Study On The Coupling Reaction Of Ferrocenyl Tosylhydrazones With Benzyl Bromides And The Synthesis Of Conjugating Ferrocenyl Polymers

This thesis studied the coupling reaction of ferrocenyl tosylhydrazones with benzyl bromides at the presence of Pd catalyst. After screening the experimental conditions, the polysubstituted styrylferrocene derivatives and 1,1’-bistyrylferrocene derivatives can be obtained in moderate to excellent yields. For its good substrate scope, more importantly, an excellent anticancer drug, ferrocifen skeleton, was simply constructed through the reaction of ferrocenyl tosylhydrazones with (bromomethylene)dibenzenes. Furthermore, the reaction can be also used to incorporated sub-functional group in phenyl moiety, such as Cl and Br, which can continue following Suzuki-Miyaura reaction. In the thesis, Br was incorporated in benzyl bromide to undergo three-component coupling reaction of ferrocenyl tosylhydrazones, benzyl bromides with aryl boric acids. Eventurally, polysubstituted biphenyl vinyl ferrocene derivatives and 1,1’-polysubstituted biphenyl vinyl ferrocene derivatives were synthesized in moderate yields. All products were characterized by 1H NMR,19F NMR,13C NMR and HRMS spectral techniques.Additionally, this thesis successfully synthesized 1,1’-bis(1-styrylprop-1-ene-2- yl)ferrocene(monomer 1),1,1’-bis[1-(4"-biphenylvinyl)prop-1-ene-2-yl] ferrocene (monomer 2),1, 1’-bis[1-(3"-biphenylvinyl)prop-l-ene-2-yl]ferrocene(monomer 3) in moderate yield through the above coupling reaction. Eventurally, linear ferrocenyl polymers with moderate molecular weight(Mn=ca.2021, Mn=ca.2190, Mn=ca.3360) can be obtained through acyclic diene metathesis (ADMET) reaction using the Grubbs catalysts in a low catalyst loading (1 mol%), in toluene or dichlorobnezene under 80℃ and vacuum condition. These polymers have exclusively trans-stilbene in structure backbones, and have high thermal stability. In order to improve the molecular weight, we also carried out the copolymerization of 1,1’-bis(1-styrylprop-1-ene-2-yl) ferrocene(monomer 1) with 9,9-di-n-octylfluorene-2,7-vinylene (mon-omer 5), the different block copolymers were obtained in good yields accounding to the different ratio of the used substrates. The products were characterized by 1H NMR, 13C NMR, GPC, MALDI-TOF, HRMS, IR techniques. Also, the optical, electroche-mical and thermostability properties were studied through UV-Vis, emission spectra, cyclic voltammetry (CV), DSC and TGA tests.