Greener organic synthetic methods: Sonochemistry and heterogeneous catalysis promoted multicomponent reactions

Ultrasound is an essential technique to improve organic synthesis from the point of view of green chemistry, as it can promote better yields and selectivities, in addition to shorter reaction times when compared to the conventional methods. Heterogeneous catalysis is another pillar of sustainable chemistry being the recycling and reuse of the catalysts one of its great advantage. In the other hand, multicomponent reactions provide the synthesis of structurally diverse compounds, in a one-pot fashion, without isolation and purification of intermediates. Thus, the combination of these protocols has proved to be a powerful tool to obtain biologically active organic compounds with lower costs, time and energy consumption. Herein, we provide a comprehensive overview of advances on methods of organic synthesis that have been reported over the past ten years with focus on ultrasound-assisted multicomponent reactions under heterogeneous catalysis. In particular, we present pharmacologically important N- and O-heterocyclic compounds, considering their synthetic methods using green solvents, and catalyst recycling.     

Solution-phase combinatorial chemistry

The use of solution phase techniques has been explored as an alternative to solid-phase chemistry approaches for the preparation of arrays of compounds in the drug discovery process. Solution-phase work is free from some of the constraints of solid-phase approaches but has disadvantages with respect to purification. This article will also illustrate some of the advances made in recent years in solution phase array chemistry including using supported reagents and simple extractive protocols for the effective preparation of high quality samples.     

p‐toluenesulfonic acid‐catalyzed synthesis of polysubstituted quinolines via Friedländer reaction under ball‐milling conditions at room temperature and theoretical study on the mechanism using a density functional theory method

The synthesis of polysubstituted quinolines was accomplished through Friedländer annulation between 2‐aminoaryl ketones and different active methylene compounds at room temperature using ball‐milling technique in the presence of p‐toluenesulfonic acid. The mechanism of the reaction investigated by density functional theory‐based modeling is also reported. This study aims at giving insight into the mechanism of the Friedländer reaction in the presence of acid catalysts. Copyright © 2014 John Wiley & Sons, Ltd.     

CIR技术红外光谱法应用研究

本文描述了通过使用CIR装置技术，实现了水溶液红外光谱分析。由三氮唑核苷、苯甲酸钠、乙酸钠等水溶液进行红外光谱分析研究，得到各自水溶液直接测定的红外光谱，并进行了定量分析研究，效果良好，说明了CIR技术具有较好的实用价值。     

Efficient seed-mediated method for the large-scale synthesis of Au nanorods

Seed-mediated methods are widely followed for the synthesis of Au nanorods (NRs). However, mostly dilute concentrations of the Au precursor (HAuCl₄) are used in the growth solution, which leads to a low final concentration of NRs. Attempts of increasing the concentration of NRs by simply increasing the concentration of HAuCl₄, other reagents in the growth solution and seeds lead to a faster growth kinetics which is not favourable for NR growth. Herein, we demonstrate that the increase in growth kinetics for high concentrations of reagents in growth solution can be neutralised by decreasing the pH of the solution. The synthesis of the NRs can be scaled up by using higher concentrations of reagents and adding an optimum concentration of HCl in the growth solution. The concentration of HAuCl₄ in the growth solution can be increased up to 5 mM, and 10–20 times more NRs can be synthesised for the same reaction volume compared to that of the conventional seed-mediated method. We have also noticed that a cetyltrimethylammonium bromide (CTAB)-to-HAuCl₄ molar ratio of 50 is sufficient for obtaining high yield of NRs.     

