Studies On The Synthesis And Properties Of Tribenzotriquinacene Derivatives

This thesis focused on the research of the novel polycyclic hydrocarbon skeleton molecules with a bowl-shaped,conformationally rigid,C₃-symmetrical property:tribenzotriquinacene（TBTQ）chemistry.A series of TBTQ single-wing extended derivatives and TBTQ-based crown ethers were synthesised and investigated as supramolecular host molecules.A number of TBTQ-based cryptophanes,dimers,salen ligand,and TBTQ o-quinones with twofold and threefold extension were also studied.It consists of the following four parts:In chapter 1,a review of literature on the recent synthesis of TBTQ key intermediate derivatives and supramolecular chemistry research,especially the supramolecular chemistry of TBTQ derivatives as hosts and the optical resolution of inherently chiral TBTQ molecules is elucidated.In chapter 2,through a surprisingly nonregioselective oxidation process,the reaction of two analogous 2-hydroxy-substituted TBTQ by o-iodoxybenzoic acid（IBX）was found to afford the corresponding C_s-and C₁-symmetrical TBTQ-o-quinones and,respectively,in 1:1 ratio and excellent combined yields.This finding represented the first example of direct introduction of a functional group into sterically hindered,inner bay-positions of a parent TBTQ skeleton.We envisioned that o-quinone units incorporated into the TBTQ scaffold were versatile synthetic intermediates since their inherent reactivity enables a number of useful conversions,such as condensation,cyclo-addition,and redox reactions.After reduction of the quinones to the corresponding catechols,electrophilic aromatic substitution could also be realized at the activated inner bay-position（s）to afford several tri-and tetrafunctionalized TBTQ compounds.The Cs symmetrical o-quinone was converted into further single-wing extended derivatives such as TBTQ-based phenazines,through condensation reactions,and to benzodioxine derivative by Diels-Alder reaction with tetracyclone.The novel TBTQ quinones and the corresponding TBTQ-catechols offer a variety of new accesses to single-wing-extended and-functionalized TBTQ derivatives.In chapter 3,we have summarized the background of synthesis and application of bowl-shaped molecules or cavitands combined with crown ethers.The key TBTQ intermediate,2,3-dihydroxy-TBTQ was synthesized in six steps using two variations of our classical cyclodehydration method by the improved strategy.TBTQ-based crown ethers were synthesized and the study of host-guest ability with a paraquat derivative and secondary ammonium salts were investigated.It was found that TBTQ-based dibenzo-24-crown-8 selectively binds the paraquat derivative as a 1:1 complex in CDCl₃/CD₃CN solution.The TBTQ-based 21-crown-7 host assembles selectively with dibutylammonium hexafluorphosphate as a 1:1 complex in CDCl₃/CD₃COCD₃.In chapter 4,we have tried some“molecular tweezers”in which two TBTQs were linked with a rigid linkage.Conversion of the C₃-trialdehyde to three diastereomeric TBTQ-based cryptophanes occurring in high yield enabled the preparation of the optically pure C₃-symmetrical TBTQ-trialdehydes.Following the methods used,the TBTQ-based salen ligand was tried to synthesize.Fouthermore,a series of“basket-like”hosts were designed by polyether linked two benzene rings of TBTQ.A new class of TBTQ o-quinones and peripheral twofold and threefold extension derivatives were also synthesized.This thesis depicted the construction of a series of single-wing-extended and functionalized TBTQ derivatives,accomplished the TBTQ-based crown ethers and the host-guest ability were explored.The results made a foundation for the further research of supramolecular chemistry of TBTQ.