论文总字数：17799字

摘 要

由于氟原子的特殊性质，在有机分子中引入含氟基团常常能极大改变母体化合物的化学、物理及生物学属性。氟原子本身含有一些特有的性质，比如极化率低和电负性高（化合物分子间作用力极弱，表面能极低，可使水的表面张力将至1015mN/m），碳氟键稳6定（C-F键能485.3kJ/mol）等。含氟官能团也具有一些特有的性质，如三氟甲基，三氟甲氧基及三氟甲硫基等所具有的强吸电子能力，强亲脂性和代谢稳定性日益引起人们的关注，因此含氟化合物在医药、农药、材料科学等领域发挥着重要的作用。到目前为止，市场上有多达30～40%的农用化学品和20%的药物中含有氟原子。但是，天然的含氟有机化合物很少，很难获得，因此开发简单、高效和高选择性的氟化方法对氟化学的发展具有重要意义。而通过炔烃及官能团化炔烃的氢三氟甲硫基化反应向分子中引入含氟基团变得更为直接和高效。

由于氟原子在医药、农药和材料等领域受到了广泛的关注，发展有效、适用及高选择性的氟化方法，成为研究的热点。炔烃来源广泛，并且炔烃的氢三氟甲硫基化反应是引入氟原子的一种非常简单有效的方法。

本文首先对近几年合成C_sp2-SCF₃的方法进行了简要的综述，然后根据本课题组的研究方向，从炔酰胺底物出发合成C_sp2-SCF₃这类分子。本文的主要任务是：Brønsted酸参与的炔酰胺顺式氢三氟甲硫基化的反应。因为炔酰胺具有良好的稳定性和反应活性，使其作为一种重要原料而受到了普遍关注。对于炔酰胺底物的合成，按照合成原料的不同，可以划分为末端炔、炔基溴和烯烃的同碳二溴代物与酰胺偶联的三种合成方法，我们主要采用末端炔和炔基溴的合成方法。末端炔是以末端炔烃为底物，酰胺为偶联试剂，在铜催化剂及碱的作用下得到炔酰胺，炔基溴是以五水硫酸铜催化炔溴与酰胺的偶联方法得到炔酰胺。

其次，利用炔酰胺在强酸条件下易形成烯亚胺活性中间体这一特性，以三氟甲硫银作为亲核试剂，在Brønsted酸双苯磺酰亚胺参与的条件下，得到了炔酰胺的顺式氢三氟甲硫基化的产物。通过对反应条件进行优化，使反应取得很好的选择性及中等至优秀的产率。

关键词：炔酰胺 氢三氟甲硫基化 Brønsted酸

ABSTRACT

Due to the special properties of fluorine atom, we introduce fluorine groups in organic molecules that the chemical, physical and biological properties of the parent compound are often greatly altered. The fluorine atom itself contains certain unique properties, such as low polarization and high electronegativity(The intermolecular forces of compound molecules are very weak with low surface energy which can lead the surface tension of the water down to 1015mN/m),the fluorocarbon bond stability(C-F bond energy is 485.3kJ/mol), Fluorine-containing functional groups also have some unique properties, such as trifluoromethyl group, trifluoromethoxy group and Trifluoromethylthio group has strong electron-withdrawing ability, stronger lipotropy and metabolic stability increasingly cause the attention of people more widely, so the fluoride compounds in medicine, pesticide, material science and other fields play an important role. So far, up to 30 to 40 percent of agricultural chemicals and 20 percent of the drugs in the market contain fluorine. However, natural fluorine-containing organic compounds are very few, it is hard to get, so developing a simple, efficient and high selectivity of fluoride method is of great significance to the development of fluorine chemical. By using the alkynene and functional alkynene group, the hydrotrifluoromethylthiolation is more direct and efficient to introduce fluorine molecules into the molecule.

Because of fluorine atoms in the fields such as medicine, pesticide and materials received widespread attention and developing effective, suitable and high selective fluorination method, is becoming a hot spot of research. Ene or alkynes have a wide range of sources, so the hydrotrifluoromethylthiolation of ene or alkynes is a very simple and effective way of introducing fluorine atoms.

This text first gives a brief summary of methods about the construction of C (sp²)-SCF₃ bond. By combining the research direction of our group vinyl trifluoromethyl thioethers was synthetized based on ynamides.

The main task of this article is: the reaction of the cis-hydrotrifluoromethylthiolation of ynamides with Brønsted acid involved. Because of ynamides’ good stability and reactive activity, it is widely regarded as an important raw material. For the synthesis of ynamides substrate, according to the synthesis of raw materials is different, can be divided into terminal alkyne, alkynyl bromine and alkenes associated with carbon dibromide and amide coupling of three kinds of synthesis methods, we mainly use the synthesis methods of terminal alkyne and alkynyl bromine. Former uses terminal alkyne as the substrate and amide as the coupling reagents, to get the ynamides under the action of copper catalyst and alkali; later is the CuSO₄·5H₂O-catalyzed coupling of alkynyl bromides with amides to get ynamides.

Next, using this feature that ynamides under the condition of strong acid to form ketenimine active intermediates, under the condition of (PhSO₂)₂NH, we use AgSCF₃ as a nucleophilic reagent to get cis-hydrotrifluoromethylthiolation of ynamides product with Brønsted acid-promoted. By optimizing the reaction conditions, the reaction schieves high selectivity and excellent yield.

Key words: ynamides hydrotrifluoromethylthiolation Brønsted acid

目录

摘 要 I

ABSTRACT II

第一章 文献综述 1

1.1前言 1

1.2氢三氟甲硫基化研究进展 1

1.3研究的内容和意义 3

第二章 炔酰胺底物的合成 4

2.1前言 4

2.2实验部分 5

2.3本章小结 6

第三章 Brønsted酸参与的炔酰胺顺式α位氢三氟甲硫基化反应 7

3.1 前言 7

3.2 三氟甲硫基银的合成 7

3.3 Brønsted酸参与的炔酰胺顺式α位氢三氟甲硫基化反应 7

3.4 本章小结 10

第四章 结论与展望 11

4.1 总结 11

4.2 展望 11

参考文献 12

附录 15

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