【作者】 赵夏；

【导师】 杨发福；

【作者基本信息】 福建师范大学 ， 有机化学， 2007， 硕士

【摘要】 杯芳烃是一类由取代苯酚和甲醛缩合而成的大环化合物，它具有独特的空腔结构和丰富的反应点，可制备具有各种官能团、构象确定、π空腔大小可调的衍生物，在分子识别、模拟酶催化、物质的检测和分离等方面都显示出其作为超分子化学中的一类重要的受体化合物的特殊价值，引起了人们的关注，被誉为继冠醚和环糊精之后的“第三代超分子主体化合物”。本论文从主客体化学识别研究的角度着眼，设计并合成了多种含有氮、硫杂原子官能团的杯[4]芳烃衍生物和硫杂杯[4]芳烃衍生物，并研究了它们的客体识别性能，取得了较有意义的研究结果。本文首先合成了新型的含酰胺和席夫碱单元的杯[4]芳烃衍生物，研究了它们的阳离子吸附性能，新化合物不仅对软硬金属离子均有较好的萃取性能，而且对Na~+和Ag~+有一定的选择性配合能力。其次，在对叔丁基硫杂杯[4]芳烃的下缘1，3位引入芳醛基，合成了硫杂杯[4]二醛基衍生物，硫杂杯[4]二醛基衍生物与苯胺、水杨酰肼、烟酰肼、异烟酰肼等通过席夫碱缩合反应得到新型硫杂杯[4]氮杂衍生物，产率分别为83％，80％，77％和79％。硫杂杯[4]二醛基衍生物与邻苯二胺、乙二酰肼、丙二酰肼、己二酰肼等通过“1+1”分子间缩合得到新型1，3-桥联硫杂杯[4]氮杂衍生物，产率分别为53％，51％，59％和66％。新化合物的结构经IR，~1H NMR，MS和元素分析等证实。最后，本文还首次合成了由杯[4]芳烃和硫杂杯[4]芳烃组成的双杯[4]芳烃，研究发现这种化合物对金属离子和氨基酸都有较好的配合能力。更多还原

【Abstract】 Calixarenes are macrocylic compounds generally formed by condensation of aldehydesand substituted phenols. Because calixarenes have a calix-shaped, hydrophobic cavity andseveral reactable positions, they have attracted considerable attentions. They are broadlyused as building blocks to construct well preorganized host molecules which have widelyapplying potential in the field of molecular recognition, enzyme mimics, etc. So they areconsidered as the third host molecule after crown ethers and cyclodextrins insupramolecular chemistry. In this thesis, the novel thiacalix[4]arene - based polymers andcalix[4]-aza, thio-crowns were designed, synthesized and their complexation propertieswere studied. Some meaningful results were obtained.Firstly, a series of new calix[4]arene derivatives were synthesized. It was found thatthey not only possessed good complexation properties for both soft and hard cations, butalso exhibited good complexation selectivity for Na~+and Ag~+. Secondly, thiacalix[4]arenebi-benzaldehyde derivative was synthesized by introducing benzaldehyde groups on1,3-position of p-tert-butylthiacalix[4]arene. Reacting compound with aniline, salicylichydrazide, nicotinic hydrazide or isonicotinic hydrazide gave series of novelthiacalix[4]arene aza derivatives by the Schiff-base condensation in the yields of 83%,80%, 77% and 79%, respectively. Treatment compound with o-phenylendiamine, oxalyldihydrazide, malonic dihydrazide and adipie dihydrazide, afforded novel bridgedthiacalix[4]arene aza derivatives by "1+1" condensation in the yields of 53%, 51%, 59%and 66%. The structures of all new compounds were characterized by IR, ESI-MS, ~1HNMR spectra and elemental analyses. At last, the first example of bisealixarene composedof calix[4]arene and thiacalix[4]arene subunits was facilely synthesized and showed goodcomplexation properties for metal cations and zwitterionieα-amino acids.更多还原