Synthesis and Chiral Recognition of a New Type of Chiral Calix[4]-arene Derivatives

Two new chiral calix[4] arenes bearing chiral pendants,which were from by-product of the antibiotic industry,were synthesized and characterized by ^1H NMR.MS-FAB and elemental analysis,Studies of ^1H NMR of the two calix[4] arene derivatives indicate that they exist in cone conformation in solution.Results of chiral recognition of the two chiral ligands 2a and 2b towards the tartaric acid derivative 3 show that ligand 2a exhibited good chiral recognition abilities compared to ligand 2b.     

Spectroscopic Study of Molecular Recognition of Ions by Chromogenic Calix[4]arene Derivatives

The complexation properties of three new chromogenic calix[4]arenes ( 1a–c) with aliphatic amines and alkali/alkali earth metal ions have been studied by UV/Vis spectroscopy. 1c shows the greatest complex forming ability and it is selective for Li⁺, Ca²⁺ and certain amines in polar solvents.     

Synthesis of Calix[4]arene Derivatives with NLO Properties

The new chromophore compounds with NLO properties were prepared by Knoevenagel condensation from forrnyl or diformyl calix[4/arene and isophorone derivatives in the presence of piperidine and acetic acid, respectively. In these chromophore calix[4]arenes, the ring locked trienes were employed as the conjugation bridge and electron acceptor in D-π-A units. The NMR spectra demonstrated that they existed in a cone conformation and consequently non-conjugated D-π-A units could be oriented at nearly the same direction.     

基于杯[4]芳烃的手性识别*

手性杯芳烃是一类重要的主体化合物,在手性识别、对映体分离和不对称催化等方面有着广泛的用途。[4]芳烃引其稳定的构象和易于修饰的特点,成为研究最为广泛的杯芳烃分子,其中大量的文献报道了能够用于对映体识别和检测的手性[4]芳烃。在手性识别的研究中,荧光、紫外和核磁是3中最常见的研究方法,本文根据这3种方法进行分类,综述了近年来以杯[4]芳烃为分子骨架的手性受体的合成及其在手性识别中的应用。最后对手性[4]芳烃的发展前景作了展望。     

Enantioselective Recognition of Calix[4]arene Derivative Bearing Bicyclic Guanidinium for D/L Amino Acid Zwitterions

The p‐tetra‐tert‐butyl calix[4] arene derivatives (3 and 4) with (5,5) chiral bicyclic guanidinium, as the receptors of amino acid zwitterions, have been synthesized via a O‐alkylation reaction of p‐tetra‐tert‐butyl calix [4] arene with cbJoromethyl chiral bicyclic guanidinium 2 in the presence of anhydrous K₂CO₃ in acetonitrile. The results obtained from liquid‐liquid competitive extraction experiments indicate that the two receptors may selectively recognize L‐aromatic amino acids, and that the enantioselective recognizability of the receptor 4 with two chiral bicyclic guanidinium units reachs up to about 90% for L‐Phe.     

Molecular Recognition Properties of Biphen[4]arene

Biphen[n]arenes (n=3, 4) are a new family of macrocyclic hosts. Here, we describe the molecular recognition behavior of hydroxylated biphen[4]arene (OHBP4) for the first time. A series of cationic guests with different sizes and shapes, including quaternary ammonium salts ( 1? PF₆ and 2? PF₆), pyridinium‐based guests ( 3? 2 PF₆– 6? 2 PF₆), and cobaltocenium hexafluorophosphate ( 7? PF₆), were chosen as model guest molecules. OHBP4 exhibits good selectivity towards the 2,7‐dibutyldiazapyrenium bis(hexafluorophosphate) ( 4? 2 PF₆) axle to form a [2]pseudorotaxane‐type complex. In contrast, hydroxylated biphen[3]arene (OHBP3) cannot bind with this big guest. In addition, OHBP4 strongly interacts with adamantane derivative 2? PF₆ and cobaltocenium 7? PF₆, which have tridimensional shape and relatively large size. The association constant of the 7 ⁺?OHBP4 complex in 1:1 (v/v) [D₆]acetone/CD₂Cl₂ solution is up to 3100±300 m ^?1.     

