碳水化合物催化合成5-氨甲基-2-羟甲基呋喃的反应途径与机制研究

5-(R)aminomethyl-2-furanmethanol(R: alkyl or H) is a kind of important chemical intermediates. It is widely used as pharmaceutical intermediate, precursor of food additives, monomer in polymerizations and intermediates of fine chemicals. At present, it is produced by two pathway in research reports and industry: one is furfuralcohol reacts with N,N,N',N'-tetra-alkylmethanediamine by electrophilic substitution, the disadvantages of which is a long reaction steps and low efficiency. Another is the reductive amination of 5-hydroxymethyl furfural (HMF) with amine or ammonia. However, at present, the raw material HMF, have still not produced by an economical method. These two processes do not meet the demand of large-scale production and requires improvement further..The two innovative pathways are proposed to research in this project. One is direct conversion of glucose to 5-(R)aminomethyl-2-furanmethanol in formic acid reductive amination system. The mechanism of six-membered ring of glucose converting to the five-membered ring of furan, differing from the isomerization mechanism of glucose to fructose, is going to be investigated deeply. Another is conversion of cellulose to 5-(R)aminomethyl-2-furanmethanol via intermediate 5-[(formyloxy)methyl]furfural(TMF). The conversion mechanism of cellulose to FMF and its function in the consecutive reaction relative to HMF are going to be studied. Meanwhile, the comparative analysis of two preparation pathways will be carried out..This project extends the raw materials form furfuralcohol and HMF to cellulose and carbohydrates such glucose, fructose and sucrose. It was expected to resolve the bottleneck problem of the current preparation processes.

5-（R）氨甲基-2-羟基呋喃（R：烷基或H）(AAMF)是一类重要的中间体化合物，在医药、食品、材料等领域有着潜在的应用前景。当前主要由糠醇与双二烷氨基甲烷反应途径和5-羟甲基糠醛（HMF）胺化还原反应途径制备。糠醇途径效率低；而5-羟甲基糠醛途径中HMF原料还不能经济制备。.本项目提出和探究两条相关联的新型制备途径：1）葡萄糖一锅法合成AAMF的技术途径。探索甲酸胺化还原体系促进葡萄糖六元环脱水重排为呋喃五元环的反应机制，克服经典的葡萄糖异构为果糖，进而转化为HMF衍生物反应路径转化率低的问题；2）纤维素经5-甲酰氧基甲基糠醛（FMF）制备AAMF的技术途径。阐明FMF在纤维素转化为AAMF过程中的作用机制及替代HMF的可行性。.本项目研究将为可再生资源如纤维素、葡萄糖、果糖和蔗糖等制备AAMF提供新的反应途径和理论依据，有望解决目前AAMF制备途径中的瓶颈问题。

5-（R）氨甲基-2-羟基呋喃（R：烷基或H）(AAMF)及2, 5-二氨甲基-呋喃等呋喃胺类化合物是一类重要的中间体化合物，在医药、食品、材料等领域，有着潜在的应用前景。.本项目研究开发了碳水化合物或其下游衍生物5-羟甲基糠醛、5-甲酰氧基甲基糠醛在甲酸还原胺化反应一锅反应体系中制备N, N-二甲基-5-氨甲基-2-羟甲基呋喃（DMMF）的反应途径，并阐明反应调控机制。建立了5-羟甲基糠醛及其衍生物经还原胺化催化反应制备5-氨甲基-2-羟甲基呋喃（AMF）的反应途径，阐明了Ni基催化剂的催化反应机制，AMF得率超过90.6 %。开发了DMMF和AMF的分离纯化工艺技术，分离纯度超过98 %。开发建立了纤维素一锅法、果糖一锅法或两步法高效制备5-甲酰氧基甲基糠醛（FMF）的工艺调控体系及分离工艺，FMF产率分别超过29.4 %和63.2 %，分离纯度超过98 %。开发了HMF经过氨化-氧化-胺化，转氨-还原技术路线，经中间体N, N-二甲基-2, 5-二亚胺基甲基-呋喃一锅两步法高效合成N, N-二甲基-2, 5-二氨基甲基-呋喃或2, 5-二氨基甲基-呋喃的技术路线，产率超过95 %。建立了超临界CO2/H2O/Zn还原胺化反应体系，阐明了Ni/CaCO3催化糠醛还原胺化为糠胺的过程调控与反应机制，开发了超临界CO2/H2O/Zn反应体系中原位还原胺化制备糠胺的技术途径，产率超过91 %。 . 本项目的研究将为可再生资源如纤维素、葡萄糖、果糖等碳水化合物制备可再生呋喃胺基化合物构建起了桥梁和和提供理论依据。