邻甲氧基羰基苄氧基取代杯[4]芳烃衍生物的合成及其性能研究

杯芳烃是继冠醚、环糊精之后的第三代主体分子[1].据文献[2,3]报道,在杯[4]芳烃下沿酚氧原子上连接乙酸酯得到的四取代衍生物对Na+有很高的选择性,核磁与晶体结构研究均证实这是由于羧酸酯的羰基和酚氧基参与了对Na+的配位,而且配位基团所形成的包络空间大小与钠离子相匹配.一般认为,随着包络空间改变,对金属离子的识别作用会有所变化[4].但目前对这方面的工作并没有给予更多的重视.我们发现,用2-溴甲基苯甲酸甲酯与杯[4]芳烃反应,得到了一种新的四取代杯[4]芳烃衍生物[2]萃取研究结果表明,该化合物对钾离子有较好的选择性.此外,在合成该衍生物的过程中,还得到了另一新的二取代衍生物(3).     

ω—氯代烷氧基杯[4]芳烃的合成

杯「４」芳烃以Ｃｌ（ＣＨ２ＣＨ２Ｏ）ｎＴｓ（ｎ＝１，２）烷基化。得到６５－８７％的下缘带有２－氯乙氧基和２－（２－氯乙氧基）乙氧基怀「４」芳烃。     

四乙氧羰基甲氧基杯[4]芳烃的合成与性质

配位作用;液膜传递;四乙氧羰基甲氧基杯[4]芳烃的合成与性质     

5,11,17,23-四叔丁基-25,26,27,28-四[3-(甲氧基羰基)苄氧基]杯[4]芳烃包合性能的研究

杯芳烃是继冠醚和环糊精后的第三代主体化合物 .这类主体分子不仅可以识别和络合阳离子 ,而且还具有包合中性有机分子的性能 [1～ 5] .杯 [4]芳烃类包合物的晶体结构测定表明 ,它们可分为分子内和分子间包合两种类型 [3 ,5] ,前者是客体分子被包合在主体分子的空穴内 ,后者是客体分子被包合在主体分子之间 .对叔丁基杯 [4]芳烃的下沿酚氧基与上沿均可进行化学修饰得到不同的杯 [4]芳烃衍生物 .最早报道的对叔丁基杯 [4]芳烃及其衍生物的分子内包合物是与甲苯或乙腈的 1∶ 1包合物 [4 ,5] ,客体分子依靠 CH3 -π的作用被包结在主体分子内[6]…     

新型杯[4]芳烃衍生物的合成

以对叔丁基杯[4]芳烃为起始原料,通过一步或两步取代反应合成了对叔丁基杯[4]芳烃的衍生物(1和2),其结构经FT-IR,^1H NMR,FAB-MS表征．     

新型硫杂杯[4]芳烃衍生物的合成

在对叔丁基硫杂杯[4]芳烃(1)的下缘1,3-位引入芳醛基制得硫杂杯[4]二醛基衍生物(3);3在水合肼中肼解制得硫杂杯[4]二醛腙基衍生物(4);4与5,5'-亚甲基二水杨酰基二水杨酰氯经缩合反应合成了具有桥连结构的硫杂杯[4]芳烃桥联氮杂衍生物(6),3,4和6为新化合物。其结构经1H NMR,IR,ESI-MS和元素分析表征。     

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.     

杯[4]芳烃衍生物的合成和构象研究

以对取代酚亚甲基桥三聚体和２，６－二溴甲基对取代酚为原料，在ＴｉＣｌ４催化下环化得到６种新的含不同取代基［Ｃｌ，Ｂｒ，ＣＨ３，Ｃ（ＣＨ３）３］的杯［４］芳烃衍生物，核磁共振谱研究表明：它们在溶液中的优势构象为锥形构象。     

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。     

气相色谱研究杯[4]芳烃衍生物

选取两种不同结构的怀「４」芳烃做固定相，研究了烃基取代苯，不同数目的甲基取代苯，稠环芳烃和醇系列化合物的保留值变化规律；讨论了杯「４」芳烃固定相与溶质分子间的弥散力作用，氢键作用及空间适应性；指出杯「４」芳烃对芳香烃等良好选择性；对乙腈和甲醇等小分子似有包结。     

Synthesis and Conformational Studies of Lower Rim Cyanomethyl Substituted Calix[4]arenes

The conformational inversion characteristics of calix[4]arenes carrying cyanomethyl groups on the lower rim have been investigated. Complete conversion from a 1,3-alternate to a partial cone conformation was observed for the 1,3-dicyanomethyl ether of calix[4]arene at room temperature, while at higher temperatures further inversion to a 1:1 mixture of partial cone and cone conformers occurred.     

