Pd(II) anchored to modified Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles as a new magnetically recoverable catalyst for epoxidation of styrene

A new support for Pd(II) was synthesized via the functionalization of Fe₃O₄ nanoparticles with N-(2-aminoethyl)acetamide. PdCl₂ was anchored to the support for obtaining a heterogeneous magnetically recoverable catalyst for Pd(II). High yield and excellent selectivity were obtained for the green epoxidation of styrene derivatives using H₂O₂ as a green oxidant in H₂O as the solvent at 100 °C. Also, the recovered catalyst is applicable for four times without significant decrease in yield.     

镍(II)配合物官能化的MCM-41催化分子氧环氧化苯乙烯

制备了镍(II)席夫碱配合物官能化的MCM-41多相催化剂MCM-41-Ni.利用X射线粉末衍射、氮气物理吸附脱附、红外光谱、热重、电感耦合等离子体原子发射光谱、元素分析和透射电镜等方法对催化剂进行了表征.以氧气为氧化剂,MCM-41-Ni在催化环氧化苯乙烯的反应中表现出较高的催化活性;苯乙烯的转化率为95.2%,环氧苯乙烷的选择性为66.7%.系统地研究了反应温度、催化剂用量、溶剂以及反应时间对反应性能的影响.催化剂经过4次循环仍然表现出较好的稳定性和催化活性.     

Nano ceria catalyzed synthesis of α-aminophosphonates under ultrasonication

A simple, efficient and general method has been developed for the one-pot three component syntheses of α-aminophosphonates. The condensation of aldehyde, amine and triethyl phosphite by employing CeO₂ nanoparticles as catalyst gave α-aminophosphonates. The catalyst showed good recyclability. Nano CeO₂ has been found to be an excellent catalyst for the green synthesis of α-aminophosphonates under ultrasound irradiation and solvent-free condition. The α-aminophosphonates are obtained in good to excellent yield. This catalyst provides cleaner conversion, short reaction time and high selectivity which makes the protocol feasible and economical attractive.     

Olefin epoxidation with tert-butyl hydroperoxide catalyzed by functionalized polymer-supported copper(II) Schiff base complex

Abstract  

A new polymer-supported Cu(II) Schiff base complex has been synthesized and characterized by elemental (including metal) analysis, FT-IR spectroscopy, UV–Vis diffuse reflectance spectroscopy, thermogravimetric analysis, and scanning electron microscopy. The catalytic performance of this complex was evaluated in the epoxidation of styrene in acetonitrile/N,N-dimethylformamide (9:1) mixture with 70% tert-butyl hydroperoxide as an oxidizing agent under liquid phase reaction conditions for selective synthesis of styrene oxide. Suitable reaction conditions have been optimized by considering the effects of various reaction parameters such as temperature, reaction time, solvent, oxidant, catalyst amount, and styrene to hydroperoxide molar ratio for the maximum conversion of styrene as well as selectivity of styrene oxide. We have also investigated the epoxidation reaction of various olefins under the optimized reaction conditions. Comparison between catalytic activities of the polymer-supported Cu(II) Schiff base complex and its homogeneous analogue showed that the polymer-supported catalyst was more active. This heterogeneous complex was reused for five times. The selectivity of the heterogeneous catalyst does not change even after five times of reusing.     

反应控制相转移催化环氧化苯乙烯

研究了磷钨杂多酸盐反应控制相转移催化H2O2直接氧化苯乙烯制环氧苯乙烷的反应,考察了溶剂、H₂O₂用量、催化剂用量、反应温度、时间、苯乙烯浓度等因素对反应的影响。 获得的适宜的反应条件为：乙酸乙酯为溶剂,n(苯乙烯)∶n(H₂O₂)∶n(催化剂)=300∶300∶1,反应温度60 ℃,反应时间6 h,反应液中苯乙烯质量分数为10%。 在该条件下,苯乙烯的转化率为85.5%,环氧苯乙烷的选择性为84.9%。 催化剂可过滤回收,循环使用2次后的活性无明显下降。     

Epoxidation of alkenes with molecular oxygen and isobutyraldehyde catalyzed by immobilized vitamin B12 within Al-MCM-41

Vit-B₁₂/ Al-MCM-41 catalyzed successfully the epoxidation either of cis or trans — stilbene with O₂ as oxidant and isobutyraldehyde as co-reductant with 86–98% reactivity and 97–100% selectivity. Other olefins such as norbornene and styrene undergo epoxidation reaction under similar conditions with good to fair selectivity. Details of the reactions will be presented in this article.     

