杯[4]芳烃及其衍生物对NR抗热氧老化性能的影响

研究了C-甲基间苯二酚类杯[4]芳烃(简称杯[4]芳烃)及其含硫衍生物(简称杯[4]芳烃-SR)对天然橡胶(NR)硫化胶力学性能和抗热氧老化性能的影响,并与常用抗氧剂2,6-二叔丁基-4-甲基苯酚(BHT)在硫化胶中的耐抽提性能进行了对比。结果表明,杯[4]芳烃和杯[4]芳烃-SR均能有效提高NR硫化胶的抗热氧老化性能。由于具有较大的相对分子质量、较小的极性以及硫元素,添加杯[4]芳烃-SR的NR硫化胶表现出了更为优良的抗热氧老化性能。在NR硫化胶中,杯[4]芳烃-SR的耐抽提性能最优,杯[4]芳烃次之,BHT最差。     

醛肟基杯[4]芳烃衍生物的合成及性能研究

利用盐酸羟胺与杯[4]芳烃二醛衍生物的亲核加成反应,设计并合成了下沿含醛肟基团的新型杯[4]芳烃衍生物,经1HNMR、MS和元素分析等表征确证其结构,测定了醛肟基杯[4]芳烃衍生物对系列金属阳离子的液液两相萃取性能,实验结果表明醛肟基杯[4]芳烃衍生物对软酸类金属阳离子具有较好的配位性能,特别是对Hg2+和Ag+的萃取率分别达到39.2%和35.6%。     

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％.     

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。     

含金刚烷胺的杯［4］芳烃衍生物的合成及抗菌活性研究

对叔丁基杯[4]芳烃与对甲苯磺酸酯基乙氧基对苯甲醛反应生成对叔丁基杯[4]芳烃-1,3-二醛基衍生物1,对叔丁基杯[4]芳烃-1,3-二醛基衍生物1与金刚烷胺进行分子间缩合反应得到含金刚烷基的新型杯[4]芳烃衍生物,并利用1H NMR,13C NMR,MS和元素分析对目标化合物的结构进行了表征。初步的抗菌试验表明,该化合物表现出较好的抑菌活性。     

杯芳烃的合成及性能研究的新进展

简要介绍了杯芳烃的结构、性能及应用,重点综述了：（1）新型杂原子杯芳烃的合成及超分子自组装;（2）杯芳烃衍生物的合成及对金属离子的识别;（3）杯[4]吡咯席夫碱衍生物的合成。     

含氟杯[4]芳烃衍生物超分子性能的研究进展

含氟杯[4]芳烃因引入具有特殊物理化学性质的含氟取代基,而具有某些优良的超分子性能,与非氟杯[4]芳烃相比在分子识别、分子自组装、荧光传感器、分子开关、液相色谱等方面存在更为广阔的应用前景。在超分子化学和氟化学的交叉领域中,成为近年来化学工作者们研究的热点,此领域的相关文献报道较少。综述了近几年含氟杯[4]芳烃衍生物新主体分子的合成,并从分子识别应用的角度,重点讨论了对新型功能化含氟杯[4]芳烃衍生物的超分子性能研究状况。     

含杯[4]芳烃的金刚烷甲酰腙的合成及抗菌活性研究

对叔丁基杯[4]芳烃与对甲苯磺酸酯基乙氧基对苯甲醛反应生成对叔丁基杯[4]芳烃-1,3-二醛基衍生物1,对叔丁基杯[4]芳烃-1,3-二醛基衍生物1与金刚烷甲酰肼进行分子间缩合反应得到含杯[4]芳烃的金刚烷甲酰腙化合物2,并利用1H NMR,13C NMR,MS和元素分析对目标化合物的结构进行了表征。初步的抗菌试验表明,该化合物表现出较好的抗菌活性。     

苯甲醛缩氨基硫脲化合物的合成及性质研究

硫代氨基脲及其衍生物,与金属配位时,有着多种配位模式,并且其金属配合物有着广谱的抗癌效果。本论文采用苯甲醛和4-苯基-3-硫代氨基脲反应制备L1,将L1作为配体与[Ru(p-cymene) Cl_2]_2反应制备配合物1,并研究其光谱活性。     

杯[4]芳烃巯基吡啶衍生物的合成

以对叔丁基苯酚为起始原料,通过缩合得到对叔丁基杯[4]芳烃,再对其下沿酚羟基进行化学修饰,得到具有化学活性的杯[4]衍生物,该化合物与具有活泼氢的4巯基吡啶反应制得新的含N、S杯芳烃衍生物,总收率15.3%。     

