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1.
考察了离子型+3价铑配合物1a和2a作为催化剂前体在1-辛烯氢甲酰化反应中的催化行为.实验结果表明,在无助剂存在下,配合物1a和2a表现出较差的催化性能,而廉价低毒的有机叔胺助剂如三乙胺或N-甲基哌啶可以显著提升配合物1a和2a的催化性能,可获得800 h-1以上的转化频率(TOF).当以哌啶功能化离子液体[PEmim]BF4兼作助剂和溶剂时,不仅可以促进配合物1a和2a对氢甲酰化反应的活性和选择性,还可实现"离子液体-有机"两相氢甲酰化反应,使得锁定在[PEmim]BF4离子液体相中的配合物1a(或2a)催化剂得以简单两相分离和回收循环使用,但在5次循环使用过程中锁定在[PEmim]BF4中的催化剂存在向有机相流失和失活的问题,导致产物壬醛的收率逐渐下降.  相似文献   

2.
为了深入研究丁烯氢甲酰化反应中可能发生的异构化与氢甲酰化反应,在Rh-BIPHEPHOS的催化作用下,对比研究了不同丁烯原料在不同温度下与合成气的反应。结果表明,1-丁烯与合成气反应时,异构化产物(2-丁烯)比氢甲酰化产物多,而以2-丁烯作为原料时,氢甲酰化反应占优势;受到1-丁烯和2-丁烯之间反应平衡的限制,温度对异构化反应有较大的正向影响。此外,在Rh-BIPHEPHOS的催化作用下,因为BIPHEPHOS较大的咬合角限制了异戊醛形成过程中的中间重排,所以产物中正戊醛的量要比异戊醛多。  相似文献   

3.
水溶性铑膦配合物催化烯烃氢甲酰化反应研究进展   总被引:1,自引:0,他引:1  
 水/有机两相体系中水溶性铑膦配合物催化的烯烃氢甲酰化反应由于具有环境友好和催化剂容易分离等优点而受到广泛关注. 其中水溶性催化剂体系已经用于丙烯氢甲酰化反应制备丁醛的工业化生产. 然而, 长链烯烃在含有催化剂的水相中溶解性较差, 反应速率较慢. 综述了有关加速水/有机两相体系中长链烯烃氢甲酰化反应的方法和进展, 包括使用具有表面活性的膦配体, 以及在催化体系中添加环糊精和表面活性剂等促进剂. 另外, 还讨论了有关内烯烃氢甲酰化反应和提高直链醛选择性的方法.  相似文献   

4.
烯烃氢甲酰化反应是工业上合成醛的重要方法.由于双膦配体良好的配位能力,形成的铑配合物有很好的催化活性,在内烯烃氢甲酰化反应中,可以有效地提高直链醛选择性.本文系统地综述了近年来双膦配体铑配合物催化均相内烯烃氢甲酰化反应的研究进展,讨论了双膦配体结构对催化剂活性和生成直链醛选择性的影响.  相似文献   

5.
研究了由 Rh(acac) (CO) 2 和 1 ,4-双 (二苯膦基 )苯 (简称 DPPB)组成的体系对烯烃氢甲酰化反应的催化作用 .考察了反应温度、压力、P/Rh比、催化剂浓度等对 1 -己烯氢甲酰化反应的影响 ,得到了较适宜的反应条件 .在相同条件下比较了该体系催化 1 -己烯、 1 -辛烯、 1 -十二烯的氢甲酰化反应的性能 .结果表明 ,随着底物碳链的增长 ,反应活性呈提高趋势 .实验证明 ,DPPB-铑配合物对苯乙烯的氢甲酰化反应有较高的催化活性和选择性 .  相似文献   

6.
离子液体[Bmim]BF4/水混合溶剂中的1-丁烯氢甲酰化反应研究   总被引:2,自引:0,他引:2  
以水溶性离子液体[Bmim]BF4和水作为混合溶剂、RhCl3/TPPTS为催化剂进行1-丁烯氢甲酰化反应.产物可方便地通过重力沉降分离,戊醛的正-异比达9.1:1(V:V)催化体系经5次循环,催化活性未见明显降低.  相似文献   

