2568-25-4Relevant articles and documents
One-step preparation of flower-like poly(styrene-co-zwitterionic ionic liquid) microspheres with hierarchical structures for supported acidic heterogeneous catalysts
Mao, Hui,Song, Yang,Qian, Dongmei,Liu, Daliang,Wu, Shuyao,Zhang, Yu,Hisaeda, Yoshio,Song, Xi-Ming
, p. 91654 - 91664 (2015)
By using a one-step copolymerization of styrene (St) and 3-(1-vinyllimidazolium-3-yl)propane-1-sulfonate (VIPS), a kind of poly(St-co-VIPS) microsphere, with a hierarchical structure composed of nanospheres or nanoparticles with diameters in the range of 70-90 nm arranged on its surface and that look like a flower, has been simply prepared in the presence of polyvinyl pyrrolidone (PVP) in an aqueous alcohol system. A formation mechanism of the flower-like poly(St-co-VIPS) microspheres is proposed by investigating the influence of reaction conditions on its morphologies and observing its growth process with time. Because of the existence of zwitterionic liquid functional groups, flower-like poly(St-co-VIPS)-acid microspheres, a novel kind of heterogeneous catalyst, were successfully prepared by immobilizing heteropoly acids and H2SO4 on the flower-like poly(St-co-VIPS) microspheres, and the heterogeneous catalysts showed better catalytic activities for esterifications, acetalizations and transesterifications than with H2SO4 as the catalyst. Especially, the heterogeneous catalysts presented excellent catalytic efficiency for the acetalization of benzaldehyde and 1,2-propanediol, which could successfully reach 96.2%. Furthermore, the crosslinked flower-like poly(DVB-co-VIPS)-H2SO4 microspheres prepared under the same conditions where only St was replaced by divinyl benzene (DVB) have better reusability than that of the flower-like poly(St-co-VIPS)-H2SO4 with poor solvent resistance, and could be reused four times without significant loss of the catalytic activity, indicating that they could act as excellent recyclable heterogeneous catalysts for the synthesis of acetals and have potential application in industry.
Visible-Light Mediated Oxidative Fragmentation of Ethers and Acetals by Means of Fe(III) Catalysis
Lindroth, Rickard,Ondrejková, Alica,Wallentin, Carl-Johan
supporting information, p. 1662 - 1667 (2022/03/14)
A new method employing iron(III) acetylacetonate along with visible light is described to effect oxidative ring opening of cyclic ethers and acetals with unparalleled efficiency. The method allows for a photocatalytic radical chemistry approach to functionalize relatively inert cyclic ethers into useful synthetic intermediates. The methodology sheds further light on the use of underexplored iron complexes in visible-light photochemical contexts and illustrates that simple Fe(III) complexes can initiate redox processes from 4LMCT excited states.
Soluble/MOF-Supported Palladium Single Atoms Catalyze the Ligand-, Additive-, and Solvent-Free Aerobic Oxidation of Benzyl Alcohols to Benzoic Acids
Tiburcio, Estefanía,Greco, Rossella,Mon, Marta,Ballesteros-Soberanas, Jordi,Ferrando-Soria, Jesús,López-Haro, Miguel,Hernández-Garrido, Juan Carlos,Oliver-Meseguer, Judit,Marini, Carlo,Boronat, Mercedes,Armentano, Donatella,Leyva-Pérez, Antonio,Pardo, Emilio
supporting information, p. 2581 - 2592 (2021/02/16)
Metal single-atom catalysts (SACs) promise great rewards in terms of metal atom efficiency. However, the requirement of particular conditions and supports for their synthesis, together with the need of solvents and additives for catalytic implementation, often precludes their use under industrially viable conditions. Here, we show that palladium single atoms are spontaneously formed after dissolving tiny amounts of palladium salts in neat benzyl alcohols, to catalyze their direct aerobic oxidation to benzoic acids without ligands, additives, or solvents. With this result in hand, the gram-scale preparation and stabilization of Pd SACs within the functional channels of a novel methyl-cysteine-based metal-organic framework (MOF) was accomplished, to give a robust and crystalline solid catalyst fully characterized with the help of single-crystal X-ray diffraction (SCXRD). These results illustrate the advantages of metal speciation in ligand-free homogeneous organic reactions and the translation into solid catalysts for potential industrial implementation.
MOFs based on 1D structural sub-domains with Br?nsted acid and redox active sites as effective bi-functional catalysts
Díaz, Urbano,Moreno, José María,Velty, Alexandra
, p. 3572 - 3585 (2020/06/25)
A novel family of lamellar MOF-type materials, which contain Br?nsted acid sites together with redox active centers, based on assembled 1D organic-inorganic nanoribbons were obtained through direct solvothermal synthesis routes, using specific monotopic benzylcarboxylate spacers with thiol substituents in thepara-position like structural modulator compounds and effective post-synthesis oxidized treatments to generate accessible sulfonic groups. Low-dimensional aluminum metal-organic materials, containing free sulfonic pendant groups (Al-ITQ-SO3H), were successfully tested in several acid reactions, such as acetalization, esterification and ring opening of epoxides with a significant impact on fine chemistry processes. The direct introduction of stabilized Pd nanoparticles, cohabitating with pendant sulfonic groups, allowed the preparation of active bi-functional MOF-type hybrid materials (Al-ITQ-SO3H/Pd) capable of carrying out one-pot two-step oxidation-acetalization reactions, exhibiting high yield and high activity during consecutive catalytic cycles.
