碱性功能化离子液体催化knoevenagel缩合反应

碱性功能化离子液体;催化;knoevenagel缩合反应;丙二氰;氰基乙酸乙酯     

新型羟基功能化离子液体的合成及在Knoevenagel缩合反应中的应用

基于1,4-二叠氮双环[2.2.2]辛烷(DABCO)的新型羟基功能化离子液体作为催化剂在无溶剂条件下催化苯甲醛与氰基乙酸乙酯或2,4-噻唑烷二酮的Knoevenagel缩合反应,在温和反应条件下,可以较高产率分别得到β-苯基-α氰基丙烯酸乙酯(≥99%)和5-苯乙烯基-2,4-噻唑烷二酮(92%).这些催化反应操作简单,产物可从反应混合物中直接分离得到,并且催化剂表现出较好的重复利用率.文章最后提出一个可能的反应机理,并进行了相关讨论.     

功能化酸性离子液体催化甲醛与烯烃的Prins缩合反应

研究了以功能化酸性离子液体为催化剂,甲醛与烯烃Prins缩合反应生成1,3-二噁烷及其衍生物,水解得到1,3-二元醇.对不同结构的离子液体、催化剂用量和反应条件进行了考察.结果表明,该体系具有良好的催化性能,反应可在较温和的条件下进行,实现了高活性和高选择性的目标.产物易分离,催化剂重复使用6次,其催化活性基本不变.     

聚乙二醇功能化离子液体的制备及其在有机反应中的应用

聚乙二醇功能化离子液体作为一个新的研究方向受到了化学研究者关注,该类离子液体已经成功地应用于许多有机合成反应中,可以明显改善催化剂性能,并可在一定程度上解决传统催化剂使用中遇到的难分离、难回收再利用的问题。本文介绍了聚乙二醇功能化离子液体的发展历程、制备方法和其作为反应介质、溶剂或催化剂在有机合成反应中应用的最新研究成果,主要包括加成反应、缩合反应、还原反应、酯化反应、硝化反应、氧化反应、水解反应、Heck反应以及Suzuki-Miyaura反应等。     

磺酸功能化离子液体催化3-羟基丙酸甲酯酯交换聚合反应

以磺酸功能化咪唑离子液体为催化剂,以3-羟基丙酸甲酯为原料,采用自身酯交换法合成了具有生物可降解性能的聚羟基脂肪酸酯.系统考察了离子液体种类、反应温度以及聚合反应时间对反应性能的影响,同时采用红外、核磁、热分析等手段对产物进行表征.研究结果表明:阴离子为CF3SO-3的磺酸功能化离子液体在120℃的低温下催化聚合反应所得聚酯Mw可达10 159,收率82.1%;通过水洗方法可有效去除产物中的离子液体催化剂,从而避免催化剂污染产物.     

设计新型液液两相催化体系:π配体离子液体

 π配体催化剂与离子液体体系相结合有助于解决反应效率、产物分离和催化剂循环等一系列均相催化体系不易解决的难题. 近几年相关的研究逐渐深入,由简单地使用离子液体作为π配体催化反应的介质向利用离子液体自身结构的方向发展,相继出现了几类不同的研究思路. 例如,利用π配体催化剂与离子液体形成络合物,使用离子型π配体改善催化剂在离子液体中的溶解性,以及合成功能化阳离子或功能化阴离子的π配体离子液体. 本文结合这几类离子液体化学键联π配体(简称π配体离子液体)的研究进展,从离子液体功能化设计的角度探讨了π配体离子液体的合成思路,为设计具有更好催化性能的功能化离子液体体系提供借鉴.     

SBA-15 固载离子液体功能化脯氨酸的制备及其催化 Knoevenagel 缩合反应

 以 L-脯氨酸为原料合成了离子液体功能化脯氨酸前驱体 (IL-Pro), 并将其固载到 SBA-15 介孔分子筛上, 制得 IL-Pro/SBA-15 催化剂. 用红外光谱、热重、N2 吸附-脱附、X 射线衍射和透射电镜等手段表征了 IL-Pro/SBA-15 催化剂, 并考察了该催化剂在 Knoevenagel 缩合反应中的催化性能. 结果表明, 固载离子液体功能化脯氨酸没有破坏 SBA-15 的有序介孔结构, 但孔体积、孔径和比面表积有所下降; IL-Pro/SBA-15 的失重峰在 250~360 oC (峰值为 310 oC). 在以苯甲醛和丙二腈为底物的 Knoevenagel 反应中, IL-Pro/SBA-15 催化剂表现出较高的活性, 缩合产物收率高达 94%; 经简单分离后催化剂可重复使用 7 次以上而活性基本保持不变.     