Molecularly Imprinted Polymer with Calix[4]arene Derivative for the Recognition of Acetanilide

Two molecularly imprinted polymers binding to analgesic acetanilide were prepared using either dual functional monomers of calix[4]arene derivative and acrylamide or single monomer acrylamide, respectively. The polymers were ground, sieved and investigated by equilibrium binding experiment to evaluate their recognition properties for the template and other substrates. Scatchard analysis showed that homogeneous recognition sites were formed in the imprinted polymer matrix. Our results demonstrated that the polymer using two functional monomers exhibited better selectivity for the template. This study may open new frontiers for the development and application of imprinted polymers, such as drug separation and purification.     

对叔丁基杯[n]芳烃酰胺衍生物的合成及其对某些金属离子的萃取性能

对叔丁基杯[n]芳烃酰胺衍生物的合成及其对某些金属离子的萃取性能;杯芳烃; 酰胺衍生物; 金属离子; 萃取; 离子识别     

四对-乙酰胺苯磺酰氧基杯[4]芳烃的合成

以对叔丁基苯酚为起始原料,通过缩合、取代反应合成了25,26,27,28-四对-乙酰胺苯磺酰氧基对叔丁基杯[4]芳烃,其结构经FT—IR,^1H NMR和FAB-MS表征。     

Synthesis of Coumarin-functionalized Calix[4]arene and Selective Recognition for L-Tryptophan

We report a novel calixarene derivative using 4-bromomethyl-7-methoxycoumarin as the pre-organized unit and apply it to investigate selectively discriminate L-tryptophan from other amino acids in DMF-acetonitrile. 5, 11, 17, 23-Tetra-tert-butyl-25,27-bis-…     

下缘芳香取代结构对杯[4]芳烃Langmuir膜的影响

The Langmuir monolayer properties of lower rim aromatically substituted calix[4]arenes, 5,11,17,23-tetra-tert-butyl-25,27-bis（2-naphth-1＇-ylacetylaminoethoxy）-26,28-dihydroxylcalix[4]arene （BNAEC）, 5,11,17,23-tetra-tert- butyl-25,27-bis（2-benzoylamino ethoxy）-26,28-dihydroxylcalix[4]arene （BBAEC） and 5,11,17,23-tetra-tert-butyl- 25,27-bis（2-cinnamoylaminoethoxy）-26,28-dihydroxylcalix[4]arene （BCAEC）, have been studied. Film balance measurements and Brewster angle microscopy （BAM） observation demonstrate that all the compounds can form Langmuir monolayers with different molecular limiting areas. BNAEC or BBAEC monolayer is able to form condensed domains during compression, while BCAEC monolayer can never form condensed domain. BNAEC monolayer is more readily to form condensed domain than BBAEC monolayer. Moreover, BNAEC monolayer can form the total condensed phase during compression even when T=28℃, while BBAEC monolayer can not when T 〉 10 ℃. The results imply that different lower rim aromatic substitutions affect essentially the intermolecular interaction and molecular packing in the monolayer at air/water interface.     

Recognition in water of bioactive substrates by a sulphonato p-tert-butylcalix[5]arene

The molecular recognition in water of neurotransmitter monoamine and trace amine hydrochlorides by p-tert-butylcalix[5]-arene 1 – bearing 4-sulphonatobutoxy groups at the lower rim – has been investigated. According to ¹H NMR measurements, the hydrophobic cavity of receptor 1 best binds tyramine hydrochloride, K_a = 5370 ± 870 M^? 1.     

Chlorination of Calix[4]arene Derivatives

New convenient method for synthesis of p-chlorinated calix[4]arenes is reported. The sulfuryl chloride was used for chlorination of unsubstituted at the lower rim calix[4]arenes. The products of this reaction were very suitable for further O-alkylation.     

Molecular recognition of amphiphilic p-sulfonatocalix[4]arene with organic ammoniums

The binding abilities and thermodynamic origin for the intermolecular complexation of two water-soluble calixarenes, p-sulfonatocalix[4]arene (SC4A) and 5,11,17,23-tetrasulfonato-25,26,27,28-tetrakis(n-butyl)-calix[4]arene (SC4A-Bu), with six organic cations: 1,4-diazabicyclo[2,2,2]octane (G1), 3,5,6,8,-tetrahydropyrazino[1,2,3,4-Imn][1,10]phenanthroline (G2), diquat (G3), paraquat (G4), 1-methylpyridin-1-ium (G5) and 1,3-dimethylimidazolium (G6), have been determined by means of isothermal titration calorimetry in aqueous solutions at pH 7.0, 298.15 K, and their binding modes have been investigated by NMR spectroscopy. The obtained results indicate that the binding modes of SC4A-Bu and SC4A change a little but their binding affinities show great difference, resulting from the distinguishable binding thermodynamics. The binding selectivity of G1 is up to 688 times for the SC4A/SC4A-Bu hosts, and SC4A-Bu prefers to include planer molecules of large π system with low electron density. The aggregation behaviours of SC4A-Bu before and after complexation with G3 were then investigated, showing that G3 is able to induce the aggregation of SC4A-Bu.     

