Cooperative Activation in the Hydrolytic Kinetic Resolution of Epoxides by a Bis‐Cobalt(III)salen‐Calix[4]arene Hybrid

A chiral, bimetallic cobalt(III)salen‐calix[4]arene hybrid structure was prepared and tested in the hydrolytic kinetic resolution (HKR) of racemic epoxides. Kinetic studies have revealed that the two catalytic units on the upper rim of the calixarene scaffold are able to activate the reactants in a cooperative and primarily intramolecular mode. High enantioselective behaviour was observed and besides, a higher stability was found for the bimetallic catalyst as compared to a monometallic reference complex.     

新型水溶有色主体分子对磺酸基苯偶氮杯[n]芳烃衍生物的合成及特性

以对氨基苯磺酸为原料，经重氮化－偶联反应合成了新型水溶性有色对磺酸基苯偶氮基杯[n]芳烃，并从结构上阐述了紫外可见吸收光谱特性及其在不同酸度下的变色原理，产物的结构用IR，1HNMR和元素分析进行了表征和证实。结果表明该类化合物具有良好的水溶性和热稳定性，并可作为良好的酸碱指示剂和新型主体化合物。     

四氮杂杯[2]芳烃[2]三嗪叠氮化衍生物的合成及其与RDX的配合研究

文合成了氮原子桥连杯[2]芳烃[2]三嗪化合物。室温下,以碳酸钾为缚酸剂,利用三聚氯氰和间苯二胺的亲核取代反应合成主体,并将其叠氮化,反应温度为40％。产物通过元素分析,红外光谱和氢谱对其结构进行了表征,并采用XRD对氮杂杯[4]芳烃及其衍生物与黑索今的配合性能进行了表征分析,结果表明主客体之间发生了相互作用。     

杯芳烃及其衍生物的应用研究进展

杯芳烃作为继冠醚和环糊精之后的第三代超分子主体化合物,其应用领域日益广泛。本文综述了杯芳烃及其衍生物在医药、分子离子识别、模拟酶、相转移催化剂等方面的研究进展。     

杯芳烃衍生物修饰电极的电化学性能研究

采用5,11,17,23-四叔丁基-25,27-二羟基-26,28-二(乙氧羰基甲氧基)杯[4]芳烃(酯-杯[4]芳烃)-PVC膜修饰玻碳电极,研究了其对Pb2+的电化学行为。研究表明:该修饰电极在碱性条件中为不可氧化过程,在酸性条件下具有良好的电化学活性,对Pb2+具有很高的响应,在3.65×10-6～4.83×10-3mol.L-1范围内线性扫描溶出伏安峰电流与Pb2+浓度具有良好的线性关系,检测限为1.28×10-6mol.L-1。     

Modification of poly acrylic acid using calix[4]arene derivative for the adsorption of toxic heavy metals

Poly acrylic acid (PAA) was grafted with p‐t‐butyl calix[4]arene diamine (distal cone) (2) to adsorb toxic heavy metal and alkali metal cations. The grafting method includes the amidation reaction of PAA with calixarene diamine derivative 2 which was carried out in N,N‐dimethylformamide (DMF) and N–methyl‐2‐pyrrolidone (NMP) as solvents. The modified PAAs (PAA‐C1 and PAA‐C2) were characterized by FTIR, ¹H‐NMR, thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). PAA‐C1 and PAA‐C2 were used to evaluate the sorption properties of some toxic heavy metal cations (Co²⁺, Cu²⁺, Cd²⁺, Hg²⁺), alkali metal cations (Na⁺, K⁺, Cs⁺), and Ag⁺. Results showed that the modified PAAs were good sorbents for heavy metal and alkali metal cations. The main goal of this project is to design hydrophobically modified PAA that is suitable for ion selective membranes and chemical sensor devices for adsorption of toxic heavy metals. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

含单种杂原子的桥联杯芳烃的合成研究进展

综述了含单种杂原子的桥联杯芳烃的合成研究进展。目前合成的大多数的杯芳烃都是碳桥联的,除了碳,如硼、硅、锗、锡、氮、磷、氧、硫、硒原子都可以作为桥联原子建构杯芳烃,其中硅、氮、氧、硫桥杯芳烃报道文献较多,介绍了含单种杂原子的桥联杯芳烃的合成条件及其应用。     

A useful approach toward the synthesis and metal extractions with polymer appended thioalkyl calix[4]arenes

This article describes a convenient method for the synthesis of two new polymeric resins via nucleophilic substitution reactions involving 5,11,17,23-tetrakis[(propylthio)methyl]-25,26,27,28-tetrahydroxycalix[4]arene 4, and 5,11,17,23-tetrakis[(methylthio)methyl]-25,26,27,28-tetrahydroxycalix[4]arene 6, as precursors with Merrifield's resin. The extraction studies were made using both liquid-liquid extraction and solid-liquid batchwise sorption procedures. The calix[4]arene based polymeric resins have high extraction ability toward metal cations and Na₂Cr₂O₇ as compared to their monomeric precursors.     

Study on an Aldol Reaction Catalyzed by Ti(IV)/Calix[n]arene Complexes

Ti(IV)/calixarene complexes, formed in situ or previously prepared with standard procedures, can be conveniently used as efficient catalysts in the aldol reaction of Chan's silyloxydiene with a range of aldehydes bearing either activating or deactivating groups, including aromatic, heteroaromatic and α,β‐unsaturated ones. The structure of both calixarene ligand and aldehyde, as well as the reaction conditions, strongly influence the efficiency of the reaction. NMR experiments in conjunction with the experimental results suggest that the structure of the catalytic species in the Ti(IV)/calixarene system prepared in situ is strongly dependent on the concentration and temperature adopted.