Nanodendritic Platinum Supported on γ‐Alumina for Complete Benzene Oxidation

The morphology of the platinum (Pt) nanoparticles has a significant effect on their activity for the catalytic oxidation of the volatile organic compounds (VOCs). In this work, the preparation of the dendritic and spherical Pt by a solution‐based approach is reported, which is supported on γ ‐ Al₂O₃ substrates, for decreasing the temperature of the complete conversion of benzene, one of the representative contaminants among the VOCs because of its carcinogenicity. The X‐ray photoelectron spectroscopy analyses reveal that the surface adsorbed oxygen is crucial for catalytic performance, and the electron transference from Pt to O is a benefit for the activation of oxygen. H₂‐TPR results indicate that the reducibility of the catalyst has a significant effect on the catalytic activity for the catalytic oxidation. In general, the dendritic Pt/Al₂O₃ catalysts, which possess more abundant and active surface adsorbed oxygen, exhibit the higher activity for the complete catalytic conversion of benzene compared with the spherical one. Moreover, the addition of a small amount of Ag (or Au), which is in order to ensure the dendritic structure, has little influence on the catalytic activity. The versatile solution‐based synthesis will be a promising method for creating the highly efficient catalysts for environmental remediation.     

High-throughput preparation and testing of ion-exchanged zeolites

A high-throughput research platform was developed for the preparation and subsequent catalytic liquid-phase screening of ion-exchanged zeolites, for instance with regard to their use as heterogeneous catalysts. In this system aqueous solutions and other liquid as well as solid reagents are employed as starting materials and 24 samples are prepared on a library plate with a 4 × 6 layout. Volumetric dispensing of metal precursor solutions, weighing of zeolite and subsequent mixing/washing cycles of the starting materials and distributing reaction mixtures to the library plate are automatically performed by liquid and solid handlers controlled by a single common and easy-to-use programming software interface. The thus prepared materials are automatically contacted with reagent solutions, heated, stirred and sampled continuously using a modified liquid handling. The high-throughput platform is highly promising in enhancing synthesis of catalysts and their screening. In this paper the preparation of lanthanum-exchanged NaY zeolites (LaNaY) on the platform is reported, along with their use as catalyst for the conversion of renewables.     

Detection of hydrogen-copper clustering in Zn1−x CuxO compounds using neutron scattering methods

The atomic and cluster structure of hydrogen-treated Cu/ZnO (the major component of methanol synthesis catalysts) was studied using Bragg powder and small-angle neutron diffraction. Isotopic substitution of Cu and H was used to obtain reliable results indicating Cu and H clustering. The clusters form on the boundaries of ZnO particles and have a complex structure: a copper cluster surrounded by an adsorbed hydrogen shell has a hydrogen core. It can be assumed that this cluster configuration has a strong effect on the catalytic activity of these compounds.     

锆对低温液相合成甲醇Cu-Cr催化剂性能的影响

用络合共沉淀法制备了Cu Cr和Cu Cr Zr低温液相合成甲醇催化剂,其比表面积分别达到了77. 9和113. 2m2 /g.在5. 5MPa、383和423K的条件下,用间歇式反应釜考察了催化剂的活性和选择性,并用化学分析的方法测定了反应后溶液中钠化合物含量的变化.结果表明, Cu Cr Zr的活性明显高于Cu Cr,其甲醇的选择性则略有下降;同时,由反应后的钠化合物分析发现, Cu Cr Zr催化体系在423K反应后,溶液中甲酸钠的浓度降低,导致催化体系失活的甲醇钠转化为甲酸钠的反应被彻底抑制.     

Solvent free synthesis of 1,3-diaryl-2-propenones catalyzed by commercial acid-clays under ultrasound irradiation

This paper presents a novel solvent free method of synthesis of trans-chalcones. The method was based on ultrasound irradiation of the reagents (aryl methyl ketones and aryl aldehydes) in presence of commercial acid-montmorillonites as catalysts. The trans-chalcones were synthesized in high yields (85–95%) and excellent selectivity in a short reaction time.     

