Aggregation behavior and catalytic activity of systems based on calix[4]resorcinarene derivatives and surfactants. 1. Mixed micellization of aminomethylated calix[4]resorcinarenes with cetyltrimethylammonium bromide in aqueous dimethylformamide

Mixed micellization of amphiphilic aminomethylated calix[4]resorcinarenes and phenols, which are their structural units, with the cationic surfactant cetyltrimethylammonium bromide (CTAB) in aqueous 10—70 vol % DMF decreases the critical micelle concentration; the resulting aggregates are larger than those in the CTAB—DMF—water systems. The micellization of CTAB with aminomethylated calix[4]resorcinarenes proceeds in two steps, while its micellization with phenols is a single-step process. The micellization characteristics depend on the structure and hydrophobicity of the amphiphilic compound and the concentration of DMF.     

Supramolecular systems of amphiphilic derivatives of calix[4]resorcinarenes and surfactants in chloroform

Aggregation of amphiphilic calix[4]resorcinarenes (CRA) modified by carboxymethyl (1), 2-hydroxyethyl (2), methylamino acetal (3), and aminomethyl (4) fragments and their interaction with some synthetic (5, 6) and natural (7, 8) surfactants in the low-polarity solvent (chloroform) were studied by permittivity measurements and FT-IR spectroscopy. Compounds 1–4 and surfactants form aggregates at critical micelle concentrations (CMC) of 2.0·10⁻⁵–7.5·10⁻⁵ and 1.7·10⁻⁵–2.0·10⁻³ mol L⁻¹, respectively. The CMC values of CRA—surfactant mixed aggregates depend on the surfactant structure and the structure and concentration of CRA. Analysis of the IR spectra of solutions of a series of amphiphilic CRA (2–4, 9, 10) and their mixtures with the cationic surfactant N-cetyl-N,N-dimethyl-N-(2-hydroxyethyl)ammonium bromide (5) showed that an increase in the concentration of the solutions in individual and mixed systems is accompanied by a decrease in the molar integral intensities and intensities in the maxima of the absorption bands of the O—H and C—H bonds down to the CMC point, after which these values change slightly. The discovered effect, which is differently pronounced for all systems studied, indicates that both the polar “head” groups and nonpolar fragments of CRA and surfactant are involved in the formation of supramolecules of the reverse micelle type in all cases. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 459–466, March, 2007.     

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.     

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.     

The aggregartion and catalytic activity of amphiphilic calix[4]resorcinolarenes and phenols in hydrolysis of phosphonous esters in water—dimethylformamide media

The amphiphilic calix[4]resorcinolarenes, aminomethylated calix[4]resorcinolarenes, o-aminomethylphenols, and their quaternary derivatives in water—dimethylformamide media (10—75 vol.% DMF) form aggregates, which catalyze the hydrolysis of phosphonous esters. The ability to self-association and the catalytic activity of the aggregates depend on the hydrophobicity of the amphiphilic compound, the pH of solution, and the content of DMF.     

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。     

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.     

The effect of self-association on the reactivity of calix[4]resorcinolarene anions with respect to esters of phosphorus acids

The kinetics of reactions of amphiphilic anions derived from calix[4]resorcinolarenes and their aggregates withp-nitrophenyl esters of phosphorus acids were studied by spectrophotometry. The effect of hydrophobicity of the substituent R and of the composition of aqueous dimethylformamide solvent (30, 50, 80% (v/v) DMF) on these processes was investigated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 275–279, February, 1998.     

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。     

Phosphorylation of oxyethylated resorcinol and calix[4]resorcinarene with P(III) acid amides

Abstract

Phosphorylation of 1,3-bis(2-hydroxyethoxy)benzene and octa(2-hydroxyethyl) calix[4]-resorcinarenes with P(III) acid amides and chloramides has been studied. It has been determined that the nature of phosphorous acid amides affects significantly the synthetic result of the reaction.     

Catalytic activity of aminomethylated calix[4]resorsinolarene aggregates in hydrolysis of esters of phosphorus acids

The reaction kinetics of aminomethylated calix[4]resorcinolarenes (AMC) withp-nitrophenyl esters of phosphorus acids (EPA) in a water—DMF solution (30 vol.% DMF) was studied by spectrophotometry and³¹P NMR spectroscopy in the presence and absence of the nonionic surfactant Triton X-100. The AMC form aggregates of micellar and nonmicellar types and are the catalysts for EPA hydrolysis. The catalytic activity of the aggregates depends on their structure, pH of the medium, and the nature of the solvent. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1361–1365, August, 2000.     

Reactions of calix[4]resorcinolarene anions with esters of carboxylic acids in H2O−DMF solvent

Reactions of calix[4]resorcinolarene anions withpara-nitrophenyl carboxylates in the H₂O−DMF medium were studied. The kinetics of this process was measured by optical spectroscopy and potentiometric titration; the step of formation of acylated calixarene and the subsequent step of its hydrolysis were detected. Self-association of long-chain calixarenes into micelles decreases their reactivity with respect to that of the monomers. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya No. 2, pp. 258–261, February, 2000.     

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.     

Effect of structural preorganization on the reactivity of carbazoylmethyl derivatives of pyrogallol and calix[4]pyrogallol

The aggregation behavior of carbazoylmethyl derivatives of pyrogallol and calix[4]pyrogallol was studied by conductometry and dynamic light scattering in water-DMF media. The formation of mixed nanoaggregates in the presence of cationic surfactants was revealed. The effect of structural preorganization of these compounds on their reactivity in the acylation by 4-nitrophenylacetate and the catalytic activity in the hydrolysis of phosphorus acid esters was studied. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2312–2317, December, 2007.     

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-.     

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.     

Protolytic properties and reactivity of aminomethylated calix[4]resorcarenes in reactions with esters of phosphorus acids

The acid-base properties and the kinetics of reactions of aminomethylated calix[4]resorcarenes (AMC) withp-nitrophenyl esters of phosphorus acids in aqueous solutions of propan-2-ol (80 vol.% PrⁱOH) were studied by potentiometry, UV spectrophotometry, and³¹P NMR spectroscopy. The effect of the length of the hydrocarbon radical and substituents at the nitrogen atom on the protolytic properties and reactivity of AMC was studied. The reactions studied occur in two stages. At the first stage, phosphorylated AMC are formed, which are hydrolyzed to the corresponding acids at the second stage. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 456–461, March, 1999.     

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.