Optimization of reaction parameters revealed that MeOH:oil, 9:1; catalyst, 3 wt.% and reaction duration of 30 min as optimum reaction conditions. The catalyst is able to tolerant free fatty acid and moisture content up to 6% and 8%, respectively. In addition, the catalyst can be reused for seven cycles while maintaining the methyl esters content at 86.3%. Ultrasound undoubtedly assisted in achieving this remarkable result in less than 1 h reaction time. For the kinetics study at 50–60 °C, a pseudo first order model was proposed, and the activation energy of the reaction is determined as 33.45 kJ/mol using Arrhenius equation.     

Progress in Developments of Inorganic Nanocatalysts for Application in Direct Methanol Fuel Cells

Significant progress has been made in the last few years toward synthesizing highly dispersible inorganic catalysts for application in the electrodes of direct methanol fuel cells. In addition, research toward achieving an efficient catalyst supporting matrix has also attracted much attention in recent years. Carbon black- (Vulcan XC-72) supported Platinum and Platinum-Ruthenium catalysts have for long served as the conventional choice as the cathode and the anode catalyst materials, respectively. Oxygen reduction reaction at the cathode and methanol oxidation reaction at the anode occur simultaneously during the operation of a direct methanol fuel cell. However, inefficiencies in these reactions result in a generation of mixed potential. This, in turn, gives rise to reduced cell voltage, increased oxygen stoichiometric ratio, and generation of additional water that is responsible for water flooding in the cathode chamber. In addition, the lack of long-term stability of Pt-Ru anode catalyst, coupled with the tendency of Ru to cross through the polymer electrolyte membrane and eventually get deposited on the cathode, is also a serious drawback. Another source of potential concern is the fact that the natural resource of Pt and the rare earth metal Ru is very limited, and has been predicted to become exhausted very soon. To overcome these problems, new catalyst systems with high methanol tolerance and higher catalytic activity than Pt need to be developed. In addition, the catalyst-supporting matrix is also witnessing a change from traditionally used carbon powder to transition metal carbides and other high-performance materials. This article surveys the recent literature based on the advancements made in the field of highly dispersible inorganic catalysts for application in direct methanol fuel cells, as well as the progress made in the area of catalyst-supporting matrices.     

3-甲基-1-磺酸咪唑硫酸氢盐催化剂用于四组分一锅法合成不对称聚羟基喹啉衍生物(英文)

3-Methyl-1-sulfonic acid imidazolium hydrogen sulfate has been used as an efficient, halogen-free,and reusable Brnsted acidic ionic liquid catalyst for the synthesis of ethyl-4-aryl/heteryl- hexahydro-trimehtyl-5-oxoquinoline-3-carboxylates via the one-pot condensation of dimedone with aryl/heteryl aldehydes, ethyl acetoacetate, and ammonium acetate under solvent-free conditions. This method has the advantage of being clean and simple, as well as providing the desired product in high yield over a short reaction time. Furthermore, the catalyst could be recycled and reused four times without any discernible reduction in activity.     

ZnAl2O4 SiO2纳米复合催化剂用于无溶剂条件下乙酸酐与醇、酚和胺的乙酰化反应简

A ZnAl₂O₄@SiO₂ nanocomposite was prepared from metal nitrates and tetraethyl orthosilicate by the sol-gel process, and characterized by X-ray diffraction, Fourier transform infrared, transmission electron microscopy, and N₂ adsorption-desorption measurements. The nanocomposite was tested as a heterogeneous catalyst for the acetylation of alcohols, phenols, and amines under solvent-free conditions. Under optimized conditions, efficient acetylation of these substrates with acetic anhydride over the ZnAl₂O₄@SiO₂ nanocomposite was obtained. Acetylation of anilines and primary aliphatic amines proceeded rapidly at room temperature, while the reaction time was longer for the acetylation of alcohols and phenols, showing that an amine NH₂ group can be selectively acetylated in the presence of alcoholic or phenolic OH groups. The catalyst can be reused without obvious loss of catalytic activity. The catalytic activity of the ZnAl₂O₄@SiO₂ nanocomposite was higher than that of pure ZnAl₂O₄. The method gives high yields, and is clean, cost effective, compatible with substrates having other functional groups and it is suitable for practical organic synthesis.     

