【作者】 张春；

【导师】 郑炎松；

【作者基本信息】 华中科技大学 ， 有机化学， 2004， 硕士

【摘要】 杯芳烃是一类由苯酚和甲醛缩合的含有洞穴的大环化合物。作为第三代主体化合物,其在分子识别,模拟酶催化,自组装等领域的研究取得了很大进展。近年来,特别是手性杯芳烃由于其特殊的结构,更是引起了人们的极大重视和兴趣。本文就手性杯芳烃的合成及其性能作了一些研究。由母体杯[4]芳烃与1,2-二溴乙烷反应制备的杯芳烃二溴化合物与(,(-氨基醇或苯基乙基胺反应合成出了下端连接有光学活性的氨基醇基团或氨基团的新手性杯芳烃,经过IR,1H NMR,13C NMR,ESI+ HRMS等谱学性质证实其处于锥型构象。用1H核磁滴定的方法研究表明(1’S,2’R)-5,11,17,23-四叔丁基-25,27-二羟基-26,28-二(1’, 2’-二苯基-2’-羟基乙胺基乙氧基)杯[4]芳烃能在极性质子性溶剂(甲醇)中形成二聚体,结合常数为34.7 M-1。用1H NMR研究了下端连接有光学活性的氨基醇基团的新手性杯芳烃对手性酸性化合物的手性识别能力,发现这些手性杯芳烃对苯甲酰酒石酸,扁桃体酸,异缬草酸具有良好的手性识别能力。下端连接有光学活性的氨基团的新手性杯芳烃对苯甲酰酒石酸,扁桃体酸具有良好的手性识别能力。由氯乙酰氯与接有氨基手性化合物反应制备的酰胺型卤代物与母体杯[4]芳烃合成的酰胺型手性杯芳烃,经过IR,1H NMR,13C NMR等谱学性质证实其处于锥型构象。更多还原

【Abstract】 Calixarenes are a class of marcrocycles derived from the condensation of phenols and formaldehyde. As the third generation host compounds, the study of them in the fields such as molecule recognition, assemble and enzyme mimics has been made great progress. The chiral calixarenes attract increasing interest in these years because of their special conformation. So some work on synthesis and properties study of chiral calixarenes had been done. New chiral calixarenes connected optical pure aminol groups and optical pure amine groups at low rim were synthesized by the reaction of optical pure α, β-amino alcohol or methylbenzylamine with calix[4]arene dibromide prepared by the reaction of 4-tert-butylcalix[4]arene with 1, 2-dibromoethane, which characterized by IR,1H NMR,13C NMR and ESI+ HRMS. The results demonstrate that they are in cone conformation.(1’R, 2’S)-5,11,17,23-Tetra-tert-butyl-25,27-dihydroxy-26,28-di(1’, 2’-diphenyl-2’- hydroxyethyl-aminoethoxy)calix[4]arene can form 1:1 dimer by self-assembly in d-methanol and the association constant of the dimer is 34.7 M-1 determined by 1H NMR titration.The chiral recognition ability of these chiral calixarenes were measured by 1H NMR spectra. It is found that these chiral calixarenes containing aminol groups have an exceptional chiral recognition ability between the enantiomers of benzoyltartaric acid, mandelic acid, 2-hydroxyisovaleric acid and the chiral calixarene containing amine group has chiral recognition ability between the enantiomers of benzoyltartaric acid, mandelic acid. Chiral calyx [4]arenas containing acylamide group were synthesized by the reaction of calix[4]arene with halides which prepared by chiral compounds containing amine group with chloroacetyl chloride. These chiral calix[4]arenas characterized by IR,1H NMR,13C NMR. The results demonstrate that they are in cone conformation.更多还原