Study On The Oxidation Synthesis Of Alkyl Sulfide And Vinyl Sulfate

Sulfur-containing organic compounds are an important class of compounds,which are widely distributed in nature and are used in many fields,such as life sciences,perfumes,flavors,medicines,foods and materials engineering.Therefore,it is of great significance to synthesize sulfur-containing organic compounds with complex and diverse structures through a green,simple,efficient,and easily available raw materials way.Since the backbone of alkyl sulfide is an important pharmaceutical intermediate,chemists have developed many methods for synthesizing alkyl sulfide.In particular,the addition reaction of sulfides to olefin has become a simple and efficient method to construct C-S bonds.That can be divided into monofunctionalization and bifunctionalization of olefins.Among them,the bifunctionalization of olefin has attracted attention because it can construct two chemical bonds at the same time,but how to construct two different group selectively and controllably at the same time is a challenging subject.In addition,vinyl sulfate is a kind of battery additives with excellent performance,which can effectively optimize battery performance,increase endurance and realize the efficient utilization of clean energy.How to establish a green and efficient catalytic oxidation method to synthesize vinyl sulfate is a big problem.Therefore,the first part of the thesis mainly review the synthesis of alkyl thioether by olefin functionalization and the synthesis of vinyl sulfate in recent years,and provides a reference for the establishment of clean,efficient,and controllable synthesis of sulfur-containing fine chemicals.The second part of the thesis aims to synthesis alkyl sulfide compounds using olefin bifunctionalization and the synthesis of vinyl sulfate under the catalytic oxidation system of TS-1.1.Research on the synthesis of alkyl thioether based on olefin bifunctionalizationIn this chapter,a new type of combined oxidation system LiIO₄·2H₂O/I₂O₅/H₂SO₄ is established.By using aryl olefins,electricity-rich aromatic hydrocarbons,and thiophenol as substrates,the sulfur/carbonization of aryl olefins can be realized only in air atmosphere,and two chemical bonds of C-S and C-C can be constructed at the same time,39 kinds of alkyl sulfide compounds can be synthesized with high selectivity,the target products can be further oxidized to sulfone and sulfoxide compounds.The method has advantages of simple operation,mild conditions,diversified substrates,no transition metals participation,and is suitable for large-scale reaction.The mechanism experiments show that there may be the formation of free radicals and carbocation intermediates in the reaction process.2.Research on the synthesis of vinyl sulfate based on TS-1 catalytic oxidation methodThis chapter establishes a catalytic and oxidation method with TS-1 as a catalyst and hydrogen peroxide as an oxidant,vinyl sulfite is converted into vinyl sulfate at 35℃ with high selectivity and the yield can reach up to 87%.This reaction is green,efficient,simple to operate,has no obvious gram amplification effect and the TS-1 can still has good catalytic performance after 23 cycle.After characterizing the newly purchased TS-1 and that has been recycled more than 20 times by XRD and XPS,it was found that structure of the catalysts remained well after the reaction.