The synthesis of platform molecules from food wastes is a topic of interest for the development of sustainable biorefineries. Starchy food wastes can serve as feedstocks to produce fine chemicals, fuels, and polymers by the hydrolysis of starch and further conversion into platform molecules such as 5-hydroxymethylfurfural (5-HMF) and 5-chloromethylfurfural (5-CMF). Conventionally, the synthesis of 5-CMF has relied on the use of concentrated hydrochloric acid (HCl) as a catalyst. However, recent studies have explored alternative methods, including eutectic solvents containing metal chlorides, which have facilitated 5-CMF production. This study presents a novel approach to synthesizing 5-CMF from starch using eutectic solvents without the need for either HCl or metal chloride additives. The synthesis was conducted using a low transition temperature mixture of choline chloride, citric acid, and boric acid in a biphasic system with dichloromethane as the extracting solvent. The synthesis was optimized using the response surface methodology through a Box–Behnken design. At 100 °C and 90 min of reaction time, up to 17 mol % 5-HMF and 13 mol % 5-CMF were produced, and in the optimized conditions of 120 °C and 135 min, up to 33 mol % 5-CMF with less than 1 mol % 5-HMF was obtained from starch. Moreover, it was shown that the low transition temperature mixture used in this study could be reused at least five times.

中文翻译：

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淀粉在低转变温度混合物中一锅法转化为 5-氯甲基糠醛和 5-羟甲基糠醛


从食物垃圾中合成平台分子是可持续生物精炼厂发展的一个令人感兴趣的话题。淀粉类食物垃圾可作为原料，通过淀粉水解并进一步转化为平台分子（如 5-羟甲基糠醛 (5-HMF) 和 5-氯甲基糠醛 (5-CMF)）来生产精细化学品、燃料和聚合物。传统上，5-CMF的合成依赖于使用浓盐酸(HCl)作为催化剂。然而，最近的研究探索了替代方法，包括含有金属氯化物的低共熔溶剂，这有利于 5-CMF 的生产。这项研究提出了一种使用低共熔溶剂从淀粉合成 5-CMF 的新方法，无需 HCl 或金属氯化物添加剂。该合成是使用氯化胆碱、柠檬酸和硼酸的低转变温度混合物在双相系统中以二氯甲烷作为萃取溶剂进行的。通过 Box-Behnken 设计，使用响应面方法对合成进行了优化。在 100 °C 和 90 分钟的反应时间下，产生了高达 17 mol% 5-HMF 和 13 mol% 5-CMF，在 120 °C 和 135 分钟的优化条件下，产生了高达 33 mol% 5-CMF从淀粉中获得少于 1 mol% 5-HMF。此外，研究表明，本研究中使用的低转变温度混合物可以重复使用至少五次。