Heterogenized peroxopolyoxotungstate catalyst on the surface of clicked magnetite‐graphene oxide nanocomposite: Magnetically recoverable epoxidation catalyst

A new heterogeneous catalyst for the epoxidation of olefins was prepared by immobilization of peroxophosphotungstate anions on the surface of clicked magnetite‐graphene oxide as magnetically recoverable support. To prepare the heterogeneous catalyst, the clicked magnetite‐graphene oxide support was prepared by thiolene click reaction of thiol functionalized graphene oxide with vinyl modified magnetite nanoparticles. The tailored support was then modified with aminopropyl groups followed by electrostatic interaction with peroxophosphotungstate anions to achieve the desired heterogeneous catalyst. Characterization of the catalyst was performed by various physicochemical methods which confirmed the successful immobilization of peroxopolyoxotungstate species on the surface of clicked magnetite‐graphene oxide. Catalytic activity of the catalyst revealed its high catalytic activity and selectivity in the epoxidation of various olefins in the presence of H₂O₂ as green oxidant. This heterogeneous catalyst can be magnetically reused several times without significant loss of activity and selectivity.     

Synthesis of magnetic CuFe2O4 nanoparticles as green catalyst for toluene oxidation under solvent-free conditions

A green method was developed for the synthesis of CuFe₂O₄ magnetic nanoparticles using a Neem leave extract. The prepared nanoparticles with an average size of 19.7 nm were used as an effective catalyst for the oxidation of various aryl alkanes in moderate to excellent yields under solvent-free conditions. The catalyst was characterized by powder- XRD, SEM and TEM study. The key advantages of this protocol are simple preparation, a recyclable heterogeneous catalytic system, and benign reaction condition with good to excellent yields with high selectivity toward acid (42–87%).     

Development of a General and Efficient Iron‐Catalyzed Epoxidation with Hydrogen Peroxide as Oxidant

The development of inexpensive and practical iron catalysts for the environmentally benign epoxidation of olefins with hydrogen peroxide as terminal oxidant is described. By systematic variation of ligands, metal sources, and reaction conditions, it was discovered that FeCl₃?6H₂O in combination with pyridine‐2,6‐dicarboxylic acid and different amines shows high reactivity and excellent selectivity towards the epoxidation of aromatic olefins and moderate reactivity towards that of aliphatic olefins.     

Magnetic d‐penicillamine‐functionalized cellulose as a new heterogeneous support for cobalt(II) in green oxidation of ethylbenzene to acetophenone

A new efficient heterogeneous catalyst is introduced for the oxidation of ethylbenzene. The catalyst was obtained in three steps: functionalization of cellulose with d ‐penicillamine, deposition of Fe₃O₄ nanoparticles on cellulose–d ‐penicillamine and then anchoring of Co(II) to the magnetic cellulose–d ‐penicillamine. High yield and excellent selectivity were achieved for the oxidation of ethylbenzene to acetophenone in ethanol under reflux conditions using H₂O₂ as a green oxidant. Also, the recovered catalyst could be applied six times without a decrease in activity.     

In situ Deposition of ‘Naked’ Gold Nanoparticles Supported on Silica Spheres as Recyclable Catalysts in Styrene Epoxidation

Tlie rational designs of particle size, morphology and surface states of the Au nanoparticles(AuNPs) are crucial for Au nanocatalyst. We herein report a method to synthesize the silica microspheres supported AuNPs(ca.1 nm) and their application in controlling the reaction conversion and selectivity in styrene epoxidation. Surfactant-ftee AuNPs deposited on silica microspheres were in situ fabricated with aid of the Ag nanoparticles (AgNPs) as sacrificial template by galvanic replacement reaction, leading to AuNPs/SiO2 catalyst directly without any post-treatment to expose crystal facets.A high conversion of 46.7% and selectivity of 91.7% to styrene oxide was achieved with H2O2 as oxidant in ethanol. The solid catalyst could be reused at least 10 reaction cycles without significant decrease in activity and selectivity. This study not only supplies an active, recoverable catalyst for styrene oxidation with green oxidant and solvent, but also demonstrates that the silica microspheres functionalized with thiol groups have a superior ability in stabilizing noble metal nanoparticles even without any surfactant.     

