Wang Gang, Geng Yage, Zhao Zejing, Zhang Qiuping, Li Xiang, Wu Zhiqiang, Bi Shuxian, Zhan Haijuan, Liu Wanyi
State Key Laboratory of High-Efficiency Utilization of Coal and Green Chemical Engineering, National Demonstration Center for Experimental Chemistry Education, College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, P. R. China.
College of Chemistry and Chemical Engineering, Ningxia Normal university, Guyuan 756000, P. R. China.
ACS Omega. 2022 Aug 30;7(36):32577-32587. doi: 10.1021/acsomega.2c04159. eCollection 2022 Sep 13.
The use of mechanical ball milling to facilitate the synthesis of organic compounds has attracted intense interest from organic chemists. Herein, we report a new process for the preparation of xanthene and pyrimidinone compounds by a one-pot method using polymeric aluminum chloride (PAC), silica gel, and reaction raw materials under mechanical grinding conditions. During the grinding process, polymeric aluminum chloride and silica gel were reconstituted in situ to obtain a new composite catalyst (PAC-silica gel). This catalyst has good stability (six cycles) and wide applicability (22 substrates). The Al-O-Si active center formed by in situ grinding recombination was revealed to be the key to the effective catalytic performance of the PAC-silica gel composites by the comprehensive analysis of the catalytic materials before and after use. In addition, the mechanism of action of the catalyst was verified using density functional theory, and the synthetic pathway of the xanthene compound was reasonably speculated with the experimental data. Mechanical ball milling serves two purposes in this process: not only to induce the self-assembly of silica and PAC into new composites but also to act as a driving force for the catalytic reaction to take place. From a practical point of view, this "one-pot" catalytic method eliminates the need for a complex preparation process for catalytic materials. This is a successful example of the application of mechanochemistry in materials and organic synthesis, offering unlimited possibilities for the application of inorganic polymer materials in green synthesis and catalysis promoted by mechanochemistry.
利用机械球磨促进有机化合物的合成已引起有机化学家的浓厚兴趣。在此,我们报道了一种在机械研磨条件下,使用聚合氯化铝(PAC)、硅胶和反应原料通过一锅法制备呫吨和嘧啶酮化合物的新方法。在研磨过程中,聚合氯化铝和硅胶原位重构得到一种新型复合催化剂(PAC-硅胶)。该催化剂具有良好的稳定性(六个循环)和广泛的适用性(22种底物)。通过对使用前后催化材料的综合分析表明,原位研磨重组形成的Al-O-Si活性中心是PAC-硅胶复合材料有效催化性能的关键。此外,利用密度泛函理论验证了催化剂的作用机理,并结合实验数据合理推测了呫吨化合物的合成途径。机械球磨在此过程中起到两个作用:不仅诱导硅胶和PAC自组装成新型复合材料,还作为催化反应发生的驱动力。从实际角度来看,这种“一锅法”催化方法无需催化材料的复杂制备过程。这是机械化学在材料和有机合成中应用的一个成功范例,为无机高分子材料在机械化学促进的绿色合成和催化中的应用提供了无限可能。