几种新型杯[4]芳烃衍生物的合成

以对叔丁基苯酚为起始原料,通过缩合、一步取代反应合成了对叔丁基杯[4]芳烃的衍生物,两步取代反应合成了对叔丁基杯[4]芳烃的衍生物。用FT-IR,^1HNMR,FAB-MS对产物的结构进行了表征。     

Electrochemistry and ion-sensing properties of calix[4]arene derivatives

The cyclic voltammetric properties of several substituted calix[4]arenes were examined in acetonitrile and dichloromethane. The compounds that contained one phenolic group in the macrocyclic cavity were able to be electrochemically oxidised at positive potentials. In acetonitrile, cyclic voltammetry experiments indicated that the phenolic compounds were oxidised in a two-electron (one-proton) process over all measured scan rates (up to 50 V s⁻¹), while in dichloromethane, the oxidation process occurred by one-electron at scan rates ≥5 V s⁻¹, to most likely form the radical cations. In both solvents, longer timescale (minutes to hours) controlled potential coulometry experiments indicated that the oxidation process occurred by two-electrons per molecule, to form reactive diamagnetic cations that could not be reduced back to the starting materials under electrolysis conditions. The ion-sensing properties of the compounds were investigated in polymer membrane ion-selective electrodes and it was found that they responded reversibly in a Nernstian fashion to Groups 1 and 2 metals and had the highest selectivity to the cesium cation.     

杯[4]芳烃醚类衍生物的合成(Ⅱ)

以对叔丁基苯酚和甲醛为起始原料，通过选用不同的催化剂，合成了一系列新的杯[4]芳烃的四醚化衍生物，并对其结构用IR、^1HNMR、^13CNMR、MR进行了表征。     

氨基硫脲基新型杯[4]芳烃衍生物的合成

通过1,3-环氧丙基杯[4]烃与硫代氨基脲开环反应,合成硫代氨基脲基杯[4]芳烃衍生物,研究了其对阳离子的吸附性能后发现,与其他氨基杯芳烃相比,该衍生物对铜离子的吸附性能较好,并且有很好的选择性。     

氮杂杯〔4〕芳烃化合物的合成

以对叔丁基杯〔4〕芳烃为原料,对其上沿的叔丁基进行修饰,经不同的合成路线,利用羟基保护、取代、去叔丁基、硝化以及还原合成了尚未报道的新型氮杂杯〔4〕芳烃衍生物。其结构经1 H NMR,13C NMR和GC-MS表征。     

新型杯[4]芳烃衍生物对Pb~(2+),Cd~(2+)的萃取性质

研究了新型杯[4]芳烃D对Pb2+,Cd2+离子的液-液萃取性质,并将其与自制的杯[4]芳烃A及其衍生物B、C对Pb2+,Cd2+离子的液-液萃取性质进行了比较。结果表明,与化合物A~C相比,D对Pb2+萃取率最高,在实验条件下,可达到42.8%;测试的四种化合物对Cd2+离子的萃取效率均不佳,未经任何修饰的杯[4]芳烃A的萃取效率最高,仅8.5%。推测对Cd2+的萃取为阳离子交换机理。     

Synthesis and binding properties of polymeric calix[4]arene nitriles

Two new polymers containing pendant calix[4]arene units with nitrile functionalities at their lower rim have been synthesized via radical initiated reactions involving a vinylic monomer 6 {5,11,17,23-tetra-tert-butyl-25,26,27-tris(cyanomethoxy)-28-(2-acryloyloxy) ethoxycalix[4]arene} and with styrene. A five atom spacer group was incorporated between the bulky calixarene core and the acrylate moiety in order to minimize steric interactions which proved to impede the polymerization. The complexation studies were made by using liquid–liquid extraction procedures. It has been deduced from the observations that both polymers show a good selectivity towards Hg²⁺ like their precursor 5,11,17,23-tetra-tert-butyl-25,26,27-tricyanomethoxy-28-(2-hydroxy)ethoxycalix[4]arene 5, which supports their utility as adsorbents or potential candidate materials for fabricating membranes and sensors, which can separate or detect Hg²⁺ metal ions in a high selectivity.     

