通过杯芳烃片段桥联合成杯[4]冠4齐聚物及其络合性能研究

通过杯芳烃片段桥联合成杯[4]冠4齐聚物,并通过两相萃取实验评估其络合性能。络合研究表明,酰胺型杯[4]冠4齐聚物（TCA[4]-III）对软金属银、铅离子和氨基酸具有选择性络合。其对色氨酸和组氨酸的萃取率分别高达87.9% 和 91.5%。     

香豆素冠醚双功能化杯[4]芳烃的合成

以对叔丁基杯[4]芳烃为原料,经碱催化合成了26,28-双(4,7-双甲氧基香豆素)-5,11,17,23-四叔丁基杯[4]-冠-6(2)。其结构经1H NMR,IR和元素分析表征,2为锥形结构。     

对叔丁基杯[10]冠醚的合成

首次合成一系列杯[10]冠醚。通过将对叔丁基杯[10]芳烃和乙二醇双对甲苯磺酸酯或多甘醇双对甲苯磺酸酯在K2CO3/甲苯或Cs2CO3/丙酮体系中反应,得到一系列杯[10]冠醚:1,2-杯[10]冠-4、1,3-杯[10]冠-2、1,2-,1,3-杯[10]冠-3、1,4-杯[10]冠-4、和1,6-杯[10]冠-4。     

硫杂杯[4]芳烃酰胺型氮杂冠醚的合成

硫杂杯[4]芳烃与N,N'-亚乙基双(2-氯乙酰胺)发生分子内"1+1"缩合反应,合成了新型硫杂杯[4]芳烃酰胺型氮杂冠醚--25,27-二羟基-26,28-(1',10'-二氧杂-4',7'-二氮杂-3',8'-二氧代亚癸基)-硫杯[4]芳烃(叔丁基硫杯[4]-1,3-酰胺冠醚)(3),产率68%.1H NMR,ESI-MS和元素分析确证3为1,3-桥联模式且为杯式构象.     

N-硫脲基套索杯[4]冠醚与四硫脲基杯[4]芳烃的合成

控制反应物的物质的量比, 杯式对叔丁基杯[4]-1,3-二乙酸乙酯衍生物1与5或50倍二乙烯三胺反应, 分别得到杯[4]氮杂冠醚2和开链的氮杂杯[4]芳烃衍生物3. 化合物2和3进一步与异硫氰酸苯酯反应得到首例侧链含硫脲基的套索杯[4]氮杂冠醚4和含4个硫脲基的杯[4]芳烃衍生物5, 产率为92%和87%. 新化合物的结构与构象经元素分析、红外、质谱、核磁共振谱等表征证实.     

多重氮杂杯[4]芳烃和双杯[4]芳烃的合成与阳离子萃取性能

多重氮杂杯[4]芳烃和双杯[4]芳烃的合成与阳离子萃取性能;杯[4]芳烃;双杯[4]芳烃;多重氮杂;萃取     

杯[4]间苯二酚芳烃Schiff碱衍生物的合成及其离子萃取性能

通过控制条件,使两种乙氧基羰基甲氧基杯[4]间苯二酚芳烃2a和2b的酯基与1,6-己二胺的一个氨基反应形成酰胺3a和3b,剩余的一个氨基再与水杨醛反应,得到了相应的杯芳烃Schiff碱衍生物4a和4b,对其进行了金属离子的液-液萃取性能研究.结果表明,Schiff碱基团的引入能大大增强杯芳烃与金属离子的配位能力,而杯芳烃空腔的存在又能提高Schiff碱与金属离子的配位选择性.     

杯冠衍生物BEHBCalixC6对铯离子萃取性能的研究

本文以杯冠BEHBCalixC6为萃取剂,二氯甲烷为稀释剂,通过液液萃取,研究了BEHBCalixC6对苦味酸铯的萃取性能.研究表明,随着主、客体摩尔比的增加,萃取率增大.在摩尔比50:1时,萃取率可以达到77%以上.考察了测量参比溶液、预饱和两相稀释剂、稀释剂种类和溶液中Na+浓度等因素对萃取率的影响.     

硫、硒杯[4]芳烃萃取银

以5,11,17,23-四（1,1-二甲基乙基）-25,27-二羟基-26,28-二[（2-乙基硫）乙氧基]杯[4]芳烃（1）和5,11,17,23-四（1,1-二甲基乙基）-25,27-二羟-26,28-二[（2-乙基硒）]乙氧基杯[4]芳烃（2）为萃取剂,研究了在弱酸性条件下杯芳烃衍生物与银的络合行为。杯芳烃衍生物与银形成1：1萃取络合物,在大量碱金属、碱土金属、常见过渡金属离子存在下,对银离子有很高的萃取率和选择性。     

新型杯[4]芳烃衍生物的合成及其氨基酸萃取性能

杯[4]-1,3-二乙酸乙酯衍生物(1)与水合肼反应生成杯[4]芳烃酰肼衍生物(2),化合物(2)与异硫氰酸苯酯反应得到含酰胺和硫脲单元的新型杯[4]芳烃衍生物(3).总产率达70%.系列氨基酸萃取实验表明化合物(3)对异亮氨酸有较好的选择性萃取能力.     

