偶氮基杯芳烃化合物的合成及其偶氮-醌腙互变异构性质

通过芳胺的重氮化-偶合反应合成了8个偶氮基杯芳烃化合物, 其结构经IR, 1H NMR, ESI-MS和元素分析表征. 通过UV-Vis, 1H NMR和IR考察了溶液pH值对所合成化合物5,11,17,23-四[(2-苯并噻唑基)偶氮基]-25,26,27,28-四羟基杯芳烃(3)和5,17-二[(1-萘基)偶氮基]-25,26,27,28-四羟基杯芳烃(4)的偶氮-醌腙互变异构的影响. 结果表明, 随着溶液pH值增加, 醌腙体在偶氮-醌腙互变异构平衡中的比例增加, 当pH≥10时, 几乎全部转变为醌腙体. 特别当溶液pH=-1时, 化合物4可以形成一种大的共轭体系, 使其λmax由477 nm红移至545 nm.     

Calix[4]arene based dendrimers

The synthesis of calix[4]arene based dendrimers containing up to seven calix[4]arene moieties is described, including the X-ray crystal structure of a tris-calix[4]arene branching derivative.     

Novel Calix[4]arene Azacrown Ether

1,3-diproyloxycalix[4]arene azacrown ether was successfully synthesized in the fixed 1,3-alternate conformation which was confirmed by a solid state structure.     

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。     

带状修饰的杯[4]吡咯对卤素阴离子识别的研究

应用分子力学／分子动力学模拟方法研究了4种带状修饰的杯[4]吡咯对卤素阴离子的识别作用.模拟结果表明, 加入带状修饰链和调节链长可以增强对某种特殊卤素阴离子的识别, 在这个过程中, 卤素阴离子与杯[4]吡咯NH上的氢形成的多氢键使主体分子与阴离子形成稳定复合物, 同时带状修饰链通过改变杯吡咯空腔大小影响主体分子与卤素阴离子的氢键相互作用, 从而调节了对不同阴离子的识别能力.     

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.     

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.     

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.     

Ultramacrocycle with Four Calix[4]arenes: Synthesis and X-Ray Crystal Structure of A Quadruple Calix[4]arene

A quadruple calix[4]arene has been synthesized efficiently from the known diaminocalix[4]arene and 4,4′-biphenyldisulfonyl chloride in just one step (38% yield). The compound has been fully characterized including the determination of the X-ray crystal structure.     

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     

Calix[4]arene nitroxide tetraradical and octaradical

1,3-Alternate calix[4]arene with para-phenylene spacers connecting nitroxide monoradicals and high-spin (S = 1) diradicals provides tetraradical and octaradical scaffolds that possess conformations with slow electron spin relaxation rates (1/T(1)). Such scaffolds may facilitate tuning of relaxation rates that are more favorable for MRI or DNP applications.     

Potassium Sensing Calix[4]arene Crown Ethers

1,3-Alternate calix[4]arene crown-5 (1) and corresponding biscrown-5 (2) were synthesized and the complexation behavior with alkali metal ions examined. For both 1 and 2, potassium ion was selectively extracted from aqueous phase into organic phase over other alkali metal ions based on two phase extraction experiment. The complexation ratio between calix[4]arene biscrown-5 (2), in which two crown cavities connect to the calix[4]arene framework by 1,3-alternate fashion and potassium metal ion is found to 1:1 by proton NMR spectroscopy and extraction equilibria. Association constants (logK_a) for 1 and 2 were determined to give 2.51 and 3.49, respectively.     

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。     

含硫脲和酰胺单元的新型杯［4］芳烃中性氟离子受体

Two-armed neutral anion receptors (4,5), calix[4]arenes beating thiourea and amide binding sites, were prepared and examined their anion-binding ability by the UV-vis spectra. The results of non-linear curve fitting and Job plot indicate that 4 or 5 forms 1：1 stoichiometry complex with fluoride by hydrogen bonding interactions. Receptors 4 and 5 have an excellent selectivity for fluoride but have no binding ability with acetate, dihydrogen phosphate and the halogen anions (Cl^-,Br^-,I^-).     

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。