Efficient three-component Gewald reactions under Et3N/H2O conditions

In a medium consisting of triethylamine and water, α-methylene ketones undergo room temperature Gewald reactions with elemental sulfur and ethyl cyanoacetate (or malononitrile) to yield 2-aminothiophene derivatives efficiently within short time periods. Because of the high polarity of the medium, products precipitate in the reaction mixtures spontaneously. This makes isolation of the products easy by simple filtration and avoids cumbersome chromatographic separations. Mechanistic studies suggest that the reactions proceed via a Knoevenagel condensation pathway.     

Novel one-pot four-component condensation cyclization reactions for the synthesis of thiazolidine-4-one and 3H-thiazoles

ABSTRACT

A novel, simple and efficient synthetic protocol has been developed for the synthesis of a series of thiazolidine-4-one and 3H-thiazole derivatives via a one-pot four-component condensation-cyclization reaction of hydrazine with allyl isothiocyanate and an α-haloketone in the presence of various aldehydes. This new protocol produces novel thiazolidine-4-one and 3H-thiazole derivatives in excellent yields. The remarkable features of this methodology are high yields, easy work-up and a one-pot simple reaction method.     

Serendipitous synthesis of 4-thioxochromen-2-one derivatives through the one-pot three-component reaction of primary amines,carbon disulfide,and 4-chlorocoumarin-3-carbaldehyde

One-pot three-component reaction between 4-chlorocoumarin-3-carbaldehyde and primary amines in the presence of carbon disulfide and triethylamine leads to 4-thioxochromen-2-one derivatives in good to excellent yields.     

H4GeW12O40/Cu3(BTC)2催化Biginelli反应合成3,4-二氢嘧啶-2(1H)-酮衍生物

采用浸渍法以金属有机骨架Cu_3(BTC)_2负载锗钨酸(H_4GeW_(12)O_(40))制备H4Ge W_(12)O_(40)/Cu_3(BTC)_2催化剂,并用该催化剂催化芳醛、尿素和乙酰乙酸乙酯通过"一锅法"Biginelli缩合反应,以无水乙醇为溶剂,合成6种3,4-二氢嘧啶-2(1H)-酮衍生物;通过熔点的测定,IR,1H NMR和MS等对产物3,4-二氢嘧啶-2(1H)-酮衍生物进行表征。结果表明:在芳醛用量为0.04 mol,n(芳醛)∶n(乙酰乙酸乙酯)∶n(尿素)=1∶1.5∶1.5,催化剂的用量占反应物料总质量的4.0%,反应温度为90℃,反应时间为90 min的条件下,目标产物收率可达63.0%~76.3%。     

A novel one-pot solvent-free synthesis of 3-alkyl-2-thioxo-1,3-thiazolidine-4-ones

An easy, highly efficient solvent-free and simple one-pot approach to the synthesis of 3-alkyl-2-thioxo-1,3-thiazolidine-4-ones is reported. The reaction of a primary amine and carbon disulfide in the presence of chloroacetyl chloride or 2-chloro-2-phenylacetyl chloride at room temperature afforded 3-alkyl-2-thioxo-1,3-thiazolidine-4-one derivatives in high yields.     

Facile synthesis of magnetic Fe3O4@Chitosan nanocomposite as environmentally green catalyst in multicomponent Knoevenagel-Michael domino reaction

Magnetic Fe₃O₄ has interesting characteristics such as large surface area, low toxicity, ferromagnetic, and biocompatible. The presence of magnetic properties in Fe₃O₄ provides an advantage in its application as a heterogeneous catalyst. This study highlights the synthesis of Fe₃O₄ modified chitosan composite and evaluates the catalytic ability in multicomponent Knoevenagel-Michael domino reaction. The synthesis and characterization of pristine Fe₃O₄ and Fe₃O₄@Chi samples were investigated. The XRD analysis combined with refinement technique indicates that the pristine Fe₃O₄ crystallized in a cubic structure with Fd-3mz symmetry and the presence of chitosan in Fe₃O₄ sample did not change its structure. The FTIR analysis also demonstrated the binding of chitosan to the Fe₃O₄ nanoparticles. TEM image reveals the presence of chitosan in the composite sample formed a core-shell interaction and covered the surface of Fe₃O₄ nanoparticles. The evaluation of Fe₃O₄@Chi catalytic ability in multicomponent Knoevenagel-Michael domino reaction demonstrated reliable catalyst performance with a yield of 92.3% at optimum conditions. Fe₃O₄@Chi could be classified as a green catalyst because it can be used repeatedly with high yield and easy separation.     