Mössbauer spectroscopy and nuclear inelastic scattering studies on polynuclear oxo-bridged iron catalyst—first results

Polynuclear iron catalysts are interesting materials because of their novel properties. In the future they may help to replace high cost and hazardous heavy metal catalysts by efficient, non toxic and economic iron compounds. In this work, we present some preliminary results on a novel polynuclear oxo-bridged iron catalyst. The chemical environment of the metal species (Fe) was studied under Gif-type conditions (Fe catalyst/Zn/O₂ in pyridine/acetic acid) with cyclohexene as substrate. Such Gif-type catalysts are able to catalyse the selective oxidation of alkanes and alkenes. The characterization was done by Mössbauer spectroscopy and nuclear inelastic scattering. In order to identify the intermediate species during the reaction (selective oxidation using molecular O₂), a freeze-quench technique was used. This also helps to understand the kinetics of the chemical reaction.     

Chemical Surface Coating: Synthesis and Characterization of a Silicon Oxynitride Coated Silica Sel

Mesoporous silica gel has been coated with a thin silicon oxynitridefilm via chemical surface coating. In the first part of the synthesis, achemically bound preceramic polysilazane coating is formed layer by layer onthe pore walls at low temperature, using SiCl₄ andNH₃ as reagents. In the second part of the synthesis, thepolysilazane coated silica gel is pyrolysed, yielding a chemically bound,thin oxynitride coating.During the synthesis, the evolution of the chemical and morphologicalcomposition has been investigated with several elemental and spectroscopicanalysis techniques as well as with nitrogen porosimetry.     

多功能胶囊催化剂在多相催化中的应用研究进展

Capsule catalysts composed of pre-shaped core catalysts and layer zeolites have been widely used in the tandem reactions where multiple continuous reactions are combined into one process. They show excellent catalytic performance in heterogeneous catalysis, including the direct synthesis of middle isoparaffins or dimethyl ether from syngas, as compared to the conventional hybrid catalysts. The present review highlights the recent development in the design of capsule catalysts and their catalytic applications in heterogeneous catalysis. The capsule catalyst preparation methods are introduced in detail, such as hydrothermal synthesis method, dual-layer method, physically adhesive method and single crystal crystallization method. Furthermore, several new applications of capsule catalysts in heterogeneous catalytic processes are presented such as in the direct synthesis of liquefied petroleum gas from syngas, the direct synthesis of para-xylene from syngas and methane dehydroaromatization. In addition, the development in the design of multifunctional capsule catalysts is discussed, which makes the capsule catalyst not just a simple combination of two different catalysts, but has some special functions such as changing the surface hydrophobic or acid properties of the core catalysts. Finally, the future perspectives of the design and applications of capsule catalysts in heterogeneous catalysis are provided.     

Diastereoselective synthesis of cyclohexadienes via tandem cyclization strategies

Molecular Diversity - A new protocol has been developed for the diastereoselective synthesis of 1,3-cyclohexadienes using vinyl malononitriles, dibenzalacetones and NaH as reagents in THF. This...     

Ultrasound irradiation as an effective tool in synthesis of the slag-based catalysts for carboxymethylation

Waste minimization strategy was applied in the current work for synthesis of the catalysts from industrial solid waste, namely desulfurization slag. The starting slag material comprising CaCO₃, Ca(OH)₂, SiO₂, Al₂O₃, Fe₂O₃, and TiO₂ was processed by various treating agents systematically varying the synthesis parameters. A novel efficient technique – ultrasound irradiation, was applied as an additional synthesis step for intensification of the slag dissolution and crystallization of the new phases. Physico-chemical properties of the starting materials and synthesized catalysts were evaluated by several analytical techniques. Treatment of the industrial slag possessing initially poor crystal morphology and a low surface area (6 m²/g) resulted in formation of highly-crystalline catalysts with well-developed structural properties. Surface area was increased up to 49 m²/g. High basicity of the neat slag as well as materials synthesized on its basis makes possible application of these materials in the reactions requiring basic active sites. Catalytic performance of the synthesized catalysts was elucidated in the synthesis of carbonate esters by carboxymethylation of cinnamyl alcohol with dimethyl carbonate carried out at 150 °C in a batch mode. Ultrasonication of the slag had a positive effect on the catalytic activity. Synthesized catalysts while exhibiting similar selectivity to the desired product (ca. 84%), demonstrated a trend of activity increase for materials prepared using ultrasonication pretreatment. The choice of the treating agent also played an important role in the catalytic performance. The highest selectivity to the desired cinnamyl methyl carbonate (88%) together with the highest activity (TOF₃₅ = 3.89*10⁻⁷ (mol/g*s)) was achieved over the material synthesized using 0.6 M NaOH solution as the treating agent with the ultrasound pre-treatment at 80 W for 4 h.     

