桥联杯[6]芳烃研究进展

综述了桥联杯[6]芳烃的合成及构象固定等方面的研究进展,并以下缘1,4位桥联杯[6]芳烃,杯[6]冠醚和杯[6]穴醚及其类似物等主体分子为重点,综述了桥联杯[6]芳烃在分子识别和超分子化学领域中的应用研究的最新进展。     

基于杯芳烃的分子容器的合成及其对有机铵的可逆识别

将三(吡啶基甲基)胺(TPA)引入杯芳烃的下缘, 合成了一种新的具有杯状结构的杯芳烃衍生物, 研究了其对有机铵的分子识别行为.     

新型主体分子噻唑偶氮基杯[n]芳烃衍生物的合成及其对重金属离子的识别

以2－氨基噻唑为原料，经重氮化－偶联反应合成了5，11，17，23－四（2－噻唑）偶氮基－25，26，27，28－四羟基杯[4]芳烃和5，11，17，23，29，35－六（2－噻唑）偶氮基－37，38，39，40，41，42－六羟基杯[6]芳烃，产物的结构经IR，^1H NMR和元素分析表征；研究了它们的光谱性能和对金属离子的识别状况，发现在pH=7.2的Tris介质中对Ag^ 和Hg^2 等有较好的光谱变化识别。     

硫杂杯[4]芳烃化学修饰的研究进展

硫杂杯[4]芳烃是由S原子取代经典杯芳烃中的桥联亚甲基而成的大环化合物,在分子识别、多核金属配合物、化学传感器等方面有广泛的应用.对硫杂杯[4]芳烃的化学修饰进行综述,有助于新型功能化硫杂杯芳烃衍生物的研究.     

四氮杂杯[2]芳烃[2]三嗪的合成及其叠氮化

以简单易得的原料、在温和的条件下高产率地合成了氮原子桥连杯[2]芳烃[2]三嗪化合物．室温下,碳酸钾为缚酸剂,利用三聚氯氰和对苯二胺的亲核取代反应合成主体,并首次将其叠氮化,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表征．从而验证了合成路线的可行性,并得出了较佳的工艺条件．     

基于杯[6]芳烃的选择性识别氟离子和丙二酸的荧光传感器

以杯[6]芳烃为平台, 通过在上沿用氨基吡啶桥连的方法固定构象, 并以氨基吡啶基团为识别位点和荧光基团, 合成了一类能识别F－和丙二酸的新型荧光化学传感器. 当氟离子与胺成氢键时, 由于光诱导电子转移效应(PET), 荧光强度淬灭; 但往这个配合物滴加丙二酸时, 荧光强度得到迅速恢复, 由此, 传感器体现了一个on/off的分子开关性质.     

苄连氮桥联双硫杂杯[4]芳烃的合成

硫杂杯[4]二醛基衍生物(1)在水合肼中肼解,合成了新化合物硫杂杯[4]二醛腙基衍生物(2);1和2在弱酸的催化下反应合成了新的具有对称结构的苄连氮双硫杂杯[4]芳烃(3);2和3的结构经1H NMR,IR,ESI-MS和元素分析表征.     

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     

基于四丹磺酰胺杯[4]芳烃的汞离子荧光化学传感器

我们方便地合成了上沿修饰四丹磺酰胺基团的杯[4]芳烃衍生物1,发现该化合物在含50％水的乙腈中显示出对汞离子高选择性和灵敏性的识别作用,竞争实验表明多数金属离子对其检测干扰较小。机理研究结果表明荧光萃灭源于由丹磺酰胺基团到汞离子的光致电子转移过程。另外,通过研究1和1-Hg2+的荧光衰减实验,以及对比双丹磺酰胺杯[4]芳烃2和单丹磺酰胺杯[4]芳烃3对汞离子的识别作用,发现化合物1的四丹磺酰胺基团具有很好的预组织和协同作用。化合物1对汞离子的检测限为3.41×10-6 mol·L-1,这可以使1成为一个潜在的汞离子荧光化学传感器。     

Synthesis and Ion Binding Properties of Cesium Selective Quadruply Bridged Calix[6]arenes

Several quadruply bridged calix[6]arenes were prepared in high yield by the reaction of various 1,4-di-O-alkylated calix[6]arenes with 1,2,4,5-tetrakis-(bromomethyl)benzene in the presence of Cs₂CO₃. The alkali metal extraction study established that this compound shows the high selectivity toward Cs⁺ among alkali metal cations. The cesium binding characteristics were investigated with ¹H NMR and UV spectroscopy.     

Synthesis of O6‐Corona[3]arene[3]pyridazines and Their Molecular Recognition Property in Organic and Aqueous Media

O₆‐Corona[3]arene[3]pyridazines were synthesized from the one‐pot macrocyclic condensation reaction of 3,6‐dichlorotetrazine with 1,4‐dihydroquinone derivatives followed by the inverse electron demand Diels‐Alder reaction of the tetrazine rings with a cyclopentanone‐derived enamine. Conversion of six ester groups within macrocycle into all sodium acetate moieties afforded a water soluble O₆‐corona[3]arene[3]pyridazine. The coronary macrocycle host formed complexes selectively with organic ammoniums and dinitrile guests in a 1: 1 stoichiometric ratio in organic solvents with association constants ranging from (2.96 ± 0.10) × 10¹ to (2.53 ± 0.33) × 10⁵ L·mol⁻¹. Water soluble O₆‐corona[3]arene[3]pyridazine was also able to complex strongly with organic ammoniums in water to give an association constant up to (2.67 ± 0.21) × 10⁴ L·mol⁻¹. The pseudo‐rotaxane and inclusion structures of the host‐guest complexes were revealed by the X‐ray crystallography.     

