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Knoevenagel缩合
APPLIED CATALYSIS A-GENERAL · 2013 · IF 3.41

One-pot synthesis of potassium-loaded MgAl oxide as solid superbase catalyst for Knoevenagel condensation

Jin Zhao,Jun Xie,Chak-Tong Au,Shuang-Feng Yin

We report a new strategy for one-pot synthesis of potassium-loaded MgAl oxides using KOH to adjust the pH value of the reaction system. The as-prepared solid superbases were studied by N 2 physisorption method, energy-dispersive X-ray spectroscopy, powder X-ray diffraction, and Fourier transform infrared. The superbasic sites were characterized by the use of Hammett indicators and CO 2 temperature-programmed desorption. We found that with a base strength ( H – ) above 26.5, the potassium-loaded MgAl oxides showed high catalytic activity for Knoevenagel condensation at room temperature. Furthermore, the higher the superbasicity and/or the more the amount of superbasic sites, the better is the catalytic activity. The findings open up a new route for the synthesis of new functional superbases using composite oxides as supports.

CAS / MDL: 105-56-6 6017-21-6
研究领域: 催化化学 · 材料科学
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FIBERS AND POLYMERS · 2018 ·Vol. 19 ·期 8 ·1611-1617 · IF 1.353

Expanding Application of Immobilized Candida Antarctica Lipase B: A Green Enzyme Catalyst for Knoevenagel Condensation Reaction

Wang Cuie,Wang Ning,Liu Xinhua,Wan Peng,He Xinwei,Shang Yongjia

We propose a green synthesis of benzopyran compound based on immobilized lipase. Firstly, by using a combined electrospun membrane and biocompatible chitosan, we show that the chitosan-functionalized electrospun PMA-co-PAA fibrous membrane can provide effective anchoring sites for immobilization of the Candida antarctica lipase B (CALB), and a maximum loading amount of CALB (152 mg/g) can be achieved. Then, the resulting membrane displays enhanced stability in catalyzing Knoevenagel condensation reaction of salicylaldehyde with active methylene compound in mixed aqueousorganic media. The catalytic activity and stability of the CALB on chitosan-modified fiber is better than its non-immobilized counterpart. Furthermore, this immobilize CALB catalyst still retained about 45 % of the initial activity after 5 cycles, which potentially had implications for the design of “green” enzyme catalyst for sustainable organic synthesis.

研究领域: 生物化学 · 绿色化学 · 材料科学
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CATALYSIS LETTERS · 2021 ·Vol. 152 ·期 4 ·1215-1223 · IF 3.186

Enzymes-Catalyzed Knoevenagel Condensation Promoted by Ionic Liquid and Deep Eutectic Solvent

Wang Yun,Cheng Hong,He Jia-Rui,Yao Qiao-Xia,Li Li-Ling,Liang Zhi-Hui,Li Xiang

The Knoevenagel condensation of acetylacetone and aromatic aldehyde catalyzed by lipase from porcine pancreas(PPL) and α-amylase from hog pancreas in ionic liquids and deep eutectic solvents was achieved for the first time. The highest yields is up to 96.1%. Mild reaction conditions, enhanced rates, improved yields and reagents’ reactivity which is different from that in standard organic solvents are the remarkable features observed in ionic liquids and deep eutectic solvents. Graphical Abstract

研究领域: 生物化学 · 有机化学
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AUSTRALIAN JOURNAL OF CHEMISTRY · 2014 ·Vol. 68 ·期 6 ·919-925 · IF 1.644

Synthesis and Thermal Stability of New Polynitrostilbenes

Jianping Wei,Fangmei Li,Junhui Xu,Xinhua Peng

New polynitrostilbenes were directly synthesised by the Knoevenagel condensation of aromatic aldehydes with nitrotoluenes. The differential scanning calorimetry results demonstrated that the introduction of an amino group and C=C double bonds could improve the thermal stability.

