Studies On The Developments Of New Functionalization Strategies Of Aryl Amides And Corannulenes

Corannulene is a kind of polycyclic aromatic hydrocarbons(PAHs),which contains interesting structure and properties.Due to the amazing properties it has attracted numerous interests in the field of material science.Corannulene is composed of a central pentagon and five closely adjacent hexagons on the pentagon’s five sides,which is considered as the smallest fragment of fullerene.Compared to the traditional planar polycyclic aromatic hydrocarbons,the novel curved structure of buckybowls gives them with additional interesting physical properties.Corannulene and its derivatives are electron abundant compounds and important host compounds in the host-guest chemistry,particularly in fullerene chemistry.The first chapter summarizes the history of corannulene.The first synthesis of corannulene was reported by Barth and Lawton.Later,Scott and Siegel improved the route of synthesis corannulene.Both of their methods have their advantages and limitations,which broaden the derivatives library of corannulene.Halogenated corannulenes such as fluorinated,chlorinated,brominated,and trifluoromethylated corannulenes have been synthesized,which of them have been synthesized in the course of corannulene synthesis as intermediates.The second chapter discussed the selection of the additives in the developments of new functionalization strategies of aryl amides.The third chapter mainly discussed the application of monobromocorannulene.Halogen derivatives of aromatic compounds are usually used to play an important role as common bridges in numerous synthetic transformations.Corannulene with alkyl,alkynyl,and aryl groups has been prepared from bromo-substituted corannulene by the mediation of transition metal.In our research,cyanocorannulene and pyridinecorannulene were obtained by the transformation of monobromocorannulene.In this chapter,the application of tetrabromocorannulene was also introduced.We got a lot of tetramethylfluoranthene compound in our lab.Tetrabromocorannulene which could not be bought were synthesized according to the literature.Tetrabromocorannulene is not only important building block for new organic materials,it also provides the possibility to extend the aromatic system of the corannulene core.Direct multiple electrophilic aromatic substitution on corannulene has shown limited but important successes.The importance of multi-halocorannulenes stems from the variety and reliability of nucleophilic aromatic substitutions and related transition-metal catalyzed couplings with nucleophiles.The forth chapter mainly introduces the future plan.Oxidation coulping of1,2,5,6-tetrakis(phenyl)-corannulene.Pd catalyzed coupling reactions of aryl halides to form a new C(sp~2)-C(sp~2)bond became one of the most powerful strategies for linking two arenes together.We want to try to couple the four phenyl groups of1,2,5,6-tetrakis(phenyl)-corannulene by oxidation.Make it form larger aromatic system and conjugate structure.We also want to apply this Friedel-Crafts acylation reaction to 1,2,5,6-tetrakis(phenyl)-corannulene.