Recent advances in the chemical-catalytic approaches for the production of 5-(halomethyl)furfurals from cellulose and its derivatives: A review

• Published in: International journal of biological macromolecules 2024-12, Vol.282 (Pt 4), p.137194, Article 137194
• Main Authors: Hong, Mei, Guo, Yuxuan, Chen, Shaoziyu, Xie, Aoshi, Zhu, Weixuan, Han, Jianlin, Liu, Shaogang
• Format: Article
• Language: English
• Subjects: 5-(Halomethyl)furfurals; 5-(Hydroxymethyl)furfural; Biomass; Biomass conversion; Catalysis; Cellulose - chemistry; Furaldehyde - analogs & derivatives; Furaldehyde - chemistry; Lignin; Renewable synthesis; Renewables
• ISSN: 0141-8130; 1879-0003; 1879-0003
• DOI: 10.1016/j.ijbiomac.2024.137194

5-Hydroxymethylfurfural (HMF) is recognized by the U.S. Department of Energy as a key platform chemical derived from renewable C6 sugars obtained from lignocellulosic biomass. Despite its importance, the economic utilization of HMF is limited by its hydrophilic properties and insufficient stability. In contrast, 5-(halomethyl)furfurals, which are hydrophobic analogs of HMF, demonstrate improved stability, making their extraction and purification easier while extending their shelf life. These compounds present an alternative opportunity for HMF in derivative chemistry. However, the literature on halogenated HMF derivatives is scattered and lacks a comprehensive review. This review aims to fill this gap by synthesizing current research, evaluating achievements and challenges, discussing pathways for the production of 5-(halomethyl)furfurals (XMF, where X = Cl, Br) from cellulose and its derivatives, detailing reaction mechanisms, and proposing improvements in catalytic systems. Future research may focus on the innovative and economically viable direct synthesis of these derivatives from biomass-derived sources for scale-up and commercialization. •The hydrophilic nature and poor stability of HMF hinder its economic viability.•5-(Halomethyl)furfurals, instead of 5-HMF, exhibit significant potential for producing high-value bioproducts.•The synthesis routes of 5-(halomethyl)furfurals from HMF and carbohydrates were summarized.•The reaction mechanism, along with the catalysts, solvents and process technology, is reviewed in detail.