Gao Xiaoqian, Tong Xinli, Zhang Yi, Xue Song
Tianjin Key Laboratory of Organic Solar Cells and Photochemical Conversion, School of Chemistry and Chemical Engineering, Tianjin University of Technology, No. 391, Binshuixi Road, Tianjin 300384, China.
iScience. 2023 Jun 25;26(7):107203. doi: 10.1016/j.isci.2023.107203. eCollection 2023 Jul 21.
The selective production of C4 bulk chemicals from biomass is significant to replace the traditional method from petroleum resource. In this work, the succinic anhydride (SAN) is directly prepared from bio-based furanic platform compounds utilizing the visible light-induced oxygenation process, in which -tetraphenyl porphyrin (HTPP) and molecular oxygen was employed as the photocatalyst and terminal oxidant, respectively. Under optimal conditions, a 99.9% conversion with 97.8% selectivity of SAN was obtained from furoic acid (FAC) at room temperature. Moreover, the transformation of furfural and furfuryl alcohol with this system can also generate SAN, and the product selectivity is controllable by tuning light intensity and time. Furthermore, the EPR detection, isotope labeling, and control experiments exhibited that the generation of singlet oxygen plays a crucial role and 5-hydroxy-2(5H)-furanone is the main intermediate during the reaction. Finally, a possible reaction mechanism for the production of SAN from furanic compound is proposed.
从生物质中选择性生产C4大宗化学品对于取代传统的石油资源方法具有重要意义。在这项工作中，利用可见光诱导的氧化过程，从生物基呋喃类平台化合物直接制备琥珀酸酐（SAN），其中分别使用四苯基卟啉（HTPP）和分子氧作为光催化剂和终端氧化剂。在最佳条件下，室温下从糠酸（FAC）获得了99.9%的转化率和97.8%的SAN选择性。此外，该体系中糠醛和糠醇的转化也能生成SAN，通过调节光强度和时间可以控制产物选择性。此外，电子顺磁共振检测、同位素标记和对照实验表明，单线态氧的产生起着关键作用，5-羟基-2(5H)-呋喃酮是反应过程中的主要中间体。最后，提出了从呋喃类化合物生产SAN的可能反应机理。
