Tetra(diethyl)amide-p-tert-butyl-thiacalix[4]arene in Cone Conformation: Synthesis and Binding Properties with Alkali,Alkaline Earth,Heavy and Transition Metal Ions

Tetra(diethyl)amide-p-tert-butylthiacalix[4]arene 1a in the cone conformation was synthesized and its binding properties towards a large variety of metal ions were established on the basis of liquid–liquid and solid–liquid extraction as well as complexation experiments. This compound is a less efficient and selective compound than the “classical” tetra(diethyl)amide-p-tert-butylcalix[4]arene 3 in the cone conformation for alkali and alkaline earth metal ions. However, Pb²⁺ is selectively extracted and complexed within heavy and transition metal ions.     

Facilitated Transfer of Alkali and Alkaline‐Earth Metal Ions by a Calix[4]arene Derivative Across Water/1,2‐Dichloroethane Microinterface: Amperometric Detection of Ca2+

The host–guest complexation reactions between 5,11,17,23‐tetra‐tert‐butyl‐25,27‐diethoxycarbonylmethoxy‐26,28‐dimethoxy calix[4]arene (BDDC4) and alkali and alkaline‐earth metal ions were investigated by facilitated ion transfer processes across water/1,2‐dichloroethane microinterface by using steady‐state cyclic voltammetry and differential pulse voltammetry. The obtained facilitated transfers for Li⁺, Na⁺, K⁺, Rb⁺ and Ca²⁺ were evaluated under the different experimental conditions, at the excess concentrations of metal ions with respect to BDDC4 and vice versa. The association constants having 1 : 1 stoichiometry for Li⁺, Na⁺, K⁺ and Rb⁺ in 1,2‐DCE were determined. Also, we demonstrated that BDDC4 can play an important role for the development of highly selective chemical sensor for Ca²⁺ among alkaline‐metal ions in the concentration range of 0.1–1.0 mM in aqueous solution.     

硫代杯[8]芳烃衍生物的合成及其对金属离子的选择性识别研究

在丙酮溶液中以碳酸铯为催化剂,以硫代杯[8]芳烃(thiacalix[8]arene,TC8A)和N,N-二乙基-2-氯乙酰胺为底物,对TC8A的下缘进行修饰合成了一种新的TC8A衍生物--硫代杯[8]芳烃二乙基乙酰胺[TC8A-CH2CON(CH2CH3)2].对含有9种金属离子的汽车尾气净化催化剂溶液进行萃取研究表明,在pH为3.0的萃取液中TC8A对其中的钯离子具有最高的选择性萃取能力,萃取率可达99.3%,TC8A-CH2CON(CH2CH3)2对其中的锆离子具有最高的选择性识别能力,萃取率可达96.7%.     

Synthesis and Characterization of Thiacalix[4] arene Derivatives with Polymerisable Groups

Introduction Calixarenes are versatile host molecules for molecular recognition and supram olecular assembly be-cause its functional groups can be readily introduced in-to the phenolic OH or the para position to realize a wide variety of functions[1-5].     

Synthesis and Electrochemical Behavior of Electroactive Bistetrathiafulvalene-attached Thiacalix[4]arene Assemblies

Tetrabromoalkylthiacalix[4]arenes(1a and 1b) reacted with excess bis(tetraethylammonium)-bis(1,3- dithiole-2-thione-4,5-dithiol)zincate(2) to give thiacalix[4]arene-thiones(3a and 3b) in the presence of Na₂S. Two novel bistetrathiafulvalene-attached thiacalix[4]arene assemblies(5a and 5b) formed via triethyl phosphite-mediated cross-coupling of thiacalix[4]arene-thiones(3a and 3b) and 4,5-biscyanoethylthio-1,3-dithiole-2-one(4). All the four new compounds were characterized by ¹H NMR, ¹³C NMR, IR, MS spectra and elemental analysis. Meanwhile, the structures of thiacalix[4]arene-thiones(3a and 3b) were identified by X-ray analysis. In addition, the cyclic voltammograms of the resulting thiacalix[4]arenes containing electroactive TTF units(5a and 5b) were provided.     

