木质素负载钯催化剂的制备及对Heck反应的催化性能

以天然木质素和PdC l2为原料,合成了木质素负载钯催化剂,用IR、XPS、TG、DTA等对其进行了表征.研究表明,该催化剂在空气氛围中能催化丙烯酸与芳基碘的Heck反应,并有一定的重复使用性能.     

木质素-四乙烯五胺负载钯配合物的制备及对Suzuki反应的催化性能

采用较温和的Mannich反应制得了木质素-四乙烯五胺,并以其为载体通过简单的方法制备了木质素-四乙烯五胺负载钯催化剂。利用TG、DTA和XPS等测试技术对其结构进行了表征。该催化剂对碘苯与四苯硼钠的Suzuki反应有较好的催化活性,在80℃下空气氛围中反应8h,以V(DMF)∶V(H2O)=2∶1混合液为溶剂,NaHCO3为碱时,反应产率高达90.2%。催化剂可以通过简单的方法回收但重复使用性能有一定下降,重复使用4次后产率降至31.3%。     

腐植酸负载Pd/Ni双金属催化剂对Heck反应催化性能的研究

制备了腐植酸负载Pd/Ni双金属催化剂, 该催化剂能够成功催化溴苯与丙烯酸、苯乙烯等乙烯基化合物的Heck反应, 产率均在85%以上; 催化剂能够不同程度地重复使用, 在催化溴苯与丙烯酸反应中, 催化剂重复使用3次后仍可得到42.9%的产率, 而在催化溴苯与苯乙烯反应中, 催化剂重复使用7次后也可得到26.7%的产率; 并且对不同取代基芳基卤与丙烯酸的反应也有很好的催化活性.     

壳聚糖基聚合物负载钯配合物的制备及对Heck反应催化性能

以壳聚糖为基本原料制得壳聚糖缩水杨醛负载钯配合物(S-CTS-Pd)和交联壳聚糖缩水杨醛负载钯配合物(CL-S-CTS-Pd)两种催化剂,利用XPS、TG、DTA等手段对其进行了表征.两种催化剂不需在惰性气体氛围中就能有效地催化芳基碘与丙烯酸、苯乙烯的Heck反应,高产率地得到反式肉桂酸、1,2二苯乙烯,芳基碘上吸电子和供电子取代基的存在对反应没有明显影响.与S-CTS-Pd相比,CL-S-CTS-Pd在较低的温度或较少的催化剂用量下,对Heck反应仍有较高的催化活性.负载催化剂CL-S-CTS-Pd重复使用性能的研究表明,在催化碘苯与丙烯酸反应重复10次后,肉桂酸的产率仍达75.3%.     

三丁胺胺化强碱性阴离子交换树脂催化苯乙腈的α-丁基化反应

以大孔型苯乙烯系三丁胺胺化强碱性阴离子交换树脂为催化剂，催化苯乙腈的α-丁基化反应，研究了反应温度，催化剂用量和反应时间等因素对反应产率的影响。并考察了催化剂的重复使用性能，结果表明：在优化条件下，该催化剂催化苯乙腈的α-丁基化反应产率高达88%以上，且催化剂具有良好的重复使用性能。     

聚偏二氯乙烯负载金鸡纳碱催化剂的合成及其对不对称Michael反应的催化性能

将天然的金鸡纳碱——辛可宁与聚偏二氯乙烯进行接枝反应,制备了聚偏二氯乙烯负载辛可宁的催化剂.将制备的催化剂用于催化不对称Michael反应,并探索了溶剂、催化剂用量、温度、底物等不同条件对其催化性能的影响.结果表明,该催化剂在甲苯中有很高的催化活性和较好的立体选择性,Michael反应中部分产率达到80%以上,e.e值达到72%,且该催化剂具有一定的重复使用性能.     

偕胺肟纤维-钯(Ⅱ)配合物的制备及其对Heck反应的催化性能研究

以聚丙烯腈纤维为基体,制备了偕胺肟纤维-钯(Ⅱ)配合物,采用FTIR、XPS等物理化学手段对其结构进行了表征.本文研究考察了该配合物在不同反应条件下对碘苯与苯乙烯的Heck反应的催化性能,结果显示:偕胺肟纤维-钯(Ⅱ)配合物在较温和的条件下即可很好的催化Heck反应,经重复使用8次后,1,2-二苯乙烯的产率仍达80%以上,并且反应结束后催化剂易于从反应体系中分离.对于其它不同底物之间的Heck反应,偕胺肟纤维-钯(Ⅱ)配合物同样显示较好的催化性能.     

