Lower Rim Substituted tert-Butyl calix[4]arenes (I). The Structure and Complexing Properties in Ion-Selective PVC Membrane Electrodes

Some di- and tetraamide tert-butylcalix[4]areneswere synthesized and described. Their ionophoric properties were studied in liquid membrane ion-selective electrodes. The correlation between thechemical structure (conformation in solution determined by ¹H NMR) and potentiometric ion-selectivity and complex formation constant havebeen studied. The PVC membrane electrodes based on tetraamides 8–11 show high sodium selectivity, are stable and long lasting. Disubstituted amides 1–7 are selective for larger and more lipophilic ions, as for exampleguanidinium ion. The crystal structure of the diamide 4 was determined by single crystal X-ray analysis. Crystals of 4 are triclinic, spacegroup P-1, with: a = 16,669(8), b = 17.795(10), c = 20.984(8) Å, =91.08(4)°, = 91.60(3)°, = 90.73(4)° and Z = 4. Ionophore 4 posseses a distorted cone conformation and is substituted at the proximal phenol rings.     

Synthesis and Conformational Studies of Lower Rim Cyanomethyl Substituted Calix[4]arenes

The conformational inversion characteristics of calix[4]arenes carrying cyanomethyl groups on the lower rim have been investigated. Complete conversion from a 1,3-alternate to a partial cone conformation was observed for the 1,3-dicyanomethyl ether of calix[4]arene at room temperature, while at higher temperatures further inversion to a 1:1 mixture of partial cone and cone conformers occurred.     

Lower Rim Substituted tert-Butylcalix[4]arenes (Part VI). Synthesis and Ionophoric Properties of 5,11,17,23-Tetra-tert-Butyl-25,26,27,28-Tetrakis(3-Diethoxyphosphorylpropoxy)Calix[4]arene

New compound – 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(3-diethoxyphosphorylpropoxy)calix[4]arene was synthesized and its complexing properties were investigated using ion-selective membrane electrodes. The compound selectively recognizes lithium and calcium ions. Stability constants of the respective complexes formed within the membrane were determined.     

Lower Rim-Upper Rim Hydrogen-Bonded Adducts of Calix[4]arenes

An upper-rim-substituted calix[4]arene tetracarboxylic acid forms hydrogen-bonded duplexes with lower-rim-substituted tetra(4-pyridyl)- and tetra(3-pyridyl)calix[4]arenes in chloroform. The formation of these adducts was studied by extraction experiments. The association constants determined via (1)H NMR dilution experiments in CDCl(3) are 7.6 x 10(3) and 1.3 x 10(3) M(-1) for the 4-pyridyl and the 3-pyridyl derivative, respectively. IR studies in the solid state and in solution indicate that the interaction is based on hydrogen bonding and that the degree of proton transfer is negligible. VPO measurements support the formation of 1:1 adducts.     

Lower Rim Substituted tert-Butyl calix[4]arene (part VII): Ionophoric Properties of Calix[4]arene-crown-6 Derivatives in Plasticized PVC-Membrane Electrodes and in Solution

The synthesis and characterization of p-tert-butylcalix[4]arene-crown-6 derivatives (compounds 2–9) are presented. Their ability to complex alkali, alkaline earth and some “softer” cations was investigated by using these compounds as ionophores in ion-selective membrane electrodes and determining the potentiometric selectivity coefficients and the complex stability constants in the membrane. The selectivities of these compounds depend on the size and nature of the substituents on the distal phenolic oxygens. The complexing properties of the two cone and partial cone conformers of compound 2 in the PVC membrane were compared with those in acetonitrile solution studied by UV absorption spectrophotometry and with alkali metal picrate liquid–liquid extraction.This revised version was published online in July 2005 with a corrected issue number.     

The study of radiolytic stability of 25,27-bis(2-propyloxy)calix[4]-26,28-crown-6(iPr-C[4]C-6)

The radiolytic stability of 25,27-bis(2-propyloxy)calix[4]-26,28-crown-6(iPr-C[4]C-6) was studied. The radiation source was ⁶⁰Co and its dose rate was 437?Gy/min and the total absorbed dose was from 10⁴ to 10⁶?Gy. The iPr-C[4]C-6 solid and 0.025?mol/L iPr-C[4]C-6/n-octanol which were pre-equilibrated with 0.01 and 3?mol/L nitric acid, respectively, were absorbed different dose and their extraction performance were researched. The degradation mechanism of them was investigated by mass spectrometry and infrared spectrum. The results show that radiolytic stability of the iPr-C[4]C-6 solid and 0.025?mol/L iPr-C[4]C-6/n-octanol are good when their absorbed dose was less than 10⁶?Gy. The extracting system of iPr-C[4]C-6/n-octanol is promising for separating cesium from high level liquid waste.     