Syntheses and Binding Properties of Novel Calix[4]arene Derivatives Containing Multiple Azo-groups

Introduction Calixarenes are excellent scaffolds that can bemodified by introducing various functional groups tocreate specific interactions between the host and guestmolecules. Thus, many calixarene derivatives contai-ning special functional groups, such as ester, amideand thiourea, have been synthesized and their excellentcomplexing capability for cations have also been stud-ied[1—4]. Lately, calixarene derivatives containing twoor more sorts of functional groups have attracted muchattentio…     

新型杯芳烃银离子选择电极的研究

报道了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」芳烃为银离子载体的ＰＶＣ膜电极的研制。该银离子选择电极不仅对银离子有良好的灵敏度和高选择性,在１０＾－１－１０＾－５ｍｏｌ／Ｌ浓度范围内有良好的线性,能斯特响应为５６ｍＶ／ｐｅＡｇ．（２５℃）碱金属、碱土金属及过渡金属离子不干扰银的测定;而且对某些阴离子也表现出近似能斯特响应（５０ｍＶ／ｐｃｘ－）。用该电极对人工试样中银含量进行测定,结果与原子吸收光度法相符。     

Mono Halogen Substituted Calix[4]pyrroles: Fine-tuning the Anion Binding Properties of Calix[4]pyrrole

Abstract

Single halogen atom (i. e. I, Br, Cl and F) substituted calix[4]pyrroles, compounds 2, 3, 4 and 5, were synthesized. Studies of these systems reveal that replacement of a single β-pyrrolic hydrogen atom can increase the anion binding ability of calix[4]pyrroles for a variety of anions (e. g. Cl^?, Br^?, H₂PO₄ ^? and HSO^? ₄) relative to normal non-halogen substituted calix[4]pyrrole 1. In the case of chloride anion, the expected relative affinity sequence of 5 > 4 > 3 > 2 was observed. This was not found to be true for Br^?, H²PO^? ₄, and HSO^? ₄. Here, the chlorine substituted calix[4]pyrrole 4 was found to display a slightly higher affinity in the case of each anion than the fluorine-bearing derivative 5. This was rationalized in terms of intermolecular NH … F hydrogen bonding interactions being present in CD₂Cl₂ solutions of 5. Support for this latter conclusion came from concentration and temperature-dependent NMR spectroscopic studies.

A matched set of mono halogen substituted calix[4]pyrroles was used to study in detail, the extent to which halogen substituents may be used to fine-tune the anion binding properties of calix[4]pyrroles.     

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.     

Calix[4]arene Polyaza Derivatives: Novel Effective Neutral Receptors for Cations and (a)-Amino Acids

Introduction Calixarenes are one of the most important supramolecular building blocks, which can be modified by introducing different functional and/or structrual groups to create a specific interaction between the host and the target molecules, such as metal cations and small organic molecules[1,2]. In particular, the recognition of amino acids is an interesting theme in biomimetic chemistry[3].     

Calix [ 4 ] arene Polyaza Derivatives： Novel Effective Neutral Receptors for Cations and α-Amino Acids

IntroductionCalixarenes are one of the most important supra-molecular building blocks, which can be modified byintroducing different functional and/or structural groupsto create a specific interaction between the host and thetarget molecules, such as meta…     

Synthesis of Flavin–Calix[4]arene Conjugate Derivatives

The synthesis of two new flavin substituted calix[4]arene derivatives, 9 and 10 , is described. The first flavin substituted calix[4]arene derivative 9 was synthesized by the reaction of 3‐methylalloxazine ( 5 ) with 25,27‐bis(3‐bromopropoxy)‐26,28‐dihydroxy‐5,11,17,23‐tetra(tert‐butyl)calix[4]arene ( 4 ) in high yield (92%). The other derivative 10 was prepared from 3‐methylalloxazine‐1‐acetic acid ( 7 ) and 25,27‐bis(3‐cyanopropoxy)calix[4]arene ( 3 ). All new compounds were characterized by a combination of FT‐IR and ¹H‐NMR spectroscopy, and elemental‐analysis techniques.