7.
采用三苯基膦羰基氢化铑作为催化剂,进行1-丁烯氢甲酰化合成戊醛反应,主要考察温度、铑浓度、配体浓度、丁烯浓度、合成气中H2和CO分压等因素对反应速率的影响.动力学研究表明温度、Rh浓度、丁烯浓度和H2分压的增加均可提高反应速度,CO分压和配体量的增加使反应速度降低.给出了RhH(CO)(PPh3)3催化1-丁烯氢甲酰化的反应动力学方程,并采用非线性最小二乘法对模型进行参数估值,计算值与实验值具有较好的一致性.  相似文献   

8.
1-辛烯在Co/CNTs催化剂上的氢甲酰化研究: 钌的促进作用   总被引:1,自引:0,他引:1  
采用等体积浸渍法制备了碳纳米管负载的钴及钴-钌双金属催化剂,并以1-辛烯的氢甲酰化反应为探针,研究了所制催化剂的催化性能;用TEM、XRD、TPR、TG技术对催化剂的形貌、物相结构、还原行为和热稳定性进行了研究。结果表明,金属钌能够促进金属钴在碳纳米管上的均匀担载,并有助于金属钴的还原,降低了催化剂的还原温度。1-辛烯的氢甲酰化反应结果表明,少量钌的加入,可明显提高反应的转化率和C9-醛的选择性;在双金属催化剂中,金属催化剂的粒径更小,分布更均匀,钌的加入对钴金属催化剂有促进作用。  相似文献   

9.
杨勇  彭庆蓉  袁友珠 《催化学报》2004,25(5):421-425
 制备了表面有机官能团化的MCM-41和MCM-48介孔分子筛以及SiO2等载体固载铑膦配合物催化剂,考察了所制备催化剂对液相己烯-1氢甲酰化的催化性能,并用X射线衍射、BET、红外光谱和原子吸收光谱等技术对载体和催化剂的组成和结构进行了表征. 结果表明,固载化铑膦配合物对烯烃氢甲酰化的催化性能与有机官能团的种类及载体的结构有关; 固载于含胺基和腈基有机官能团化介孔分子筛载体的铑膦配合物表现出较高的催化活性和稳定性.  相似文献   

10.
基于非离子表面活性膦配体的临界溶解温度特性 ,研究了以 Rh Cl3· 3H2 O为催化剂前体、聚氧乙烯基取代膦为配体原位合成的膦铑配合物催化剂 ,对有机单相体系中苯乙烯氢甲酰化反应的催化性能 .考察了反应温度、压力及不同聚氧乙烯基取代膦 -铑配合物催化剂对反应的影响 .以 Rh/PETPP配合物为催化剂时 ,在 T=10 0℃ ,p=6 .0 MPa (CO/H2 =1∶ 1)条件下 ,反应 3.5 h后 ,烯烃转化率和产物醛收率可分别达 96 .7%和 92 .6 %  相似文献   

11.
In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.  相似文献   

12.
KMnO4-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.  相似文献   

13.
The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.  相似文献   

14.
Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.  相似文献   

15.
The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.  相似文献   

16.
A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.  相似文献   

17.
The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp3)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp2)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp2)?H and aliphatic 1,5- and 1,6-C(sp3)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp3)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp2)?H insertion.  相似文献   

18.
19.
An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.  相似文献   

20.
Quercetin, the polyphenolic compound, which has the highest daily intake, is well known for its protective effects against aging diseases and has received a lot of attention for this reason. Both quercetin 3-O-β-d-glucuronide and quercetin 3′-O-β-d-glucuronide are human metabolites, which, together with their regioisomers, are required for biological as well as physical chemistry studies. We present here a novel synthetic route based on the sequential and selective protections of the hydroxyl functions of quercetin allowing selective glycosylation, followed by TEMPO-mediated oxidation to the glucuronide. This methodology enabled us to synthesize the five O-β-d-glucosides and four O-β-d-glucuronides of quercetin, including the major human metabolite, quercetin 3-O-β-d-glucuronide.  相似文献   

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