Synthesis and Cation Complexation of Lariat Calix[4 ] crowns

Calixcrowns carrying bridging polyethyleneoxy moieties on the lower rim, which combine calixarene and crown ether in a single molecule, are a novel class of host compounds which have attracted increasing attention because of their increased ability for selective complexation of cations and neutral molecules compared with crown ethers or cal ixarenes.     

Cation Complexation by a Lower Rim Calix(4)arene Derivative: Structural,Electrochemical and Thermodynamic Studies

The synthesis and characterization (¹H and ¹³C NMR) of a partially substituted lower rim p-tert-butylcalix(4)arene, namely, 5,11,17,23-tetra-4-tert-butyl-25,27-bis(diethylphosphate amino)ethoxy-26,28-dihydroxycalix[4]arene (1), are reported. The solution thermodynamics of the ligand in a variety of solvents at 298.15?K was investigated through solubility (hence standard Gibbs energy of solution) measurements while the calorimetric technique was used to derive the standard solution enthalpy. These data were used to calculate the standard entropy of solution. An enthalpy–entropy compensation effect is shown and, as a result, slight variations are observed in the transfer Gibbs energies of this ligand from the reference to other solvents. ¹H NMR, conductance and calorimetric measurements were carried out to establish the degree of interaction of the ligand with univalent (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺ and Ag⁺) and bivalent (Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Pb²⁺, Cd²⁺, Hg²⁺, Cu²⁺, Zn²⁺) cations in acetonitrile, methanol, N,N-dimethylformamide and propylene carbonate. No complexation was found between this ligand and univalent cations in these solvents. As far as the bivalent cations are concerned, interaction between 1 and these cations was found only in acetonitrile. The versatile behaviour of this ligand with bivalent cations in this solvent is reflected by the formation of complexes of different stoichiometry. Thus the interaction of 1 with alkaline-earth (Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺) and Pb²⁺ metal cations leads to the formation of 1:2 (cation:ligand) complexes. However, for other bivalent metal cations (Cu²⁺, Zn²⁺, Cd²⁺ and Hg²⁺) the complex stoichiometry was found to be 1:1. The results are discussed in terms of the key role played by acetonitrile in processes involving calix[4]arene derivatives.     

Synthesis and Characterization of Partially Substituted at Lower Rim Phosphorus Containing Calix(4)arenes

The synthesis and characterization of several new phosphorus-containing partially lower rim substituted derivatives of 5,11,17,23-tetra(t-butyl) calix(4)arene (I) and 5,11,17,23-tetra(t-octyl)calix(4)arene (II), namely 5,11,17,23-tetra(t-butyl)-25,27-dihydroxy-26,28-bis(diphenylphosphinoyl-oxy) calix(4)arene (IV); 5,11,17,23-tetra(t-butyl)-25-hydroxy-26,27,28-tris(tetramethyldiamido-phosphinoyl-oxy) calix(4)arene (Vb); 5,11,17,23-tetra(t-butyl)-25,27-dihydroxy-26,28-bis(dimethyl-phosphinoyl-methoxy) calix(4)arene (VI); 5,11,17,23-tetra (t-octyl)-25,27-dihydroxy-26,28-bis(dimethyl-phosphinoyl-methoxy) calix(4)arene (VII) are reported. The structure of the synthesized calix(4)arene derivatives are identified and confirmed by elemental analysis, IR, ¹H, ¹³C, ³¹P{¹H} NMR spectroscopy and mass spectrometry as and X-ray crystallographic analysis of 5,11,17,23-tetra(t-butyl)-25,27-dihydroxy-26,28-bis(dimethyl-phosphinoyl-methoxy) calix(4)arene VI. According to the NMR spectra, all calix(4)arenes are in cone conformation.     

Complexation of the cesium cation with 1,3-alternate-25,27-bis(1-octyloxy)calix[4]arene-crown-6

From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Cs⁺(aq) + I^?(aq) + 1(nb) ? 1·Cs⁺(nb) + I^?(nb) taking place in the two–phase water–nitrobenzene system (1 = 1,3-alternate-25,27-bis(1-octyloxy)calix[4]arene-crown-6; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log K _ex (1·Cs⁺, I^?) = 2.9 ± 0.1. Further, the stability constant of the 1·Cs⁺ complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log β_nb (1·Cs⁺) = 8.8 ± 0.1. Finally, by using quantum–mechanical DFT calculations, the most probable structure of the resulting cationic complex species 1·Cs⁺ was derived.     

