The Inclusion Properties of a New Watersoluble Sulfonated Calix[4]resorcinarene towards Alkylammonium and N-Methylpyridinium Cations

The inclusion behaviour of a new water-soluble sulfonated calix[4]resorcinarene towards alkylammonium and N-methylpyridinium cations has been investigated on the basis of ¹H NMR spectroscopy and pH-potentiometry data. The inclusion of the N-methylpyridinium cation has been found to be dependent on pH with the preferable inclusion of the methyl substituent in alkaline and the aromatic ring in neutral aqueous media.     

丙醛间苯二酚杯[4]芳烃烷基化衍生物的合成

以间苯二酚和丙醛为原料合成了丙醛杯[4]芳烃(1),1经不同的烷基化反应合成了新的丙醛杯[4]芳烃烷基化衍生物,其结构经1H NMR和IR表征。     

Thermochemical Investigation of Some Selected Solvates of Calix[4]resorcinarene

Lipophilic calix[4]resorcinarene derived from lauryl aldehyde forms stable crystalline solvates with a range of organic solvents: acetone, 1,4-dioxane, methylethylvketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidinone, butyronitrile, methanol, 1,2-dimethoxybenzene and acetonitrile. The composition and thermal stability of these solvates was followed by thermogravimetric method, indicating a stoichiometry ranging from 1 to 3 (calixresorcinarene/solvent). The activation energy was evaluated for the selected solvates. Molecular modelling, using Hyperchem 5.0 software, was applied to the selected solvates. This revised version was published online in August 2006 with corrections to the Cover Date.     

新型正丁醛杯[4]芳烃醚衍生物的合成

以正丁醛间苯二酚杯[4]芳烃为原料,经酯化、水解、酰氯化后再与9-蒽甲醇反应,合成了蒽单取代的正丁醛间苯二酚型杯[4]芳烃醚衍生物。其结构经1H NMR和IR表征。     

间苯二酚杯芳烃树枝醇类化合物的合成

用间苯二酚杯芳烃的氧代乙酸乙酯类衍生物1a～1b分别与三羟甲基甲胺和二乙醇胺在乙醇/甲苯中进行酰胺化反应, 合成了四种新型的间苯二酚杯芳烃树枝醇化合物2a～2d, 树枝醇2a～2d外缘的羟基用乙酸酐酯化, 得到全乙酰基衍生物3a～3d. 化合物结构都用¹H NMR, IR和元素分析等方法进行了表征, 对树枝醇化合物的聚集状态进行了光学显微镜观察.     

无溶剂法合成杯[4]芳烯星形化合物

以对苯二甲醛、乙酸酐为原料合成对苯二甲醛单缩醛, 接着与间苯二酚反应, 制备了含醛基杯[4]芳烯. 利用季戊四醇与含醛基杯[4]芳烯反应, 进而再与3-[4-(2,5-二氧杂环戊基)苯基]-9-[4-二(甲羰氧基)甲基苯基]-2,4,8,10-四氧杂螺环[5.5]十一烷反应, 合成了杯[4]芳烯星形化合物, 收率为65.2%. 产品结构经 IR, ¹H NMR, MS 和元素分析进行了表征.     

Structural Characterization of l-proline and Morpholine Appended Chiral Calix[4]resorcinarene Molecules

Calix[4]resorcinarenes serve as host molecules for small guest molecules. Recently calixarenes have been appended to chiral molecules in an attempt to promote chiral recognition. To take advantage of both cavity host and chiral substituent properties the position of the chiral moiety is important. We report the synthesis and structural characterization of two calix[4]resorcinarene based molecules that have helical chirality in the solid state. The calix[4]resorcinarene 1 has chiral l-proline ethyl ester substituents positioned perpendicular to the cavity whereas the calix[4]resorcinarene 2 has morpholines positioned parallel to the cavity which extend the depth of the cavity. Compound 1 is one of the first compounds to show the position of chiral centers with respect to the calixarene cavity. 1H and 13C NMR spectroscopy indicate that the helical chirality of 2 is retained at low temperature in nonpolar solvents.     