Fe3O4@SiO2@D-NHCS-Tr as an efficient and reusable catalyst for the synthesis of indol-3-yl-4H-chromene via a multi-component reaction under solvent-free conditions

Fe₃O₄@SiO₂@D-NHCS-Tr was used as an efficient catalyst in the three-component reaction between indole derivatives, salicylaldehyde, and active methylene compounds under solvent-free conditions to the synthesis of indol-3-yl-4H-chromene derivatives. The features of this method include the green conditions of the reaction, easy separation, eco-friendly and cost-effectiveness of the catalyst, and high yield in short reaction times.     

Covalent supporting of novel dioxo‐molybdenum tetradentate pyrrole‐imine complex on Fe3O4 as high‐efficiency nanocatalyst for selective epoxidation of olefins

A novel Mo(VI) tetradentate Schiff base complex based on two pyrrole‐imine donors was anchored covalently on Fe₃O₄ nanoparticles and characterized using physicochemical techniques. The catalytic epoxidation process was optimized in terms of the effects of solvent, reaction temperature, kind of oxidant and amount of oxidant and catalyst. Then the novel heterogeneous nanocatalyst was used for the efficient and selective catalytic epoxidation of internal alkenes (cyclohexene, cyclooctene, α‐pinene, indene and trans ‐1,2‐diphenylethene) and terminal alkenes (n ‐heptene, n ‐octene, n ‐dodecene and styrene) using tert ‐butyl hydroperoxide (70% in water) as oxidant in 1,2‐dichloroethane as solvent. The prepared nanocatalyst is very effective for the selective epoxidation of cis ‐cyclooctene with 100% conversion, 100% selectivity and turnover frequency of 1098 h⁻¹ in just 30 min. The magnetic nanocatalyst was easily recovered using an external magnetic field and was used subsequently at least six times without significant decrease in conversion.     

溴化锌-卤化正四丁基铵高效催化合成苯乙烯环状碳酸酯

溴化锌-卤化正四丁基铵二元催化剂高效催化合成苯乙烯环状碳酸酯, 当n-Bu4NI/ZnBr2摩尔比为2时, 在短时间内(30 min)可将苯乙烯环氧化物几乎完全转化为环状碳酸酯, 无其它副产物的生成. 在ZnBr2/n-Bu4NX的催化体系中加入Au/SiO2 氧化催化剂时, 能将苯乙烯直接氧化, 然后碳酰化实现“一锅法”制备环状碳酸酯. 在此合成路线中担载的纳米金催化第一步苯乙烯环氧化反应; ZnBr2/n-Bu4NBr催化第二步CO2环加成反应. 在温和的反应条件下(80 ℃, 1 MPa, 4 h)将环状碳酸酯的产率提高到42%.     

Al(HSO4)3: an efficient and heterogeneous reusable catalyst for the synthesis of 1-amidoalkyl-2-naphthols under thermal solvent-free conditions

An efficient green protocol for the synthesis of 1-amidoalkyl-2-naphthols using a three-component, one-pot condensation reaction of 2-naphthol, aromatic aldehyde and amides in the presence of Al(HSO₄)₃ as heterogeneous catalyst under thermal solvent-free conditions has been described. The present procedure offers advantages such as shorter reaction times, simple work-up procedure, excellent yields, recovery and reusability of catalyst.     

Tin(IV) bis(perfluoroalkanesulfonyl)amide complex as a highly selective Lewis acid catalyst for Baeyer-Villiger oxidation using hydrogen peroxide in a fluorous recyclable phase

Sn[N(SO₂C₈F₁₇)₂]₄ catalyst was shown to give an excellent yield and selectivity in a fluorous biphasic catalytic system for Baeyer-Villiger oxidation of cyclic ketones by 35% aqueous hydrogen peroxide, a green, safe and cheap oxidant. Furthermore, the catalyst was completely recovered and reused in the fluorous immobilized phase without loss of activity.     

