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。     

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.     

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．     

新型生色杯[4]芳烃衍生物的合成及其对CU2+的识别

设计并合成了含偶氮基、酰胺基和席夫碱基的新型生色杯[4]芳烃衍生物(1),其结构经1H NMR,IR,MS和元素分析表征.荧光光谱研究表明,1在λex/λem=370 nm/422 nm处有最大峰;1与Cu2+配合时荧光显著猝灭.     

Selective Electrochemical Recognition of o-Phenylenediol by a Novel Calix[4]arene Derivative

A new type of calixarene-modified electrode has been prepared by directly coating the surface of a glassy carbon electrode with tetrahydrofuran solution containing 25,26,27,28-tetra-（3-amidino thiopropoxy）-5,11,17,23-tetratert-butylcalix[4]arene, and applied to the investigation of electrochemical behavior of phenylenediols. The results showed that the modified electrode could selectively recognize o-phenylenediol, making the over-potential of o-phenylenediol dropped and peak current increased greatly. The anodic peak current is proportional to the concentration of o-phenylenediol in the range of 1.0×10^-5-1.0×10^-4 mol·L^-1 with the detection limit （SIN=3） of 1.0×10^-7 mol·L^-1. The recognizing mechanism, including electrochemical process and binging sites, was also discussed using voltammetry.     

含氮手性杯[4]芳烃对羧酸的手性识别

Chiral nitrogen-containing calix[4]arene was easily synthesized by the reaction of 25,27-di（2-bromoethoxy）- 26,28-dihydroxy-5,11,17,23-tetrakis（t-butyl）calix[4]arene with S-（-）-1-phenylethylamine in excellent yield, and showed good ability to recognize the enantiomers of mandelic acid and 2,3-dibenzoyltartaric acid. This finding has potential application to assay and separation of enantiomers of the carboxylic acids.     

对磺酸基杯[4]芳烃与血红蛋白相互作用的光谱研究

用荧光光谱法和紫外可见分光光度法研究了表面活性剂存在下对磺酸基杯[4]芳烃与牛血红蛋白的相互作用机理。由Stern-Volmer方程及紫外可见吸收光谱图确定对磺酸基杯[4]芳烃对血红蛋白的荧光猝灭过程为动态猝灭,求出了猝灭常数。由热力学参数判断二者之间的作用力主要是疏水作用。依据能量转移理论得出荧光给体-受体间的距离r。在同步荧光光谱中,对磺酸基杯[4]芳烃的加入对血红蛋白构象的改变不大。     

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.     

含酰胺和硫脲单元的杯[4]芳烃衍生物的合成

杯[4]芳烃．1,3-二乙酸乙酯衍生物与水合肼反应生成杯[4]芳烃酰肼衍生物(2),2与异硫氰酸苯酯反应得到新型含酰胺和硫脲单元的杯[4]芳烃衍生物,总产率85％。     

新型多重氮杂杯[4]芳烃衍生物的合成

对叔丁基杯[4]芳烃-1,3-二醛基衍生物1与水杨酰肼、烟酰肼、异烟酰肼反应, 合成了具有开链结构新型杯[4]多重氮杂衍生物2a～2c, 产率分别为88%, 85%和90%. 化合物1与乙二酰肼、丙二酰肼、己二酰肼反应, 得到具有桥联结构的新型杯[4]多重氮杂衍生物3a～3c, 产率分别为86%, 89%和90%. 新化合物的结构经元素分析、质谱、核磁共振谱等表征证实, 杯[4]芳烃单元均为1,3-取代且采取锥式构象.     

杯[4]芳烃四丁醚的选择性硝化

硝化反应;杯[4]芳烃四丁醚的选择性硝化     

杯[4]芳烃黄原酸酯衍生物的合成与阳离子萃取性能

以二氧六环作溶剂, 杯[4]芳烃二甲氧基二羟乙氧基衍生物2与氢氧化钾、二硫化碳作用合成了杯芳烃黄原酸盐衍生物3, 并进一步与碘甲烷或氯化苄反应首次合成了含黄原酸酯基的杯芳烃衍生物4a和4b. 阳离子萃取试验表明该新型杯芳烃衍生物比单硫杂杯芳烃衍生物具有更好的过渡金属离子萃取性能.     