New calix[4]arenedimethacrylate derivatives for dental composites

Calix[4]arenes were double alkylated with various alkylhalogenides and the residual OH functions were subsequently dimethacrylated with methacryloyl chloride. The successful synthesis of polymerizable calixarenes was proved using ¹H NMR spectroscopy, matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry and differential scanning calorimetry. The polymerization behaviour was confirmed by copolymerization with methacrylic acid methyl ester. Furthermore, the flexural strength, the flexural modulus of elasticity, the exothermic course of the photo‐curing reaction and the polymerization shrinkage of experimental dental filling composites containing the modified calixarenes were evaluated. Copyright © 2012 Society of Chemical Industry     

杯[8]芳烃母体化合物的合成

以对叔丁基苯酚与多聚甲醛为原料,进行缩聚反应,合成了一种带叔丁基的杯[8]芳烃母体化合物,产率65%;再通过反Friedel-Crafts反应,脱除了其苯环上的叔丁基,产率81%。考察了升温速率、回流温度、N2通入速率等对目标产物产率的影响。产物结构经IR和1H-NMR表征。     

Methacrylated calix[4]arene phosphonic acids as functionalized crosslinker for radical polymerization

We describe the synthesis of 5,11,17,23‐tetra‐tert‐butyl‐25,27‐dioxypropylphosphonic acid‐26,28‐dimethacryloyloxy‐calix [4]arene and 5,11,17,23‐tetra‐tert‐butyl‐25‐oxypropylphosphonic acid‐27‐hydroxy‐26,28‐dimethacryloyloxy‐calix[4]arene starting from para‐tert‐butyl‐calix[4]arene. The complete reaction was proved by matrix‐assisted laser desorption ionization time of flight mass spectrometry and nuclear magnetic resonance spectroscopy. The influence of these compounds on the kinetics of the radical polymerization of methyl methacrylate was shown by dilatometry. Furthermore, the adhesive properties of dental adhesives containing these calix[4]arene derivatives were investigated. Copyright © 2012 Society of Chemical Industry     

氮杂杯[6]芳烃的合成与表征

以三聚氯氰和对苯二胺为原料,碳酸钾或氢氧化钾作为缚酸剂,合成氮杂杯[6]芳烃第一步中间体N,N’-二(4,6-二氯-1,3,5-均三嗪-2-基)-1,4-苯二胺(Ⅰ)和第二步中间体2,4-二(4-胺基苯胺基)-6-氯-1,3,5-均三嗪(Ⅱ),再由(Ⅰ)和(Ⅱ)合成最终产物氮杂杯[6]芳烃。通过红外光谱分析法和核磁共振氢谱法对产物进行了表征,证实其为目标产物,从而验证了合成路线的可行性。     

蒽醌冠醚双功能化杯[4]芳烃的合成与表征

以对叔丁基杯[4]芳烃为原料,经碱催化两步合成了26,28-双（2-亚甲基蒽醌）-5,11,17,23-四叔丁基杯[4]-25,27-冠-6。产物经IR、1HNMR表征和元素分析表征,该衍生物为锥形结构并与设计思想一致。     

芘冠醚双功能化杯[4]芳烃的合成与表征

以杯[4]芳烃为原料,经碱催化合成了26,28-双(1-乙酰基芘)-5,11,17,23-四叔丁基杯[4]-冠-6,产物结构经IR、1HNMR和元素分析表征。该衍生物为锥形结构。     

Droplet-based microreactor system for stepwise recovery of precious metal ions from real metal waste with calix[4]arene derivatives

ABSTRACT

Stepwise recovery of silver(I), palladium(II) and platinum(IV) with suitable calix[4]arene extractants was carried out by investigating the extraction and stripping process using a droplet-based microreactor system. The highest percentages of silver, palladium (100%) and platinum ion (37.2%) were extracted from a real waste only within 4.00s using a microreactor system compared with 24 and 72 h to reach extraction equilibrium in a batch method. Fourier transform infrared spectroscopy studies revealed a very good relation in peak shifts on the metal complexation with calix[4]arene derivatives after extraction and stripping. The droplet-based microreactor system emerges as an effective tool to be applied in metal recovery.     

