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.     

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。     

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.     

Solubilization and acidic and receptor properties of calix[4]resorcinarenes in aqueous solutions of oxyethylated dodecanol Brij-35

Solubilization of calix [4]resorcinarenes (Cn) with a varied length of hydrophobic substituents (R =Me, Pr, C₅H₁₁, C₇H₁₅, C₉H₁₉, and C₁₁H₂₃) in aqueous solutions of oxyethylated dodecanol Brij-35 was studied by the solubility method and 1D and 2D ¹H NMR spectroscopy. The solubilization of Cn in micellar solutions of Brij-35 is caused by the formation of mixed Cn-Brij-35 aggregates and is weakened substantially with the elongation of R. It was shown by pH-metry and 1D ¹H NMR spectroscopy that the receptor properties of the Cn anions toward the tetramethylammonium cations in the mixed aggregates differ substantially from those for the monomeric molecules in aqueous-organic and aqueous solutions. In particular, the binding of the tetramethylammonium cations does not result in screening of their N-Me fragments with the cyclophane cavity of the receptor.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 376–382, February, 2005.     

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.     

Hydrophosphinoyl derivatives of calix[4]resorcinarenes

Calix[4]resorcinarene reacts with N,N,N",N"-tetraethyl-P-ethylphosphonous diamide to give dioxaphosphocines, whose hydrolysis with intracavity water yields phosphinoyl derivative of calix[4]resorcinarene.     

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.     

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。     

Crystal Structure of C-(n-propyl)calix[4]resorcinarene and its Complex with Caffeine

Abstract

The crystal structures of the all-cis epimer of C-(n-propyl)calix[4]resorcinarene (1) and its caffeine complex are reported. 1 · CH₃CN · H₂O (2) crystallizes in the tetragonal space group P4, a = 14.3645(9), c = 9.3344(8) Å, V = 1926(2) ų. Refinement led to a final conventional R ₁ value of 0.047 for 3406 reflections and 236 parameters. The caffeine complex 1 · C₈H₁₀N₄O₂ · CH₃OH · H₂O (3) crystallizes in the triclinic space group P1, a = 11.2892(4), b = 13.0367(8), c = 16.9700(11) Å, α = 82.902(2), β = 79.713(3), γ = 88.053(2)°, V = 2438(2) ų. Refinement led to a final conventional R ₁ value of 0.067 for 6393 reflections and 641 parameters. The resorcinarene displays the usual bowl shape in both compounds. The caffeine molecule in 3 is hydrogen bonded to two resorcinarene and one water molecules and one of its methyl groups is included in the cavity of a third macrocycle, suggesting CH₃…π interactions. Extended hydrogen bonding patterns involving phenolic protons and solvent molecules are also present in both compounds.     

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.     

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.     

A Watersoluble Sulfonatomethylated Calix[4]resorcinarene as Artificial Receptor of Metal Complexes

The binding of different sized and shaped metal complexes [Co(His)₂]ClO₄(1), [Co(en)₂C₂O₄]Cl (2) and [K18-crown-6]SCN (3)(en-ethylendiamine, His-L-histidynate-anion) with a new tetrasulfonatomethylcalix[4]resorcinarene([H₈X]Na4) was investigated in neutral and alkaline aqueous media by NMR and pH-metrictitration methods and compared with those of recently studied NMe₄Br (4). The resultsobtained indicate that the outer-sphere coordination of complexes 1–3 by[H₈X]^4- proceeds via the interaction of hydrophobic fragments of the guestswith both the negatively charged rim and the hydrophobic cavity as a -base. Thenature of binding does not change for cations 1, 2 and 4 on going from[H₈X]^4- in neutral to [H₄X]^8- in alkaline media, while the inclusionof 3 decreases on going from [H₈X]^4- to [H₄X]^8-.     

Reactivity of supramolecular systems based on calix[4]resorcinarene derivatives and surfactants in hydrolysis of phosphorus acid esters

The formation of mixed micelles of amphiphilic calix[4]resorcinarenes with aminomethyl (AMC, PAMC), tris(hydroxymethyl)amide (THAC) fragments and the cationic surfactant cetyl trimethylammonium bromide (CTAB) in water and aqueous DMF solutions (10-50% DMF) leads to the decrease of the critical micelle concentration of the systems and the increase of the size of the mixed micelles in comparison with CTAB micelles. The catalytic activity of the mixed systems in the hydrolysis of phosphorus acid esters is higher than those of CTAB micelle and AMC, PAMC or THAC aggregates.     

Photoactive Eu(III) and Tb(III) complexes of calix[4]arenes with pyridine-N-oxide pendant groups

Two calix[4]arenes with four 2-pyridyhnethyl-l-oxide pendant groups at the lower rim have been synthesized, and their Tb(III) and Eu(III) complexes are fluorescent upon UV light excitation at 312 nm. The complexes are not stable in aqueous solution, completely losing their luminescent properties.     

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.     

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.     

Synthesis and aggregation properties of novel amino acetals with the calix[4]resorcinol platform

Reactions of calixarenes with methylaminoacetaldehyde dimethyl acetal and formalin gave Mannich bases with the calixarene platform. It was found by dielcometric titration that calix[4]resorcinols with acetal groups in the aminomethyl fragment form head-to-head supra-molecular aggregates in chloroform at low concentrations. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 888–891, May, 2006.     

5-碘[杯(4)芳烃偶氮]氨基喹啉光度法测钯

合成了新试剂5 碘[杯(4)芳烃偶氮]氨基喹啉(ICAQ),并研究了该试剂与钯显色反应条件。结果表明,在pH10.2～11.0的Na2CO3 NaHCO3缓冲介质中,在TritonX 100存在下,试剂与钯发生显色反应,生成1∶1稳定络合物。建立了测定钯的光度法新体系,λmax=625nm,ε=1.42×105L·mol-1·cm-1,钯质量浓度在0～0 80μg/mL内符合比尔定律。方法用于钯催化剂中钯的测定,结果与原子吸收法相符,平行6次测定的RSD在2.5%～3.0%。     

5-碘[杯(4)芳烃偶氮]氨基喹啉光度法测钴

合成了新试剂 5 碘 [杯 (4 )芳烃偶氮 ]氨基喹啉 (ICAQ) ,并研究了该试剂与钴显色反应条件。在弱碱性介质中 ,不加任何辅助试剂 ,ICAQ与钴发生显色反应 ,生成 1∶1稳定络合物。λmax=61 5nm ,ε=4.78× 1 0 5L·mol- 1 ·cm- 1 ;钴含量在 1 0～ 1 3 0 μg L内符合比尔定律。方法用于维生素B1 2 、茶叶、水样中微量钴的测定 ,结果令人满意。     

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.