Polyaniline-supported acid as an efficient and reusable catalyst for a one-pot synthesis of β-acetamido ketones via a four-component condensation reaction

Polyaniline-supported acid salts such as polyaniline-hydrochloride, polyaniline-sulfate and polyaniline-nitrate were prepared by oxidation of aniline using ammonium persulfate as oxidizing agents. Polyaniline salts were used as catalyst for the preparation of β-acetamido ketones. Polyaniline-sulfate salt was found to be the best catalyst for the preparation of β-acetamido ketones. Present methodology offers several advantages, such as cheaper process, easy synthesis of stable catalyst, simple work-up procedure, and excellent activity with less amount of catalyst and in addition, the catalyst can be easily recovered after completion of the reaction and reusable without affecting its activity.     

磷酸钛铵的低热固相合成及其催化合成乙酸丁酯的研究

以Ti(SO4)2和(NH4)3PO4.3H2O为原料,在室温下研磨反应混合物,进行固相反应,然后在80℃下密封保温反应96 h,用水洗去混合物中的可溶性无机盐,80℃下烘干,即得纳米级磷酸钛铵产品。采用TG/DTA、IR、XRD和TEM对产品及其热解产品进行表征,采用均匀设计法考察了磷酸钛铵催化合成乙酸丁酯的性能。结果表明,80℃干燥3 h得到的是无定型磷酸钛铵产品,平均粒径约为40 nm,磷酸钛铵在合成乙酸丁酯中是一种极好的非均相催化剂。     

Efficient synthesis of novel 1,3-diyne-based sulfonamides using CuCl2/Et3N as a robust catalytic system

An efficient and practical synthesis of 1,3-diyne-based sulfonamides using CuCl₂/Et₃N as a catalytic system is disclosed. Mild reaction conditions, atom-economy and high yields (50–91%) make this method an attractive option for the preparation of 1,3-diyne-based sulfonamide derivatives.     

Facial synthesis of a novel Ag4V2O7/g-C3N4 heterostructure with highly efficient photoactivity

A novel Ag₄V₂O₇/g-C₃N₄ heterostructure was synthesized by a facial etching method in ammonia solution using Ag₂VO₂PO₄/g-C₃N₄ as a self-sacrifice precursor. With the concentration of ammonia solution increasing from 0.05 to 0.2 M, phase transformation took place, described as: Ag₂VO₂PO₄/g-C₃N₄ → Ag₂VO₂PO₄/Ag₄V₂O₇/g-C₃N₄ → Ag₄V₂O₇/g-C₃N₄. Compared with pristine Ag₂VO₂PO₄/g-C₃N₄, the etched samples of Ag₄V₂O₇/g-C₃N₄ and Ag₂VO₂PO₄/Ag₄V₂O₇/g-C₃N₄ exhibited dramatically improved activity for the degradation of methylene blue (MB), methyl orange (MO) and imidacloprid under visible light irradiation. When etched with 0.15 M ammonia solution, an Ag₄V₂O₇/g-C₃N₄ heterostructure was obtained that exhibited the highest photoactivity. This photocatalyst was nearly 9.1, 3.0, and 24.3 times more efficient than pristine Ag₂VO₂PO₄/g-C₃N₄ for degradation of MB, MO and imidacloprid, respectively. The excellent photocatalytic performance can be ascribed to the as-obtained well-defined Ag₄V₂O₇/g-C₃N₄ heterojunction, which improves the separation and transfer efficiency and prolongs the lifetime of photoinduced charges. In addition, the stability and dominant radicals were investigated.     

Solvent-free synthesis of 1-[3-alkyl-4-methyl-2-thioxo-2,3-dihydrothiazole-5-yl]-ethanones in a multicomponent reaction

A simple and efficient one-pot synthesis of 1-[3-alkyl-4-methyl-2-thioxo-2,3-dihydrothiazole-5-yl]-ethanones from the reaction of primary alkylamines and carbon disulfide in the presence of 3-chloro acetylacetone is described. This protocol has several advantages such as lack of need for a solvent and catalyst, high yields, mild conditions and short reaction times.     

