TiO2ZrO2 composite: Synthesis,characterization and application as a facile,expeditious and recyclable catalyst for the synthesis of 2-aryl substituted benzoxazole derivatives

The activity of an efficient mesoporous TiO₂ZrO₂ composite catalyst for the synthesis of 2-aryl substituted benzoxazole derivatives using 2-aminophenol and substituted benzaldehydes/heterocyclic aldehydes at moderate temperature was studied. The catalyst was prepared by a co-precipitation method and characterized by X-ray diffraction, BET surface area and scanning electron microscopy. The effect of temperature, solvents and catalyst concentration on the synthesis of benzoxazole derivatives was systematically investigated. Short reaction times, green-reaction profiles, good to excellent yields, reliable cost efficiency, simple workup conditions and reusability of an eco-friendly catalyst are the noteworthy highlights of the reported method. The catalyst could be easily recovered and reused several times without any significant loss in the yield. The use of the present catalytic system to mediate the title chemical synthesis in a synthetic operation is important for the development of new atom-economic strategies and this is efficient in building complex structures from simple starting materials in an environmentally benign fashion.     

MWCNTs-ZrO2 as a reusable heterogeneous catalyst for the synthesis of N-heterocyclic scaffolds under green reaction medium

A simple, efficient, and facile heterogeneous multi-walled carbon nanotubes-zirconia nanocomposite (MWCNTs-ZrO₂) has been synthesized using natural feedstock coconut juice (água-de-coco do Ceará). The synthesized catalyst was characterized by Fourier transform infrared spectroscopy, X-ray diffraction, field emission scanning electron microscopy, and X-ray photoelectron spectroscopy analysis. The heterogeneous nanocomposite has been used for one-pot synthesis of various N-heterocyclic compounds like pyrazoles, 1,2-disubstituted benzimidazoles, 2-arylbenzazoles, and 2,3-dihydroquinazolin-4(1H)-ones under green reaction medium at room temperature. This novel method has several advantages, such as short reaction time, simple work-up, excellent yield, and green reaction conditions. The catalyst was recycled up to four times without significant loss in catalytic activity.     

Synthesis and characterization of new organic–inorganic nanohybrid film (TBA)PWFe/PVA/CTS as an efficient and reusable amphiphilic catalyst for ODS of real fuel

In this work, we report a new catalytic oxidative desulfurization (CODS) system based on (TBA)PWFe/PVA/CTS nanohybrid film as a highly active catalyst. The nanohybrid material was successfully fabricated by the composition of tetra (n‐butyl) ammonium salt of Fe‐substituted phosphotungstate, ((n‐C₄H₉)₄N)₄[PW₁₁Fe(H₂O)O₃₉] abbreviated as (TBA)PWFe, polyvinyl alcohol (PVA), and chitosan (CTS). The composite was characterized using various analytical techniques including FT‐IR, UV–vis, XRD, and SEM. The results revealed the hydrogen‐bonding interaction between inorganic (TBA)PWFe clusters and organic polymers. The catalytic activity of (TBA)PWFe/PVA/CTS was evaluated in the CODS of real gas oil. Also, the solutions of heterocyclic thiophenic compounds (HTCs) in n‐heptane were tasted as simulated fuels. It was found that the removal efficiency of HTCs in the presence of (TBA)PWFe/PVA/CTS catalyst reached as high as 95% at 60 °C after 2 h. The significant catalytic performance of the nanohybrid film might be attributed to its amphiphilicity and multifunctional active sites, which enhances adsorption and oxidation of sulfur compounds. Moreover, the (TBA)PWFe/PVA/CTS composite can be easily recovered and reused by simple filtration, making it a suitable catalyst for cleaner processing.     

Sulfonated palladium(II) N‐heterocyclic carbene complex immobilized on nano–micro size poly(4‐vinylpyridinium chloride) for Suzuki‐Miyaura cross‐coupling reaction

The sulfonated palladium(II) N‐heterocyclic carbene complex Pd^II(NHC)SO₃^?, supported on poly(4‐vinylpyridinium chloride), was used as a heterogeneous, recyclable and active catalyst for the Suzuki–Miyaura reaction. This catalyst was applied for coupling of various aryl halides with phenylboronic acid and the corresponding products were obtained in excellent yields and short reaction times. The catalyst was characterized using Fourier transform infrared and diffuse reflectance UV–visible spectroscopies, scanning electron microscopy and elemental analysis. After each reaction, the catalyst was recovered easily by simple filtration and reused several times without significant loss of its catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Efficient synthesis of β-aminoketones catalyzed by Fe3O4@ quillaja sapogenin/Ni (II) as a novel magnetic nano-catalyst

