在水-四氢呋喃中纤维素转化为5-羟甲基糠醛及副产物鉴定

在酸性条件下，水-四氢呋喃混合溶剂中转化纤维素制备了平台化合物5-羟甲基糠醛（HMF）．在纤维素浓度仅为2.4wt%时，可以得到38.6%的HMF，但是随着纤维素浓度的增加，胡敏素和乙酰丙酸成为主要产物．利用液相色谱-多级串联质谱联用技术检测到了分子式为C9H16O4、 C10H14O4、 C11H12O4、C12H10O5 和C12H16O8的一系列副产物．C9H16O4是通过四氢呋喃开环为1,4-丁二醇再与乙酰丙酸酯化反应得到，而C10H14O4是通过四氢呋喃开环后与HMF醚化得到．C11H12O4是由5-羟甲基糠醛与乙酰丙酸发生酯化反应得到，C12H10O5是由HMF自身醚化得到，而C12H16O8是HMF与葡萄糖经过缩醛反应得到．HMF的自身醚化反应及HMF与1,4-丁二醇的醚化反应是主要的副反应．

Conversion of Cellulose to 5-Hydroxymethylfurfural in Water- Tetrahydrofuran and Byproducts Identification

Conversion of cellulose into platform chemical 5-hydroxymethylfurfural （HMF） in water-tetrahydrofuran （THF） co-solvents under acidic condition was studied. 38.6% of HMF was obtained with low cellulose concentration of 2.4wt%, but levulinic acid （LA） and solid humins became the main products with high cellulose concentration. The soluble byproducts were analyzed by high performance liquid chromatography/multiple stage tandem mass spec-trometry, and chemicals with formula of C9H16O4、 C10H14O4、 C11H12O4、C12H10O5 and C12H16O8 were detected. THF could participate in the reaction via ring-opening into 1,4-butanediol followed by esterification with LA into C9H16O4 or etherification with HMF into C10H14O4. C11H12O4 was formed by esterification of HMF with LA, C12H10O5 was formed by self-etherification of HMF, while C12H16O8 was formed by acetalization of HMF with glucose. Self-etherification of HMF and etherification of HMF with 1,4-butanediol were identified as two main side reactions.