微波辐射促进杯芳烃酯类衍生物的快速合成

微波辐射条件下,以对叔丁基杯[6]、杯[8]芳烃为原料,采用氯乙酸乙酯为烃基化试剂,PEG-400为催化剂,可高效地制得下缘被酯基取代的产物.该方法较之传统方法,操作简单、反应时间大大缩短、污染减少.     

杯[4]芳烃咪唑盐的微波合成及在氟化反应中的应用

以杯[4]芳烃为起始原料,首先制得中间体杯[4]芳烃双溴代烷基衍生物,然后经微波辐射和阴离子交换,共得9种杯[4]芳烃咪唑盐衍生物,化合物的结构与构象经元素分析、IR、1HNMR、19FNMR、31PNMR表征.研究了它们在对氯硝基苯氟化反应中的催化性能以及对K+的萃取性能.结果表明,这9种化合物在氟化反应中的催化效果良好,对氟硝基苯的收率为80.89％～92.67％;同时化合物对K+具有较好的萃取效果,其中以化合物25,27-二[4-(3-甲基咪唑)乙氧基]-26,28-二羟基-5,11,17,23-四叔丁基杯[4]芳烃六氟磷酸盐的萃取效果最好,萃取率可达75.45％.     

对叔丁基杯[4]及杯[6]芳烃的合成及其对铜离子的萃取研究

以对叔丁基苯酚和甲醛为原料,分别对对叔丁基杯[4]及杯[6]芳烃的合成和萃取性质进行了研究．结果表明,在本研究范围内,以KOH为催化剂,对叔丁基杯[6]芳烃的最高产率为77．8％;以NaOH为催化剂,对叔丁基杯[4]芳烃的最高产率为47．3％。对于对叔丁基杯[4]和杯[6]芳烃,最佳的反应回流温度都为140℃。对叔丁基杯[6]芳烃对模拟废水中的铜离子具有一定的萃取效果,最高萃取率为70．3％。     

超声条件下磺化杯芳烃的高效合成

采用超声辐射,以对叔丁基杯[n]芳烃为原料,先通过逆Fridel-Crafts反应脱去叔丁基,得到杯[n]芳烃,进一步磺化,可高效制得磺化杯[n]芳烃。两步反应约0.5~1 h即可完成,收率可达到90%以上。该方法较传统加热方法,操作简单,反应时间大大缩短。     

杯芳烃的合成及其对二氧化碳的吸附研究

以对叔丁基苯酚和甲醛溶液为原料,在酸碱条件下采用两步法合成杯[4]芳烃和杯[6]芳烃,并对这两种产物进行了结构表征。同时将合成的杯芳烃进行了对二氧化碳的吸附,发现对叔丁基杯[6]芳烃对二氧化碳的吸附百分比为1．516％。     

对叔丁基杯[6]芳烃合成方法的改进

对叔丁基杯[6]芳烃是杯芳烃的一种基本原料,而杯芳烃由于其环腔大小可调,可进行多种化学修饰等特点,从而有模拟酶催化、传输、分离与富集等方面具有广阔的应用前景,目前大多数杯[6]芳烃的衍生物都是以从对叔丁基杯[6]芳烃出发经适当步骤进行合成的,因而能够以高产率得到对叔丁基杯[6]芳烃具有重要意义。经多年摸索与研究,Gutsche等人将对叔丁基杯芳烃其产率提高到80%以上,但实验方法不易掌握、不易重复,而且和得到的粗产品中往往含有一定量的对叔丁基杯[8]芳烃、对叔丁基杯[4]芳烃等副产品,因而在重结晶纯化以后导致对叔丁基杯[6]芳烃的产…     

杯芳烃／聚丙烯共混体系耐热氧性能的研究

合成了对叔丁基杯[4]、杯[6]、杯[8]芳烃,并用热重法和烘箱老化评价了共混体系的耐热氧性能。结果表明,杯芳烃能明显提高聚丙烯的耐热氧性能,其耐热氧能力为：对叔丁基杯[6]芳烃＞对叔丁基杯[4]＜2,6－二叔丁基－4－甲基苯酚。     

对叔丁基杯[6]芳烃与黑索金的配合研究

对叔丁基苯酚和甲醛在KOH催化下制备对叔丁基杯[6]芳烃。用荧光光谱法研究了对叔丁基杯[6]芳烃与黑索金(RDX)在溶液中的相互作用,结果表明对叔丁基杯[6]芳烃与RDX在溶液中存在较强的配合作用,RDX的激发峰发生明显红移,荧光强度增强,主客体间发生了包合作用。通过对叔丁基杯[6]芳烃-RDX配合物的发射光谱与紫外光谱分析,确定了在DMF溶液中对叔丁基杯[6]-RDX配合物的化学计量比为1∶1,稳定常数为325.70。     

含氮杯[4]芳烃的合成

以对叔丁基苯酚为起始原料,经过3步反应,在母体杯芳烃的下沿引入3种不同的含氮基团,得到5种含氮杯[4]芳烃,并通过1HNMR和熔点测定确定了产物结构.实验中发现,当母体杯芳烃下沿引入的溴代烷基变长时,进一步引入含氮基团,只能得到1,3位环化的含氮杯[4]芳烃.     

