Zheng Wanping, Feng Shanshan, Hu Changwei
Key laboratory of green chemistry and Technology Ministry of Education, College of Chemistry, Sichuan University, Chengdu, Sichuan, 610064, P. R. China.
ChemSusChem. 2024 Feb 22;17(4):e202301364. doi: 10.1002/cssc.202301364. Epub 2023 Nov 17.
Oxime chemicals are the building blocks of many anticancer drugs and widely used in industry and laboratory. A simple but robust hierarchically porous zeolite (HTS-1) catalyst was prepared by hydrothermal methods and used for the preparation of vanillin oxime from vanillin in NH ⋅ H O/DIO (v/v 1/10) system. The results of the catalyst characterization showed that the larger pore size and more framework Ti were conducive to promote the transformation of the substrates. The conversion of vanillin and the yield of vanillin oxime were both higher than 99 % under optimized reaction conditions. It was found that the reaction proceeded by oxidation of NH to hydroxylamine (NH OH), and oximation of hydroxylamine with vanillin to obtain vanillin oxime, where the rate-controlling step was the hydroxylamine formation, and the apparent activation energy was 26.22 kJ/mol. The corresponding oximation products could also be obtained by extending this method to other compounds derived from lignin. Furthermore, the catalytic system was used directly to the conversion of birch biomass to obtain oxime products such as vanillin oxime, syringaldehyde oxime, and furfural oxime etc. This work might give insights into the sustainable production of N-containing high-value products from lignocellulose.
肟类化合物是许多抗癌药物的组成部分,在工业和实验室中广泛应用。通过水热法制备了一种简单而稳定的分级多孔沸石(HTS-1)催化剂,并将其用于在NH ⋅ H O/DIO(体积比1/10)体系中由香草醛制备香草醛肟。催化剂表征结果表明,较大的孔径和更多的骨架钛有利于促进底物的转化。在优化的反应条件下,香草醛的转化率和香草醛肟的产率均高于99%。研究发现,反应通过将NH氧化为羟胺(NH OH),以及羟胺与香草醛肟化得到香草醛肟进行,其中速率控制步骤是羟胺的形成,表观活化能为26.22 kJ/mol。通过将该方法扩展到其他木质素衍生化合物,也可以得到相应的肟化产物。此外,该催化体系直接用于桦木生物质的转化,以获得香草醛肟、丁香醛肟和糠醛肟等肟类产物。这项工作可能为从木质纤维素可持续生产含氮高价值产品提供思路。