One-pot three-component synthesis of some novel ethyl 3-alkyl-2-thioxo-2,3-dihydrothiazole-4-carboxylates under solvent- and catalyst-free conditions at room temperature

A green and efficient one-pot three-component synthesis of some novel ethyl 3-alkyl-2-thioxo-2,3-dihydrothiazole-4-carboxylates from the reaction of primary alkyl or benzyl amines, carbon disulfide and ethyl bromopyruvate is introduced. This straightforward technique gave the looked-for products in high yields during 1.5–3?h without need for catalyst or solvent assistance.     

In situ synthesis of Si2N2O/Si3N4 composite ceramics using polysilyloxycarbodiimide precursors

In situ synthesis of Si₂N₂O/Si₃N₄ composite ceramics was conducted via thermolysis of novel polysilyloxycarbodiimide ([SiOSi(NCN)₃]_n) precursors between 1000 and 1500 °C in nitrogen atmosphere. The relative structures of Si₂N₂O/Si₃N₄ composite ceramics were explained by the structural evolution observed by electron energy-loss spectroscopy but also by Fourier transform infrared and ²⁹Si-NMR spectrometry. An amorphous single-phase Si₂N₂O ceramic with porous structure with pore size of 10–20 μm in diameter was obtained via a pyrolyzed process at 1000 °C. After heat-treatment at 1400 °C, a composite ceramic was obtained composed of 53.2 wt.% Si₂N₂O and 46.8 wt.% Si₃N₄ phases. The amount of Si₂N₂O phase in the composite ceramic decreased further after heat-treatment at 1500 °C and a crystalline product containing 12.8 wt.% Si₂N₂O and 87.2 wt.% Si₃N₄ phases was obtained. In addition, it is interesting that residual carbon in the ceramic composite nearly disappeared and no SiC phase was observed in the final Si₂N₂O/Si₃N₄ composite.     

Facile synthesis of some novel 4-{3-aryl-3, 4-dihydro-2H-benzo[b][1,4] thiazin-2-yl}-2H-chromen-2-one derivatives

A protocol for chemoselective one pot synthesis of 4-{3-aryl-3, 4-dihydro-2H-benzo[b][1,4]thiazin-2-yl}-2H-chromen-2-ones 4 and 4-{3-aryl-3, 4-dihydro-2H-benzo[b][1,4]thiazin-2-yl}-2H-chromen-2-ones 6 under refluxing conditions has been developed. Starting from 4-bromomethylcoumarin and Schiff base, which is derived from o-aminothiophenol and substituted aromatic aldehydes, the intermediate sulfide spontaneously underwent intramolecular carbanion addition across the azomethine carbon.     

On the mechanism of the selective catalytic reduction of NO to N2 by H2 over Ru/MgO and Ru/Al2O3 catalysts

Steady-state and transient kinetic experiments were performed in a versatile microreactor flow set-up with magnesia- and alumina-supported ruthenium catalysts in order to elucidate the mechanism of the selective catalytic reduction (SCR) of nitric oxide with hydrogen. Both Ru/MgO and Ru/γ-Al₂O₃ were found to be highly active catalysts converting NO and H₂ into N₂ and H₂O with selectivities close to 100% at full conversion, although Ru-based catalysts are known to be active in the synthesis of NH₃ from N₂ and H₂. Frontal chromatography experiments with NO at room temperature revealed that NO and its dissociation products displace adsorbed atomic hydrogen (H−*) almost completely from hydrogen-precovered Ru surfaces. Obviously, NO and H₂ compete for the same adsorption sites, H−* being the weaker bound adsorbate. Temperature-programmed surface reaction (TPSR) experiments in H₂ subsequent to NO exposure demonstrated that higher heating rates and lower partial pressures of H₂ shift the selectivity from NH₃ to N₂. Therefore, the coverage of H−* is concluded to govern the branching ratio between the rate of associative desorption of N₂ (2N−*→N₂ + 2*) and the rate of hydrogenation of N−* (N−* + 3H–* →NH₃ + 4*). Finally, the steady-state coverages of N- and O-containing adsorbates were derived by interrupting the SCR reaction and hydrogenating the adsorbates off as NH₃ and H₂O. By solving the site balance, the Ru surfaces were found to be essentially N₂ is attributed to the very low coverage of H−* due to site blocking by a N + O coadsorbate layer, favouring the recombination of N−* instead of its hydrogenation to NH₃. This revised version was published online in August 2006 with corrections to the Cover Date.     