Mechanistic Study of Unprecedented Highly Regioselective Hydrocyanation of Terminal Alkynes: Insight into the Origins of the Regioselectivity and Ligand Effects

Density functional theory (DFT) calculations were performed to gain insight into the mechanism of the nickel-catalyzed hydrocyanation of terminal alkynes with Zn(CN)₂ and water to exclusively generate the branched nitrile with excellent Markovnikov selectivity. After precatalyst activation to give the LNi(0) active species, the transformation proceeds via the following steps: (1) oxidative addition of H₂O to the LNi(0) provides the intermediate LNi(II)H(OH); (2) ligand exchange of LNi(II)H(OH) with Zn(CN)₂ gives the intermediate LNi(II)H(CN); (3) alkyne insertion to the LNi(II)H(CN) forms the alkenyl nickel complex, followed by the reductive elimination step reaching the final product. This mechanism is kinetically and thermodynamically more favorable than that of the experimental proposed ones. On the basis of the experimental observations, more water molecules cannot further improve the reaction as it has also been rationalized. Furthermore, the origin of the high regioselectivity of the product, the variable effectiveness of the metal mediator as function of ligands, as well as the high yield of the alkyl-substituted alkynes substrates, is analyzed in detail. © 2019 Wiley Periodicals, Inc.     

Enhancement of the catalytic performances and lifetime of Ni/γ-Al2O3 catalysts for the steam toluene reforming via the combination of dopants: inspection of Cu,Co, Fe,Mn, and Mo species addition

In this work, the influence of metallic dopant addition in 10 wt % Ni/γ-Al₂O₃ catalyst on the material physico-chemical properties and catalytic activity for the toluene steam reforming was studied. Seventeen doped Ni/γ-Al₂O₃ catalysts were synthesized by the sol–gel process. The aim of this study was to determine which elements were the most suitable for the doping of 10 wt % Ni/γ-Al₂O₃ catalysts. The influence of the dopants was studied through different physico-chemical techniques. It appeared that some dopants showed lower catalytic performances due to high carbon deactivation. On the contrary, some dopants increased the resistance to coking while also improving the catalytic activity. Different mechanisms were proposed to explain these modifications of catalytic behavior. Among all doped Ni/γ-Al₂O₃ catalysts, the samples that combined Mn + Mo or Co + Mo dopants showed the best catalytic performances at 650 °C. Both samples showed high toluene reforming activity and low amounts of carbon deposit.     

A Single‐Atom Manipulation Approach for Synthesis of Atomically Mixed Nanoalloys as Efficient Catalysts

Synthesis of well‐defined atomically mixed alloy nanoparticles on desired substrates is an ultimate goal for their practical application. Herein we report a general approach for preparing atomically mixed AuPt, AuPd, PtPd, AuPtPd NAs(nanoalloys) through single‐atom level manipulation. By utilizing the ubiquitous tendency of aggregation of single atoms into nanoparticles at elevated temperatures, we have synthesized nanoalloys on a solid solvent with CeO₂ as a carrier and transition‐metal single atoms as an intermediate state. The supported nanoalloys/CeO₂ with ultra‐low noble metal content (containing 0.2 wt % Au and 0.2 wt % Pt) exhibit enhanced catalytic performance towards complete CO oxidation at room temperature and remarkable thermostability. This work provides a general strategy for facile and rapid synthesis of well‐defined atomically mixed nanoalloys that can be applied for a range of emerging techniques.     

One-phase supported titanium-based catalyst for polymerization of ethylene. IV. Effect of alkyl group at organoaluminium compound on catalyst performance

The effect of a basic layer (SiO₂—R₃Al intermediate) in the one-phase silica supported titanium-based catalyst was investigated using the simple model catalyst systems obtained by reacting the activated silica gel consecutively with R₃Al and TiCl₄. Mode of the interaction of SiO₂ with R₃Al—resulting in the formation of the basic layer—was observed via analysis of the concentration of the unreacted OH groups on the silica surface employing IR spectroscopy and via analysis of the concentration of aluminium in solvent using AA spectroscopy. It was found that nature of the alkyl group in R₃Al modified the structure of the basic layer, thus influencing the catalyst performance including the concentration of both the sum of Ti²⁺ and Ti³⁺ and the ESR-active Ti (III) centers. The sum of Ti²⁺ and Ti³⁺ ranged from 45 to 52 mol % and the amount of the ESR-active Ti (III) species ranged from 6 to 17 mol % of the all titanium content. A significant effect of alkyl group at organoaluminium compound on the molecular weight distribution of the resulting polymer was observed. © 1996 John Wiley & Sons, Inc.