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[4]芳烃偶氮衍生物的合成及其金属离子萃取性能

杯芳烃作为超分子化学的重要组成部分,近年来得到了快速发展并成为化学家的研究热点。以脱叔丁基-杯[4]芳烃为原料合成了杯[4]芳烃偶氮衍生物,其结构经IR和1H NMR所表征。研究了该主体分子对金属离子的萃取性能,实验结果表明,该主体分子对Mg2＋具有较高的萃取作用。讨论了主客体间配位作用的机制。     

对叔丁基杯[4]芳烃巯基吡啶衍生物的合成

以对叔丁基苯酚为起始原料,通过缩合得到对叔丁基杯[4]芳烃,再对其下沿酚羟基进行化学改性,得到具有化学活性的杯[4]衍生物中间体,该中间体与具有活泼氢的2-巯基吡啶反应制得新的含N、S杯芳烃衍生物,总收率14.4%。     

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。     

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.     

Extraction of Pb2+ with p-tert-butylcalix [4]-, [5]-, [6]Arene Carboxylic Acid Ligands and their Monomeric Counterpart: A Thermodynamic Approach

Studies on extraction equilibrium constants at different temperatures and thermodynamic parameters of solvent extraction of Pb²⁺ ion with carboxylic acid derivatives of different ring size calixarenes and structure related monomeric compound have been carried out. The extraction equilibrium constants corresponding to calix[n]arene (n?=?4, 5, 6) derivatives decrease in the order [5]arene > [6]arene > [4]arene. In all cases, the complexation process is primarily enthalpy driven. The favorable enthalpic contribution for extraction of Pb²⁺ is in the order hexamer ≈ monomer > tetramer > pentamer. However, the unfavorable entropic loss follows the order: monomer > hexamer > tetramer > pentamer. Overall stability of the host-guest complex is the function of entropy-enthalpy compensation and the free energy of complexation is minimum for the pentamer, followed by tetramer ≈ hexamer and monomer. Although the carboxylic acid derivative of calix[4]arene is more preorganized than the calix[5]arene derivative, extraction of Pb²⁺ ion with the tetramer passes through greater entropic loss than that with the pentamer and the degree of preorganization of calix[4]arene derivative is far from perfect for the complexation and extraction of Pb²⁺ ion. As compared to tetrameric and hexameric counterparts, the structural features of the carboxylic acid derivative of calix[5]arene prior to complexation contribute much to interact with the Pb²⁺ ion and form a thermodynamically stable complex. Supplementary materials are available for this article. Go to the publisher's online edition of Solvent Extraction and Ion Exchange to view the supplemental file.     

Dichromate Extraction by Calix[4]arene Appended Amberlite XAD-4 Resin

In the present article a comparative extraction efficiency of dichromate by a calix[4]arene derivative (d) and a newly synthesized calix[4]arene appended Amberlite XAD-4 resin (5) are reported. The liquid and solid phase extraction methods have been applied to ascertain the extraction efficiency of both the calix[4]arene derivative and the resin. Different parameters have been optimized such as pH, dosage, concentration, and temperature. Analysis of experimental data has been carried out by log-log plot analyses and the determination of characteristic parameters of each isotherm model such as Freundlich, Langmuir, and Dubinin-Radushkevich (D-R). The kinetic adsorption experiments show that the adsorption process follows pseudo second order kinetics. The adsorption mechanism has been investigated by Reichenberg (R-B) and Morris-Webster equations. From the thermodynamic parameters it is concluded that the adsorption process is endothermic and spontaneous in nature at higher temperature. The results show that the resin-5 has good capability to efficiently remove dichromate from aqueous media.     

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。     

Synthesis,extraction, and adsorption properties of calix[4]arene‐poly(ethylene‐glycol) crosslinked polymer

Novel calix[4]arene‐poly(ethylene glycol) crosslinked polymer (CCP) has been synthesized by the polycondensation reaction between a p‐tert‐butylcalix[4]arene derivative and dihydroxyl capped poly(ethylene glycol) (DHPEG, M_n = 1000) catalyzed by neodymium tosylate. The hydrogel, consisted of 66.9% water and 33.1% CCP, can selectively extract aromatic organic molecules from aqueous solution according to the diameter of the guest molecules, which infers that the diameter of the calix[4]arene cavity is about 5.4 Å and the conformation of calix[4]arene units altered from cone conformation to 1,3‐alternate conformation during the polycondensation reaction. Furthermore, CCP can also adsorb naphthalene from gas phase, showing much higher capacity than active carbon does, which may have some potential applications in the field of separation and environment protection. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008