H4SiW12O40/SiO2催化一锅法合成4-苯基-6-甲基-5-乙氧羰基-3,4-二氢嘧啶-2(H)-酮

采用一锅法Biginelli反应以H4SiW12O40/SiO2为催化剂,以苯甲醛、乙酰乙酸乙酯和尿素为原料,无水乙醇为溶剂合成了4-苯基-6-甲基-5-乙氧羰基-3,4-二氢嘧啶-2(H)-酮。探讨了原料摩尔比、反应温度、催化剂用量及反应时间对收率的影响。结果表明,固定苯甲醛用量为0.04 mol的条件下,n(苯甲醛)∶n(乙酰乙酸乙酯)∶n(尿素)=1∶1.5∶1.5,催化剂的用量占反应物料总质量的2.0%,反应温度为90℃,反应时间为60 min,产品平均收率可达71.7%。通过熔点的测定,IR,1HNMR和MS对合成的3,4-二氢嘧啶酮化合物进行了表征。     

Investigation of g-C3N4/ZnAl2O4 and ZnO/ZnAl2O4 nanocomposites: From synthesis to photocatalytic activity of pollutant dye model

The fabrication of nanocomposite photocatalytsts with excellent photocatalytic activity is an important step in the improved degradation of organic dyes. A series of nanocomposite photocatalysts was synthesized with g-C₃N₄ and ZnO loading contents of 10, 20 and 30%. The nanocomposites were characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET) surface area analysis, X-ray photoelectron spectroscopy (XPS) and diffuse reflectance spectroscopy (DRS). The optical band gaps of g-C₃N₄, ZnO and ZnAl₂O₄ were about 2.79, 3.21 and 3.55 eV, respectively. Methylene blue (MB) was degraded over the prepared photocatalysts under UV irradiation. Photocatalytic activity was about 9.1 and 9.6 times higher, respectively, on 20%g-C₃N₄/ZnAl₂O₄ and 20%ZnO/ZnAl₂O₄ nanocomposite photocatalysts than on pure ZnAl₂O₄ spinel powders. Recycling experiments showed that 20%g-C₃N₄/ZnAl₂O₄ and 20%ZnO/ZnAl₂O₄ nanocomposite photocatalysts exhibited good stability after five cycles of use.     

Hydrothermal synthesis,crystal structure and fluorescent properties of a novel 1D polymer: VO2(C7H3O4N)Ag(C10H8N2)·H2O

The hydrothermal synthesis of V₂O₅, AgNO₃, pyridine-2,6-dicarboxylic acid (H₂pdc) and 2,2′-bipyridine (bpy) in water at 160 °C for 4 days yields a novel 1D coordination polymer VO₂(C₇H₃O₄N)Ag(C₁₀H₈N₂)·H₂O (1). Each V center chelates to a tridentate ligand pdc^2? and coordinates to two O atoms, while the square based pyramid conformation of Ag center consists of three O atoms and a bpy molecular. V and Ag polyhedra alternate by either carboxyl or oxo bridges to further form a unique 3d–4d heterometal-based 1D double-chain ribbon.     

In-situ reaction synthesis of porous Si2N2O-Si3N4 multiphase ceramics with low dielectric constant via silica poly-hollow microspheres

In the present work, a novel and facile process has been proposed to fabricate porous Si₂N₂O-Si₃N₄ multiphase ceramics with low dielectric constant (ε_r＜4.0). Since silica poly-hollow microspheres could serve as the source of SiO₂ and the pore-forming agent, they have been introduced into Si₃N₄ slurry through the gelcasting technique. This process is benefited from the liquid phase sintering reaction between SiO₂ and Si₃N₄ with the aid of sintering additives, leading to in-situ synthesis of Si₂N₂O phase and porous structure. The content of silica poly-hollow microspheres has great influence on the properties of the final products. It indicates that Si₂N₂O phase would become the major phase when the content of silica poly-hollow microspheres was above 25 wt%. Furthermore, the micromorphology results reveal that the content of pores with many smaller aggregate microspheres increases as microspheres amount rises. As a result, along with the addition of silica poly-hollow microspheres, the bulk density decreases to 1.32±0.01 g/cm³, and open porosity ranges from 28.4±0.4% to 52.0±0.5%. Porous Si₂N₂O-Si₃N₄ multiphase ceramics prepared with 25 wt% silica poly-hollow microspheres addition possess flexural strength of 42.3±3.8 MPa, low dielectric constant of 3.31 and loss tangent of 1.93×10⁻³. It turns out to be an effective method to fabricate porous Si₂N₂O-Si₃N₄ composites with excellent mechanical and dielectric properties, which could be applied to radome materials.