title: Formyl-Modified Polyaniline for the Catalytic Dehydration of Fructose to 5-Hydroxymethylfurfural.
abstract: We report an unprecedented solid organic-base catalyst, formyl-modified polyaniline (FS-PAN), for the dehydration of fructose to 5-hydroxymethylfurfural (HMF) with a high yield of 90.4 mol %. We demonstrate that the nitrogen atoms incorporated between the phenyl rings in the backbone of the polyaniline chain contribute to the basicity of the catalyst. The grafting of electron-withdrawing formyl groups to the imine nitrogen atoms leads to a significant increase of basicity of the polymer catalyst owing to the greater localization of electrons at the amide nitrogen atom formed. A linear dependence of the yield of HMF on the grafting level of formyl groups in FS-PAN indicates that the amide acts as the active phase. A possible reaction mechanism for this organic-base-catalyzed dehydration reaction is proposed. The side-reaction of HMF rehydration is inhibited thoroughly, and the condensation of any reaction intermediates to undesirable oligomers is restrained by this base catalyst. This organic-base catalyst can be recycled completely without loss of activity. This research highlights the first application of a highly effective and stable solid base catalyst for the transformation of renewable carbohydrates into fine chemicals.
authors.affiliation: Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, Sichuan, 610064, PR China.
authors.forename: Liangfang
authors.initials: L
authors.lastname: Zhu
authors.affiliation: Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, Sichuan, 610064, PR China.
authors.forename: Jinhang
authors.initials: J
authors.lastname: Dai
authors.affiliation: Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, Sichuan, 610064, PR China.
authors.forename: Mingyang
authors.initials: M
authors.lastname: Liu
authors.affiliation: Research Institute for New Materials Technology, Chongqing University of Arts and Sciences, Chongqing, 402160, PR China.
authors.forename: Dianyong
authors.initials: D
authors.lastname: Tang
authors.affiliation: Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, Sichuan, 610064, PR China.
authors.forename: Shuqing
authors.initials: S
authors.lastname: Liu
authors.affiliation: Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, Sichuan, 610064, PR China. changweihu@scu.edu.cn.
authors.forename: Changwei
authors.initials: C
authors.lastname: Hu
mesh_terms: D000814:Aniline Compounds / Q000737:chemistry*; D002384:Catalysis; D005632:Fructose / Q000737:chemistry*; D005662:Furaldehyde / Q000031:analogs & derivatives* / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D007097:Imines / Q000737:chemistry; D012997:Solvents / Q000737:chemistry; D013696:Temperature; D014867:Water / Q000737:chemistry
chemical_list: D000814:Aniline Compounds; D007097:Imines; D012997:Solvents; C416807:polyaniline; D014867:Water; D005632:Fructose; C008046:5-hydroxymethylfurfural; D005662:Furaldehyde
keywords: biomass; carbohydrates; heterogeneous catalysis; organocatalysis; oxygen heterocycles