Synthesis of novel calix[4]crown telomers and selective extraction of cesium ions

p-tert-Butylcalix[4]diazacrown-4 telomer, which contains hard and soft ion binding sites, was synthesized. It exhibited high selectivity toward cesium ions. The binding sites may complex alkali metal ions selectively.     

Synthesis of novel calixcrown derivatives with selective complexation towards cesium ions

A series of novel calix[4]arenecrown-6 derivatives with an alkenyl loop of various sizes 5-8 were synthesized via intramolecular ring closing olefin metathesis and characterized by ~1H NMR,~(13)C NMR and ESI-HRMS.Their complexation property towards cesium ion was studied by ~1H NMR technique.Two-phase extraction of alkali metal ions using UV-vis spectroscopy revealed remarkably different extractabilities.These results indicate that the complexation capacities towards cesium ions can be tuned and controll...     

A di-aza-benzo crown ether derived fromp-tert-butyl calix[4]arene. Synthesis and complexation of zinc cation

Di-aza-benzo crown etherp-tert-butyl calix[4]arene (1) has been prepared by hydrogenating the already known Schiff-base precursor (2). The metal ion complexing ability of (1) toward zinc cation is presented. The formation of a 2:1 (Zn: (1) complex and the location of zinc cations were deduced from¹H-NMR investigations.     

Synthesis of a novel calix[4]arene-based fluorescent ionophore and its metal ions recognition properties

A novel fluorescent ionophore derived from calix[4]arene and pyrazoline was designed and synthesized. Its molecular structure was confirmed by 1H NMR and element analysis. The resulting material shows specific fluorescent behavior toward the Zn2+ ion among the other divalent metal ions, such as Co2+, Ni2+, Cu2+. The primary results indicate this ionophore material is a potential material for developing efficient fluorescent Zn2+ chemosensors.     

Cesium ion selective electrode based on calix[4]crown ether-ester

The potentiometric response characteristics of cesium ion selective PVC membrane electrode employing calix[4]crown ether-ester as an ionophore were investigated. The electrode exhibit a good response for cesium ion over wide concentration range of 5.0x10(-6)-1.0x10(-1) M with a Nernstian slope of 59 mV per decade. The detection limit of electrode is 5.0x10(-6) M. The electrode was found to have selectivity for cesium ion over alkali, alkaline and transition metals. The response time of the electrode is less than 20 s and can be used for more than 4 months without observing any divergence in potentiometric response. The electrode response was stable over wide pH range.     

Synthesis and Complexation Properties towards Alkali Cations of a Photosensitive Azo-modified Calix[4]crown Ether in the 1,3-Alternate Conformation

We report the synthesis and complexation properties towards alkalications of a photosensitive azo-modified calix[4]crown 5 in the1,3-alternate conformation. Selectivity of the cis-isomer towards Cs⁺ andRb⁺ was observed.     

含酰胺基和酯基的新型杯[4]冠醚的合成及其对金属离子的识别能力

利用杯[4]芳烃与含酰胺基和酯基的丙二酸酯衍生物的"1+1"分子间缩合合成了一例新型结构的杯[4]-1,3-冠醚;利用核磁共振、红外光谱、质谱及元素分析表征了其结构,并测定了其对金属离子的识别能力.结果表明,合成的新型杯[4]冠醚对金属阳离子和阴离子均有较好的识别能力.     

Synthesis and cation complexation of calix[4]azacrowns and a spirobiscalix[4]azacrown

The synthesis and complexation properties of three new derivatives, one spirobiscalix[4]azacrown (1) and two calix[4]azacrown (2 and 3), are reported. Complexation studies of the three ligands toward transition and heavy metal cations have been carried out and monitored by UV absorption spectrophotometry in acetonitrile. Mononuclear complexes were detected for all complexes, whereas binuclear species (M₂L) were also formed in the case of ligand 1 with Cu²⁺ and Pb²⁺. The extraction properties of 1, 2 and 3 toward Cu²⁺, Zn²⁺, Pb²⁺, Ag²⁺ and Cd²⁺ are also reported. The results showed that complexation is the main factor affecting extraction with ligands 2 and 3, while with ligand 1 it is not.     

Synthesis and Cesium Binding Affinity of New 25,27-Bis(alkyloxy)calix[4]arene-crown-6 Conformers in Relation to the Alkyl Pendent Moiety

The preparation of new 25,27-bis(alkyloxy)calix[4]arenes-crown-6 in the cone, partial-cone and 1,3-alternate conformation is reported. We have also investigated the alkylation of the cone monoalkylated calix[4]arene-crown-6 achieved using Cs 2 CO 3 . This reaction afforded a mixture of cone and partial-cone calix[4]arenes-crown-6 having an alkyl chain anti or syn to the polyether ring. Conformations have been probed using 1 H, 13 C, 2D-NMR and NOESY analysis, and using X-ray crystallography. Extraction experiments using a two-phase solvent method involving cesium picrate were performed for these newly synthesized conformers. They reveal and confirm the strong preference for the 1,3-alternate conformers. The affinity of 1,3-alternate calixarenes for Cs + has been assessed by complexation measurements (log g ) using a spectrophotometric technique. No significant Cs + extraction difference was observed in relation to the nature of the alkyl chains on the aromatic rings. 1 H NMR studies of the 1,3-alternate calixarene Cs + complexes confirms the cation's spacial position between the two aromatic rings, due to cation- ~ interactions.     

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.