A new nano-magnetic core–shell Fe₃O₄@quillaja sapogenin/Ni (II) was synthesized and characterized thoroughly using various tests including energy-dispersive X-ray spectroscopy (EDS), Brunauer–Emmett–Teller (BET), thermo-gravimetric analysis (TGA), high-resolution transmission electron microscopy (HR-TEM), vibrating sample magnetometer (VSM), Fourier transform infrared (FT-IR) spectroscopy, inductively coupled plasma (ICP), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The achievements demonstrated that the proposed agents were beneficial to synthesis the derivatives of β-aminoketone. Moreover, it was possible to recover the catalyst by means of simple magnetic decantation quickly. Besides, no reduction in the activity of the catalyst occurred, even though it was utilized in various reactions.     

Magnetic NiFe2O4 nanoparticles: efficient,heterogeneous and reusable catalyst for synthesis of acetylferrocene chalcones and their anti‐tumour activity

A robust synthesis of magnetic NiFe₂O₄ nanoparticles via a hydrothermal technique was investigated. The prepared magnetic NiFe₂O₄ nanoparticles were characterized using powder X‐ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy (TEM), high‐resolution TEM, energy‐dispersive X‐ray spectroscopy, thermogravimetric analysis, infrared spectroscopy and vibrating sample magnetometry. XRD and TEM analyses confirmed the formation of single‐phase ultrafine nickel ferrite nanoparticles with highly homogeneous cubic shape and elemental composition. Moreover, the prepared magnetic NiFe₂O₄ nanoparticles were used as an efficient, cheap and eco‐friendly catalyst for the Claisen–Schmidt condensation reaction between acetylferrocene and various aldehydes (aromatic and/or heterocyclic) yielding acetylferrocene chalcones in excellent yields, with easy work‐up and reduced reaction time. The products were purified via crystallization. The structures of the produced compounds were elucidated using various spectroscopic analyses (¹H NMR, ¹³C NMR, GC–MS). The catalyst is readily recovered by simple magnetic decantation and can be recycled several times with no discernible loss of catalytic activity. Furthermore, the prepared chalcone derivatives were evaluated for their anti‐tumour activity against three human tumour cell lines, namely HCT116 (colon cancer), MCF7 (breast cancer) and HEPG2 (liver cancer), and showed a good activity against colon cancer. Copyright © 2016 John Wiley & Sons, Ltd.     

[PZnMo2W9O39]5− immobilized on ionic liquid-modified silica as a heterogeneous catalyst for epoxidation of olefins with hydrogen peroxide

The epoxidation of alkenes with hydrogen peroxide catalyzed by [PZnMo₂W₉O₃₉]^5-, ZnPOM, supported on ionic liquid-modified silica, Im-SiO₂, is reported. The immobilized catalyst, [ZnPOM@Im-SiO₂] was characterized by elemental analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), FT-IR and UV–Vis spectroscopic methods. This new synthesized hybrid catalyst was applied for efficient epoxidation of various olefins with aqueous H₂O₂ in acetonitrile under reflux conditions. This solid catalyst can be easily recovered by simple filtration and reused several times without significant loss of its catalytic activity.     

Pd immobilized on thiol-modified magnetic nanoparticles: A complete magnetically recoverable and highly active catalyst for hydrogenation reactions

A palladium-based catalyst supported on thiol-modified superparamagnetic nanoparticles was successfully prepared by co-precipitation method. These magnetic nanomaterials were characterized by elemental analysis (EA), inductively coupled plasma (ICP), X-ray powder diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), fourier transform-infrared (FT-IR), thermogravimetric analysis (TGA) and vibrating sample magnetometry (VSM). The conversions of various aromatic nitro and unsaturated compounds can receive a really high yield with the existence of magnetic nanomaterials. The turn-over frequency (TOF) can be 66.46 h⁻¹ in ethanol under a H₂ atmosphere at room temperature. In this paper, the conversions of aromatic nitro bearing a variety of substituents were 93.56–100%, moreover, the catalyst afforded over 90% yield in the reducing unsaturated compounds. Another advantage is that the magnetite nanoparticles modified by thiol group can be separated just through the external magnetic force and can be reused atleast ten times without any significant loss in activity.     

