The Amination Of 5-HMF To Prepare 2,5-Bis(Aminomethyl) Furan

With the rapid development of the world economy,oil,coal,natural gas and other traditional fossil energy are consumed more and more.Energy depletion and renewable energy development have been increasingly concerned by humanbeings.With the growth of the demand and prices of fossil energy,seeking new energy to achieve sustainable development is a priority.Biomass energy sources are attracting more and more attention due to its vast availability and low cost.Biomass platform molecules which called 5-hydroxymethylfurfural(HMF)can be obtained from dehydration of fructose and glucose.It can be used as a raw material to prepare furan-2,5-dimethanamine(FDA)that are used to synthesize value-added products such as functional polyamide.In this paper,the preparation of FDA in one-step amination and the preparation of FDA by DFF in two-step method were studied.One-step preparation method:CuNiAl/CaCO3 is the catalyst of the reaction.The temperature,ammonia partial pressure,hydrogen partial pressure,reaction time,solvent,reaction heating mode and so on are studied in this paper.And the optimal reaction conditions are showed as below:0.5mmol HMF,50eq NH3,1 bar H2,120 mg cat,3 mL Dioxane.After pre-strring at room temperature for 4 h,the temperature was raised to 150℃ for 16 h,giving a yield of 52%.FDA was prepared by HMF in two-step preparation method with DFF:butylamine was selected as DFF aldehyde-based protection agent,the supported catalyst CuNi1120 90mg,DFF 2mmol,360mmol NH3,13bar H2,4mmol BuNH2 were used,the mixture was heated to 80℃and proceeded 18h,giving yield of FDA 81%.The yield of the FDA was 48%when the reaction was carried out at 100℃ for 18 hours using an unsupported catalyst Raney-Co 25 mg,DFF 2 mmol,128 mmol NH3,8 bar H2,4 mmol BuNH2.