由Mannich反应合成新型Salen配体

以乙二胺或乙二胺衍生物为碱,与甲醛、对甲酚通过Mannich反应生成了四种N,N′-双(水杨醛)乙二胺(salen)配体,其中3个为新化合物.其结构经1H NMR,IR,MS和元素分析表征.     

Synthesis and Crystal Structure of a New Salen Complex

Salen Schiff base complexes are some of the most important stereochemical models in transition metal coordina tion chemistry, with their ease of preparation and structural variation. [1] Salen complexes are extensively used as organic reaction catalysts, it was reported to be used in asymmetric cyclopropanation, epoxidation, aziridination, hydrolysis, alkylation, Diels-Alder reaction, reduction, oxidation etc. Here we report the synthesis and structure of a new salen nickel complex 4.     

九种Salen型多齿新配体的合成

利用乙二胺及其衍生物的Mannich反应在无催化剂的条件下合成了9种Salen型新的配体,化合物1和2在无溶剂条件下合成,化合物3a～3g在Salen配体中引入呋喃杂环,对其与金属的配位提供了多种可能性.所得化合物结构经元素分析,IR,MS,1H NMR等确认,同时用X射线单晶衍射测定了化合物1和3b的晶体结构.     

几种新型聚合物配体的合成及其固载化铑催化剂的醛化性能研究

本文使用交联聚苯乙烯为载体合成了几种新型的聚合物配体和固载化铑催化剂,考察了它们对二异丁烯和戊烯-1氢甲酰化反应的催化性能,探讨了催化剂的铑脱落现象。     

新型手性磷化合物的合成及其作为配体催化剂在某些不对称合成反应中的应用

从L-氨基酸、D-樟脑、(-)-假麻黄碱、(-)-α-苯乙胺、(S)-(-)-联萘二酚等旋光源出发,合成了26个三配位及四配位手性磷化合物.作为配体催化剂,试验了它们在潜手性酮及亚胺的不对称硼烷还原反应、醛与二乙基锌的不对称烷基化反应以及醛的不对称硅腈化反应中的催化活性.发现其中有些催化剂有很好的立体选择性.     

Synthesis of Resins with Chiral Salen Complexes

The enormous growth in the use of polymer resin supports in solid phase combinatorial synthesis, and related methodologies, has re-stimulated interest in the area of polymer-supported transition metal complex catalyst .The recently developed chiral salen-based for the enantioselective ring opening of meso epoxides and kinetic resolution of terminal epoxides are appealing candidates for immobilization on solid support. The catalysts are reading prepare from inexpensive components, and are amenable to modification for attachment to a solid support.     

酚氧基修饰的AlPS-PVPA固载手性Salen Mn(III)催化剂的合成及催化烯烃不对称环氧化研究

以有机共聚物-无机杂化材料聚（苯乙烯-苯乙烯基膦酸）-磷酸铝（AlPS-PVPA）为载体,酚氧基为连接基团,轴向配位手性salen Mn（Ⅲ）制备了新型固载手性salen Mn（Ⅲ）催化剂,并运用FT-IR,UV-vis,XPS,SEM,TG,元素分析等手段对其进行了表征.以m-CPBA为氧化剂,茚和α-甲基苯乙烯为底物,考察了催化剂对非功能化烯烃不对称环氧化反应的催化性能.结果表明,在相同的条件下,固载催化剂3a~3d在不加助催化剂NMO时显示出了优良的催化活性,其转化率和ee值均比添加了轴向配体NMO时有很大的提高（ee%,99.2 vs.45.9; conv%,98.6 vs.64.6）,这种现象与大多数文献报道相反.此外,催化剂容易分离,且回收使用9次仍能保持较好的催化活性.     

新型手性双核Salen配合物的合成与表征

采用新型Salen中间体I(由3，5-二叔丁基水杨醛、2，6-二酰基-4-甲基苯酚、(R，R)环己二胺为原料合成)合成了4个新型手性双核Salen配合物[Zn₂L·3H₂O (2)、Cu₂L·H₂O (3)、CO₂L (4)、Ni₂L (5)]，(L是由中间体I和邻苯二胺合成的手性二聚Salen配体)。用¹H NMR、FTIR、UV-Vis、CD光谱对配体和配合物进行了表征，详细讨论了红外光谱、电子吸收光谱、圆二色光谱的性质。采用激子耦合理论解释了此类手性化合物圆二色谱的Cotton效应和Cotton裂分，Cotton裂分的方向依赖于环己二胺的构象，(R，R)环己二胺决定了Salen化合物的手征性为负。     

手性不对称Salen Ni配合物的模板法合成及表征

本文采用过渡金属镍(Ni)作为金属模板合成了2个未见报道的手性不对称Salen Ni配合物，该法具有反应步骤少、纯化处理简单、产率高的显著优点。用¹H NMR、FTIR、UV-Vis、CD光谱及元素分析对配合物进行了详细的表征，证明该模板合成法的可靠性。此外，对该法合成的手性不对称Salen Ni配合物的红外光谱、电子吸收光谱、圆二色光谱的性质做了进一步研究。     

新型Co(salen)化合物的合成，表征及其硫醚不对称氧化反应(英)