研究领域: 有机化学 · 材料科学
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ChemistrySelect · 2024 ·Vol. 9 ·期 4 ·e202304217 · IF 1.9

Carbon Dots as New Effective Catalysts for Knoevenagel Condensation Reaction and Synthesis of Cyclic Carbonates under Solvent-free Conditions

Jinfa Yu,Zhaoqin Luo,Xiangying Sun

Graphical NCDs-1, which is the first carbon dot by the microwave method using ethylenediamine and L-arginine, can serve as an efficient heterogeneous catalyst for the synthesis of cyclic carbonates from epoxides with CO 2 and Knoevenagel condensation under mild and solvent-free condition. A simple and convenient method for catalytic reactions with amine-terminated carbon dots was developed. Carbon dots (CDs) as new efficient catalysts have been developed for the Knoevenagel condensation reaction and the synthesis of cyclic carbonates under solvent-free conditions. Six kinds of carbon dots with different numbers of amino groups were synthesized. The amine-terminated carbon dot (NCDs-1) was synthesized using arginine and ethylenediamine by a microwave technique, and its catalytic action was studied. NCDs-1 with the highest numbers of amino groups was used as new metal-free and effective heterogeneous catalysts to perform essential Knoevenagel condensation and cycloaddition reactions in solvent-free conditions. 1 H NMR was used to demonstrate the Knoevenagel condensation mechanism, in situ Fourier infrared spectroscopy was used to investigate CO 2 cycloaddition and a catalytic mechanism was postulated. NCDs-1 showed a yield of 96.3±1.5 % for Knoevenagel condensation of benzaldehyde and malononitrile. In addition, NCDs-1/TBAB showed a yield of (97.0±1.0 %) of 4-phenyl-1,3-dioxolan-2-one for styrene oxide at 100 °C and 0.1 MPa in 1.5 h. A simple and convenient method for catalytic reactions with amine-terminated carbon dots was developed.

研究领域: 化学 · 材料科学
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RSC Advances · 2018 ·Vol. 8 ·期 5 ·2357-2364 · IF 2.936

Efficient promiscuous Knoevenagel condensation catalyzed by papain confined in Cu3(PO4)2 nanoflowers

Jianyun Yu,Xinxin Chen,Min Jiang,Anming Wang,Linlin Yang,Xiaolin Pei,Pengfei Zhang,Stephen Gang Wu

To develop an efficient and green immobilized biocatalyst for promiscuous catalysis which has a broad scope of applications, hybrid nanoflower (hNF) confined papain as a biocatalyst has been proposed and characterized in this study. hNFs were firstly prepared through mixing CuSO4 aqueous solution with papain in phosphate saline (PBS) at room temperature. The resulting hNFs were characterized by SEM and verified through a hydrolysis reaction with N-benzoyl-DL-arginine amide as substrate. Under optimal conditions, this nano-biocatalyst demonstrated a 15-fold hydrolytic activity compared with papain of free form, along with better thermal stability. A series of reaction factors (reaction temperature, time, and solvent) have been investigated for Knoevenagel condensation reactions with hNFs as catalyst. At optimal conditions, product yield of the hNFs catalyzed reaction was 1.3 fold higher than that of the free enzyme with benzaldehyde and acetylacetone as substrates. A few aldehydes and methylene compounds have also been used to test the generality and scope of this new enzymatic promiscuity. To sum up, the obtained hNFs demonstrate better catalytic properties than free papain and the inorganic metal-salt crystal can function as both support and promotor in biocatalysis.

