Synthesis of Bis(hydroxylmethylfurfuryl)amine Monomers from 5-Hydroxymethylfurfural

• Published in: ChemSusChem 2016-06, Vol.9 (11), p.1255-1258
• Main Authors: Xu, Zhanwei, Yan, Peifang, Liu, Kairui, Wan, Lu, Xu, Wenjuan, Li, Huixiang, Liu, Xiumei, Zhang, Z. Conrad
• Format: Article
• Language: English
• Subjects: Aliphatic compounds; Amines; Amines - chemical synthesis; Amines - chemistry; biomass; Biopolymers; Catalysis; Catalysts; Chemistry Techniques, Synthetic; Furaldehyde - analogs & derivatives; Furaldehyde - chemistry; Furans - chemical synthesis; Furans - chemistry; green chemistry; Hydrogenation; Ligands; Monomers; polymers; renewable resources; ruthenium; Ruthenium - chemistry; Synthesis
• ISSN: 1864-5631; 1864-564X
• DOI: 10.1002/cssc.201600122

We report the synthesis of bis(hydroxylmethylfurfuryl)amine (BHMFA) from 5‐hydroxymethylfurfural (5‐HMF) by reacting 5‐HMF with primary amines in the presence of homogeneous RuII catalysts having sterically strained ligands. BHMFA is a group of furan‐based monomers that offer great potential to form functional biopolymers with tunable properties. A range of primary amines, such as aliphatic and benzyl amines, are readily converted with 5‐HMF to form the corresponding BHMFA in good yields. The reaction proceeds through reductive amination of 5‐HMF with primary amine to form secondary amine, followed by reductive amination of 5‐HMF with in situ generated secondary amine to produce BHMFA. New Ru‐te: Furan‐based bis(hydroxylmethylfurfuryl)amines (BHMFAs) were synthesized by Ru‐catalyzed hydrogenative amination of 5‐HMF with primary amines. BHMFAs represent a new class of bio‐based monomers with great potential to produce a new type of functional biopolymers with tunable properties.