合成并表征了新的Co(salen)化合物（2a～2c和3a～3c）。手性Co^Ⅱ(salen)化合物2a～2c在硫醚的不对称氧化反应中显示了中等的反应活性，但只获得了较低对映选择性（8%～21% ee），而手性Co^Ⅲ(salen)化合物3a～3c在该反应中没有反应活性。通过研究整个配体的构象影响对化合物的低对映选择性进行了讨论。     

Heterogenization of Salen Metal Molecular Catalysts in Covalent Organic Frameworks for Photocatalytic Hydrogen Evolution

Integrating a molecular catalyst with a light harvester into a photocatalyst is an effective strategy for solar light conversion. However, it is challenging to establish a crystallized framework with well-organized connections that favour charge separation and transfer. Herein, we report the heterogenization of a Salen metal complex molecular catalyst into a rigid covalent organic framework (COF) through covalent linkage with the light-harvesting unit of pyrene for photocatalytic hydrogen evolution. The chemically conjugated bonds between the two units contribute to fast photogenerated electron transfer and thereby promote the proton reduction reaction. The Salen cobalt-based COF showed the best hydrogen evolution activity (1378 μmol g⁻¹ h⁻¹), which is superior to the previously reported nonnoble metal based COF photocatalysts. This work provides a strategy to construct atom-efficient photocatalysts by the heterogenization of molecular catalysts into covalent organic frameworks.     

微波固相法制备Mn(Salen)/Al-HMS催化剂

微波固相法制备Mn(Salen)/Al-HMS催化剂;Mn(Salen)络合物;Al-HMS;微波辐射;苯乙烯;环氧化反应     

手性双核Salen配合物的合成与谱学性质

Six novel chiral dinuclear Salen complexes [Cu₂L₁·H₂O (3a), Cu₂L₂(3b), Ni₂L₁·2H₂O (4a), Ni₂L₂(4b), Mn₂Cl₂L₁·H₂O (5a), Mn₂Cl₂L₂ (5b)] have been synthesized(L₁ and L₂ are chiral dimeric Salen ligands with different chain length which were synthesized from (R,R)-diaminocyclohexane, salicylaldehyde, 4,4′-(1,10-decaneoxy)salicylaldehyde, 4,4′-(1,6-hexyloxy)salicylaldehyde). These compounds were charactered by elemental analysis, ¹H NMR, FT-IR, UV-Vis and CD spectra. The FT-IR, UV-Vis and CD spectra were discussed and compared with those of monomeric ligand and complex in detail. It was found that the spectra properties of compounds of different chain length were almost alike, and the properties of dimeric and monomeric compound were similar too. Furthermore Cotton effect and Cotton split of CD spectra of these chiral compounds were explained by the exciton interaction theory. It seemed that the direction of Cotton split depend on the configuration of diaminohexane. (R,R)-diaminohexane determine the chirality of Salen compounds as negative, and the positive and negative component of Cotton split lie at higher and lower energy respectively.     

Synthesis of Some New Polyfunctionalized Pyridines

5‐Methyl‐2,4‐dihydro‐3H‐pyrazol‐3‐one and/or 5‐methyl‐2‐phenyl‐2,4‐dihydro‐3H‐pyrazol‐3‐one was reacted with arylidenemalononitrile in the presence of sodium alkoxide to give 2‐amino‐6‐alkoxy‐4‐arylpyridine‐3,5‐dicarbonitrile 4a–e instead of the reported pyrazolo[3,4‐b]pyridine‐5‐carbonitriles. The same products 4a–e were prepared via reaction of arylidenemalononitrile with sodium alkoxide in an appropriative alcohol. However, the new synthetic route for preparation of their positional isomer 4‐amino‐6‐alkoxy‐2‐arylpyridine‐3,5‐dicarbonitrile 7a–j has been achieved via reaction of 2‐aminoprop‐1‐ene‐1,1,3‐tricarbonitrile with different aromatic aldehydes under the same conditions.     

Synthesis of Some New Polysubstituted Cyclopropanes

The synthesis of new chloro containing substituted cyclopropanes is described.     

某些新的氟代有机硅化合物的合成

本文用含硅氢键化合物与含双键的氟化合物的加成反应,制备了一系列未见报导的含氟有机硅化合物。在用氯丙烯与2,2,3,3-四氟丙醇制2,2,3,3-四氟丙基烯丙醚时,对方法进行了改进,提高了产率。本文还报道了含氟有机硅聚合物方面的工作。     

一种新型Al(Salen)非对称手性催化剂的合成

由L－苯丙氨酸出发，6步合成了光学活性的3－苯基－（1，25）－丙二胺，然后与水杨醛衍生物反应制得非C2对称的手性Salen，与溴化二乙基铝反应得到非对称手性催化剂。     

Solvent-free Synthesis of Flavanone over New Hybrid Mesoporous Base Catalysts

Benzyl and anthracenemethyl groups were respectively bonded to the N atoms of 3-aminopropyl functionalized mesoporous SBA-15(APS-SBA-15) to obtain two new base catalysts over which the condensation reaction of benzaldehyde and 2'-hydroxyacetophenone was studied.Good catalytic activities and high selectivities for flavanones were obtained in solvent-free reactions,which is attributed to the effect of benzyl and anthracenemetyl groups on the base sites of catalysts and the steric hindrance of futher reaction ...