基于杂多酸的负载离子液相催化在醇氧化中的应用

采用溶胶-凝胶法制备的离子液体功能化的二氧化硅对于杂多酸是一种可行的载体,三种商用杂多酸成功的负载在离子液体功能化的二氧化硅上作为醇氧化的催化剂.利用FTIR、XRD、XPS对该种负载离子液相催化剂进行了表征.基于磷钨酸的负载离子液相催化剂活性最好,高产率(大部分＞93%)的得到了相应的羰基化合物.且该催化剂经过简单的...     

功能化离子液体在Knoevenagel缩合中的研究进展

离子液体具备熔点低、不可燃性、热稳定性好、溶解性好、可设计性及可重复利用性等一系列优点,因此常以催化剂、溶剂的形式应用于有机合成领域中.从离子液体阳离子电荷中心所在位置的不同出发,分别介绍了近年来非环类、环类及负载型功能化离子液体在Knoevenagel缩合反应中的应用进展,并对功能化离子液体的结构特点、催化活性及某些催化剂可能的催化机理等方面展开了论述.     

DABCO离子液体催化Knoevenagel缩合反应

以三乙烯二胺(DABCO)为原料,通过两步法制备了离子液体[DABCO-PDO][PF6];将其用于催化芳香醛与多种活性亚甲基化合物(丙二腈,氰基乙酸乙酯,苯并噻唑乙腈,苯乙腈)的Knoevenagel缩合反应;讨论了可能的反应机理,并基于催化剂的双重催化作用阐述了反应的高效性.结果表明,该反应体系无需任何溶剂,在室温(25℃)下就能进行,催化剂用量小,反应时间短,收率高,反应后处理简单,反应普适性较高;且催化剂重复使用5次后仍保持很高的催化活性.     

Organic Reactions in Ionic Liquids: Ionic Liquid Promoted Knoevenagel Condensation of Aromatic Aldehydes with (2‐Thio)Barbituric Acid

Abstract

The Knoevenagel condensation of aromatic aldehydes with (2‐thio)barbituric acid proceeded efficiently in reusable ionic liquids, EAN, BmimBF₄, and BmimPF₆ at room temperature in the absence of any catalyst with high yields.     

A Practical Knoevenagel Condensation Catalyzed by PEG400 and Anhydrous K2CO3 Without Solvent

Abstract

Knoevenagel condensation of aromatic aldehydes with active methylene compounds under solvent‐free conditions to synthesize arylidene compounds in good to excellent yields using powdered anhydrous K₂CO₃ and PEG400 as catalysts has been described.     

On Regioselectivity of Aldol Condensation of Aromatic Aldehydes with Borate Complex of Acetylacetone

While cinnamoyl acetone 1 is obtained in good yield by a condensation of 3 molar excess of a borate complex of acetylacetone with benzaldehyde, products of Knoevenagel condensation 2 are predominantly obtained with furfural and 5-substituted furfurals. Cinnamoyl acetone 1 can be further condensed with furfural to form unsymmetrical curcuminoid 5. Compound 2a does not produce any new products under the same conditions. Compounds 3 and 5 are good inhibitors of growth of protozoan Trichomonas vaginalis.     

Knoevenagel condensation of aldehydes with active methylene compounds catalyzed by MgC2O4/SiO2 under microwave irradiation and solvent-free conditions

MgC₂O₄/SiO₂ catalyzes the efficient Knoevenagel condensation of aldehydes with active methylene compounds in solvent-free conditions under microwave irradiation to give alkenes derivatives in excellent yields. MgC₂O₄/SiO₂ can be reusable for Knoevenagel condensation. However, ketones have been found to be unsatisfactory in the reaction under the same conditions.     

