铁、锰、铜和水杨醛缩金刚烷胺席夫碱配体原位催化5-羟甲基糠醛氧化制备5-甲酰基呋喃-2-羧酸  

In-situ oxidation of 5-hydroxymethylfurfural to 5-formylfuran-2-carboxylic acid catalyzed by iron, manganese, copper and salicylic amantadine Schiff base ligands

作　　者：白继峰 程曼芳 卢虹竹 侯明波[2] 杨雨 王景芸[1] 周明东[1] BAI Ji-feng;CHENG Man-fang;LU Hong-zhu;HOU Ming-bo;YANG Yu;WANG Jing-yun;ZHOU Ming-dong(School of Petrochemical Technology,Liaoning Shihua University,Fushun 113001,China;PetroChina Fushun Petrochemical Company No 2 Petroleum Plant,Fushun 113004,China)

机构地区：[1]辽宁石油化工大学石油化工学院,辽宁抚顺113001 [2]中国石油抚顺石化公司石油二厂,辽宁抚顺113004

出　　处：《燃料化学学报》2022年第4期418-427,共10页Journal of Fuel Chemistry and Technology

基　　金：兴辽英才计划(XLYC1902085);辽宁省自然科学基金(20170540590);中石油创新基金(2018D-5007-0507)资助。

摘　　要：本研究将铁、锰、铜和金刚烷胺缩水杨醛衍生的席夫碱配体组成的原位催化剂用于催化5-羟甲基糠醛(5-Hydroxymethylfurfural,简称HMF)选择性氧化制备5-甲酰基呋喃-2-羧酸(5-formyl-2-furancarboxylic acid,简称FFCA)。通过核磁共振(NMR)、红外(FT-IR)和单晶衍射对配体和配合物进行了表征,并对氧化反应时间、反应温度、MnCl_(2)·4H_(2)O与配体物质的量比、氧化剂和催化剂用量等反应条件进行优化,在最优化条件下,HMF转化率为100%,并且可以获得收率为52.1%的FFCA。根据反应结果对Mn金属配合物催化的HMF氧化反应过程进行了分析。To synthesize simple and efficient catalysts and their application in catalytic conversion of biomass platform compounds to prepare high value-added chemicals has always been the focus of researchers. In this paper,a catalyst composed of iron, manganese, copper and Schiff base ligand derived from amantadine salicylaldehyde was in-situ constructed to catalyze the selective oxidation of 5-hydroxymethylfurfural(HMF) to prepare 5-formyl-2-furancarboxylic acid(FFCA). The ligands and complexes were characterized by nuclear magnetic resonance(NMR), infrared spectroscopy(IR) and single crystal diffraction, and the reaction conditions such as oxidation reaction time, reaction temperature, molar ratio of MnCl_(2)·4H_(2)O to ligand, oxidant and catalyst dosage, etc, were optimized. Under the optimized conditions, 100% conversion of HMF and the FFCA with a yield of 52.1% can be obtained. Finally, on the basis of the reaction results, the HMF oxidation reaction process catalyzed by Mn metal complexes was analyzed.

关 键 词：5-羟甲基糠醛 氧化 席夫碱 原位催化 5-甲酰基呋喃-2-羧酸 

分 类 号：O643.36[理学—物理化学]