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双语推荐:二聚Salen

以苯酚和邻叔丁基酚为起始原料,合成了一个新型手性二聚Salen配体5,5-亚甲基-双-[(R,R)-{N-(3-叔丁基水杨醛)-N''-(3'',5''-双-叔丁基水杨醛)}-1,2-苯乙胺],并运用多种谱学手段对其进行表征.在邻叔丁基酚的羟基邻位甲酰化过程中,首次运用三乙胺代替六甲基磷酰胺(HMPA)定位,取得了很好的效果.成功合成了中间体N-(2-羟基-3,5-叔丁基苯甲醛)-(1R,2R)-1,2-苯基乙胺的新方法.
This paper reports the synthesis and characterization of a novel chiral dimeric Salen ligand 5,5-metheylene di-[(R,R)-{N-(3-tert-butyl salicylidine)-N''-(3'',5''-di-tert-butyl salicylidene)}-1,2-diphenyleth-ylenediamine]) which using phenol and 2-tert-butylphenol as starting materials. In the procedure of the ortho-formylation of 2-tert-butylphenol, we first employ a method which substituter triethylamine for hexamethylphosphoramide in a highly ortho regioselective formation with a good yield. Furthermore, a new method is established to synthesize N-(2-hydroxy-3,5-di-tert-butylbenzaldehyde)-(1R,2R)-1,2-diphenyl-ethylenediamine.

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手性salen化合物是近几年发展起来的用于不对称催化反应的高效催化剂,自合成以来一直受到人们的关注。目前均相手性salen研究已相对成熟,但距离实现进一步的工业化还有很大差距。手性 salen化合物的固载化可望实现手性salen的工业化应用,已成为本领域的研究热点。从无机载体、有机载体和近几年发展起来的有机-无机复合载体3个方面综述了固载手性salen化合物的不同方法及研究进展,并做了分析比较。
Since chiral salen compounds were synthesized,they developed rapidly.Chiral salen compounds were widely used as catalysis for asymmetric reactions,but it was difficult to achieve industrial production.The im-mobilization of chiral salen compounds was found to be more effective to be applied to industrial production,and it attracted more and more attention.This review summarized different strategies and development to immobi-lize chiral salen compounds,going from organic supports,inorganic supports and new types of organic-inorganic hybrid material supports.The analysis and comparison of supported chiral salen compounds were also presented.

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以3,5-溴-2-羟基苯甲醛及1,4-胺氧丁烷、1,3-胺氧丙烷、1,2-胺氧乙烷为原料,在无水乙醇溶剂中合成了3种新型的Salen双肟化合物。以Salen双肟化合物及乙酸钴为原料,合成了一种过渡金属Co配合物。采用IR、元素分析、1H NMR及TG-DTA等手段对化合物作了表征。结果表明,所合成的新型Salen双肟化合物与钴(Ⅱ)离子有较强的配位能力。
Three kinds of novel Salen-type bisoxime compounds were synthesized from 3,5-dibromo-2-hydroxybenzaldehyde and home-made 1,4-bis( aminooxy)butane,1,3-bis( aminooxy)propane,1,2-bis (aminooxy)ethane in anhydrous ethanol solvent. A kind of transition metal cobalt(Ⅱ)complex was also prepared from the Salen-type bisoxime compound and cobalt(Ⅱ)acetate. The ligands and complexes were characterized by IR,elemental analysis,1 H NMR and TG-DTA. The results indicated that the novel Salen-type bisoxime compounds had good capability of coordination with cobalt(Ⅱ)ions.