Effect of ultrasonic power on the structure of activated carbon and the activities of Ru/AC catalyst

Ruthenium-based materials are the second-generation catalysts for ammonia synthesis. Ruthenium is less inhibited by ammonia, less sensitive to poisons, and more active than the traditional iron-based catalyst. The relatively high cost of Ru compared to that of iron requires a high dispersion of the metal on a suitable support. Carbon-supported Ru catalysts with promoters have been reported to be active for ammonia synthesis. The ultrasonic technique has been proven to be beneficial to the preparation of supported catalysts. In this paper, the effects of ultrasonic treatment on the surface texture, oxygen groups of activated carbon (AC) as well as ruthenium dispersion were investigated by the employments of N(2) physisorption, TPD-MS and CO chemisorption respectively. It have been shown that ash content in AC can be effectively eliminated by ultrasonic pretreatment, at the same time, the BET surface area and total pore volume are reduced, and the amount of the decomposable surface oxygen groups are decreased. Furthermore the ash content decrease and the mesopore surface area increase with the ultrasonic power increasing. The activities of a series of barium-potassium-promoted Ru/AC catalysts for ammonia synthesis were tested at 10,000 h(-1), 10.0 MPa and 400 degrees C. The results show that the activities of Ru/AC catalysts which were prepared by ultrasonic treatment are greatly increased, and the optimum pretreatment power is 100 W. The ash content of this carbon support is decreased from 1.39% to 1.15%. As a result, the catalytic activity is improved from 65.3 to 83.8 mmol g(-1) h(-1).     

Multidimensional chromatography coupled with mass spectrometry for target-based screening

Summary The synthesis of structural analogs and the process of drug discovery have evolved dramatically through recent advances in solid-phase synthesis reagents and automated screening systems. As molecular diversity strategies emerge, the need for automated target-based selection of lead candidates becomes equally important. Multidimensional automated chromatographic techniques coupled to electrospray ionization mass spectrometry facilitate the selection process and provide maximum characterization information in a single screening run. The capture of tightly bound affinity leads by target biomolecules, followed by subsequent release and high-resolution separation with sensitive detection, significantly reduces the time required to identify and characterize lead compounds. This automated multidimensional chromatographic approach coupled with mass spectrometry, Selectronics, was used with several organic and natural libraries to demonstrate an automated target-based screening technique to select for high-affinity binders as potential lead compounds.Abbreviations ESI electrospray ionization - HPLC high-performance liquid chromatography - HTS high-throughput screening - ESI-TOF electrospray ionization time-of-flight - SAR structure-activity relationship     

Diagnosis of deactivation sources for vanadium catalysts used in SO2 oxidation reaction and optimization of vanadium extraction from deactivated catalysts

Physico-chemical analysis (X-ray, FTIR) and/or methanol oxidation reaction test were performed on fresh and deactivated vanadium catalysts used in H₂SO₄ manufacturing. It allowed the diagnosis of catalyst deactivation sources, as well as the processes of regenerating and recycling the worn out catalyst in converter. One of these processes is hydrometallurgical method. It consists in treating the deactivated catalyst with alkaline or acidic reagents and forming vanadate solution. A simple and non-costly operation of chemical attack permits the extraction of vanadium from silica in deactivated catalyst. The extracted vanadium can be used for the confection of regenerated catalysts or metallic tools. After optimization, this method can be used for industrial application.