摘 要

三氟甲磺酰基是吸电子性最强的官能团之一，也具有较强的亲脂性，常用于药物、催化剂、配体以及材料中。通过三氟甲磺酰化将氟原子引入炔类化合物中，具有良好的应用前景。本课题以三价碘盐作为三氟甲磺酰化的反应底物，用三氟甲亚磺酰钠与其反应将三氟甲磺酰基引入炔类化合物中，在非常温和的条件下以良好的产率合成了炔基三氟甲基砜，并拓展了相当数量的底物，验证了本方法较广的适用范围。同时，本文还利用本方法成功进行了炔的全氟烷基磺酰化反应，为该类化合物的合成提供了一个非常优秀的方法。

关键词：炔的三氟甲磺酰化 三价碘盐 三氟甲基亚磺酸钠

Abstract

Trifluoromethylsulfonyl is one of the strongest electron-withdrawing functional group, it also has high lipophicity so that can be applied to medicines, catalysts, ligands, and materials. Introduction fluorine atoms into molecules by the method of trifluoromethylsulfonylation has good application prospect. We build the alkynyl trifluoromethyl sulfones by the reaction of trivalent iodized salt and sodium trifluoromethanesulfinate, which is in mild reaction conditions and has good yields, we also have investigated the scope of the reaction which is verified compatible with a wide range of functional groups. In addition, the perfluoroalkylsulfonylation of alkynes have been successful carried out by this way. So we create an excellent method to synthesize these compounds.

Key words： Trifluoromethylsulfonylation of alkynes；Trivalent iodized salt；Sodium trifluoromethanesulfinate

目 录

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

1.1 氟化学的发展历史...............................................................................................................1

1.2 引入氟原子的作用...............................................................................................................2

1.3 三氟甲磺酰基的性质与应用...............................................................................................3

1.4 三氟甲磺酰化的研究现状...................................................................................................4

1.4.1 烷烃的三氟甲磺酰化....................................................................................................4

1.4.2 芳环的三氟甲磺酰化....................................................................................................4

1.4.3 炔的三氟甲磺酰化........................................................................................................5

1.5 课题研究目的与内容...........................................................................................................6

第2章 炔的三价碘盐的制备........................................................................................................8

2.1 主要实验试剂与仪器...........................................................................................................8

2.2 含不同取代基的芳基乙炔原料的制备..............................................................................10

2.2.1 实验原理.......................................................................................................................10

2.2.2 实验步骤.......................................................................................................................10

2.2.3 结果与讨论...................................................................................................................11

2.3 Koser试剂的制备............................................................................................................. ...11

2.3.1 实验原理.......................................................................................................................11

2.3.2 实验步骤.......................................................................................................................11

2.3.3 结果与讨论...................................................................................................................11

2.4 炔的三价碘盐的制备..........................................................................................................12

2.4.1 实验原理.......................................................................................................................12

2.4.2 实验步骤.......................................................................................................................12

2.4.3 结果与讨论...................................................................................................................12

第3章 炔的三氟甲磺酰化反应...................................................................................................14

3.1 主要实验试剂与仪器..........................................................................................................14

3.2 反应条件的筛选与优化......................................................................................................15

3.2.1 对三价碘上阴离子的筛选...........................................................................................15

3.2.2 对反应温度、时长的筛选...........................................................................................15

3.2.3 对反应底物投料比的筛选...........................................................................................16

3.2.4 小结...............................................................................................................................17

3.3 炔的三氟甲磺酰化反应......................................................................................................17

3.3.1 实验原理.......................................................................................................................17

3.3.2 实验步骤.......................................................................................................................17

3.3.3 结果与讨论...................................................................................................................17

3.4 炔的全氟烷基磺酰化反应..................................................................................................19