氟烷基次磺酸及其衍生物的合成及性质研究

Alkanesulfenic acids and their derivatives, such as alkanesulfenyl halides and alkanesulfenamides, are verstile reactive organic intermediates. Although the chemistry of nonfluorine alkanesulfenic acids and their derivatives has been well studied, the properties and synthetic utilities of fluoroalkanesulfenic acids and their derivatives have scarcely been investigated due to the lack of effective synthetic method. In this project, based on the synthetic technique of perfluoroalkanesulfenic acids developed in our laboratory recently, practical methods for the synthesis of fluoroalkanesulfenic acids and their derivatives will be studied, various per(poly)fluoroalkanesulfenic acids, per(poly)fluoroalkanesulfenyl halides and per(poly)fluoroalkanesulfenamides will be prepared, and their properties and applications in organic synthesis will be further studied. A series of new fluorine-containing building blocks and other compounds containing fluorine and sulfur will also be synthesized.

次磺酸及其衍生物如次磺酰卤和次磺酰胺是重要的活泼有机中间体，虽然一般的次磺酸及其衍生物的化学已经研究得比较充分，由于合成方法的限制，氟烷基次磺酸及其衍生物的性质以及在有机合成中的应用几乎未有研究。本项目在我们实验室前期发展的全氟烷基次磺酸合成技术的基础上，研究开发实用有效的合成方法，合成各种全氟和多氟烷基次磺酸及其衍生物，如氟烷基次磺酰卤、氟烷基次磺酰胺等，并深入研究它们的性质及反应规律，探索其在氟烷基化反应及有机合成中的应用，发展一些有效的合成新方法，用于新型含氟合成砌块和其它含氟含硫化合物的合成，进一步丰富次磺酸及其衍生物的化学。

本项目对氟烷基次磺酸及其衍生物氟烷基次磺酰氯的制备和性质进行了较为系统的研究，发展了一种合成氟烷基次磺酸的简便方法，实现了氟烷基次磺酸与烯烃、炔烃和联烯的加成以及与胺类化合物的反应，由氟烷基次磺酸制备了相应的次磺酰氯并研究了其与杂原子亲核试剂、芳烃、烯烃等化合物的反应，发展出一系列合成氟烷基亚砜及RFS取代化合物的有效方法。同时结合有机氟化学发展趋势和课题组相关研究的进展，开展了基于三氟甲基次磺酰氯和亚磺酰氯中间体的三氟甲硫基化反应、（三）氟甲基取代化合物的合成方法等研究，合成了一系列三氟甲（硫）基或一氟甲基取代的含氟化合物。在国内外核心专业期刊上发表研究论文15篇。