摘 要

本文主要研究了苯乙炔及其衍生物三价碘盐的合成并考察它们的三氟甲硫基化和三氟甲硒基化反应。研究内容分为三部分：

第一部分参考相关文献制备Koser试剂PhI(OH)OTs。

第二部分通过苯乙炔及其衍生物与Koser试剂反应，制备苯乙炔及其衍生物的三价碘盐PhI(C≡CAr)OTs。

第三部分通过苯乙炔及其衍生物的三价碘盐PhI(C≡CAr)OTs与亲核性的三氟甲硫基试剂[Me₄N][SCF₃]和三氟甲硒基试剂[Me₄N][SeCF₃]反应，从而来制备苯乙炔及其衍生物的三氟甲硫基化和三氟甲硒基化产物。

研究结果初步验证了通过三价碘盐实现末端炔烃三氟甲硒基化和三氟甲硫基化的策略是可行的，且此类反应所需时间短，官能团耐受性很好，产率较高。

本文主要亮点是选用了制备容易、反应活性高的三价碘盐，在无任何添加剂的条件下实现了末端炔烃三氟甲硫（硒）基化。

关键词 ：苯乙炔及其衍生物；炔基（苯基）碘盐；三氟甲硫基化；三氟甲硒基化

Abstract

The thesis mainly focuses on the synthesis of phenylacetylene and its derivatives’ alkynylphenyl iodonium salts and the effects of their trifluoromethylthiolation and trifluoromethylselenolation reaction. It mainly includes three aspects:

The first part is the preparation of the Koser’s reagent PhI(OH)OTs.

The second part is the reactions of phenylacetylene and its derivatives with the Koser’s reagent to prepare their alkynylphenyl iodonium salts.

The third part discussed the reactions of phenylacetylene and its derivatives’ alkynylphenyl iodonium salts with the nucleophilic trifluoromethylthiolation reagent [Me₄N][SCF₃] and trifluoromethylselenolation reagent [Me₄N][SeCF₃] to prepare their trifluoromethylthiolated and trifluoromethylselenolated products.

The results preliminarily show that it is feasible that introducing trifluoromethylthio and trifluoromethylseleno into phenylacetylene and its derivatives via their alkynylphenyl iodonium salts. Besides, the time of the reaction is very short, the functional group’s tolerance and the yields of this reaction are very good.

The highlight of this paper is choosing an alkynylphenyl iodonium salt that can be prepared easily and has high reaction activity to prepare the target products without the presence of any catalysts.

Key Words：Phenylacetylene and its derivatives; Alkynylphenyl iodonium salts; Trifluoro- methylthiolation; Trifluoromethylselenolation

目 录

第1章 绪论.....................................................................................................................................1

1.1 氟元素性质简介....................................................................................................................1

1.2 三氟甲硫基性质简介............................................................................................................1

1.3 末端炔烃三氟甲硫基化的研究现状....................................................................................3

1.4 末端炔烃三氟甲硒基化简介................................................................................................5

1.5 研究目的、内容以及意义....................................................................................................5

第2章 Koser 试剂的合成..............................................................................................................7

2.1主要实验试剂与仪器.............................................................................................................7

2.2 Koser 试剂的合成..................................................................................................................7

2.2.1 实验原理.........................................................................................................................7

2.2.2 实验步骤.........................................................................................................................8

2.2.3 结果与讨论.....................................................................................................................8

第3章 苯乙炔及其衍生物的三价碘盐的合成............................................................................10

3.1 主要实验试剂与仪器...........................................................................................................10

3.2 苯乙炔衍生物的合成...........................................................................................................11

3.2.1 实验原理........................................................................................................................11

3.2.2 实验步骤........................................................................................................................12

3.2.3 结果与讨论....................................................................................................................12

3.3 苯乙炔及其衍生物三价碘盐的合成...................................................................................13

3.3.1 实验原理........................................................................................................................13

3.3.2 实验步骤........................................................................................................................13

3.3.3 结果与讨论....................................................................................................................13

第4章 苯乙炔及其衍生物的三氟甲硫（硒）基化............................................. ......................15

4.1 主要实验试剂与仪器...........................................................................................................15

4.2 三氟甲硫基四甲基铵盐的合成...........................................................................................16

4.2.1 实验原理........................................................................................................................16

4.2.2 实验步骤........................................................................................................................16

4.3 三氟甲硒基四甲基铵盐的合成...........................................................................................16

4.3.1 实验原理........................................................................................................................16