Synthesis,Characterization and Coordination Properties of a Novel Thiacalix[4]arene with Diagonal Quinolin-8-yloxy Pendants

A novel conic thiacalix[4]arene derivative (1) with diagonal quinolin-8-yloxy pendants via oxyethylene spacer has been synthesized in one step. The coordination properties of the new ligand towards Ni^2 + , Co^2 +  and Zn^2 +  ions were studied by UV–vis, fluorescent spectra and ¹H NMR titration. The results showed that 1 formed very stable complexes with the three metal ions, and the stoichiometries of 1-Ni^2 + , 1-Co^2 +  and 1-Zn^2 +  were 1:1, 1:2 and 1:2, respectively.     

Thiacalix[4]arene 1,2,3-triazole-polyethylene glycol polymers: Synthesis and dye adsorption properties

By reacting alkynylthiacalix[4]arenes with polyethylene glycol azido compounds, a series of novel thiacalix[4]arene 1,2,3-triazole-polyethylene glycol netty polymerswere conveniently prepared in good yields. Their structures and morphologies were studied by ¹H NMR, IR, and elemental analysis and SEM images. On average, approximately 28-31 thiacalixarene units exist in each polymeric molecule. These novel polymers possess excellent adsorption ability for both cationic and anionic dyes. The saturation adsorption capacity for Congo red reached 1.3-1.4 mmol/g. They exhibit high and stable adsorption ability in the scope of pH 5-9, and maintain good properties in five cycles.     

Synthese,Charakterisierung und Magnetische Eigenschaften eines tetranuklearen,Thiacalix[4]aren‐stabilisierten Mangankomplexes

Synthesis, Characterization and Magnetic Properties of a Tetranuclear, Thiacalix[4]aren stabilized Manganese Complex Synthesis, characterization and magnetic properties of the compound [(TCA)(TCAH)Mn₄(acac)] ( 1 ) are reported, the first tetranuclear thiacalix[4]aren stabilized manganese complex synthesized under conventional conditions.     

杯芳烃偶氮类衍生物对金属离子的萃取作用

通过杯芳烃的酚羟基的直接烃基化反应,在杯芳烃的下缘引入2,3′-二甲基-4-氨基偶氮苯发色团,得到了一系列杯芳烃偶氮衍生物(n=4,6,8)a-c.研究了它们对碱金属,碱土金属及过渡金属等十种金属离子的萃取作用.结果表明此类杯芳烃偶氮衍生物对过渡金属离子有良好的选择性识别作用,其中空腔较大的杯[8]芳烃偶氮衍生物c的萃取效果尤为显著.     

系列新型硫杂杯[4]芳烃氮杂衍生物的合成

在对叔丁基硫杂杯[4]芳烃的下缘1,3位引入芳醛基, 合成了硫杂杯[4]二醛基衍生物2. 化合物2与苯胺、水杨酰肼、烟酰肼、异烟酰肼等通过席夫碱缩合反应得到新型硫杂杯[4]氮杂衍生物3a～3d, 产率分别为83%, 80%, 77%和79%. 化合物2与邻苯二胺、乙二酰肼、丙二酰肼、己二酰肼等通过“1＋1”分子间缩合得到新型1,3-桥联硫杂杯[4]氮杂衍生物4a～4d, 产率53%, 51%, 59%和66%. 新化合物的结构经IR, ¹H NMR, MS和元素分析等证实.     

磺化硫杂杯[4]芳烃修饰纳米金的制备及对水溶液中Cr3+的比色检测

在不需外加还原剂的条件下一步原位合成了磺化硫杂杯[4]芳烃修饰的纳米金,并将其作为比色探针对金属离子进行检测。研究表明,磺化硫杂杯[4]芳烃修饰的纳米金能够选择性的识别CrP3+P,其检测限可达到1μM。     

F-Induced ‘turn-on’ fluorescent chemosensor based on 1,3-alt thiacalix[4]arene

A new thiacalix[4]arene based fluorescent sensor 1 bearing two naphthyl groups has been synthesized in 1,3-alternate conformation. In the absence of fluoride ion, the receptor 1 is in ‘off-state’ showing no fluorescence emission. The presence of fluoride ion triggered the fluorescence emission to ‘on-state’. The receptor shows pronounced selectivity for fluoride ions. In THF, the presence of F⁻ ions induces the formation of a 1:1 (G:H) complex.     