Synthesis and Properties of Upper Rim Schiff Base Calix[4]arenes

The synthesis and properties of upperrim Schiff base calix[4]arenes are described in thisarticle. Tetrakis-p-bromomethylcalix[4]arene(1) reacts with hexamethylenetetramine to givetetrakis-p-formylcalix[4]arene (2) in highyield. Then upper rim Schiff base calix[4]arenes 3 can be easily synthesized by 2 reacting withappropriate alkylamines. The complexation ability of3 toward transition metals Pb²⁺, Cu²⁺and Co²⁺ was studied by UV-VIS spectrophotometry.     

Synthesis of （p-Formylphenyl）azo Calix[4]arenes

Five novel azo calix[4]arenes were reported. The p-aminobenzaldehyde was diazotized with sodium nitrite in aqueous hydrochloride solution. Mono-, bis-, tris- and tetrakis(p-formylphenyl)azo calix[4]arenes (including proximal and distal isomers) were obtained respectively by diazo-coupling in different molar ratio to calix[4]arene(1) under pH=7.5--8.5 at 0-5℃. All (p-formylphenyl)azo calix[4]arenes were characterized by ^1H NMR, ^13C NMR, IR, MS (ESIMS) spectroscopies and elemental analysis.     

邻甲氧基羰基苄氧基取代杯[4]芳烃衍生物的合成及其性？…

杯芳烃是继冠醚、环糊精之后的第三代主体分子 [1] .据文献 [2 ,3]报道 ,在杯 [4]芳烃下沿酚氧原子上连接乙酸酯得到的四取代衍生物对 Na+ 有很高的选择性 ,核磁与晶体结构研究均证实这是由于羧酸酯的羰基和酚氧基参与了对 Na+ 的配位 ,而且配位基团所形成的包络空间大小与钠离子相匹配 .一般认为 ,随着包络空间改变 ,对金属离子的识别作用会有所变化[4] .但目前对这方面的工作并没有给予更多的重视 .我们发现 ,用 2 -溴甲基苯甲酸甲酯与杯 [4 ]芳烃反应 ,得到了一种新的四取代杯 [4]芳烃衍生物 2 ,萃取研究结果表明 ,该化合物对钾离子有较…     

Synthesis of （p—Substituted phenyl）azo Calix[4] arenes

A novel method for the preparation of chromogenic calixarenes with azo groups was reported.p-Substituted(-NO2,-CH3,-Cl)amilines were diazotized with isoamyl nitrite in EtONa/EtOH under refluxing condition.Fifteen mono-,bis-,tris-and tetrakis(p-substituted phenyl)azo calix[4]arenes (including proximal and distal isomers) were obtainged respectively by diazo-coupling in different molar ratio to calix[4]arenes(1) under pH=7.5-9.0 in non-aqueous solution at 0-5℃.^1H NMR and ^13C NMR spectra of (p-substtituted phenyl)azo calix[4]-arenes indicated that they existed in cone conformation in solution.     

邻甲氧基羰基苄氧基取代杯[4]芳烃衍生物的合成及其性能研究

杯芳烃是继冠醚、环糊精之后的第三代主体分子[1].据文献[2,3]报道,在杯[4]芳烃下沿酚氧原子上连接乙酸酯得到的四取代衍生物对Na+有很高的选择性,核磁与晶体结构研究均证实这是由于羧酸酯的羰基和酚氧基参与了对Na+的配位,而且配位基团所形成的包络空间大小与钠离子相匹配.一般认为,随着包络空间改变,对金属离子的识别作用会有所变化[4].但目前对这方面的工作并没有给予更多的重视.我们发现,用2-溴甲基苯甲酸甲酯与杯[4]芳烃反应,得到了一种新的四取代杯[4]芳烃衍生物[2]萃取研究结果表明,该化合物对钾离子有较好的选择性.此外,在合成该衍生物的过程中,还得到了另一新的二取代衍生物(3).     

上端含长链烷基的手性杯[4]芳烃合成

脱叔丁基的杯[4]芳烃与长链的叔醇或者叔氯代烷烃进行傅-克反应, 在其上端引入长链烷基. 然后在下端引入光学活性的1-苯基乙胺基团, 得到了一系列上端含长链烷基的手性杯[4]芳烃.     

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.