Graphene Oxide Supported Oxovanadium (IV) Complex for Catalytic Peroxidative Epoxidation of Styrene: An Eye-Catching Impact of Solvent

Graphene oxide (GO) supported transition metal complexes are apprised as sturdy and everlasting heterogeneous catalysts. GO surface was functionalized with 3-triethoxysilylpropylamine (TSPA) and this amino functionalized GO (A-f-GO) nanocomposite with vanadyl Schiff base complex (VO-f-GO) was prepared and to give credence of its potentiality, it was chosen for the selective epoxidation of styrene using environmentally benign 30% H₂O₂ to styrene oxide (SO). To evade the detrimental exposure of “inborn” water, a selective high boiling and potent hygroscopic solvent, ethylene glycol was chosen to make this transformation productively successful. With the assistance of theoretical studies, we have probed the effect of H₂O₂ on to structural properties, binding mechanism and electronic properties of the catalyst and substrate. Adsorption energy (E_ad), energy band gap (E_g) and HOMO-LUMO were also calculated. Based on DFT calculations, resonance Raman and UV/Vis studies, we confirmed the formation of metal-peroxo species and propose the plausible catalytic pathway. The influence of the diverse experimental parameters, like substrate to oxidant mole ratio, catalyst concentration, type of solvents, solvent amount, time, temperature and oxidant were tested. A clear relationship was found between different reaction parameters like solvent amount, oxidant, catalyst concentration and temperature etc. and product distribution. This heterogeneous catalyst yielded styrene oxide as nearly the sole product (selectivity = 98.7%) with a conversion value of 99.2% in the oxidation of styrene with hydrogen peroxide in ethylene glycol.     

MnO2/graphene oxide: A highly efficient catalyst for imine synthesis from alcohols and amines

α‐MnO₂ nanocrystals supported on graphene oxide (α‐MnO₂/GO) was prepared through a soft chemical route and evaluated for the first time as a novel, eco‐friendly and efficient catalyst in the coupling reaction of alcohols and amines to imines. The well‐organized α‐MnO₂/GO was characterized using various techniques. The results show that MnO₂ nanocrystals are highly dispersed on the GO sheets and interconnected with each other, leading to large available surface area, which greatly enhances the catalytic performance of conventional MnO₂. Under mild conditions, the catalyst exhibits excellent catalytic activity and selectivity with O₂ serving as terminal oxidant. Various imines can be smoothly obtained in good to excellent yield. Importantly, the catalyst is easily recovered and can be reused six times with no significant loss of activity.     

双二茂铁基醛亚胺钼（ＶＩ）配合物的合成及催化性能

通过二茂铁甲醛与丙二胺反应得到双二茂铁基醛亚胺配体N~1,N~3-双二茂铁亚甲基丙烷-1, 3-二胺(FcMP), FcMP与MoO_2Cl_2(THF)_2的四氢呋喃溶液作用, 合成了双二茂铁基醛亚胺钼(VI)配合物. 以配合物为催化剂, 叔丁基过氧化氢为氧化剂, 分别以苯乙烯和环己烯为底物, 考察了温度、时间、催化剂量及溶剂对于烯烃均相环氧化反应的催化性能的影响. 结果表明, 在最优实验条件下, 反应12 h, 环己烯的转化率为88%, 环氧环己烷的选择性为98%;苯乙烯的转化率为84%, 氧化苯乙烯的选择性为76%. 催化剂经简单分离可回收使用, 且催化活性基本保持不变. 同时对环氧化反应的机理进行了初步探讨.     

Mixed matrix vanadium oxide catalytic nanocomposite membrane for styrene oxidation

Mesoporous nanocomposite membranes with vanadium oxide–carbon nanotubes (V_xO_y-CNTs) embedded in γ-Al₂O₃ were successfully synthesized using the dip coating method. The membranes were evaluated for styrene oxidation to determine the optimum styrene conversion and benzaldehyde selectivity. Several factors that influence the preparation of defect-free coatings, such as the type of binder, the binder addition time and surface support treatments, were investigated. The physico-chemical permeation properties of the membranes were characterized using scanning electron microscope, transmission electron microscope (TEM), X-ray Diffraction XRD, Nitrogen adsorption (BET) and Thermogravimetric TGA. Response surface methodology (RSM) was used to investigate the effects of oxidant (H₂O₂) concentration, temperature, contact time and catalyst loading on styrene conversion and the selectivity of benzaldehyde. Based on the RSM analysis, the optimal oxidation conditions included a reaction temperature of 45 °C, a differential pressure of 1.5 bars, a molar ratio of H₂O₂: styrene of 1.5:1 and a catalyst loading of 30 %. These conditions resulted in the maximal styrene conversion of 25.6 and 84.9 % benzaldehyde selectivity.