Metal-Free Synthesis Of Alkyl Sulfides And Bifunctionalization Of Phenolic Hydroxyl Sulfide

Alkyl sulfides are widely found in natural products and participate in the synthesis of ligands and organic semiconductor materials.In the field of drugs,alkyl sulfides with higher saturation than aryl sulfides,which is conducive to improving the clinical success rate,makes its application in the field of drugs not to be ignored.In view of the numerous applications and potential values of the above alkyl sulfide,it is of great significance to study the synthesis of alkyl sulfide.Transition metal catalysts provide powerful tools for constructing C(sp~2)-S bond formation by coupling or addition reactions,but their application of C(sp~3)-S bond formation is largely limited due to the facile?-hydrogen elimination.The second chapter of this paper introduced a method of synthesis of alkyl sulfides by metal-free catalyzed halides.In this method,a variety of sulfides and halides compounds were investigated,including aryl alkyl sulfide with various functional groups,dialkyl sulfide,benzyl halides and alkyl halides.This method had a wide range of functional group tolerance while synthesized various alkyl sulfides with good yield,up to 97%.The product obtained by this reaction could further undergo alkynylation,phenylation,phenoxylation and sulfonylation reaction in good yield.At the same time,when the reaction was scaled up to the gram scale while the yield did not decrease significantly,which indicated the high potential industrial application value of the method.In this reaction,the nucleophilic substitution of sulfides and halides was firstly carried out to form intermediate.Then the alkyl group was taken off and alkyl sulfide product was obtained.In addition,the experimental results show that DMAC can promote the reaction.The third chapter of this paper introduced a method of double functionalization of alkyl sulfide with phenolic hydroxyl groups.Phenol acetylation could be carried out by alkyl transfer reaction with benzyl bromide or alkyl iodi de.Therefore,during the reaction,not only the selective fracture of C(sp~3)-S bond,but also the phenolic hydroxyl group could be converted into ester group.