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5,11,17,23-四叔丁基-25,26,27,28-四[3-(甲氧基羰基)苄氧基]杯[4]芳烃包合性能的研究 总被引:2,自引:0,他引:2
杯芳烃是继冠醚和环糊精后的第三代主体化合物 .这类主体分子不仅可以识别和络合阳离子 ,而且还具有包合中性有机分子的性能 [1~ 5] .杯 [4]芳烃类包合物的晶体结构测定表明 ,它们可分为分子内和分子间包合两种类型 [3 ,5] ,前者是客体分子被包合在主体分子的空穴内 ,后者是客体分子被包合在主体分子之间 .对叔丁基杯 [4]芳烃的下沿酚氧基与上沿均可进行化学修饰得到不同的杯 [4]芳烃衍生物 .最早报道的对叔丁基杯 [4]芳烃及其衍生物的分子内包合物是与甲苯或乙腈的 1∶ 1包合物 [4 ,5] ,客体分子依靠 CH3 -π的作用被包结在主体分子内[6]… 相似文献
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间苯二酚杯芳烃是超分子化学的第3代主体分子。介绍了间苯二酚杯芳烃的结构、衍生化途径及其衍生物的用途。 相似文献
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分子识别是生物识别的基础,其机理的研究对理解生命现象具有重要意义。水溶性杯芳烃是研究分子识别的重要主体分子,本实验报道合成了水溶性的5,11,17,23,29,35,41,47-八(N,N-二甲氨甲基)-杯[8]芳烃(以下简称杯胺),采用荧光法测定了其与二苯胺磺酸钠的包结常数,研究了包结作用。以杯胺为流动相添加剂,二苯胺磺酸钠为溶质,采用色谱法进行了对比研究,结论相符。 相似文献
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杯芳烃是由苯酚单元通过亚甲基连接而成的空腔型分子,具有衍生位点多,构象丰富等特点,被称为第三代主体分子。在分子层次,依手性因素的结构特点不同,可将手性杯芳烃分为具有手性亚单元的杯芳烃、固有手性杯芳烃和桥手性杯芳烃。在超分子层次,杯芳烃自身或杯芳烃与其他分子或离子在溶液中、晶态中或二维表面可通过非共价键力形成多种拓扑结构的纳米手性聚集体。研究手性杯芳烃和基于杯芳烃的超分子手性组装体的合成、结构和性能,不仅在理解手性起源、手性结构等方面具有理论意义,而且有望获得以分子识别为基础的手性传感器、手性催化剂、手性分离材料、手性载体和手性纳米材料。本文综述近十年来有代表性的分子手性杯芳烃和以杯芳烃为组分的超分子手性聚集体的设计、合成、结构和功能。着重展示杯芳烃骨架在形成新颖分子手性和超分子手性上的优势,以及杯芳烃单元在实现特定功能如手性识别时发挥的作用。相信随着杯芳烃合成技术和杯芳烃超分子设计的发展,必将进一步发挥杯芳烃的结构优势,涌现出更多性能优异的手性杯芳烃功能分子和超分子手性杯芳烃功能材料。 相似文献
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杯芳烃衍生物在分析化学中的应用 总被引:15,自引:6,他引:15
杯芳烃衍生物是以杯芳烃为“分子平台”,经过不同的衍生化而得。根据杯芳烃的空腔大小,构象及其衍生官能团与客体分子间的适应程度,杯芳烃衍生物可实现对金属离子及有机分子的选择性识别。本文介绍了芳烃衍生物在分析化学领域,包括萃取分离,液膜分离,色谱分析及光分析中的应用情况。 相似文献
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Masami Iyo Kosuke Tsutsui Atsushi Kameyama Tadatoimi Nishikubo 《Journal of polymer science. Part A, Polymer chemistry》1999,37(16):3071-3078
Novel polyfunctional (meth)acrylates with a calixarene backbone [calixarene (meth)acrylates] were synthesized in good yields by certain reactions of p-methylcalix[6]arene (1a) or p-tert-butylcalix[6]arene (1b) with (meth)acrylate derivatives such as acryloyl chloride, methacryloyl chloride, (2-methacryloxy)ethyl isocyanate, and glycidyl methacrylate. Polyfunctional acrylate 6a having poly(oxyethylene) spacer chain between 1a and acrylate groups was also synthesized by the reaction of the poly(oxyethylene) modified 1a with acrylic acid. Calixarene acrylate 6a was liquid at room temperature, although the other calixarene (meth)acrylates were solid at room temperature. The initial decomposition temperature (IDT) of the resulting calixarene (meth)acrylates was measured by the thermogravimetric analysis to evaluate the thermal stability, and it was found that some of the IDTs of the calixarene acrylates were over 400°C. This means that calixarene (meth)acrylates have very good thermal stability. The photopolymerization of the resulting some calixarene (meth)acrylates with (2-phenyoxy)ethyl acrylate as a reactive diluent in the presence of photoinitiator proceeded smoothly upon irradiation with UV light. Therefore, polyfunctional (meth)acrylates with a calixarene backbone can be expected to be novel and thermally stable photoreactive acrylate oligomers. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3071–3078, 1999 相似文献