CdS/TiO2纳米管复合结构的制备与光电性能研究

利用阳极氧化法在钛金属基底表面制备一层TiO2纳米管阵列薄膜,然后通过水热反应在TiO2纳米管上负载CdS纳米粒子,形成CdS/TiO2纳米管的复合结构。利用SEM、XRD、XPS、UV-Vis等手段对其形貌和结构进行表征。进一步考察了CdS/TiO2纳米管的光电性能和光催化活性,结果表明,相比于TiO2纳米管,CdS/TiO2纳米管复合结构在紫外光和可见光下都具有更好的光催化活性及光电性能。     

Mg-catalyzed one-pot preparation of benzimidazoles and spirooxindoles by an immobilized chlorophyll b on magnetic nanoparticles

Chlorophyll b was extracted from Heliotropium europaeum plant, then immobilized on magnetic nanoparticles (Fe₃O₄@SiO₂@Chl-Mg) and found as an efficient and green catalyst for the preparation of a variety of benzimidazoles and spirooxindoles in mild conditions. The catalyst was fully characterized by Fourier-transform infrared (FTIR), ultraviolet–visible (UV–vis) spectroscopy, X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), thermogravimetric (TGA), vibrating sample magnetometer (VSM), transmission electron microscopy (TEM), and dynamic light scattering (DLS) analyses. To prove the catalytic influence of Mg over the reactions, the catalytic activity of the demetalated chlorophyll b as well as some other control experiments was investigated. High to excellent yields were achieved for all entries, whether benzimidazole or spirooxindole derivatives at short reaction times. The catalyst could be recovered and reused for several consecutive runs by a simple external magnetic field without any considerable reactivity loss. The properties of the recovered catalyst were investigated by various analyses. Finally, the reasonable mechanisms were proposed for the reactions based on the literature.     

CdS/TiO2纳米管复合结构的制备与光电性能研究

利用阳极氧化法在钛金属基体表面制备一层TiO₂纳米管阵列薄膜, 然后通过水热反应在TiO₂纳米管上负载CdS纳米粒子, 形成CdS/TiO₂纳米管的复合结构。利用SEM、XRD、XPS、UV-Vis等手段对其形貌和结构进行表征。进一步考察了CdS/TiO₂纳米管的光电性能和光催化活性, 结果表明, 相比于TiO₂纳米管, CdS/TiO₂纳米管复合结构在紫外光和可见光下都具有更好的光催化活性及光电性能。     

Ligand-free catalytic system for the synthesis of diarylethers over Cu2O/Cu-CNTs as heterogeneous reusable catalyst

Various substituted diarylether derivatives were prepared by using heterogeneous reusable Cu₂O- and Cu-coated carbon nanotubes (Cu₂O/Cu-CNTs) as catalyst under ligand-free conditions, which provided good to excellent yields. The catalyst was characterized by TEM, XRD, and AAS analysis. The effects of solvent, base, and amount of catalyst for the O-arylation were investigated. The catalyst could be recovered by simple filtration from the reaction mixture without further treatment and reused several times with consistent catalytic activity. In addition, CNTs could also be recovered from the used Cu₂O/Cu-CNTs by a simple acid treatment.     

Green synthesis of 3,4-disubstituted isoxazol-5(4H)-ones using ZnO@Fe3O4 core–shell nanocatalyst in water

An effective and environmentally benign methodology for the synthesis of isoxazol-5(4H)-one derivatives has been developed using a ZnO@Fe₃O₄ core–shell nanocatalytic system. The one-pot, multicomponent reaction of an aromatic/heterocyclic aldehyde, hydroxylamine hydrochloride and ethyl acetoacetate under aqueous conditions at slightly elevated temperature resulted in the formation of title compounds in extremely good yields. The present new protocol is environmentally friendly as it offers heterocyclization with some interesting promising features such as safety, atom efficiency, low cost, mild conditions, minimal waste, catalyst recyclability, water as a solvent, easy workup and possession of excellent functional group tolerance for the synthesisis of structurally diverse isoxazole derivatives. All products were characterized by spectral and analytical methods. A representative title derivative was studied for its structure by single crystal X-ray diffraction method.     

镍磷物质的量比对负载型Ni2P/MCM-41催化剂结构及加氢脱硫性能的影响

以MCM-41为载体,采用一种简捷、温和法制备了负载型Ni₂P/MCM-41催化剂。用H₂程序升温还原(H₂-TPR)、X射线衍射(XRD)、N₂吸附比表面积测定(BET)和X射线光电子能谱(XPS)分析对催化剂进行了表征。以1%(质量分数)二苯并噻吩(DBT)的十氢萘溶液为原料,在连续固定床反应装置上,研究了初始Ni/P物质的量比对催化剂HDS活性的影响,并考察了催化剂的稳定性。结果表明,初始Ni/P物质的量比为1/2和1/3的前驱体,在390 ℃下还原时得到单一的Ni₂P相。初始Ni/P物质的量为1/2时,得到的催化剂活性最好。在反应温度340 ℃、压力3.0 MPa、氢/油体积比500、质量空速2.0 h^-1时,DBT的转化率接近100%。     

Polymerization of styrene and 2-vinylpyridine using AlEt3 VCl3 heteroaromatic bases

A study has been made on Ziegler-Natta polymerization, under various conditions, using styrene and 2-vinylpyridine as monomers, AlEt₃-VCl₃ as catalyst system and the heterocyclic bases, pyridine, α- and γ-picolines as co-catalyst. The influence of the temperature and times for formation of the active species prior to the polymerization reaction (formation time) in the presence of the heterocyclic bases have been analyzed.     

