Reaction Method Study On Thiosulfonate And Asymmetric Sulfoxide

Organic sulfides are rich in variety,unique in nature and widely used.At present,it ranges from food additives to polymer conductive materials,and also has a good prospect for development.Among various sulfur compounds,thiosulfonate and asymmetric sulfoxide have many unique properties,which are particularly important.In recent years,although the methodological studies on the synthesis of two types of organic sulfide have been reported in a large number of literatures,both of them require the addition of metal or ligand and the conditions are harsh.There are few simple,green and efficient synthesis methods.Based on the above research status,the author of this thesis have reported a brandnew way through the free radical coupling pathway,and without metal catalysis,including the following two parts:1.In metal-free condition,a series of thiosulfonate compounds were synthesized by directly constructing S?=O?₂-S bond with disulfide and sulfonyl hydrazide as template substrates and hydrogen peroxide as oxidant through free radical coupling.At the same time,the oxidant and its equivalent,and other factors were screened to obtain the best reaction conditions,and then a total of 28 thiosulfonates were obtained at a good yield,and whose structures were confirmed by NMR,IR,MS and other characterization methods.Finally,a control experiment was designed to verify that the reaction is a free radical coupling mechanism.Thiosulfonate were synthesized for the first time effectiently without metal catalysis.2.Using benzoyl peroxide and disulfide compounds as template substrates,asymmetric sulfoxide was successfully obtained under the condition of no noble metal catalysis with only base.At the same time,various factors affecting the reaction were screened,and 26 asymmetric sulfoxides were obtained with a medium yield,and whose structures were determined by NMR,HRMS and other characterization methods.The mechanism of free radical coupling was also verified.This method does not need to add precious metals and ligands,the reaction conditions are mild,and the byproducts are few,which further enrich the research on synthesis methodology of asymmetric sulfoxide.