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Tadatomi Nishikubo Atsushi Kameyama Kousuke Tsutsui Masami Iyo 《Journal of polymer science. Part A, Polymer chemistry》1999,37(12):1805-1814
New photoreactive p-methylcalix[6]arene (MCA) derivatives containing cationically polymerizable groups such as propargyl ether (calixarene 1), allyl ether (calixarene 2), and ethoxy vinyl ether (calixarene 3) groups were synthesized with 80, 74, and 84% yields by the substitution reaction of MCA with propargyl bromide, allyl bromide, and 2-chloroethyl vinyl ether (CEVE), respectively, in the presence of either potassium hydroxide or sodium hydride by using tetrabutylammonium bromide (TBAB) as a phase transfer catalyst (PTC). The p-tert-butylcalix[8]arene (BCA) derivative containing ethoxy vinyl ether groups (calixarene 4) was also synthesized in 83% yield by the substitution reaction of BCA with CEVE by using sodium hydride as a base and TBAB as a PTC. The MCA derivative containing 1-propenyl ether groups (calixarene 5) was synthesized in 80% yield by the isomerization of calixarene 2, which contained allyl ether groups, by using potassium tert-buthoxide as a catalyst. The photochemical reactions of carixarene 1, 3, 4, 5, and 6 were examined with certain photoacid generators in the film state. In this reaction system, calixarene 3 containing ethoxy vinyl ether groups showed the highest photochemical reactivity when bis-[4-(diphenylsulfonio)phenyl]sulfide bis(hexafluorophosphate) (DPSP) was used as the catalyst. On the other hand, calixarene 1 containing propargyl ether groups had the highest photochemical reactivity when 4-morpholino-2,5-dibuthoxybenzenediazonium hexafluorophosphate (MDBZ) was used as the catalyst. It was also found that the prepared carixarene derivatives containing cationically polymerizable groups such as propargyl, allyl, vinyl, and also 1-propenyl ethers have good thermal stability. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1805–1814, 1999 相似文献
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[structure: see text] The first examples of epoxy-p-quinol and diepoxy-p-quinol calixarene derivatives have been obtained by base-promoted direct addition of O(2)(oxygenation) to calixarene phenol rings. The regio- and stereochemistry of these derivatives was determined by 2D NMR studies, in conjunction with MM3 calculations, and X-ray crystallography. Both the oxygenation and the subsequent carbonyl reduction occur with a preferential attack to the less hindered exo face of the calixarene rings. 相似文献
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The Wurtz-Fittig reaction of tetraiodo calixarene 3 with Na/Me3SiCl in DME gave a mixture of tetrakis- and tris-silylated calixarenes (6 and 7). Tris(silyl) calixarene 7 was assigned the flattened cone conformation. A model study using p-bromoanisole and p-iodoanisole with Na/Me3SiCl gave the best results with p-bromoanisole in toluene. Attempts to extend this reaction to the tetrabromo calixarene 4 resulted in slow reactions giving mixtures of products. However, the Wurtz-Fittig reaction of the bromo benzyloxycalixarene 5 was faster, giving the debenzylated silyl ether 12. 相似文献
