高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

新型三维单核Zn(II)配合物多位点协同催化单和双取代喹唑啉酮的绿色合成

徐一铭,史燚威,王鑫,朱志慧,宋志国,王敏   

  1. 渤海大学化学与材料工程学院
  • 收稿日期:2025-08-16 修回日期:2025-10-14 网络首发:2025-10-16 发布日期:2025-10-16
  • 通讯作者: 宋志国 E-mail:songzhiguo@qymail.bhu.edu.cn
  • 基金资助:
    教育部产学合作协同育人项目2024年第一批次（批准号：231105940171618, 230805940290824）资助

Green synthesis of mono- and disubstituted quinazolinones by multi-site synergistic catalysis of novel three-dimensional single-nuclear Zn(II) complexes

XU Yiming，SHI Yiwei，WANG Xin，ZHU Zhihui，SONG Zhiguo，WANG Min   

  1. College of Chemistry and Materials Engineering, Bohai University
  • Received:2025-08-16 Revised:2025-10-14 Online First:2025-10-16 Published:2025-10-16
  • Contact: SONG Zhiguo E-mail:songzhiguo@qymail.bhu.edu.cn
  • Supported by:
    Supported by the Ministry of Education’s Industry-University Collaborative Education Project of the First Batch in 2024, China(No.231105940171618, 230805940290824)

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摘要： 本文分别选用对氨基苯磺酸根（4-ABS-）和对甲基苯磺酸根（4-MBS-）为主配体、选用4,4'-联吡啶（4,4'-bipy）为辅助配体，与Zn(II)盐通过溶剂热法合成了两种锌基配合物：[Zn(4,4'-bipy)(H2O)4]·(4-ABS)2 (1)和[Zn(4,4'-bipy)(H2O)4]·(4-MBS)2 (2)。采用单晶X射线衍射（S-XRD）、红外光谱（IR）、热重分析（TGA）、粉末X射线衍射（P-XRD）和场发射扫描电子显微镜（SEM）对配合物进行了表征。考察了配合物1和2催化合成2,3-二苯基-2,3-二氢喹唑啉-4(1H)-酮反应的性能，并以催化效果较好的配合物1进行底物普适性实验，结果表明，在无溶剂条件下，使用少量催化剂，在短时间内得到较高产率的产物，并且该绿色工艺适用于多种不同的原料胺/铵和含不同取代基的芳香醛。此外，利用密度泛函理论（DFT）对配合物1和三种反应物进行结构优化，通过计算分析前线分子轨道（NBO），推测反应顺序及配合物1对三种反应物的核心活性区；通过分析分子表面静电势（ESP）、平均局部离子化能（ALIE）和Mulliken电荷进一步详细地预测了配合物1的活性位点和反应底物的反应位点。最后，结合DFT阐述了配合物多位点协同催化的反应机理。

关键词: 锌基配合物, 晶体结构, 2,3-二氢喹唑啉-4(1H)-酮, 催化机理, 密度泛函理论

Abstract: In this study, two zinc-based complexes [Zn(4,4'-bipy)(H2O)4]·(4-ABS)2 (1) and [Zn(4,4'-bipy)(H2O)4]·(4-MBS)2 (2) were obtained through solvothermal synthesis with Zn(II) salts using p-aminobenzenesulfonate (4-ABS-) and p-methylbenzenesulfonate (4-MBS-) as the main ligands and 4,4'-bipyridine (4,4'-bipy) as the auxiliary ligand. The complexes were characterized by single-crystal X-ray diffraction (S-XRD), infrared spectroscopy (IR), thermogravimetric analysis (TGA), powder X-ray diffraction (P-XRD), and field-emission scanning electron microscopy (SEM). The performance of complexes 1 and 2 in catalyzing the synthesis of 2,3-diphenyl-2,3-dihydroquinazoline-4(1H)-one was investigated, and complex 1 with better catalytic effect was chosen for substrates universality experiments. The experimental results show that high-yield products could be obtained using a small amount of catalyst in short time under solvent-free conditions. This green process was applicable to a variety of raw materials amines/ammonium compounds and aromatic aldehydes with different substituents. In addition, density functional theory (DFT) was used to optimize the structures of complex 1 and the three reactants. Through computational analysis of the frontier molecular orbitals (NBO), the reaction sequence and the core active sites of complex 1 for the three reactants were inferred. The active sites of complex 1 and the reaction sites of the reaction substrates were further predicted in detail by analyzing the electrostatic potential (ESP) of the molecular surface, the average local ionization energy (ALIE) and the Mulliken charges. Finally, the reaction mechanism of multi-site synergistic catalysis of the complexes was explained in combination with DFT.（CCDC: 2171834, 1; 2225758, 2）

Key words: Zinc-based complexes, Crystal structure, 2,3-Dihydroquinazolin-4(1H)-one, Catalytic mechanism, Density functional theory (DFT)

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