Derivatization Reaction Of Furan Platform Compounds

As a highly abundant and carbon-neutral renewable energy resource,biomass resources are abundant in source,cheap in price,environmentally friendly and reproducible,which made them to be an ideal substitute for fossil fuels.Furaldehydes,particularly furfural(FF)and 5-hydroxymethylfurfual(HMF)are considered to be two of the most value-added biomass building blocks or platform chemicals,can be transformed into more high value-added chemicals,such as furoin,furil,5,5’-dihydroxymethyl furoin(DHMF)and 5,5’-bihydroxymethyl furil(BHMF).However,many problems about the conversion are raised,such as harsh reaction conditions,poor product selectivity and complex reaction systems.Thus,it is essential to develop more efficient and mild catalytic system to solve these problems,and to provide new methods and ideas for these basic reactions.The main contents of this paper are listed as follows:In the first chapter,we introduced the current development of biofuels from biomass and the platform molecules derived from biomass.Then,we reviewed the lasted development of the preparation methods and representative application examples of platform molecules furfural and HMF.Finally,the catalytic system progress of this paper is introduced.In the second chapter,we present a new route about the upgrading of furfural and HMF to C10 and C12 furoins.Six Na+/montmorillonite(MMT)-supported thiazolium(TM)ionic liquids(ILs),MMT-[TM],which are precatalysts to N-heterocyclic carbene(NHC)catalysts,have been synthesized and employed to catalyze highly selective of furfural and HMF into C10 and C12 furoins.Thus,supported NHC catalysts,generated in situ from activation of MMT-[TM]with Et3N,afford C10 and C12 furoins in 99%and 98%yield,respectively.Among the MMT-[TM],five supported[TM]salts carrying the electron-donating group exhibit excellent catalytic activity.This condensation reaction is also carried out under solvent-free conditions,and the catalysts can be readily recycled,showing no noticeable loss in their catalytic activity over four consecutive recycles.In the third chapter,an efficient and selective catalytic system of quaternary ammonium octamolybdate and quaternary ammonium dectungstate for the oxidation of C10 and C12 furoins into furil and BHMF are reported.Under the optimized reaction conditions,tetra-hexadecyltrimethyl ammonium octamolybdate([CTAB]4Mo8O26)catalyst showed excellent yield to furil(-100%)and BHMF(～94%)in a shorter reaction time compared to other catalysts considered.The great difference in performance of quaternary ammonium octamolybdate and quaternary ammonium dectungstate in C10 and C12 furoins oxidation with air was attributed to their different structure,and made the Mo based catalyst display high activity for the oxidation reaction.Thus,these desired features possessed by the current catalyst system have enabled the development of the greener and more environmentally benign process for the oxidation of furoin and DHMF.In the forth chapter,we present the summary of this paper.In conclusion,this thesis mainly foucsed on the conversion of biomass derived platform molecules of furfural and HMF into different chemicals through different catalytic systems,the performances of different catalysts with different activities and the influence on the products were studied and explored.Through the development of new catalytic systems,more applications of platform molecule will be present.