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采用温和的化学表面改性和自组装方法成功制备了埃洛石纳米管负载salen钼(HNTs-SL-Mo)催化剂,运用透射电镜、X射线衍射、红外光谱、诱导偶合等离子体谱和X射线光电子能谱表征了催化剂的形态、大小和分散性等性质。结果证明了salen结构的存在和埃洛石配位钼催化剂的成功制备。制备的催化剂在各种烯烃的环氧化反应中均有很好的活性,且活性高于均相催化剂。对比实验表明,在固定MoO(O2)2(DMF)2时, salen结构发挥了重要作用,不能用N原子作为单一配体来代替。本文还推测了钼和salen配体可能的连接方式和该催化剂催化烯烃环氧化反应的机理。该催化剂在重复使用8次后其活性未见明显下降,表现出优异的重复使用性能。由于埃洛石是一种廉价易得的材料,因此它可为设计效果独特的催化剂提供一个选择。
Halloysite‐nanotube‐supported Mo salen (HNTs‐Mo‐SL) catalysts were successfully prepared using a facile chemical surface modification and self‐assembly method. The morphologies, sizes, structure, and dispersion of the as‐prepared catalysts were investigated by transmission electron microscopy, X‐ray diffraction, and Fourier‐transform infrared, inductively coupled plasma, and X‐ray photoelec‐tron spectroscopy, which confirmed the existence of the Mo salen structure and successful synthesis of the HNTs‐Mo‐SL catalyst. The immobilized catalyst was found to be highly reactive in the epoxi‐dation of a wide range of alkenes, including linear, cyclic, and aromatic alkenes. The immobilized catalyst exhibited a higher catalytic activity for alkene epoxidation than homogeneous Mo. In con‐trast experiments, it was determined that the salen structure played an important role in immobi‐lizing MoO(O2)2(DMF)2 and improving the conversion and efficiency of alkene epoxidation,

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报道了一种用于端炔水合反应的水溶性salen-Co(Ⅲ)配合物催化剂,在使用硫酸作为共催化剂的条件下能高效得到产物甲基酮。该催化剂用量少,反应结束后可利用简单的萃取实现产物与催化剂分离,简化了后处理过程。此外,催化剂还可回收重复使用,但催化剂活性会略有下降。
A water-soluble salen-Co(III) complex was studied as catalyst for hydration of terminal alkynes to methyl ketones in the presence of H2SO4 as a co-catalyst. The products were obtained with excellent yields using relatively low catalyst loadings and a simple protocol. Notably, the products were easily separated from the catalyst after reaction by extraction, and the catalyst could be recovered and reused with only a slight loss of activity.

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参照文献方法,合成了N,N’-双(2-羟基-1-萘甲醛)缩邻苯胺、乙胺和1,3-丙胺的3种Salen配体及其与Mn(Ⅲ)、Co(Ⅲ)形成的6种配合物,探究了它们对碱基的荧光猝灭效应。结果表明,对于同一碱基来说,Mn(Ⅲ)配合物比Co(Ⅲ)更易使碱基发生荧光猝灭;同种配合物与不同的碱基作用时,其猝灭强度大小顺序为胞嘧啶>腺嘌呤>鸟嘌呤,呈现出配合物对碱基作用的选择性;配合物的结构对荧光的猝灭也有影响。
Three kinds of Salen-Mn(Ⅲ)complexes [Mn(Ⅲ)Lx]CH3 COO and three kinds of Salen-Co (Ⅲ) complexes [Co (Ⅲ)Lx ]CH3 COO (L1 =N,N''-bis (2 -Hydroxy -1 -naphthaldehyde ) o -phenylenediamine,L2 =N,N''-bis (2-Hydroxy-1 -naphthaldehyde)ethylenediamine,L3 =N,N''-bis (2-Hydroxy-1 -naphthaldehyde ) 1 ,3 -diaminopropane ) were synthesized.The results of their fluorescence quenching effect with DNA base show that Mn (Ⅲ)complexes is easier make fluorescence quenching than Co (Ⅲ)complexes with the same base.Quenching intensity is Cytosine>Adenine>Guanine while with the same complexes.The fluorescence quenching selectivity of complexes to bases was presented in the experiment,and the fluorescence quenching could be influenced by the structure of complexes as well.