1,3-取代杯[4]芳烃三联吡啶配体的合成及其离子识别性能的研究

设计合成了1,3-取代杯[4]芳烃三联吡啶新型配体L1, 通过紫外吸收光谱的变化研究了配体L1对于Fe(II), Zn(II), Ni(II)等离子的识别作用.     

锥形构象含氟杯芳烃衍生物对铜离子的高选择性识别

合成了具有锥形构象的含氟功能基团的杯芳烃衍生物1~3,并用单晶X射线衍射和核磁共振证实了其锥形构象。在混合溶剂中,研究了杯芳烃衍生物1~3对多种金属离子的识别行为。测试了化合物1~3的紫外-可见吸收光谱和荧光发射光谱,结果显示铜离子对化合物1~3具有明显的荧光猝灭特性,而其它金属离子（如Na^',K^',Cs^',Mg^2',Ca^2',Ba^2',Fe^3',Cd^2',Mn^2',Co^2',Ni^2',Zn^2'）对化合物1~3的紫外-可见吸收光谱和荧光发射强度无显著的影响,表明化合物1~3对铜离子的识别具有高选择性。     

四硫脲基杯[4]芳烃衍生物的合成

对叔丁基杯[4]-1,3-二乙酸乙酯与过量的二乙基三胺反应,生成含有游离氨基的杯芳烃酰胺衍物(2),2再与异硫氰酸苯酯反应合成了含4个硫脲基的杯[4]芳烃衍生物,其结构经1H NMR,IR,MS和元素分析表征。     

杯芳烃偶氮类衍生物对金属离子的萃取作用

通过杯芳烃的酚羟基的直接烃基化反应,在杯芳烃的下缘引入2,3′-二甲基-4-氨基偶氮苯发色团,得到了一系列杯芳烃偶氮衍生物(n=4,6,8)a-c.研究了它们对碱金属,碱土金属及过渡金属等十种金属离子的萃取作用.结果表明此类杯芳烃偶氮衍生物对过渡金属离子有良好的选择性识别作用,其中空腔较大的杯[8]芳烃偶氮衍生物c的萃取效果尤为显著.     

含酰胺和席夫碱单元的杯[4]芳烃衍生物的合成与配合性能

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, 然后进一步与相应的芳醛反应, 高产率地合成了三个新型的含酰胺和席夫碱单元的杯[4]芳烃衍生物3a～3c和一例新型杯[4]冠醚4. 阳离子萃取实验表明新型杯芳烃衍生物比只含有酰胺基或席夫碱基的杯芳烃衍生物有更强的软金属离子配合性能, 杯[4]冠醚4还对Ag^＋有较好的选择性萃取能力.     

Synthesis and Characterization of Calix[4]arene Functionalized Poly(ethylene glycol) Derivatives

Calix[4]arenes with both ligating and methoxy poly(ethylene glycol) groups appended have been synthesized using several approaches, involving the formation of sulfonyl ester groups on the wide rim, Schiff base derivatives on the narrow rim, and thioether groups on both the wide and narrow rims. These new derivatives have been characterized by a combination of infrared and ¹H NMR spectroscopy. Compounds 10 and 11 are insoluble in both water and aqueous poly(ethylene glycol), but the other new compounds are soluble.     

Two Novel Self-Assemblies of the Calix[4]arene Derivatives and Their Structures

Two newly identified supramolecule structures arise from self-assembly of theCalix[4]arenes derivatives 1 and 2: one ethyl ester of 1 (or 2) enters into the cavity of another 1 (or 2) forming a 1D long chain structure. The interaction force of the molecules and the crystallization energy might be an important driving force for forming theself-assembled calix[4]arene. Supplementary Data relating to this article (atomic coordinates, hydrogen coordinates, isotropic displacement parameters, anisotropic displacement parameters, selected geometrical parameters and observed and calculated structure factors) are deposited in the British Library.     

Synthesis of Pyridylazo-substituted Chromogenic Calix[4]arenes

Calixarenes are a versatile class of macrocyclic compounds which have attracted extensive interest due to their ability to form host-guest complexes and act as enzyme mimic, especially when appropriately functionalized1. Introduction of azo group to calixarenes can make the later to be easily detected in the process of molecular recognition, azo groups have been introduced into calixarenes by the diazo-coupling reaction of calix[4]arene with BF4- or chloride salt of substituted benzene diazon…