Method for improving activity of propylene epoxide catalyst and co-producing ketal (acetal)
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Paragraph 0020; 0037; 0038; 0039, (2019/01/17)
The invention provides a method for synthesizing propylene epoxide and co-producing ketal (acetal) by taking a by-product PG as a raw material in propylene epoxidation in the presence of heteropoly acid as a catalyst. Negative effects of alcohol substances to the activity of the catalyst in epoxidation reaction are eliminated, the activity of the catalyst is improved, the catalyst is used stably,meanwhile, downstream application of the by-product PG is expanded, and a preparation method for ketal (acetal) is provided. The method has the advantages of gentle reaction conditions, good catalyzing stability, good catalyst using effect, and resource utilization of the by-product.
Facile synthesis of acetal over a supported novel Br?nsted and lewis acid ionic liquid catalyst
Liu, Ruifeng,Dai, Liming,Zhao, Qian,Xie, Yingjie,Jiang, Tingshun
, p. 4396 - 4405 (2019/05/08)
A novel Br?nsted and Lewis acid ionic liquid (IL) chlorinated butyrolactam chlorozincinate (CPCl-ZnCl2) was synthesized by a hydrothermal process and characterized by Fourier transform infrared (FT-IR). The Fe-SBA-15 mesoporous materials with different Si/Fe mole ratios were prepared by direct synthesis method. The supported ionic liquid (IL/Fe-SBA-15) with various IL contents were prepared by a wet impregnation method and characterized by X-ray diffraction (XRD), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and N2 physical adsorption. The acidity was measured by FT-IR spectroscopy using pyridine as probes. The catalytic property was tested in acetalization of cyclohexanone with ethylene glycol. The results demonstrated that the IL/Fe-SBA-15 catalysts were of higher catalytic activity compared to Fe-SBA-15. Under optimal conditions, the acetalization could reach to 92.6% cyclohexanone conversion with 99.3% acetal selectivity. After 5 cycles, the cyclohexanone conversion decreased slightly. Also, the catalyst showed good catalytic property in the other acetalization of cyclohexanone and benzyl alcohol.
Robust acidic pseudo-ionic liquid catalyst with self-separation ability for esterification and acetalization
Shi, Yingxia,Liang, Xuezheng
, p. 1413 - 1421 (2019/05/04)
The novel acidic pseudo-ionic liquid catalyst with self-separation ability has been synthesized through the quaternization of triphenylphosphine and the acidification with silicotungstic acid. The pseudo-IL showed high activities for the esterification with average conversions over 90%. The pseudo-IL showed even higher activities for acetalization than traditional sulfuric acid. The homogeneous catalytic process benefited the mass transfer efficiency. The pseudo-IL separated from the reaction mixture automatically after reactions, which was superior to other IL catalysts. The high catalytic activities, easy reusability and high stability were the key properties of the novel catalyst, which hold great potential for green chemical processes.
8-Hydroxy-2-methylquinoline-modified H4SiW12O40: A reusable heterogeneous catalyst for acetal/ketal formation
Liu, Li-Jun,Luan, Qing-Jie,Lu, Jing,Lv, Dong-Mei,Duan, Wen-Zeng,Wang, Xu,Gong, Shu-Wen
, p. 26180 - 26187 (2018/08/04)
A heteropoly acid based organic hybrid heterogeneous catalyst, HMQ-STW, was prepared by combining 8-hydroxy-2-methylquinoline (HMQ) with Keggin-structured H4SiW12O40 (STW). The catalyst was characterized via elemental analysis, X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), thermogravimetric analysis (TG) and potentiometric titration analysis. The catalytic performance of the catalyst was assessed in the ketalization of ketones with glycol or 1,2-propylene glycol. Various reaction parameters, such as the glycol to cyclohexanone molar ratio, catalyst dosage, reaction temperature and time, were systematically examined. HMQ-STW exhibited a relatively high yield of corresponding ketal, with 100% selectivity under the optimized reaction conditions. Moreover, catalytic recycling tests demonstrated that the heterogeneous catalyst exhibited high potential for reusability, and it was revealed that the organic modifier HMQ plays an important role in the formation of a heterogeneous system and the improvement of structural stability. These results indicated that the HMQ-STW catalyst is a promising new type of heterogeneous acid catalyst for the ketalization of ketones.
Palladium on Carbon-Catalyzed Chemoselective Oxygen Oxidation of Aromatic Acetals
Yasukawa, Naoki,Asai, Shota,Kato, Maho,Monguchi, Yasunari,Sajiki, Hironao,Sawama, Yoshinari
supporting information, p. 5604 - 5607 (2016/11/17)
The development of an unprecedented chemoselective transformation has contributed to forming a novel synthetic process for target molecules. Chemoselective oxidation of aromatic acetals has been accomplished using a reusable palladium on carbon catalyst under atmospheric oxygen conditions to form ester derivatives with tolerance of aliphatic acetals and ketals.
Phosphorus promoted SO42-/TiO2 solid acid catalyst for acetalization reaction
Zhong, Shaofeng,Ou, Qiongrong,Shao, Linjun
, p. 3005 - 3008 (2015/11/27)
A novel phosphorus modifed SO42-/TiO2 catalyst was synthesized by a facile coprecipitation method, followed by calcination. The catalytic performance of this novel solid acid was evaluated by acetalization. The results showed that the phosphorus was very effcient to enhance the catalytic activity of SO42-/TiO2. The solid acid owned high activity for the acetalization with the yields over 90%. Moreover, the solid acid could be reused for six times without loss of initial catalytic activities.