Ethylene polymerization promoted by dinuclear titanium p-tert-butylthiacalix[4]arene complexes

The dinuclear titanium p-tert-butylthiacalix[4]arene complexes 1 and 2 after activation with methylaluminoxane have been tested as homogeneous catalysts for the polymerization of ethylene. The results show that the catalytic activity of 1, although still poor, is higher than those of the related mononuclear titanium complexes bearing calix[4]arene as ligand. The molecular weight of the polyethylene produced are high (M_W up to 1.4 × 10⁶ Dalton) with broad molecular weight distribution. The polyethylenes have high melting point (133-142 °C) indicating a linear polymer microstructure which was confirmed by ¹³C NMR analysis.     

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。     

Selective extraction of Fe3+ by a polymeric calix[4]arene

A polymeric compound containing more than one calixarene molecule was synthesized by reacting the oligomer ( 2 ) with 25,26,27-tribenzoyloxy-28-hydroxy calix[4]arene. After basic hydrolysis of 3a , the polymeric calixarene ( 3b ) was utilized for selective extraction of some metal cations from aqueous phase to organic phase. It was found that the compound ( 3b ) was selective toward Fe³⁺ from an aqueous solution containing Cu²⁺, Ni²⁺, Co²⁺ and Fe³⁺ cations. The mechanism of the extraction process was discussed. © 1994 John Wiley & Sons, Inc.     

硫杂杯[4]芳烃酰胺基硫脲衍生物的合成

硫杂杯[4]芳烃四乙酸乙酯衍生物与水合肼反应生成硫杂杯[4]芳烃四酰肼衍生物(3),3与异硫氰酸苯酯反应得到新型硫杂杯[4]芳烃酰胺基硫脲衍生物,总产率61%。     

Synthesis of Flavin–Calix[4]arene Conjugate Derivatives

The synthesis of two new flavin substituted calix[4]arene derivatives, 9 and 10 , is described. The first flavin substituted calix[4]arene derivative 9 was synthesized by the reaction of 3‐methylalloxazine ( 5 ) with 25,27‐bis(3‐bromopropoxy)‐26,28‐dihydroxy‐5,11,17,23‐tetra(tert‐butyl)calix[4]arene ( 4 ) in high yield (92%). The other derivative 10 was prepared from 3‐methylalloxazine‐1‐acetic acid ( 7 ) and 25,27‐bis(3‐cyanopropoxy)calix[4]arene ( 3 ). All new compounds were characterized by a combination of FT‐IR and ¹H‐NMR spectroscopy, and elemental‐analysis techniques.     

Spectrophotometric study of the supramolecular complexes of [60]- and [70]Fullerenes with biscalix[6]arene and crown[4]calix[6]arene

[60]- and [70]Fullerenes have been shown to form 1:1 supramolecular complexes with bis[2-(5,11,17,23,29,35-hexa-tert-butyl-37,38,39,40,41-pentahydroxycalix[6]arenyl-oxy ethyl ether) (1) and 5,11,17,23,29,35-hexa-tert-butyl-37,38,40,41-tetra hydroxyl-39,42-(crown-4)calix[6]arene (2) in CHCl3 medium by electronic absorption spectroscopy. Formation constants (K) of the complexes of [60]- and [70]fullerenes with 1 and 2 have been determined at room temperature from which free energy of formation values of the complexes have been estimated. The very high formation constant value of [60]fullerene/1 complex (5900 dm3 mol-1) in indicative of formation of inclusion complex. Moreover, PM3 calculations reveal that intermolecular interaction between [60]fullerene and 1 proceeds through quite deep energy molecular orbital.     

Unprecedented cyclisations of calix[4]arenes under the Mitsunobu protocol. Part 3: Thiacalix[4]crowns versus dimers

Intermolecular couplings versus intramolecular ring closures were observed in the reaction of p-tert-butylthiacalix[4]arene and diethylene glycols affording dimers 2 and/or the inherently chiral 1,2-thiacalix[4]crown-3 derivatives 5 under the Mitsunobu protocol. The enantiomeric separation of 5a was achieved by chiral HPLC. The reaction of thiacalix[4]monocrowns 1 with diethylene glycols failed to give crowned thiacalix-tubes 7, instead biscrowns 8 were formed. Partially alkylated double thiacalix[4]arenes 10, 11 were obtained via the base promoted alkylations of a thiacalixarene dimer 2a containing diethyleneoxy linkers.     

Transition metal ion selective ortho-ester diazophenylcalix[4]arene

New chromogenic dizophenylcalix[4]arene 1 showing selective color change to transition metal ions over other alkaline and alkaline earth metal ions has been prepared in the cone conformation and tested for its usefulness.