新型间苯二酚杯芳烃硫脲衍生物对阴离子的识别

通过间苯二酚杯芳烃连续三步反应, 以较高产率合成了分子中连有8个和12个硫脲端基的间苯二酚杯芳烃的酰胺衍生物. 用紫外可见光谱法研究了两个代表性化合物4,6,10,12,16,18,22,24-八[6-(苯基硫脲基)-己氨甲酰基甲氧基]-2,8,14,20-四苯基杯[4]间苯二酚芳烃(THBC)和4,6,10,12,16,18,22,24-八[2-(苯基硫脲基)-1-甲基乙基-1-氨甲酰基甲氧基]-2,8,14,20-四苯基杯[4]间苯二酚芳烃(TPBC), 对各种阴离子(AcO^－, H₂PO₄^－, HSO₄^－, H₂PO₄^2－, C₁₂H₂₅-C₆H₄-SO₃^－, Cr₂O₇^2－, B₄O₇^2－, Cl^－, Br^－)的识别性能, 结果表明它们对AcO^－, H₂PO₄^－, HSO₄^－等阴离子有较好的配位作用, 能形成1∶3的配合物.     

Synthesis of Calix[4]resorcinarene Amide Derivatives

Three different synthetic routes were developed to introduce carbamoyloxy functional groups at the upper periphery of two calix[4]resorcinarenes. By treating activated esters 2a-b with excess corresponding amine such as 3-(dimethylamino)propylamine 3, ct-phenethylamine 4 and triethylenetetramine 5, six amide derivatives 6a-8b were obtained in high yield (Route 1). The pyridine-linked amide derivatives 9a-b were prepared by using acid chloride intermediate (Route 2).The amide derivatives 10a-b were obtained in moderate yields by direct alkylation of phenolic hydroxyl groups of la-b with N,N-dipropylchloroacetoamide in the presence of K2CO3/KI in acetone (Route 3).     

Synthesis of Calix[4]resorcinarene Schiff Bases

Introduction Calix[4]resorcinarenes are cyclic tetramers in which four resorcinol units are linked via alkylmethylene bridges in the o-position to each resorcinic hydroxyl group[1]. Their structures resemble that of p-butylcalix[n]arenes and render them of interest as host compounds in many contemporary fields of supramolecular chemistry.     

Synthesis of New Calix[4]arenes Functionalizated by Acetylhydrazide Groups

A series of new calix[4]phenols, calix[4]resorcinols and calix[4]pyrogallols with acetylhydrazide substitutes has been␣synthesized with high yields by hydrazinolysis of ester group containing calix[4]arenes. The synthesized calix[4]phenols adopt the cone conformation while the calix[4]resorcinol and calix[4]pyrogallol derivatives prefer the boat conformation. The amide fragment of the hydrazide groups predominantly exists in the trans-conformation. The binding ability of synthesized calix[4]arenes toward transition and alkali metals by solvent extraction has been investigated.     

The Molecular Complexes of Calix[4]resorcinolarene with Diglycidylmethyl Phosphonate

The formation of strong molecular complexes of calix[4]recorcinolarene with the polyfunctional phosphoorganic compound diglycidylmethyl phosphonate was observed in organic media. Complexes of different compositions were obtained with the ratio of the initial reagents of 1 : 1 and 1 : 4. Three complexes were isolated and characterized by elemental analysis; their ¹H and ¹³C NMR spectroscopic parameters are also discussed.     

Convenient Preparation of Self-Assembled Monolayers Derived from Calix[4]resorcinarene Derivatives Exhibiting Resistance to Desorption

Crown conformers of O-carboxymethylated calix[4]resorcinarenes (CRA-CMs) bearing four perfluorooctyl- and octylazobenzene residues at the lower rim of the cyclic skeleton were synthesized to investigate the resistance to desorption of CRA-CMs forming self-assembled monolayers on aminosilylated silica substrates and the surface energy photocontrol based on E- to-Z photoisomerization of the azobenzene moiety. In comparison with CRA-CM monolayers on silica substrates, the desorption of CRA-CMs on the aminated substrate was remarkably suppressed even when CRA-CM monolayers were sonicated in polar solvents and even in water. The high desorption-resistance was attributable to multi-point adsorption of CRA-CMs through COOH/NH₂ interactions. UV-Vis spectral studies revealed that CRA-CM substituted with p-octylazobenzene exhibited high E- to-Z photoisomerizability up to 92% in self-assembled monolayers, while less photoisomerizability was observed for CRA-CM bearing p-perfluorooctylazobenzenes due to the steric hindrance of the larger perfluoroalkyl chains. Photoinduced changes of contact angles for water up to 8.3° were observed for a CRA-CM monolayer.     