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GU Jin-ying HE Wan-ping SHI Xian-fa JI Liang-nian 《高等学校化学研究》2008,24(1):106-109
Three novel types of chiral calixarene derivatives 5, 8, and 10 were designed and synthesized by introducing chiral units to parent calixarenes. Their chiralities were confirmed by rotational analysis. Chiral recognition properties of these host compounds towards L- and D-threonine were studied by UV-Vis spectroscopy. The results indicated that calixarene derivatives 5 and 8 exhibited good chiral recognition capabilities toward L- or D-threonine. Although calixarene derivative 10 had no evident chiral recognition ability, the supramolecules of calixarene derivative 10 with L- or D-threonine showed a hypochromic effect or hyperchromic effect respectively. Therefore, calixarene derivative 10 might serve as a good chiral UV-indicator. 相似文献
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Tadatomi Nishikubo Atsushi Kameyama Hiroto Kudo Kousuke Tsutsui 《Journal of polymer science. Part A, Polymer chemistry》2002,40(9):1293-1302
New photoreactive calixarene derivatives containing spiro ortho ester groups (calixarenes 3a–3c ) were synthesized by the reaction of 2‐bromomethyl‐1,4,6‐trioxaspiro[4.4]nonane with 2,8,14,20‐tetramethyl‐4,6,10,12,16,18,22,24‐octakis(carboxymethoxy)calix[4]resorcinarene, 5,11,17,23,29,35‐hexamethyl‐37,38,39,40,41,42‐hexakis(carboxymethoxy)calix[6]arene, and 5,11,17,23,29,35,41,47‐octa‐tert‐butyl‐49,50,51,52, 53,54,55,56‐octakis‐(carboxymethoxy)calix[8]arene, which were prepared by the reaction of C‐methylcalix[4]resorcinarene, p‐methylcalix[6]arene, and p‐tert‐butylcalix[8]arene, respectively. The thermal stability of the obtained calixarene derivatives containing spiro ortho ester groups was examined with thermogravimetric analysis, and it was found that these calixarene derivatives had good thermal stability. The photoinitiated cationic polymerization of spiro ortho ester groups in calixarene derivatives 3a–3c was examined with certain photoacid generators in the film state. Interestingly enough, the reaction of calixarene derivatives did not proceed with only photoirradiation; however, the reaction proceeded smoothly when the photoirradiation was followed by heating. Furthermore, calixarene 3a , composed of a C‐methylcalix[4]resorcinarene structure, showed the highest photochemical reactivity in this reaction system. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1293–1302, 2002 相似文献
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新一代大环化合物杯芳烃(calixarcne)的研究已引起广泛的兴趣,它是由酚环和亚甲基组成的环多聚体,其结构呈杯状.杯底OH及杯盖R基可被各种基团取代,在其环形结构中具有适当体积的洞穴,在此空穴中能容纳客体而形成主客体配合物,可模拟酶催化的初始过程,在催化及分析分离等方面也有广泛的应用.但杯芳烃的配位化学研究很少,本文首先合成了对叔丁基杯[4]芳烃、对叔丁基杯[6]芳烃及对叔了基杯[8]芳烃(分别简称杯[4]、杯[6]及杯[8]),研究它们对铜的萃取,并探讨了萃取机理. 相似文献
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新一代大环化合物杯芳烃(calixarcne)的研究已引起广泛的兴趣,它是由酚环和亚甲基组成的环多聚体,其结构呈杯状.杯底OH及杯盖R基可被各种基团取代,在其环形结构中具有适当体积的洞穴,在此空穴中能容纳客体而形成主客体配合物,可模拟酶催化的初始过程,在催化及分析分离等方面也有广泛的应用.但杯芳烃的配位化学研究很少,本文首先合成了对叔丁基杯[4]芳烃、对叔丁基杯[6]芳烃及对叔了基杯[8]芳烃(分别简称杯[4]、杯[6]及杯[8]),研究它们对铜的萃取,并探讨了萃取机理. 相似文献