离子液体中无膦、无铜、钯催化的Sonogashira交联反应的研究

研究了离子液体中无膦、无铜、钯催化剂在Sonogashira交联反应中的催化性能. 系统考察了反应温度、溶剂、钯源、碱等因素的影响及底物的适用性. 研究结果表明, 该催化体系对各种电子效应的碘代烷和末端炔烃的Sonogashira交联反应是十分有效的, 反应在温和的条件下取得较好的收率. 此外, 该催化体系有很好的重复使用性, 循环四次后催化活性只有略微的降低.     

一种无机-有机高分子杂化催化剂Pd(0)-CS/MCM-41的制备及其性能研究

将天然高分子聚合物壳聚糖负载到MCM-41介孔分子筛上,再在室温与氯化钯乙醇溶液作用,制得了一种无机-有机天然高分子杂化催化剂Pd(0)-CS/MCM-41,并利用XPS、FTIR、XRD、热重等手段对其进行了表征。以碘代苯与丙烯酸的Heck芳基化反应考察了所得催化剂的催化性能。结果表明,催化剂具有较高的催化活性和良好的重复使用性能,催化剂在氮气保护下能有效地催化碘代苯与丙烯酸的Heck反应,高产率地得到反式肉桂酸。经8次重复使用后,肉桂酸的产率仍达80%以上。     

以类水滑石CuZnAl为前驱体制备的催化剂对C—N交叉偶联反应的性能研究

以类水滑石Cu Zn Al为前驱体,经600℃焙烧制备了一系列不同Cu/Zn/Al摩尔比的催化剂.对催化剂进行了XRD、BET、AAS及XPS等表征,并测定了该催化剂催化碘苯与咪唑C—N交叉偶联合成1-苯基咪唑的催化性能.结果表明,当Cu/Zn/Al摩尔比为2∶1∶1时,其活性组分Cu分散均匀且催化性能达到最佳.在130℃空气气氛中,KOH存在的条件下,反应24 h,1-苯基咪唑的产率可达到85.8%,实现了C—N偶联反应在多相催化体系中进行.催化剂可回收不产生环境污染,经5次重复使用其催化性能下降不明显.     

Palladium-Nafion SAC-13 catalysed depolymerisation of lignin to phenols in formic acid and water

Guaiacol, pyrocatechol and resorcinol, were isolated and quantified as the major products from catalytic pyrolysis of lignin of various origin. The novel procedure utilises formic acid as the hydrogen source in combination with a palladium catalyst and Nafion^® SAC-13 as a solid acid catalyst with water as reaction medium. The reaction is conducted at moderate pyrolysis temperature and short reaction time. Several palladium based catalysts and different types of lignin were investigated. The lignins and the model compounds demonstrated various chemical behaviour, under identical reaction conditions; various phenols were formed from the lignins, while the model compounds were hydrodeoxygenated, demethylated and demethoxylated.     

Nano tetraimine Pd(0) complex as an efficient catalyst for phosphine‐free Suzuki reaction in water and copper‐free Sonogashira reaction under aerobic conditions

A nano tetraimine Pd(0) complex catalyst was successfully used as an efficient heterogeneous catalyst for the phosphine‐free palladium‐catalysed Suzuki coupling reaction in water at 80 °C. This nano tetraimine Pd(0) complex was also used for copper‐free Sonogashira reaction in dimethylformamide at 100 °C. The catalyst was easily recovered from the reaction mixture by centrifugation and reused for at least six cycles without any significant loss in its catalytic activity. Analysis of the reaction mixture using inductively coupled plasma analysis showed that leaching of palladium from the catalyst was negligible. The reactions can be performed efficiently for aryl iodides, bromides and also chlorides. Copyright © 2016 John Wiley & Sons, Ltd.     

聚苯乙烯苄基(8-氨基喹啉)负载鈀催化剂的催化加氢性能

本文在带有8-氨基喹啉螯合基团的树脂上负载了二氯化钯,再经甲醇-水还原合成混合价态钯催化剂。考察并比较了两类催化剂的加氢活性及选择性,发现混合价态钯催化剂具有活性高、选择性强、金属不易流失的特点。     

Formation of Four Different Aromatic Scaffolds from Nitriles through Tandem Divergent Catalysis

A zinc bromide complex, formed by the sequential reaction of nitriles with a Reformatsky reagent and terminal alkynes, is used as an intermediate for divergent palladium‐catalyzed reactions. The reaction pathway of the intermediate is precisely controlled by the choice of the reaction solvent or the palladium catalyst to quickly form four different aromatic scaffolds—arylamines, aminoindenes, pyrroles, and quinolines—starting from readily available nitriles.     