研究领域: 生物化学 · 材料科学 · 酶工程
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Journal of Flow Chemistry · 2018 ·Vol. 8 ·期 1 ·29-34 · IF 1.658

A continuous-flow procedure for the synthesis of 4-Benzylidene-pyrazol-5-one derivatives

Yu Jiangang,Xu Jianguo,Li Jie,Jin Yi,Xu Wanghui,Yu Zhiqun,Lv Yanwen

A two-step flow reactor has been set up for an expeditious synthesis of 4-benzylidene-pyrazol-5-one derivatives. This procedure involved cyclization of aromatic hydrazine/ β -keto ester and subsequent Knoevenagel condensation reaction with aromatic aldehydes in tandem without isolation of intermediates. Residence time was reduced to less than 2 min in total through conducting this reaction at a relatively high temperature. Accordingly, 15 samples were achieved and isolated in moderate to excellent yields. ᅟ

研究领域: 有机化学 · 药物化学
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DYES AND PIGMENTS · 2020 · IF 4.613

Ratiometric fluorescent strategy for malononitrile determination in organic and aqueous medium and biological imaging

Yan Gong,Xinjie Guo,Baohui Teng,Qian Zhang,Peng Zhang,Caifeng Ding

Malononitrile is a versatile dinitrile compound with high reactivity, which has wide prospect in application for multisynthetic organic medical chemistry and industrial manufacture. Considering of the transformation to HCN in animal tissue metabolism, malononitrile has potential environmental pollution and health risks. Here, a ratiometric fluorescent probe 4-(benzothiazol-2-yl)-2-hydroxy benzaldehyde (HBTA) for detection of malononitrile in organic and aqueous phase is developed on the basis of reaction-triggered fluorophore for the first time. The ratiometric assay with malononitrile-responsive fluorescence signal was contributed by Knoevenagel condensation and intramolecular cyclization , which was confirmed by HR-MS analysis and NMR titration spectra. In addition, this ratiometric probe provided a fancy strategy for detection of malononitrile with fast response, high sensitivity and selectivity, declaring excellent imaging performance in vivo capable of semi-quantification for malononitrile level.

研究领域: 有机化学 · 分析化学 · 环境科学 · 生物医学
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CRYSTENGCOMM · 2020 ·Vol. 22 ·期 24 ·4147-4153 · IF 3.117

Imidazole-induced self-assembly of polyoxovanadate cluster organic framework for efficient Knoevenagel condensation under mild conditions

Ming-Yu Dou,Dan-Dan Zhong,Xian-Qiang Huang,Guo-Yu Yang

Polyoxometalate (POM) cluster organic frameworks (POMCOFs) are an emerging class of catalytic materials, providing an opportunity to develop fascinating catalysts with well-defined, tunable, active sites for a range of chemical transformations. Although remarkable progress on numerous POMCOF materials has been reported, the synthesis of polyoxovanadate (POV) cluster organic frameworks (POVCOFs) has seldom been reported. Thus, the exploration of novel POVCOFs still attracts considerable research interest. Additionally, Knoevenagel condensation as a versatile tool for the construction of CC bonds still continues to be a challenge at room-temperature and under solvent-free conditions. Herein, three POV-based clusters, [Ni(1-bIm)4]2(V4O12)·H2O (1), [Ni(1-eIm)(H2O)4]2(V10O28)(1-eImH)2·2H2O (2) and [Ni(H2O)5]2(V10O28)(1-pImH)2·4H2O (3) (1-bIm = 1-butylimidazole; 1-eIm = 1-ethylimidazole and 1-pIm = 1-propylimidazole), have been made. 1 was controllably achieved by an imidazole-induced self-assembly strategy and exhibited a 2D POVCOF in which circular [V4O12]4− clusters are bridged by four six-coordinated Ni(II) atoms (NiN4O2 model). 2 and 3 are obtained at lower pH values. Notably, among the three POV-based clusters, POVCOF 1 displays highly efficient heterogeneous solvent-free catalytic activity (yields of up to 99%) and excellent recyclability in Knoevenagel condensation at room temperature.

