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微波辅助下糠醛在三氟甲磺酸钪作用下一锅法串联转化为γ-戊内酯

Microwave-Assisted One Pot Cascade Conversion of Furfural to γ-Valerolactone over Sc(OTf).

作者信息

Li Fukun, Yang Ronghe, Tian Zheng, Du Ziting, Dai Jinhang, Wang Xingmin, Li Ning, Zhang Jie

机构信息

College of Environment and Resources, Chongqing Technology and Business University, Chongqing, 400067, P. R. China.

Dencare (Chongqing) Oral Care Co., Ltd, Chongqing, 400067, P. R. China.

出版信息

Chemistry. 2023 Sep 15;29(52):e202300950. doi: 10.1002/chem.202300950. Epub 2023 Aug 16.

Abstract

γ-Valerolactone (GVL) is considered as a star biochemical which can be used as a green solvent, fuel additive and versatile organic intermediate. In this study, metal triflate (M(OTf) ) was utilized as the catalyst for one-pot transformation of furfural (FF) to GVL in alcohol media under microwave irradiation. Alcohol plays multiple functions including solvent, hydrogen donor and alcoholysis reagent in this cascade reaction process. And process efficiency of GVL production from FF upgrading is strongly related to the effective charge density of selected catalyst and the reduction potential of selected alcohol. Complex (OTf) -M-O(H)R, presenting both Brønsted acid and Lewis acid, is the real catalytic active species in this cascade reaction process. Among various catalysts, Sc(OTf) exhibited the best catalytic activity for GVL production. Various reaction parameters including the Sc(OTf) amount, reaction temperature and time were optimized by the response surface methodology with the central composite design (RSM-CCD). Up to 81.2 % GVL yield and 100 % FF conversion were achieved at 143.9 °C after 8.1 h in the presence of 0.16 mmol catalyst. This catalyst exhibits high reusability and can be regenerated by oxidative degradation of humins. In addition, a plausible cascade reaction network was proposed based on the distribution of product.

摘要

γ-戊内酯(GVL)被认为是一种明星生物化学物质,可用作绿色溶剂、燃料添加剂和通用有机中间体。在本研究中,金属三氟甲磺酸盐(M(OTf) )被用作催化剂,在微波辐射下于醇介质中实现糠醛(FF)一锅法转化为GVL。在该串联反应过程中,醇发挥多种作用,包括溶剂、氢供体和醇解试剂。FF升级制备GVL的过程效率与所选催化剂的有效电荷密度和所选醇的还原电位密切相关。同时呈现布朗斯特酸和路易斯酸的配合物(OTf) -M-O(H)R是该串联反应过程中的实际催化活性物种。在各种催化剂中,Sc(OTf)对GVL的制备表现出最佳的催化活性。采用中心复合设计的响应面法(RSM-CCD)对包括Sc(OTf)用量、反应温度和时间在内的各种反应参数进行了优化。在0.16 mmol催化剂存在下,于143.9 °C反应8.1 h后,GVL产率高达81.2%,FF转化率达100%。该催化剂具有高可重复使用性,可通过腐殖质的氧化降解进行再生。此外,基于产物分布提出了一个合理的串联反应网络。

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