摘 要

香豆素类化合物以苯并吡喃酮作为骨架的的一种天然产物，香豆素还可以看作是顺式邻羟基桂皮酸发生分子内脱水而形成，它在有机合成和现在研究当中起了很重要的作用以及占有了很重要的位置。香豆素及其衍生物具有多种活性，因此应用于各个领域，它在食品，化妆品及饮料当中作为增香剂，已经成为了我们生活中不可缺少的必需品。同时它表现出的抗微生物等重要的生物活性，把它带进了农业，工业，医药等更多行业，引起了更多研究者的关注，比如通过研究发现蛇床子素，秦皮乙素等天然香豆素对植物病原菌具有抑制作用，让更多人去合成并研究了香豆素及其衍生物的性质及应用。另外其具有的抗肿瘤，抗菌，抗氧化，抗HIV等医药活性，更加丰富了香豆素及其衍生物的应用范围。

香豆素的合成，性质，应用在国内和国外已经有了不少研究，在常规方法的基础上，研究新的合成方法以及合成出更多新的香豆素及其衍生物，这是一项具有意义和价值的研究工作。以香豆素母体作为主要骨架，可以合成出更多不同结构和性质的香豆素化合物，因此，合成出来的香豆素衍生物具有不同的官能团以及合成方法和合成检测手段。国内和国外近年的合成研究主要包括常规的合成方法的优化与新的合成方法的研发，如 perkin合成法，Knoevenagel合成法， Pechmann合成法等香豆素合成方法的进一步研究，通过反应溶剂的影响和反应催化剂的影响效果来优化出最佳合成方案以及微波合成法，离子液体法等新的手段引入到香豆素及其衍生物的合成研究工作当中，从而提高产物收率，达到更有效的合成效果。

本文主要尝试从同一个原料出发，选不同路线，合成出2种新的香豆素衍生物，期望得到预料的结果，其合成路线为：以香豆素-3-羧酸作为原料，与水合肼反应，合成酰肼类香豆素，接着第一步得到的酰肼类香豆素衍生物作为原料，无水乙醇作为溶剂，六氢吡啶作为催化剂，分别跟乙酰二茂铁和3-乙酰基香豆素通过缩合反应得到目标产物1和目标产物2。通过研究不同催化剂的使用，用量，反应时间等条件来优化出了目标产物1的最佳合成方案，目标产物的分子结构由红外光谱，紫外光谱得到验证。本论由于反应条件，反应溶剂等因素的影响，目标产物2没达到期望的结果。

研究结果表明，香豆素类及其衍生物的药物活性与香豆素上取代基的种类及其位置有关，本实验合成的目标产物具有荧光性质和电化学效应的香豆素衍生物之一，可以应用于医药，工业，染料，香料和农药等多种领域当中，因此其合成，性质，应用均具有研究价值。

关键词：香豆素；衍生物；合成； 研究现状；红外光谱；紫外光谱；

Abstract

Coumarin compounds as benzo-pyrone skeleton, found in nature in a natural product lactones, coumarin may also be considered as intramolecular dehydration cis-o-hydroxycinnamic acid generator is formed, it in organic synthesis and study which now plays an important role and occupies a very important position. Coumarin and its derivatives have a variety of active and therefore used in various fields, it is in the food, cosmetics and beverages as a flavoring agent, which has become our lives an indispensable necessity. At the same time it shows antimicrobial and other important biological activity, put it into more sectors such as agriculture, industry, medicine, etc., caused more attention of researchers, for example, found that Osthol, Aesculetin through research and other natural coumarin on plant pathogenic bacteria inhibited the synthesis and let more people to study the properties and applications of coumarin and its derivatives. In addition it has anti-tumor, anti-bacterial, anti-oxidation, anti-HIV and other pharmaceutically active, richer range of applications and Its Derivatives.

Coumarin, the nature of the application at home and abroad has been a lot of research, on the basis of the conventional method, the study of new synthetic methods and synthetic more new coumarin and its derivatives, which is a term research work has meaning and value. Coumarin parent as the main skeleton, coumarin compounds can be synthesized more different structures and properties, therefore, synthesized coumarin derivatives having different functional groups as well as synthetic methods and synthetic tests. At home and abroad in recent years including the synthesis of optimized conventional synthetic methods and the development of new synthetic methods, such as in-depth study perkin synthesis method, Knoevenagel synthesis, Pechmann synthesis method, etc. Synthetic Methods and improvement, optimization of reaction synthesis was conducted to study the impact of the solvent reaction, new means to improve the synthesis and microwave synthesis catalyst, the ionic liquid is introduced into the synthesis method research coumarin and its derivatives which, in order to improve the yield, to achieve more effective synthesis effect.

In this paper, the design and synthesis of two kinds of new coumarin derivatives, expect good drug activity and potential applications. Synthetic route the target product were as follows: 3-carboxylic acid as a starting material, reaction with hydrazine hydrate, coumarin synthesized hydrazides, hydrazides coumarin derivative as a raw material obtained by the first step and then, no aqueous ethanol as a solvent, Hexahydropyridine as a catalyst, respectively, with acetyl ferrocene and 3-acetyl-coumarin by a condensation reaction to give the desired product. 1 and 2 the desired product. By studying the use of different catalysts, reaction time and other conditions to optimize the best out of the target product synthesis scheme 1, the molecular structure of the target product by IR, UV verified. On the influence of the reaction conditions, solvents and other factors, the desired product 2 did not achieve the desired results.

The results show that coumarin derivatives and their pharmaceutically active species and position of substituents on the coumarin about this experiment synthetic product has one goal coumarin derivative fluorescence properties and electrochemical effects , which can be applied to many areas of medicine, industry, dyes, perfumes and pesticides, so the synthesis, properties, applications have research value.

Key Words：Coumarin; derivatives; synthesis; research status;IR;UV;

目 录

第1章 绪论 1

1.1 香豆素简介 1

1.2 香豆素衍生物的合成研究进展 2

1.2.1 香豆素骨架的合成 2

1.2.2 香豆素衍生物的合成 2

1.2.2.1 perkin法 2

1.2.2.2 Knoevenagel法 3

1.2.2.3 Pechmann法 4

1.2.3 香豆素衍生物合成最新研究进展 4

1.3香豆素衍生物的国内外研究现状及应用 7

1.3.1 医药领域 7

1.3.1.1 抗HIV活性 7

1.3.1.2 抗癌活性 7

1.3.1.3 抗肿瘤活性 8

1.3.2 香料领域 9

1.3.3 燃料领域 9

1.3.3 农药领域 9

1.4 香豆素衍生物的发展趋势 9

1.5 本文的目的及内容 10

第二章 香豆素衍生物合成方案研究 11

2.1 合成路线 11

2.2 反应原理 11

第三章 实验部分 12

3.1 实验仪器与试剂 12

3.1.1 主要实验试剂 12

3.1.2 主要实验仪器 12

3.2 实验步骤 13

3.3 表征检测 14

第四章 结果与讨论 15

第五章 结论 21

参考文献 22

致谢 24

第-章 绪论

1.1香豆素简介