Study On The Synthesis Of Amines And Oxazolidinone Compounds From Biomass-based Platform Compounds

Recently,the issues of environment and energy have focused the attention of the whole world.Therefore,green renewable resources are the main direction for future development.Biomass is an important type of renewable resources with huge potential in catalyst,which has attracted extensive attention from researchers.In addition,platform molecules derived from biomass-based feedstocks are used more widely.It can be used to prepare platform downstream molecules through different elementary reactions.These high value-added chemicals can be used in various chemical fields.Therefore,in the paper we studied the biomass-based platform molecules,furfural and 5-hydroxymethylfurfural,and made them into useful chemicals by a simple and effective reaction.The results are shown as follows:?1?In the article,we demonstrated a method for the construction of oxazolidone rings through coupled carboxylation cyclization by using phenylacetylene,ketones,amines and carbondioxideassubstrates.Besides,weconstructedthefour-component coupling/carboxylation cyclization optimization system.In an autoclave,the reaction was carried out at 85°C oil bath and 0.5 MPa for 12 h,using phenylacetylene,furfural?or5-hydroxymethylfurfural?,organic amines as substrates,CuI?30%mmol?as catalyst,ethanol?5 mL?as solvent.Finally,we got oxazolidinone compounds in mild reaction conditions with high yield.The structure of the product was examined by HNMR and CNMR.Moreover,we found that the system is also suitable for primary amines.?2?Among the numerous methods for synthesizing amine compounds,reductive amination of carbonyl compounds is the most common and effective method.In this paper,the reductive amination reaction took place between furfural?or 5-hydroxymethylfurfural?and organic amines.For the reductive amination reaction,The optimal conditions for the reductive amination reaction is at 85°C for 12 h under N₂ atmosphere,using tris?pentafluorophenyl?borane?5 mmol%?as catalyst,phenyl silane?1.2 eq?as reducing agent,toluene?3 ml?as solvent.In addition,the effect of organic amines on the reaction was also examined in the test.The higher yield for can be obtained when aromatic amines worked as the substances.Finally,a series of amine compounds were synthesized by this method.The yield was determined by GC and the structure of the product was examined by HNMR and CNMR.?3?Without organic amines,we predicte that the system may reduce furfural to furfuryl alcohol.To prove this idea,we tried to explore the conditions of the reduction reaction.We found that tris?pentafluorophenyl?boron Alkane?5 mmol%?as the catalyst,PhSiH₃?1.2 eq?as the reducing agent,1,4-dioxane?3 ml?as the solvent,the yield of furfuryl alcohol is optimally 96%when the reaction was carried out in 60°C for 8 h.