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。     

Adsorption of amino acid derivatives on calixarene carboxylic acid impregnated resins

Macrocyclic host molecules calixarene carboxylic acid derivatives are found to act as powerful extractants for biologically important amino compounds. A series of adsorbents were prepared from a methacrylate-based polymer Amberlite XAD-7 by impregnation with various calixarene derivatives, for adsorptive recovery of amino acid derivatives. The larger macrocycles calix[6]arene and calix[8]arene carboxylic acid derivatives were more effective for adsorption of amino acid derivatives on the impregnated resin than the calix[4]arene derivative. Since adsorption proceeds mainly via electrostatic interaction, the carboxylic acid groups introduced into the calixarene platform were important for adsorption of cationic amino acid derivatives. The adsorption selectivity for amino compounds using adsorbent impregnated with the calix[6]arene carboxylic acid derivative depends simply on the hydrophobicity of the adsorbates.     

杯芳烃合成研究进展

杯芳烃是一类超分子主体化合物,主要有杯[4]、杯[6]和杯[8]芳烃的杯芳烃衍生物、杯芳烃聚合物及杯芳烃配合物等。介绍了不同杯芳烃及其衍生物的合成工艺的研究进展。     

Novel linear molecular aggregation tethered by hydrogen-Bonded interaction within the crystalline calix[4]arene derivatives

Single crystals of two calix[4]arene derivatives, that is, 5,11,17,23-tetra-tert-butyl- 25,27-bis[2-[N-(3-methoxy-4-methoxy-benzylidene)-amino]ethoxy]-26,28- dihydroxy calix[4]arene (1) and 5,11,17,23-tetra-tert-butyl-25,27-bis[2-[3- pyridine carbonyl-amino]ethoxy]-26,28-dihydroxy calix[4]arene (2), were prepared and their crystal structures have been determined by X-ray crystallographic study. As compared with calix[4]arene derivative 1 possessing CN functional group, compound 2 bearing the NH group could form not only intermolecular hydrogen bonds between the hydrogen atom in NH group and the oxygen atom in CO of an adjacent calix[4]arene molecule, but also intramolecular hydrogen bonds between the N—H⋯OC moieties in solid state, giving a rare linear molecular aggregation.     

Effect of additives on nickel-phosphorus deposition obtained by electroless plating: Characterization and corrosion resistance in 3%(mass) sodium chloride medium

Nichel-phosphorus (Ni-P) coatings are deposited on mild steel by using an electroless plating process. The effect of three calix[4]arene derivatives, namely tetra methyl ester-P-tertbutyl calix[4]arene (Calix1), tetra acid-P-tert-butyl calix[4]arene (Calix2) and tetra methyl P-tert-butyl-thicalix[4]arene ester (Calix3) on the deposition rate, the deposit composition, and the morphological surface was investigated and the study of growth mechanisms has delivered useful information about the surface properties of deposit. It is found that these additives modify the deposition rate and the nickel crystallization process. In fact, the Calix1 and Calix3 act as an accelerator, while Calix2 acts as an inhibitor for the nickel electroless. Furthermore, it is shown that the chemical bath is more stable with calix[4]arene derivatives addition and the obtained deposits are compact and adherent. It is observed also that the nickel content increases with additives. On the other hand, the X-ray diffraction showed that the orientation peaks are intensified at {1 1 1} in the presence of Calix2, confirming obtained results of EDAX spectrum. The cyclic voltammetry revealed that the tested additives strongly influence the cathodic process and slightly affect the hypophosphite oxidation. Finally, it is found that these compounds improve the anticorrosion efficiency of Ni-P coating on the mild steel substrate in 3% (mass) NaCl, where its polarization resistance increases with Calix2 and Calix3 addition.     

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     

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 of novel silica gel immobilized‐calix[4]arene amide ionophores and their anion binding abilities toward phosphate and chromate anions

This article describes the synthesis and characterization of four new calix[4]arene ionophores 5–7 and 9 and corresponding two new silica gel‐immobilized calix[4]arene ionophores containing pyridine 10 and 11 via modification of calix[4]arene monoamide derivatives 5 and 6 with aminopropyl silica gel, respectively. The extraction studies have been performed using liquid–liquid extraction for receptors 5–7 and 9 and solid–liquid batchwise sorption procedures for receptors 10 and 11 . Obtained extraction results showed that the immobilized‐calix[4] arene ionophores 10 and 11 have high extraction ability toward chromate and phosphate anions as compared to their corresponding monomeric precursors 5 and 6 . © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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。