A New Tubular Arrangement of a Dimethylsilyl Bridged Calix[4]resorcinarene

Abstract

The functionalization of calix[4]resorcinarene 1 (R ₁=H, R ₂=Me) with dichlorodimethylsilane leads to the formation of the dimethylsilyl-bridged cavitand 2 which, during the work up of the reaction product, encapsulates a molecule of water 2·H₂O crystallizes in the C2/c system (a = 23.892 Å, b = 8.493 Å, c = 43.035 Å, β = 100.05°, reflections: 5385, 2376 (F>4.0 [sgrave](F)), R=9.17%, calculated density=1.213 Mg/m³) with eight molecules per unit cell. The main feature of the crystal packing is the alternating pairs of up-down disposed cavitands along the c direction and well developed columns in the b direction. The molecules of water are completely encapsulated, but there are some close contacts with the methylene bridge from the upper molecule. Molecular orbital calculations show that the lowest energy conformer of cavitand 2 is that with all four silicon atoms oriented inward and the energies of the other conformers are so high that they cannot be accessed at normal temperature. Ab initio calculated electrostatic potentials correlate well with the relative positions of the cavitands in the crystal structure.     

Calix[4]resorcinarene Ionophore in the Ion-Selective Electrodes with Plasticized Poly(vinylchloride) Membranes

Synthetic ionophore calix[4]resorcinarene was incorporated into the poly(vinyl chloride) (PVC) plasticized membrane of an ion-selective electrode (ISE). Calixarene interactions with quaternary ammonium and alkaline metals cations in the organic and water-organic media were carefully investigated by various authors. We studied the effects of choline and Na⁺ cations present in the working solution on the ionophore which was incorporated into a membrane phase. Due to the pH sensitivity of the ionophore, a study was undertaken in a wide range of pH values. The different characteristics of calix[4]resorcinarene interactions with these cations were discovered by the ISE with the PVC plasticized membrane containing this ionophore, which respond to both the choline and Na⁺ cations due to the variation of working solution pH.     

The Synergistic Extraction of Lanthanide Ions by a Mixture of Calix[4]resorcinarene or its Dimethylamino-, Piperidyl- or Trimethylammoniummethylated Derivatives and 1,10-Phenanthroline in n-Heptanol

The alkylaminomethylatedcalix[4]resorcinarene derivatives, modified bydimethylamino-, piperidyl- and trimethylammoniummoieties, have been synthesised to investigate theirextractability towards lanthanide ions and to comparewith the extractability of calix[4]resorcinarene. Both calix[4]resorcinarene and its derivatives have beenshown to synergistically affect lanthanide ionextraction from neutral aqueous solutions by1,10-phenanthroline through outer-sphere interactionof lanthanide bis-phenanthrolinate cations withdeprotonated forms of calix[4]resorcinarene. Thederivatives with dimethylamino- andpiperidylmethylated moieties are shown to be moreeffective extractants in comparison with theunsubstituted one.     

Separation of Pyrimidine Bases on a HPLC Stationary RP-18 Phase Coated with Calix[4]resorcinarene

Lipophilic calix[4]resorcinarenes, derived from lauryl aldehyde and resorcinol, are strongly adsorbed on the modified silica gel RP-18 for HPLC chromatography, while their solutions are passed through the column. The calix[4]resorcinarene-coated RP-18 phases were found to be useful beds for HPLC separation of uracil, thymine and cytosine.     

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.     

Thermal analysis of calix[4]resorcinarene complexes with secondary and tertiary amines

Tetra-n-undecylcalix[4]resorcinarene forms solid adducts with secondary and tertiary amines. Thermal decomposition of these complexes was investigated by means of thermogravimetry (TG) and differential scanning calorimetry (DSC). It was found that deamination of complexes occurs as multi-step process. The stoichiometry of complexes was evaluated on the basis of TG studies and total heats of deamination were calculated from DSC measurements.Presented at the CCTA9 31.08-05.09 2003, Zakopane PolandThis work was supported by Grant No. 3T09A 02419 from The Polish Committee for Scientific Research. The authors thank to prof. W. Zielenkiewicz for helpful discussion during realisation of this project and prof. T. Borowiak for X-ray structure of the tetra-n-undecylcalix[4]resorcinarene. tetra-n-undecylcalix[4]resorcinarene.     

Interaction of monolayers of calix[4]resorcinarene derivatives with copper ions in the aqueous subphase

Stable monolayers of novel amphiphilic calix[4]resorcinarene derivates at the air–water interface were prepared. Their interactions with copper ions from the aqueous subphase were investigated by measuring surface pressure–area and surface potential–area isotherms, as well as by Brewster angle microscopy. Theoretical aspects of interpreting the dependence of the surface pressure on the bulk copper ions concentration were discussed. The interaction of copper ions with calix[4]resorcinarene derivates was interpreted in terms of Gibbs–Shishkovsky adsorption equation.