Application of Microwave irradiation Techniques for the Knoevenagel Condensation

The reaction rate of Knoevenagel condensation can be dramatically enhanced by irradiating the reaction mixture containing an aldehyde, diethyl malonate, P₂O₅, piperidine, and chlorobenzene with a commercial microwave oven. Six Knoevenagel condensation products were synthesized within 5–15 min in good yields.     

Fe3O4–cysteamine hydrochloride magnetic nanoparticles: New,efficient and recoverable nanocatalyst for Knoevenagel condensation reaction

Fe₃O₄ magnetic nanoparticles (MNPs) were obtained using a reduction–precipitation method. These MNPs were modified with cysteamine hydrochloride. This catalyst was characterized using a number of physicochemical measurements. The Fe₃O₄–cysteamine MNPs, as an efficient and heterogeneous catalyst, were successfully used for Knoevenagel condensation under mild conditions. The activity of this nanomagnetic catalyst in the Knoevenagel condensation of aromatic aldehydes and malononitrile is described. Easy preparation of the catalyst, easy work‐up procedure, excellent yields and short reaction times are some of the advantages.     

Alum catalyzed simple and efficient synthesis of 5-arylidene-2,4-thiazolidinedione in aqueous media

Abstract

Alum (KAl(SO₄)₂·12H₂O) is an inexpensive, efficient, and non-toxic catalyst used for the synthesis of 5-arylidine-2,4-thiazolidinediones by the Knoevenagel condensation of aromatic aldehydes with 2,4-thiazolidinedione in aqueous media at 90°C. This method affords the 5-arylidine-2,4-thiazolidinediones in short reaction times, high yields, and green aspects by avoiding toxic catalysts and hazardous solvents.     

Neue cyclische Ester der Malonsäure und deren Kondensationsprodukte mit Aldehyden

The reaction of malonylchloride with ethylene glycol or dithioglycol at low temperatures and high dilution leads to cyclic condensation products of 2∶2 composition, of which the first one reacts with aldehydes to give alkenes (Knoevenagel condensation). On the other hand, malonyl chloride and pinacol react under the same conditions to give a linear oligomeric condensation product. The Knoevenagel condensation products are electrically neutral organic Lewis acids (pK′ _L -values: 8.3₅ and 7.8₅). Mass-spectra, NMR-, UV- and IR-spectra were employed for structural determinations.     

Synthesis,structure, and base-catalytic performance of a laminar zinc phosphite-phosphate

A two-dimensional zinc phosphite-phosphate [C₃H₆(OH)NH₃][Zn₂(HPO₃)(PO₄)] (1) was hydrothermally synthesized with 2-hydroxypropylammonium cation as the structure-directing agent. This compound has been characterized by single-crystal X-ray diffraction, IR spectroscopy, and powder X-ray diffraction (XRD). Its microporous framework is constructed by ZnO₄, PO₄, and HPO₃ tetrahedral building blocks with 3, 4, and 6-ring channels. With 1 as base catalytic support, the Knoevenagel condensation reaction of benzaldehyde and ethyl cyanoacetate gives a yield of 59%.     

Magnetic nanoparticle supported amine: An efficient and environmental benign catalyst for versatile Knoevenagel condensation under ultrasound irradiation

Amine functionalized silica coated Fe₃O₄ nanoparticles (SiO₂@MNP-A) were successfully prepared as a novel heterogeneous amine. The catalyst was characterized by XRD, FT-IR, TEM, magnetic measurement, elemental analysis and was found to be a magnetically separable and highly active catalyst for ambient Knoevenagel condensation of aromatic aldehydes and α-aromatic (heteroaromatic or polyaromatic)-substituted methylene compounds in water under ultrasonic irradiation to afford the corresponding products in good to excellent yields. Very interestingly, SiO₂@MNP-A successfully catalyze the reaction of the non-cyano substituted compound with benzaldehyde to achieve a key intermediate for the preparation of Atorvastatin calcium in green and atom-economic manner. In addition, the catalyst SiO₂@MNP-A can be reused for 8 times without any obvious loss of its activity. The role of ultrasonication in the Knoevenagel condensation was also discussed with the assistance of UV–vis spectrometry.