研究领域: 材料化学 · 催化化学
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CHEMISTRY-A EUROPEAN JOURNAL · 2020 ·Vol. 26 ·期 28 ·6147-6157 · IF 4.857

Co-hydrolysis and Seed-Induced Synthesis of Basic Mesoporous ZSM-5 Zeolites with Enhanced Catalytic Performance

Zhaoqi Ye,Yang Zhao,Hongbin Zhang,Yahong Zhang,Yi Tang

Graphical Seed-induced synthesis : Basic mesoporous ZSM-5 with adjustable alkaline-earth metal species have been synthesized by an acid co-hydrolysis and seed-induced method. Its mesostructure together with the high dispersity of basic guest species was realized by this non-classical crystallization process. For zeolite catalysts, the regulation of active site and pore structure plays an important role in the enhancement of their catalytic performance. In this work, a one-pot and organic template-free co-regulation route is proposed to straightforwardly synthesize basic mesoporous ZSM-5 zeolites with adjustable alkaline-earth metal species. The synthesis pathway combines two decisive strategies: 1) the seed-induced interface assembly growth method and 2) the acidic co-hydrolysis/condensation of aluminosilicate species and alkaline-earth metal (e.g., Mg, Ca, Sr, or Ba) sources. It is interesting that the mesoporous structure was self-evolved through particle-attached seed-interfacial crystallization without the assistance of any template. Meanwhile, the incorporation of alkaline-earth metals species is homogeneous and highly dispersed in the solid products during the whole crystallization process, and finally generate the superior basicity. Catalysis tests of the as-synthesized samples displayed their novel performance in the typical base reaction of Knoevenagel condensation, even for bulky substrates owing to the enhanced diffusion arising from the meso/microporous network. This finding opens new possibilities for facile, cost-effective, and environmentally friendly synthesis of mesoporous high-silica zeolites with tunable acid/base properties, and deepens our understanding of the particle-attached crystallization.

研究领域: 材料科学 · 催化化学
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Reaction Kinetics Mechanisms and Catalysis · 2018 ·Vol. 125 ·期 2 ·789-806 · IF 1.515

Ru(OH)x supported on polyethylenimine modified magnetic nanoparticles coated with silica as catalyst for one-pot tandem aerobic oxidation/Knoevenagel condensation of alcohols and active methylene compounds

Yan Huaipu,Zhang Hong-Yu,Wang Liping,Zhang Yuecheng,Zhao Jiquan

The immobilization of ruthenium species on polyethylenimine (PEI) modified magnetic nanoparticles coated with silica afford a multifunctional catalyst (Fe 3 O 4 @SiO 2 @PEI@Ru(OH) x ) for the aerobic oxidation/Knoevenagel condensation of alcohols and active methylene compounds. A wide scope of alcohols and malononitrile could be converted to their corresponding condensation products in excellent yields under mild conditions. This catalyst has advantages of leaching-free of ruthenium species and ease of recovery by an external magnet. The activity deactivation of the catalyst was investigated and was ascribed to the transformation of surface Ru 3+ to Ru 4+ in the process of aerobic oxidation of alcohols.

CAS / MDL: 9002-98-6 78-10-4
研究领域: 化学催化 · 材料科学
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RSC Advances · 2016 ·Vol. 6 ·期 96 ·94113-94118 · IF 3.289

Synthesis and application of core–shell magnetic metal–organic framework composites Fe3O4/IRMOF-3

Weigang Li,Gang Li,Dan Liu

A new type of magnetic core–shell structured MOF composite (Fe3O4/IRMOF-3) was successfully prepared by a facile mixed solvothermal method. Fe3O4 nanoparticles and polyvinylpyrrolidone (PVP) are the magnetic core and promoter, respectively. Fe3O4 nanoparticles are encapsulated completely inside the MOF matrix. PVP not only functions as the stabilizer to make the Fe3O4 nanoparticles well dispersed but also provides the ability to adsorb IRMOF-3 precursors onto the surface of the Fe3O4 nanoparticles. The composite possesses high crystallinity, porosity characteristics, a rapid magnetic response and good stability. In addition, the catalytic performance of Fe3O4/IRMOF-3 is investigated via the Knoevenagel condensation reaction of benzaldehyde and ethyl cyanoacetate. The conversion of ethyl cyanoacetate reaches 98.3% after 4 hours. More importantly, the catalyst can be quickly separated by a magnet and reused many times.

研究领域: 材料科学 · 化学工程
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