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硫化镉/氧化铈/碳酸银纳米复合材料作为用于克诺文纳格尔缩合反应和乙酰化反应的高效多相催化剂。

CdS/CeO/AgCO nanocomposite as an efficient heterogeneous catalyst for Knoevenagel condensation and acetylation reactions.

作者信息

Seid Getachew A, Taddesse Abi M, Babu Neelaiah, Yassin Jemal M

机构信息

Department of Chemistry, Dire Dawa University, P.O. Box 1362, Dire Dawa, Ethiopia.

Department of Chemistry, Haramaya University, P.O. Box 138, Dire Dawa, Ethiopia.

出版信息

Sci Rep. 2025 May 21;15(1):17567. doi: 10.1038/s41598-025-01567-1.

Abstract

Knoevenagel condensation and acetylation reactions play a critical role in organic synthesis by facilitating the formation of carbon-carbon bonds and the modification of functional groups; however, limitations like low efficiency and demanding reaction conditions and time underscore the necessity for developing better techniques to enhance their practical applications. In this study, a ternary nanocomposite of CdS/CeO/AgCO was synthesized by varying the molar ratio of CdS to CeO/AgCO using the precipitation method. This heterogeneous catalyst was developed for Knoevenagel condensation and acetylation reactions applications. The optical properties, functional groups, crystalline structure, morphology, and surface area of the synthesized catalysts were characterized using UV-Vis-DRS, FTIR, XRD, SEM, and N adsorption-desorption isotherms, respectively. For the Knoevenagel condensation reaction between benzaldehyde and malononitrile, the optimal conditions were found to be the use of water as a solvent, at 10% w/w catalyst loading based on the total reagent mass, and room temperature (20 °C). Under these conditions, CdS/CeO/AgCO with a CdS: CeO/AgCO weight ratio of 3:1 gave high yields, 92.19 ± 0.41 in 33 min for Knoevenagel condensation and 93.8 ± 1.19 in just 3 min for the acetylation reaction. The reaction conditions were tested for different aromatic aldehydes with malononitrile, yielding high isolated products. The reusability of the CdS/CeO/AgCO (3:1) catalyst was assessed, with only a 6.4% decrease in yield after sixth consecutive runs under optimal reaction conditions. Furthermore, the optimized catalyst, CdS/CeO/AgCO (3:1), was evaluated for its catalytic activity in the acetylation of an aniline derivative. The structures of the synthesized products, 2-benzalidinemalononitrile and acetanilide, were confirmed by spectrometric techniques such asH-NMR,C-NMR, and FTIR analysis.

摘要

克诺文纳格尔缩合反应和乙酰化反应通过促进碳 - 碳键的形成和官能团的修饰在有机合成中发挥着关键作用;然而,诸如效率低、反应条件苛刻以及耗时等局限性凸显了开发更好技术以增强其实际应用的必要性。在本研究中,采用沉淀法通过改变硫化镉与氧化铈/碳酸银的摩尔比合成了硫化镉/氧化铈/碳酸银三元纳米复合材料。这种多相催化剂是为克诺文纳格尔缩合反应和乙酰化反应应用而开发的。分别使用紫外 - 可见 - 漫反射光谱(UV - Vis - DRS)、傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)、扫描电子显微镜(SEM)和氮吸附 - 脱附等温线对合成催化剂的光学性质、官能团、晶体结构、形态和表面积进行了表征。对于苯甲醛和丙二腈之间的克诺文纳格尔缩合反应,发现最佳条件是以水为溶剂,基于总试剂质量的催化剂负载量为10%(w/w),反应温度为室温(20℃)。在这些条件下,硫化镉与氧化铈/碳酸银重量比为3:1的硫化镉/氧化铈/碳酸银在33分钟内克诺文纳格尔缩合反应的产率高达92.19±0.41,在乙酰化反应中仅3分钟产率就达到93.8±1.19。对不同芳香醛与丙二腈的反应条件进行了测试,得到了高产率的分离产物。评估了硫化镉/氧化铈/碳酸银(3:1)催化剂的可重复使用性,在最佳反应条件下连续六次运行后产率仅下降6.4%。此外,还评估了优化后的催化剂硫化镉/氧化铈/碳酸银(3:1)对苯胺衍生物乙酰化反应的催化活性。通过诸如氢核磁共振(¹H - NMR)、碳核磁共振(¹³C - NMR)和傅里叶变换红外光谱(FTIR)分析等光谱技术确认了合成产物2 - 亚苄基丙二腈和乙酰苯胺的结构。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b030/12092740/4983b9651940/41598_2025_1567_Fig1_HTML.jpg

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