Studies On The Synthesis And Supramolecular Chemistry Of Tribenzotriquinacene Derivatives

This thesis was focused on the research of the novel polycyclic hydrocarbon skeleton molecules with C3-symmetrical property-tribenzotriquinacene(TBTQ)chemistry.A number of TBTQ cryptophane or hemicryptophanes was synthesized by a"metamorphosis-to-half' strategy from hexakis(chloromethyl)-TBTQ starting material.A series of TBTQ cavitands was investigated as supramolecular host molecules for cations,anions and other guest molecules.In chapter I,the recent synthesis of TBTQ derivatives and supramolecular chemistry research were summarized,especially the host-guest chemistry of TBTQ derivatives and C60 molecule.In chapter 2,based on the summary of synthesis and applications of cryptophanes and hemicryptophanes,a series of tri-functional TBTQ derivatives was synthesized by a "metamorphosis-to-half' strategy from hexakis(chloromethyl)-TBTQ.A[Cd3L2]type TBTQ metallo-cryptophane was obtained by TBTQ-triacid(H3L)and Cd(II)through coordination bond self-assembly.The syntheses of oxygen-or nitrogen-containing hemicryptophanes by covalent bond or dynamic covalent bond by the cavitands were accomplished.These studies of TBTQ open up a new direction in supramolecular self-assembly and molecular recognition in host-guest chemistry applications.In chapter 3,based on the background of synthesis and application of cavitands,hexakis[(8-quinolinyloxy)methyl]-TBTQ derivative was synthesized and the study of host-guest ability with cations was investigated,the results revealed that the molecule with a 1:2 complex mode to selective identification Ag(I).A series of TBTQ cavitand hosts containing 1,2,3-triazole groups was synthesized by the "click"reaction,the triazole acted as anion sensor groups was explored.Benzodihydroisopyrroles TBTQ derivatives were · synthesized by the improved"metamorphosis-to-half" strategy,which could be used as the host molecule to recognize C60 molecule.In chapter 4,the exploration of total synthesis of trichodermaketone A was tried.Its tricyclic skeleton containing dihydrofuran structure was constructed by interrupted Feist-Benary reaction.This thesis depicted the construction of a series of tri-functional cavitands starting from C3-hexakis(chloromethyl)-TBTQ,accomplished the coordination self-assembly of TBTQ-triacid to form a TBTQ metallo-cryptophane and the construction of hemicryptophanes adopted oxygen and nitrogen elements.A series of TBTQ supramolecular hosts were synthesized and the host-guest abilities were explored.The results made a foundation for the further research of supramolecular chemistry of TBTQ.At last,the tricyclic skeleton of trichodermaketone A was constructed.