Syntheses of Chiral Calix [4] arene Derivatives Bearing Amino Acid Residue

The syntheses of chirai calix[4]arene derivatives bearing amino acid residue at the lower rim or upper rim by three different methods were reported.     

一种新型含喹啉环杯[4]芳烃衍生物的合成

以对叔丁基苯酚为起始原料,把酯基和具有荧光性质的喹啉环引入杯芳烃大环分子中,通过缩合,两步取代反应,获得了具有荧光性质的新型含喹啉环杯[4]芳烃衍生物。其结构经1H NMR,IR,MS和元素分析表征。     

硒功能化杯[4]芳烃对金属离子的识别及在PVC基质支撑液膜的传输作用

提出以PVC为基质的支撑液膜传输体系，研究了以新研制的硒功能化杯[4]芳烃 为活性载体，邻苯二甲酸二辛酯（DOP）为膜溶剂的PVC基质支撑液膜对金属离子的 传输性能。采用双层夹心膜电位法测定了活动载体-金属离子在膜中的配合物生成 常数，对离子在膜中的传输速率、选择性系数以及生成常数之间的相关性作了研究 。使用该体系发现，在8种金属离子中汞具有最快的传输速率；进一步讨论了硒功 能化杯[4]芳烃对金属离子的识别作用和支撑液膜传输机理。     

杂金属杯[4]配位聚合物的合成与表征

合成了4个杂金属杯[4]配位聚合物{[Cd（L）（tpa）]·3H₂O}_n（1）,{[Zn₂（L）₂（tpa）₂]·3H₂O}_n（2）,{[Co（L）（oba）]·2DMA·0.5H₂O}_n（3）和{[Zn（L）（oba）]·DMA}_n（4）（L=2-（1H-咪唑基-甲基）-6-（3-（1H-咪唑基-甲基）-5-叔丁基-2-羟基）苄基-4-叔丁基苯酚,H₂tpa=对苯二甲酸,H₂oba=4,4''-二苯醚二甲酸）,并通过元素分析、热重、红外光谱、固态紫外、单晶X射线衍射和粉末X射线衍射对其进行了表征。单晶结构分析表明晶体1是单斜晶系,P2₁/n空间群,而晶体2,3和4均为三斜晶系,P1空间群。化合物1,2,3和4是由0维[M（N₄O₂C₂₉H₃₆）]（M=Zn,Co,Cd）的杂金属杯[4]与配体对苯二甲酸和4,4''-二苯醚二甲酸形成的一维配位聚合物。     

杂金属杯[4]配位聚合物的合成与表征

合成了4个杂金属杯[4]配位聚合物{[Cd（L）（tpa）]·3H₂O}_n（1）,{[Zn2（L）₂（tpa）₂]·3H₂O}_n（2）,{[Co（L）（oba）]·2DMA·0.5H₂O}_n（3）和{[Zn（L）（oba）]·DMA}_n（4）（L=2-（1H-咪唑基-甲基）-6-（3-（1H-咪唑基-甲基）-5-叔丁基-2-羟基）苄基-4-叔丁基苯酚,H₂tpa=对苯二甲酸,H₂oba=4,4''-二苯醚二甲酸）,并通过元素分析、热重、红外光谱、固态紫外、单晶X射线衍射和粉末X射线衍射对其进行了表征。单晶结构分析表明晶体1是单斜晶系,P2₁/n空间群,而晶体2,3和4均为三斜晶系,P1空间群。化合物1,2,3和4是由0维[M（N₄O₂C₂₉H₃₆）]（M=Zn,Co,Cd）的杂金属杯[4]与配体对苯二甲酸和4,4''-二苯醚二甲酸形成的一维配位聚合物。