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有机合物-无机杂化载体-(苯乙烯-苯乙烯基膦酸)-磷酸氢锆-轴向固载手性Salen Mn髥催化剂,将其应用于非官能烯烃的多相不对称环氧化反应。结果表明:在没有昂贵轴向添加剂参与下,产率与对映选择性均急剧增加。以间氯过氧苯甲酸(m-CPBA)为氧化剂催化氧化α-methylstyrene,转化率从25.0%上升到98.8%;对映选择性从5.3%提高到67.3%。催化剂在循环使用5次以后,催化活性无明显改变。
The chiral Mn(Ⅲ) salen catalyst axially immobilized onto an organic-inorganic hybrid support-phenoxy modified zirconium poly (styrene-phenylvinylphosphonate)-phosphate (ZPS-PVPA) can afford dramatically increased conversion and ee (Enantiomeric excess) value in the absence of expensive O-coordinating axial bases for the asymmetric epoxidation.Especially for the epoxidation of α-methylstyrene in the m-chloroperbenzoic acid (m-CPBA) oxidant system (cony.%:from 25.0% to 98.8%; ee%:from 5.3% to 67.3%).Moreover,the assynthesized catalyst is relatively stable and can be recycled at least five times without significant loss of activity and enantioselectivity.
阐述了不饱和羧酸类(甲基丙烯酸、丙烯酸和乙烯基苯甲酸)、芳香杂环类(吡啶类、咪唑类和喹啉类)、水杨醛类希夫碱以及Salen配体等功能单体的性能、优点、用途等方面的研究进展,以及基于上述单体制备的离子印迹合物吸附特性和应用性能等,展望了离子印迹合物功能单体未来的发展方向:一是功能单体种类需要进一步丰富;是其所具有的性能和功能等还有待于完善。其中,季铵盐化5-氯甲基水杨醛类希夫碱功能单体具有强亲水性能和多官能团特性,对其进行性能研究将会是探索此类功能单体在应用方面的热点内容之一。
This paper is aimed to describe the research progress in several functional monomers in terms of their performance,advantages,and applications. The elaborated functional monomer contains the categories of organic acids (methacrylic acid,acrylic acid and vinyl benzoic acid),aromatic heterocyclic (pyridine , imidazole , amides and quinolines) , the Schiff base and Salen ligand. Furthermore,the adsorption characteristics and application performances of ion-imprinted polymer produced with the above-described monomers are illustrated. Combined with our recent works in salicylaldehyde Schiff bases functional monomer containing quaternary ammonium ion , the development trend of functional monomer is also prospected. Not only species of functional monomers requires further enriched,but also their function and performance have to be improved. Among those, the functional monomer of 5-chloro methyl salicylic aldehyde Schiff’s base modified with quaternary ammonium salt possesses shows

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使用不同空间位阻的苯氧链接手臂修饰的(苯乙烯基-苯乙烯膦酸)-磷酸氢锆轴向固载手性MnIII(Salen)催化剂(Cat1–Cat3),随后在间氯过氧苯甲酸(m-CPBA)为氧化剂的体系中考察了固载催化剂的催化性能.同时,在相同氧化体系下测试了一系列均相催化剂类似物(Cat4–Cat6).结果表明,在非均相条件下,可调变苯氧链接手臂的邻位取代基对催化剂活性起着重要作用,环氧化产物的对映选择性随着取代基位阻的增加而增大,但产物转化率有一定程度下降.此外,非均相催化剂即使在没有轴向助剂的参与下(通常需要添加,为了增大催化活性)仍然表现出非常高的催化活性,尤其对α-甲基苯乙烯反应,其对映选择性从6.8%增加到76.8%,转化率从19.8%上升到90.7%.制备的非均相催化剂11次的循环使用实验表明,在前5次使用后催化剂活性与对映选择性没有明显变化.
We have developed a series of chiral MnI I(Salen) (chiral Jacobsen’s catalyst) catalysts that were axially supported onto zirconium poly(styrene-phenylvinylphosphonate)-phosphate through tunable phenoxyl linkers of varying steric hindrance, and evaluated their perfor-mance as catalysts (Cat1-Cat3) for the epoxidation of unfunctionalized olefins using m-chloroperbenzoic acid as an oxidant. The corresponding non-supported analogues (Cat4-Cat6) were also prepared and tested under similar conditions. The results demon-strated that the incorporation of substituents at the ortho-positions of the tunable phenox-yl linkers had a critical effect on the catalytic activity. Furthermore, the enantioselectivity increased as the steric hindrance imposed by the linker increased, although this also led to a decrease in the conversions under the same reaction conditions, especially for heteroge-neous epoxidation. The heterogeneous system also displayed high ee values and conver-sions in the absence of
介绍了在不同手性配体和路易斯酸的催化下内消旋环氧化合物的不对称开环反应与外消旋末端环氧化合物的水解动力学拆分与开环反应;并指出了环氧化合物的这两种反应在不对称合成与手性药物领域的应用价值以及在工业上广阔的应用前景.
Progresses in asymmetric ring opening(ARO) of meso epoxides with different chiral ligand, and the hydrolytic kinetic resolution(HKR) of racemic terminal epoxides catalyzed by chiral Salen metal complex were introduced. These two reactions are very useful not only for asymmetric synthesis but also for chiral chemicals and chiral drugs both in laboratory and large-scale production.

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