| The incorporation of fluorine atom into organic molecules can alter the physical, chemical or physiological activities of the original molecules. In recent years, the perfluorocyclobutyl (PFCB) aryl ether polymers and trifluoromethylthioethers caused widespread concern for their special structure and properties. In this thesis, the synthesis of arylphosphine oxide functionalized PFCB aryl ether, and trifluoromethyl thioethers from disulfides were investigated.Part I:A novel monomer functionalized with phosphine oxide for the synthesis of perfluorocyclobutyl aromatic ether polymers,4-bromo-3-(diphenylphosphonyl)-1-(1,2,2-trifluorovinyloxy)benzene2was prepared from m-anisidine by diazotization, bromination, Pd-catalyzed coupling, oxidation, fluoroalkylation and Zn reductive dehalogenation reactions in turn. And this monomer dimerized successfully to form the perfluorocyclobutyl unit under microwave irradiation. Then1-bromo-4-(1,2,2-trfluorovinyloxy)benzene was applid to the [2π+2π] thermal dimerization to afford the dimer4,4’-(perfluorocyclobutane-1,2-diyl) bis(oxyl)bis(bromobenzene)14which was reacted with iso-propylboronate to provide [4-[[2-(4-bromophenoxy)-1,2,3,3,4,4-hexafluorocyclobutyl] oxy]phenyl]boronic acid19consisting of one perfluorocyclobutyl aryl ether unit. This boronic acid intermediate can be polymerized to form perfluorocyclobutyl aryl ether polymer via Pd(PPh3)4-catalyzed Suzuki coupling reaction.Part II:In order to overcome the disadvantage that only half of the sulfur atom can be utilized in the process of trifluoromethylation of disulfide, copper catalyzed oxidative coupling and PhI(OAc)2mediated trifluoromethylation of a disulfide were investigated. The optimized condition was established in which PhI (OAc)2(2.0eq.), K3PO4(2.0eq.), DMF (0.1M) were used at80℃. The yield of aryl trifluoromethylthioethers was improved to63%determined by19F NMR under the optimized condition. A wide range of disulfides with electron donating and electron withdrawing subsitutions can be assembled through this procedure. |
