Study Of Construction,Modification And Properties Of Novel Macrocycle

Due to its unique structural characteristics and interesting reactivity,the discovery of effective methods to synthesize macrocyclic compounds is one of the most popular topics in modern chemical research.Since the synthesis of the first generation macrocylic host-crown ether in 1969's,the supramolecular chemistry has been developed over 40 years.Without any exaggeration,almost each breakthough in the field of supramolecular chemistry has companied with the discovery of natural macrocycle or the invention of artificial macrocycle.The recently elaborated macrocycles with diverse structures and sizes with rigid,non-collapsible backbones has been paid much attention among researchers.Yet,critical challenges still remain in the efficient construction of functional macrocycles with precise control over the structures,including the ring sizes,structures and functions.This thesis consists of three parts based on the study of construction,modification and properties of novel macrocycle as follows:1.Synthetic study of constructing a novel aromatic oligoamide macrocycle.Considering the rich-elctronic cavity of calixarene and the rigid backbone of cucurbituril,we try to design a novel aromatic oligoamide macrocyle with triangle-column shape cavity.We use Ts-protected compound 2-4 as substrate and wish to get trimer product 2-2,the final product could be obtained after deprotecting-Ts.Even though,we do not get macrocycle,it is not difficult to speculate the product features in:First,it has potential abilities to recognize the specific guests owing to its shape-persistent cavity;Second,the rich-electronic system determines the recognition of ?-system and cation guests;Third,the contained amide group could offer possibilities to combine the guests which accept or donate hydrogen-bond.2.Synthesis of diacetylene macrocycle bearing dibenzylphosphine oxide group and its Topochemical Polymerization in the solid-state.Following our research on dibenzylphosphine macrocycle,novel diacetylene macrocycles 3-1 and 3-2 bearing dibenzylphosphine oxide were synthesized via Eglinton acetylenic intramolecular coupling.The X-ray analysis of macrocycle 3-1 and 3-2 demonstrated that the tubular supramolecular structure was formed by self-assembly of the phosphine oxide group in macrocycle 3-1,but not in macrocycle 3-2,which provided the possibility for diacetylene topochemical polymerization in solid state of macrocycle 3-1.UV-vis,Roman spectroscopy indicated that macrocycle 3-1 can undergo topochemical diacetylene polymerization on its surface with light irradiation;DSC,solid-state 13C NMR spectroscopy and X-ray powder diffraction confirmed that macrocycle 3-1 can undergo topochemical diacetylene polymerization in the inner structure with heating,but macrocycle 3-2 cannot,either with light irradiation or heating.3.The recognition of n-alkyl phosphonic by mono-squaramide-functionalized pillar[5]arenes.According to our group deeply study in the host-guest chemistry of pillararene system,we designed a novel mono-squaramide-functionalizedpillar[5]arene:4-la,by which n-hexylphosphonic acid(HPA)could be recognized.The results of 1H NMR titration,Job's Plot,ESI-MS and 2D NMR experiments reveal that 4-la forms a 1:1 stoichiometric complex with HPA and its association constants(log K/M-1)with HPA is determined to be 4.61 ± 0.05,suggesting the stronger binding ability of 4-la with HPA.The result showed that there exsisted coordinative interaction by hydrogen-binding,which came from NH group on the squaramide and HPA,and C-H---? interaction between cavity of pillararene and alkyl-chain of HPA.To compare with 4-1a,4-1b with the electron-withdrawing group(CF3)on the phenyl ring of squaramide moiety is synthesized as well,which shows the similar selective binding ability for HPA but with slightly stronger binding ability than 4-1a.