高分子钯络合物催化的亚胺化合物的加氢反应

制备了一系列以二氧化硅为载体的侧链上含有各种氮配位基团的聚硅氧烷-钯络合物,这些高分子钯络合物能够在常温常压下催化亚胺化合物的加氢反应并表现出不同程度的催化活性.对其中聚-(N,N-二乙酰基)-γ-氨丙基硅氧烷-钯络合物催化的亚苄基苯胺的加氢反应做了比较深入的研究,发现该催化剂在反应中是稳定的并给出唯一的加氢产物,络合物中的N/Pd原子比、反应温度以及不同底物对反应速度的影响也被报道.     

钯-离子液体/钛硅复合氧化物催化剂的合及在胺羰化中的应用

长期以来 ,工业上一直使用光气合成法生产异氰酸酯类化合物 ,极易造成环境污染和人员伤害 ,因此研究无光气且环境友好的新工艺已引起广泛关注 .就经济角度考虑 ,由硝基类化合物进行还原羰化[1～ 4 ] 或胺类化合物进行氧化羰化 [5～ 13] 制备异氰酸酯比较有利 ,但是存在金属配合物催化剂的还原失活等问题[14 ,15] .室温离子液体作为一种具有特殊催化性能和可调控溶解能力的新型溶剂和反应介质已用于有机反应中 [16 ] ,但将其作为反应介质的含氮化合物进行羰化研究尚未见报道 .本文将离子液体应用于以硅酸四乙酯 ( TEOS)和钛酸四丁酯 ( TBO…     

(聚酰胺-胺树枝状大分子)-水杨醛席夫碱钯配合物的Heck反应催化性能研究(英文)

用元素分析、红外光谱、紫外光谱、荧光光谱和核磁等分析手段对合成出的1.0G树枝状大分子-水杨醛席夫碱钯配合物(PAMAMSAPd)进行了表征。用其作为催化剂,研究了碘代苯与丙烯酸在有机溶剂中的偶联反应。对于碘代苯与丙烯酸的偶联反应,最佳反应条件为:惰性气氛,10mmol PhI,nPhI∶nAA∶nEt3N=1∶1.5∶2.5,3.0×10-3g PAMAMSAPd, 4mL DMF和100°C的反应温度。在该条件下,产物肉桂酸的产率可达96.5%。该树枝状大分子配合物是一种无磷、高效和稳定的Heck反应催化剂。且该催化剂经简单的过滤、溶剂洗涤进行回收,重复使用3次,产率仍能达到90.2%。     

An Efficient and Practical Process for Pd/Cu Cocatalyzed Homocoupling Reaction of Terminal Alkynes Using Sodium Percarbonate as a Dual Reagent in Aqueous Media

A new process for the Pd/Cu co-catalyzed homocoupling reaction of terminal alkynes was developed. The reaction was carried out in aqueous media with sodium percarbonate as both a clean oxidant and a base. Meanwhile, a palladium complex immobilized on a synthetic PS-PEG400-PPh2 resin was used as the catalyst, which may be recovered by simple filtration and reused for several times with high activity.     

Palladium pincer complex-catalyzed trimethyltin substitution of functionalized propargylic substrates. An efficient route to propargyl- and allenyl-stannanes

Palladium pincer complex-catalyzed reaction of functionalized propargyl chloride (and mesylate) derivatives with hexamethylditin gives allenyl- and propargyl-stannane products. This catalytic activity is in sharp contrast with the reactivity of commonly used palladium(0) catalysts inducing addition of hexamethylditin to the triple bond. The product distribution of the pincer complex-catalyzed reaction is controlled by the substituent effects of the propargylic substrate: electron-withdrawing functionalities give mainly allenyl stannane products, while with electron-donating groups the main product is propargyl stannane. The catalytic reaction proceeds under very mild conditions tolerating many functionalities such as OH, OAc, NR3, and NR2Ac groups. Our mechanistic studies indicate that the key intermediate of the reaction is a monotrimethylstannane palladium pincer complex. A remarkable feature of the studied catalytic process is that the palladium catalyst does not undergo redox reactions, but its oxidation state is restricted to palladium(II). Since palladium(0) intermediates does not occur in this process, the catalyst is very stable and highly chemoselective.     

Polymer-supported DABCO–palladium complex as a stable and reusable catalyst for room temperature Suzuki–Miyaura cross-couplings of aryl bromides

Polymer-supported DABCO–palladium complex was observed as to be efficient and reusable catalytic system for the Suzuki–Miyaura cross-coupling reaction. In the presence of 0.25 mol % of the polymer-supported DABCO–palladium complex, a variety of aryl bromides were coupled with arylboronic acids efficiently in an aqueous ethanol at room temperature under air. Moreover, the reaction was very rapid, and the catalyst could be recovered readily from the reaction by simple filtration and could be reused at least five times.