【作者】 石志强；

【导师】 冯亚青；

【作者基本信息】 天津大学 ， 应用化学， 2009， 博士

【摘要】 合成能选择性结合重金属及过渡金属离子,并引起光学如发光、荧光性质的变化,从而能识别特定金属离子的荧光传感器是超分子领域的一个热门课题。杯[4]芳烃氮杂冠醚由于其与软金属离子结合能力强,活性位可选择,是构造主体分子的理想材料。本论文通过对杯[4]芳烃氮杂冠醚上仲氮原子的修饰,获得了连有荧光基团邻苯二甲酰亚胺和萘二酰亚胺单元的多个系列化合物,其中连接萘二酰亚胺的氮杂冠醚衍生物对铜离子有非常好的选择性,颜色变化明显,该类化合物可作为潜在的荧光传感器。采用多甘醇双对甲苯磺酸酯对杯[4]芳烃仲氮原子进行修饰,得到了氮杂穴醚,季铵盐结构和N-取代的杯[4]芳烃氮杂冠醚系列衍生物,并利用1H NMR、13C NMR、IR和MS对所合成的三个未见文献报道的新化合物进行了结构表征。结果表明均为锥式构象,且由于多甘醇链状结构空间链节长度不同,分别形成了杯[4]芳烃穴醚,含有吗啉单元的螺醚,类似准轮烷的结构。采用四种邻苯二甲酰亚胺化合物对杯[4]芳烃下沿进行修饰,通过硝化、还原、溴乙酰化和亲核取代等一系列反应得到了下沿含有邻苯二甲酰亚胺基杯[4]芳烃类系列衍生物,并利用1H NMR、13C NMR、IR和MS对所合成的四个未见文献报道的新化合物进行了结构表征。结果表明,所合成的化合物均为锥式构象。分别将六个邻苯二甲酰亚胺衍生物与杯[4]芳烃氮杂冠醚反应,得到了空间位置不同的两系列共六个杯[4]芳烃氮杂冠醚衍生物;再将四个萘二甲酰亚胺衍生物与杯[4]芳烃氮杂冠醚反应,得到了类似的两系列共四个杯[4]芳烃氮杂冠醚衍生物,并利用1H NMR、13C NMR、IR和MS对所合成的十个未见文献报道的新化合物进行了结构表征。结果表明,所合成的化合物均为锥式构象。对这四系列代表化合物进行与金属离子结合的荧光测定实验,结果显示连有萘二酰亚胺的杯芳烃氮杂冠醚衍生物对铜离子有很好的选择性识别能力,荧光增强,颜色变化明显,从而具备作为荧光传感器的潜在应用价值。更多还原

【Abstract】 The synthesis of fluorescent sensors, which can selectively recognize and sensing heavy and transition metal ions through color or fluorescence changes, has received increasing interest in supramolecular chemistry. Calix[4]azacrown deriatives are good candidates as receptors of fluorescent probe molecules, due to their binding strength and selectivity toward soft-metal ions through the three-dimensional encapsulating assistance of the appended side arm on the nitrogen atom. In this paper, we report several novel series of calix[4]azacrown detivatives with phthalimide and naphthalimide groups, one of which can selectively recognize Cu2+ and the color change is visible and may be useful fluorescent sensor.By using three multi-oxyethyl p-methylbenzenesulfonate compounds, three novel derivatives of calix[4]azacrown connecting with the nitrogen atom have been synthesized and structurally characterized by 1H NMR、13C NMR、IR and MS. And all the three compounds adopt cone conformation. Due to different length of the chains, A novel ?tren‘type calix[4]azacrown ether and a novel ?spiro‘type calix[4]azacrown containing morpholine unit and a expected [2]pseudorotaxane was prepared.With introducing four phthalimide compounds into calix[4]arene on the low rim after ipso-nitration, reduction, bromo-acetamidation and substitution, we have successfully obtained four new compounds including three new intermediates. All these compouds are confirmed by 1H NMR、13C NMR、IR and MS and the data means that all of them adopt the cone conformation.By the reaction of phthalimide compounds and calix[4]azacrown, two series, six new calix[4]azacrown derivatives were prepared. Then with introducing naphthalimide compounds into calix[4]azacrown, four novel derivatives of calix[4]azacrown connecting with the nitrogen atom have been synthesized and structurally characterized by 1H NMR、13C NMR、IR and MS. And all the ten compounds adopt cone conformation. After fluorescent properties research of metal ions, the results showed that one of which can selectively recognize Cu2+ ,the color change is visible and may be a useful fluorescent sensor.更多还原