含卤素端基的单取代对-叔丁基杯[6]芳烃的合成与表征

用THF作为反应溶剂, K₂CO₃作碱, 对-叔丁基杯[6]芳烃与二溴丁烷、二溴己烷和1,4-二氯丁炔-2反应以中等产率选择性地合成了含有卤素端基的单取代对-叔丁基杯[6]芳烃2a～2c. 2a和2b可与对甲苯磺酸甲酯(MeOTs)反应高产率地得到全甲基化产物3a和3b. 通过核磁共振谱(¹H NMR)和质谱(FAB-MS)表征, 发现所有化合物都具有预期结构, 2a～2c和3b在室温下是锥式构象, 而3a没有固定构象.     

Synthesis and Structure of Novel Double Flexible Spacer Bridged Biscalix[4]arenes

25, 25′, 27, 27′‐Bis(1,3‐dioxypropane)‐bis(5, 11, 17, 23‐tetra‐tert‐butylcalix[4]arene‐26,28‐diol) (4) and 25, 25′, 27, 27′‐bis(1, 4‐dioxybutane)‐bis (5, 11, 17, 23‐tetra‐tert‐butylcalix‐[4]arene‐26, 28‐diol) (5) were synthesized by the reaction of p‐tert‐butylcalix[4]arene (1) with preorganized 25, 27‐bis(3‐bromoproxyl)calix[4]arene‐26, 27‐diol (2) and 25, 27‐bis(3‐bromobutoxyl)calix[4]arene‐26, 27‐diol (3) in the presence of K₂CO₃ and KI. Compounds 4 and 5 were characterized with X‐ray analysis and the selectivity of 4 and 5 toward K⁺ over other alkali metal ions, alkaline metal ions as well as NH₄⁺ were investigated with an ion‐selective electrode.     

以含氨基酸1,3-桥联杯[4]芳烃为涂层的压电石英传感器对有机胺和有机醇的选择性识别研究

分别以三种新型含氨基酸1,3-桥联杯[4]芳烃衍生物作为压电石英传感器的敏感涂层,测定了一系列相同浓度的有机胺和有机醇蒸气．三种敏感涂层均对正构胺和正构醇表现出明显高的响应值．烷烃基支链越多,相应的频率变化就越小,说明涂层膜对气体分子的选择性识别主要是分析物的位阻效应、氢键及空腔疏水力共同作用的结果．含胱氨酸的1,3-桥联杯[4]芳烃衍生物涂层对各种蒸气的响应值均高于另外两种涂层,桥联杯芳烃的构象和衍生桥环的大小及构成均对涂层识别胺和醇的异构体有重要影响．本文也研究了实验条件的优化．     

Synthesis and complexation properties towards metal ions of new tri-substituted thiacalix[4]arenes

New thiacalix[4]arenes appended with three amide functions have been prepared. Their conformations have been solved thanks to ¹H NMR 2D correlation spectroscopy (COSY) and nuclear overhauser and exchange spectroscopy (NOESY). The complexation ability of these ligands towards various metal ions (Cd^2 + , Pb^2 + , Pd^2 + , Ni^2 + , Hg^2 + , Hg⁺, Ag⁺, Zn^2 +  and Cu^2 + ) has been investigated by the UV–vis absorption and the stoichiometry of the metal–ligand complexes was determined.     

Synthesis of fully lower‐rim,carbonate‐bridged calix[8]arenes and their curing behavior

Novel fully lower‐rim, carbonate‐bridged calix[8]arene derivatives were successfully synthesized in high yield by the condensation of p‐alkyl substituted calix[8]arenes with triphosgene. Different bases and catalysts were used for the preparation depending on the p‐alkyl substituted groups of the calix[8]arenes. The conformational features of the derivatives were examined by ¹H NMR analysis. Thermosetting formulations were prepared from a mixture of bisphenol A polycarbonate with calix[8]arene carbonate derivatives using sodium benzoate as a catalyst. Their crosslinking behaviors were studied using differential thermal/thermogravimetric analysis. No glass‐transition temperatures were observed after annealing at 280–300 °C. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1149–1155, 2001     

Synthesis and binding studies of novel bisthiacalix[4]arenes with diimime linkages

A series of novel bisthiacalix[4]arenes with diimine linkages of different aromatic or heteroaromatic dialdehydes have been synthesized. The structure of one of the bisthiacalixarene has been analyzed by X-ray crystallography. These molecules quantitatively extract silver ion from aqueous into organic phase under neutral conditions.     

Synthesis of （p-Formylphenyl）azo Calix[4]arenes

Five novel azo calix[4]arenes were reported. The p-aminobenzaldehyde was diazotized with sodium nitrite in aqueous hydrochloride solution. Mono-, bis-, tris- and tetrakis(p-formylphenyl)azo calix[4]arenes (including proximal and distal isomers) were obtained respectively by diazo-coupling in different molar ratio to calix[4]arene(1) under pH=7.5--8.5 at 0-5℃. All (p-formylphenyl)azo calix[4]arenes were characterized by ^1H NMR, ^13C NMR, IR, MS (ESIMS) spectroscopies and elemental analysis.