Synthesis and characterization of calix[4]arene-based copolyethers and polyurethanes. Ionophoric properties and extraction abilities towards metal cations of polymeric calix[4]arene urethanes

Copolyethers and polyurethanes containing lower and upper rim calix[4]arene units in the fixed cone conformation were prepared in good yield by polycondensation reactions of distal calix[4]arene diols with bisphenol-A/dibromomethane and 2,4-tolylendiisocyanate (TDI), respectively. In a similar way were prepared calix[4]arene-crown-5 and -crown-6 polyurethanes in the fixed 1,3-alternate conformation by condensation of TDI with lower rim calixcrown-5 and calixcrown-6 diols. However, the poor solubility in common organic solvents of the copolyether derivatives (M_w=11,100-11,600 g/mol) hampered further studies on their ionophoric properties. Aiming to obtain model compounds for the investigation of both extraction abilities and ionophoric properties of the polyurethane materials, several bis-urethanes were also synthesized by reaction of the calix[4]arene diols with p-tolylisocyanate (TI). The extraction ability measurements of monomeric and polymeric calix[4]arene urethanes (M_w=12,300-83,500 g/mol) towards alkali metal cations (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺) and Ag⁺showed a remarkable efficiency and selectivity of calixcrown-6 polyurethane toward Rb⁺, Cs⁺and Ag⁺.     

Anion complexation by calix[4]arene-TTF conjugates

Calix[4]arenes bearing tetrathiafulvalene (TTF) moieties appended to the upper rim via the amidic functions were synthesized and used for ¹H NMR and UV/Vis complexation studies towards selected anions. It was found that the complexation affinity towards H₂PO₄⁻ dramatically depends on the substitution pattern of the calixarene moiety. As a result, the proximally disubstituted derivative has a complexation constant by two orders of magnitude higher than the distally disubstituted analogue. The differences between proximal and distal receptors were also documented by their behaviour during the oxidation of the attached TTF units.     

Synthesis and absorption spectra of some novel hetaryldisazocalix[4]arene derivatives

In this study, a convenient method for the synthesis of thirteen novel disazo dyes containing 25,26,27‐tribenzoyloxy‐28‐hydroxycalix[4]arene have been described. 5,11,17,23‐Tetra‐tert‐butyl‐25,26,27,28‐tetrahydroxycalix[4]arene, 25,26,27,28‐tetrahydroxycalix[4]arene and 25,26,27‐tribenzoyloxy‐28‐hydroxycalix[4]arene were synthesised based on previously published literature. 2‐Arylhdrazone‐3‐ketiminobutyronitriles were synthesised and reacted with hydrazine hydrate to afford the corresponding 5‐amino‐4‐arylazo‐3‐methyl‐1H‐pyrazoles. Thirteen novel hetaryldisazocalix[4]arene derivatives were achieved by diazotisation of 5‐amino‐4‐arylazo‐3‐methyl‐1H‐pyrazoles using nitrosylsulphuric acid, coupled with 25,26,27‐tribenzoyloxy‐28‐hydroxycalix[4]arene. The obtained hetaryldisazocalix[4]arene dyes were characterised based on Fourier Transform–infrared, proton nuclear magnetic resonance and mass spectroscopic techniques, as well as elemental analysis. The solvatochromic behaviour of these dyes in various solvents was examined. Acid‐base effects on the visible absorption maxima of the dyes were also reported.     

Electrochemical response of ferrocenium filled calix[4]arene capsules in solution and immobilized on gold

Hydrogen-bonded dimers of tetra-urea calix[4]arenes are able to include ferrocenium ions as a guest. Heterodimeric capsules are exclusively formed in 1:1 mixtures of tetra-arylurea calix[4]arene 1 with tetra-tosylurea calix[4]arene 2. Sulfide groups attached via spacers on the urea rim of 1 allow their binding to metal surfaces rendering simultaneously their dissociation more difficult. Thus, the electrochemical response of encapsulated ferrocenium could be studied in a self-assembled monolayer (SAM) in addition to the solution electrochemistry with cyclic voltammetry. The stability of the electrochemically active monolayers was tested after a heat treatment (225 °C for 30 min in N₂ atmosphere) and multiple cycling (up to 1200 cycles), which could be required for a possible application as molecular based information storage.     

The synthesis and characterization of novel metalloporphyrazine containing crown ether linked calix[4]arene moieties

The synthesis and characterization of novel magnesium porphyrazine, peripherally symmetrically derived from 1,3-alternate 26,28-[35,36-dicyano-34,37-dithia-29,32,40,43-tetraoxa-35-en]calix[4]arene-crown-5, were carried out. This compound was prepared starting from cis-1,2-dicyano-1,2-ethylenedithiolate and 1,3-alternate 26,28-bis(5′-chloro-3′-oxapentyloxy)calix[4]arene-crown-5. The new macrocycle was characterized using the techniques of UV–vis, ¹H, ¹³C NMR, IR, MS and elemental analysis.