论文总字数：17163字

摘 要

含氮杂环化合物包括咪唑、吡唑、噻唑、三唑、三嗪、吡啶、嘧啶、吡咯等。它们广泛应用于工业生产中，如石油冶炼、焦化、医药、农药等。其中一些具有多种生物活性，如抗菌、抗结核、抗病毒、抗肿瘤、抗炎、抗氧化和抗疟疾。含氮杂环结构是天然产物分子的其中一种组成部分，它有很多种类，在新药研发过程中也占有极其重要的地位。此外，它还广泛用于合成染料、感光材料、表面活性剂、新型催化剂的制作。

硝化反应是向有机物分子中引入硝基的反应过程。早在很久以前，历经科学的发展，人们发现了将苯硝化成硝基苯的方法，这也为后续研究奠定了基础。之后，由于人们的不断钻研，以及印染工业的不断发展，硝化反应的应用前景变得越来越乐观，特别是在有机合成工业中。然而，传统方法不仅产生大量有害物质，浓酸和浓碱难以处理，对环境和人体健康构成极大威胁，而且产量极低。近年来，过渡金属催化的碳氢官能化在分子合成的发展引起了越来越多的关注。最近使用钌催化剂在使用邻位导向基团辅助环金属化的间位选择性C-H官能化中显示出优异的催化性能。

本课题设计了一种新型高效的钌催化含氮杂环取代芳烃类化合物间位选择性硝基化的方法，AgNO₂作为硝基源，HPcy³ ·BF₄₋作为配体，新戊酸作为添加剂，DCE作为溶剂，与传统方法相比，该研究探索了一种更温和且更环保的方法来实现取代芳烃的间位硝基化。

关键词：含氮杂环化合物 硝化反应 钌催化 间位选择性 亚硝酸银

Nitration of N-heterocyclic substituted aromatics catalyzed by ruthenium

Abstract

Nitrogen-containing heterocyclic compounds, including imidazole, pyridine, thiazole, triazole, triazol, pyridine, pyridine, etc., are widely used in industrial production, For example, in petroleum metallurgy, coking, medicine, pesticide and other fields, some of them have multiple biological activities, for example, antibacterial, tuberculosis and others.The nitrogen-containing heterocyclic structure is one of the components of natural product molecules. It has many types and also plays an extremely important role in the development of new status. Except for this, it is also broadly used in the production of synthetic dyesstuff, sensitive materials, surface active agents, and novel catalyst.

Nitrification is a reaction process that introduces nitro groups into organic molecules. A long time ago, after the development of science, people discovered the method of nitrification of benzene into nitrobenzene, which also laid the foundation for subsequent research. Since then, due to the continuous research of people and the continuous development of the printing and dyeing industry, the application prospect of nitrification reaction has become more and more optimistic, especially in the organic synthesis industry. However, the traditional methods not only produce a large number of harmful substances, which are difficult to deal with concentrated acid and alkali, which greatly threaten the environment and human health, but also have a very low yield. Last several years, the function of transition metal-catalyzed hydrocarbons has triggered a wave of heat in the development of numerat compose. Recently, ruthenium catalysts have shown excellent catalytic performance in the metaselective C-H functionalization of ring metallization assisted by ortho oriented groups.
In this paper, a novel and efficient method of ruthenium catalyzed inter site selective nitration of N-heterocyclic substituted aromatic compounds was designed. AgNO₂ was used as nitro source, Hpcy³ · BF_4- as ligand, neopentanoic acid as additive, DCE as solvent. Make a comparison with the previous methods, this research explored a more environmentally method, through continuous experimentation and discussion, you will get many unexpected gains and achieve the goal of replacing the nitrification of aromatic compounds.

Keywords: Nitrogenous heterocyclic compounds; Nitration reaction; Ruthenium catalysis; Intersite selectivity; Silver nitrite

目录

摘 要 I

Abstract II

前言 1

第一章 绪论 2

1.1 含氮杂环化合物及其衍生物的简介 2

1.1.1 含氮杂环化合物简介 2

1.1.2 硝基芳烃简介 2

1.2 传统及改进制作硝基化合物反应描述 2

1.2.1 传统做法及弊端 2

1.2.2 钌催化含氮杂环取代芳烃间位硝化反应 5

1.2.3 自由基 7

1.3 研究的目的和意义 8

第二章 实验思路与实验准备 10

2.1 实验思路来源 10

2.2实验材料及仪器 11

2.2.1实验仪器 11

2.2.2实验溶剂 11

第三章 实验路线及条件筛选 12

3.1反应的条件探索及其优化 12

3.1.1反应的路线 12

3.2.优化反应条件 12

3.2.1催化剂的筛选 12

3.2.2硝基源的摸索 13

3.2.3溶剂及温度的挑选 14

3.3底物普适性研究 15

3.3.1芳基噻唑类化合物 15

3.3.2芳基吡唑类化合物 16

3.4克级放大（研究潜在实际应用） 17

第四章 反应机理探究 18

第五章 结论与展望 20

5.1 结论 20

5.2 展望 20

参考文献 21

致谢 24

前言

含氮杂环化合物及其衍生物在医学、农业和染料，以及橡胶、香料等产业中的应用非常广泛，所以研究员们开始深入探索含氮杂环化合物的高效合成方法及应用。如今已经开发出一些含有噻唑环、吡唑环、噁唑环的化合物的药品、肥料及其他产品，比如含有噻唑环的药品有阿莫西林、呱拉西林、氨苄西林等临床药品，含有吡唑环的杀虫剂吡虫啉、杀菌剂噻菌灵、除草剂羟草酮等农药产品，含有噁唑环的达那唑、噁唑菌酮等等产品。

其中，硝基化合物是含氮杂环化合物不可缺少的一部分。与脂肪族硝基化合物相比，芳香族硝基化合物应用广泛。可制备农药和医药产品，可使芳烃上的其他取代基活化，可还原性制备氨基（-NH₂）化合物，比如染料、药物等。另外还具有一定的有机物功能。

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