Calix[4]arene methylenebisphosphonic acids as calf intestine alkaline phosphatase inhibitors

Calix[4]arenes bearing one or two methylenebisphosphonic acid fragments were prepared via addition of diethylphosphite to the parent calix[4]arene aldehydes. The resulting compounds displayed stronger inhibition of calf intestine alkaline phosphatase than simple methylenebisphosphonic or 4-hydroxyphenyl methylenebisphosphonic acids. The action of these phosphorylated calix[4]arenes is concordant with partial mixed-type inhibition. The inhibition constants Ki and Ki' for the calix[4]arene bis(methylenebisphosphonic) acid in Tris-HCl buffer at pH 9 are 0.38 microM and 2.8 microM respectively. The replacement of the phosphoric acid moieties on the macrocycle with diethylphosphonates results in a sharp decrease of its inhibitory action. Preorganizing phosphonic acid fragments using a calixarene platform therefore provides a promising approach for the design of efficient alkaline phosphatase inhibitors.     

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.     

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.     

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.     

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.     

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.     

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     

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。     

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。     

Azocalix[4]arene Strapped Calix[4]pyrrole: A Confirmable Fluoride Sensor

A new chromogenic fluoride sensor based on 1,3-di-p-nitrophenylazocalix[4]arene-calix[4]pyrrole (1) was designed and synthesized. The color of the solution of probe 1 changed upon the addition of any F(-), CH(3)CO(2)(-), PhCO(2)(-), and H(2)PO(4)(-) ions. However, from these ions the highly specific sensing of F(-) is achieved by the addition of Ca(2+) which leads to a color change from light sky blue (of 1·F(-)) back to the original light orange color of 1.     

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.     

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．     

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。     

Synthesis of New Rigid Dimeric Calix[4]arene

A new Dimeric calixarene from the head to head linkage of two calix[4]arene units fixed in the cone conformation was synthesized via Sonogashira cross-coupling reaction. The structure of 10 was confirmed by NMR, MS and IR-spectroscopy.     

Synthesis of Schiff Base Calix [4] arene Crowns

This letter reports the synthesis of Schiff base calix [4] arene crowns containing m-xylylene phenol subunit, in which calix [4] arene Schiff base crowns 2a,2b and 2c were formed by 1:1 condensation of calix [4] arene diamine 1 with dialdehydes (2,6-diformyl-4-chlorophenol 3a,2,6-diformyl-4-methylphenol 3b,2,6-diformyl-4-tert-butylphenol 3c)under high dilute condition in refluxing anhydrous ethanol in 65-70% yield.