【作者】 刘明霞；

【导师】 王进；

【作者基本信息】 山东师范大学 ， 有机化学， 2024， 硕士

【摘要】 β-氨基醇是许多天然物质及人工合成分子中的常见骨架结构,如抗HIV药物、生物活性鞘脂、抗癌药物等。三芳基甲烷结构广泛存在于各种天然产物、合成药物及功能分子骨架中,例如染料、缓蚀剂、抗癌药物等。因此,探索构建这两类化合物骨架的新型合成方法具有重大意义。基于本课题组在电化学还原偶联反应领域的前期研究基础,本论文旨在探索开发β-氨基醇类及三芳基甲烷类化合物高效合成的新方法。本论文成功实现了芳香醛与芳香醛亚胺或芳基肼通过电化学还原偶联合成β-氨基醇或三芳基甲烷类化合物的反应。第一个工作介绍了电化学芳香醛与亚胺还原偶联反应制备β-氨基醇类化合物的过程,包含反应设计、反应条件优化、反应底物适用范围研究、反应机理研究等内容。通过各种变量筛选发现最优反应条件为:N-苄叉苯胺（0.2 mmol）,苯甲醛（3 eq）,n-Bu₄NPF₆（2 eq）,Zn片为阳极,Cu片为阴极,DMA（4 m L）,电流为5 m A,以良好的产率得到目标产物。该反应以电子得失代替传统还原剂的使用,通过阴极直接还原芳香醛亚胺的方式产生α-胺基自由基阴离子,并与芳香醛反应获得目标产物β-氨基醇。我们还进一步将氨基醇产物用于后续合成应用中,制备了恶唑烷-2-酮及氮杂环丙烷等化合物,有力证明了该反应有望在药物研发以及在功能分子骨架等领域中得到应用。本文第二个工作介绍了电化学芳香醛与芳基肼还原偶联反应制备三芳基甲烷类化合物的过程,包含反应设计、反应条件优化、反应底物适用范围研究、反应机理研究等内容。通过各种变量筛选发现最优反应条件为:盐酸苯肼（0.2 mmol）,苯甲醛（1 eq）,LiClO₄（1 eq）,Sn片为阳极,Al片为阴极,DMA（4 m L）,电流为20 m A,以中等至良好的产率得到目标产物。该反应以电子得失代替传统还原剂的使用,具有原料廉价易得、反应效率高、操作方便等优点。为探索三芳基甲烷类化合物的实用性,我们进一步将三芳基甲烷产物用于后续合成应用中,制备了一系列新型的染料,这些化合物在材料科学等领域展现出潜在的应用价值。总之,本论文开发了一种在电化学条件下,利用芳香醛与亚胺或肼发生还原偶联反应,高效、绿色制备β-氨基醇或三芳基甲烷类化合物的新方法。该方法采用廉价金属电极材料,通过外加电源提供恒定电流进行电化学反应,具有操作简便、高效环保、底物适用范围广、反应条件温和等诸多优点。更多还原

【Abstract】 β-Amino alcohols are common skeletal structures in many natural substances and synthetic molecules,such as the anti HIV drug,biologically active,anticancer drug,etc.The triarylmethane structure widely exists in the skeleton of various natural products,synthetic drugs,and functional molecular,such as dyes,corrosion inhibitors,anticancer drugs,etc.Therefore,exploring new synthesis methods for constructing the scaffolders of these two types of compounds is of great significance.Based on the preliminary research foundation of our research group in the field of electrochemical reduction coupling reactions,the aim of this paper is to explore and develop a new method for efficient synthesis ofβ-amino alcohols and triarylmethane compounds.This paper successfully achieved the reaction of aromatic aldehydes with aromatic aldehydes imines or arylhydrazines intoβ-amino alcohols or triarylmethane compounds by electrochemical reduction coupling.The first work introduces the process of electrochemical reduction coupling reaction between aromatic aldehydes and imines to prepareβ-amino alcohol compounds,including reaction design,optimization of reaction conditions,study of the applicable range of reaction substrates and study of reaction mechanisms.The optimal reaction conditions are:N-benzylidene aniline（0.2 mmol）,benzaldehyde（3 eq）,n-Bu₄NPF₆（2eq）,Zn sheet as anode,Cu sheet as cathode,DMA（4 m L）,current of 5 m A.The target product was obtained with good yield.This reaction replaces the use of traditional reducing agents with electron gain and loss,generatesα-amino radical anions through direct reduction of aromatic aldehydes imine at the cathode,and reacts with aromatic aldehydes to obtain the target productβ-amino alcohol.We further applied the amino alcohol product in subsequent synthesis applications,preparing compounds such as oxazolidine-2-one and azacyclopropane,which strongly proves that this reaction has the potential to be applied in drug development and functional molecular frameworks.The second work introduces the process of electrochemical reduction coupling reaction between aromatic aldehydes and arylhydrazine to prepare triarylmethane compounds,including reaction design,optimization of reaction conditions,study of the applicable range of reaction substrates and study of reaction mechanisms.The optimal reaction conditions are:phenylhydrazine hydrochloride（0.2 mmol）,benzaldehyde（1 eq）,Li Cl O₄（1 eq）,Sn sheet as anode,Al sheet as cathode,DMA（4 m L）,current of 20 mA.The target product is obtained with moderate to good yields.This reaction replaces the use of traditional reducing agents with electron gain and loss and has the advantages of cheap and easily obtainable raw materials,high reaction efficiency and simple operation.To explore the practicality of triarylmethane compounds,we further applied triarylmethane products in subsequent synthesis applications and prepared a series of novel dyes,which have shown potential application value in materials science and other fields.In conclusion,a new method for efficient and green preparation ofβ-amino alcohols or triarylmethane compounds by reductive coupling of aromatic aldehydes with imine or hydrazine under electrochemical conditions was developed in this paper.This method uses cheap metal electrode materials and provides constant current through external power source for electrochemical reactions.It has many advantages such as simple operation,high efficiency and environmental protection,wide application range of substrate and mild reaction conditions.更多还原