Boehmite@SiO2@ Tris (hydroxymethyl)aminomethane-Cu(I): a novel,highly efficient and reusable nanocatalyst for the C-C bond formation and the synthesis of 5-substituted 1H-tetrazoles in green media

In this work, a versatile protocol was introduced for the preparation of a new Cu(I) supported complex on Silica supported boehmite nanoparticles (Boehmite@SiO₂@Tris-Cu(I)). The structure of the catalyst was comprehensively characterized using Fourier transform infrared spectroscopy (FT-IR), X-Ray Diffractometer (XRD), energy-dispersive X-ray spectroscopy (EDS), inductively coupled plasma atomic emission spectroscopy (ICP), X-ray mapping, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) techniques. The catalytic activity of this catalyst was studied in the Suzuki cross-coupling reaction and synthesis of 5-substituted 1H-tetrazole derivatives in ethanol and PEG-400 respectively as green solvents. In this sense, simple preparation of the catalyst from the commercially available materials, high catalytic activity, simple operation, short reaction times, high yields and use of green solvent are some advantages of this protocol. Finally, it is worth mentioning that this nanocatalyst was easily recovered, and reused for several times without significant loss of its catalytic efficiency. In addition, stability of the catalyst after recycling was confirmed by FT-IR technique.     

Synthesis of novel pyrazole‐based triazolidin‐3‐one derivatives by using ZnO/ZrO2 as a reusable catalyst under green conditions

An efficient approach for the synthesis of 10 novel pyrazole‐based 1,2,4‐triazolidin‐3‐one derivatives catalyzed by ZnO‐loaded ZrO₂ as heterogeneous catalyst with ethanol as solvent is described. The structure of the mixed metal oxide catalyst was characterized by various instrumental techniques (scanning electron microscopy, transmission electron microscopy, X‐ray diffraction and Brunauer–Emmett–Teller). In smooth reactions, products were accomplished in excellent yields (90–94%) with short reaction times (≈ 45 min). ZnO/ZrO₂ catalyst exhibited good recyclability. The catalyst is reused six times without any noticeable loss of activity. The major advantages of this method are operational simplicity, mild conditions, simple work‐up procedure and broad functional group tolerance.     

Manganese(III) porphyrin anchored onto multiwall carbon nanotubes: An efficient and reusable catalyst for the heterogeneous reduction of aldehydes and ketones

Reduction of a variety of carbonyl compounds with NaBH₄, using Mn-porphyrin, meso-tetrakis(4-hydroxyphenyl)porphyrinatomanganese(III), supported onto functionalized multiwall carbon nanotubes has been investigated. The heterogeneous catalyst was characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV–vis spectroscopy. The amount of catalyst loading on the nanotubes was determined by atomic absorption spectroscopy. Thermogravimetric analysis (TGA) demonstrated that the nanocatalyst was thermally stable to almost 300 °C, exhibiting high thermostability of the catalyst over a broad range of temperatures. This heterogeneous catalyst proved to be an efficient catalyst in the aerobic reduction of various aldehydes and ketones with NaBH₄. In the presence of the nanocatalyst, NaBH₄ can readily reduce a variety of aldehydes in good to excellent yields (50–100%) and ketones in excellent yields (100%) to their corresponding alcohols. The separation of the catalyst is very simple and economic. Also, FTIR spectra after four successive cycles showed that the catalyst was strongly anchored to the nanotubes.     

Efficient, solventless N-Boc protection of amines carried out at room temperature using sulfamic acid as recyclable catalyst

A simple, rapid, and efficient protocol for the chemoselective N-Boc protection of amines using sulfamic acid as catalyst is described. N-Boc protection of various structurally diverse aliphatic, aromatic, alicyclic, and heterocyclic amines (1°, 2°, 3°) was carried out with (Boc)₂O using sulfamic acid as catalyst (5 mol %) at room temperature under solventless conditions. The advantages of this method are simplicity, shorter reaction times (1-15 min), a cost-effective catalyst, and excellent isolated yields (90-100%); it is also environmentally benign. Moreover, the combined use of ultrasound and sulfamic acid achieves a synergic effect that is especially marked in the N-Boc protection of deactivated (sterically hindered and electron-deficient) amines. The catalyst possesses distinct advantages: ease of handling, cleaner reactions, high activity, and excellent chemoselectivity.