Research On The Synthesis Of Diaryl Sulfides And Fluoroalkyl Compounds

Exploring the method of constructing C–S and C–F bonds is an important part of in which chemists have been researching.Compounds containing C–S bond structural units are widely used in the organic synthesis,materials sciences,and pharmaceutical industries.Meanwhile,the C–F bonds structural unit in compounds usually cause significant changes in lipophilicity,chemical stability,and biological activity.At present,the main method for constructing C–S and C–F bonds is by transition metal-catalyzed C–S and C–F coupling reaction.However,most of these require harsh reaction conditions.At the same time,most of the transition metals used in the reaction are expensive and toxic.In this aspect,much greener method of effectively building C–S and C–F bonds still deserves further exploration.Based on previous studies,several ultrapure water and copper catalyzed reaction systems were designed for the synthesis of compounds containing sulfur and fluorine.In this thesis,a new method for the synthesis of diaryl sulfides is developed.The?-naphthol and p-methylbenzenesulfonyl hydrazide are utilized as template substrates,and the preparation of 22 different types of diaryl sulfides is greatly successful without using any catalyst and additives,the products were isolated in moderate to good yields ranging from 30%to 89%.Meanwhile,the biggest advantage of this reaction is that only raw materials and water are in the whole reaction system,and the by-products are just hydrogen,water and nitrogen.After that,the intermediates of the reaction were successfully separated and identified,which provided strong evidences for the experimental mechanism.Also,we explored a non-activated terminal olefin as a substrate,using CuBr₂ as a catalyst,4,4-di-tert-butyl-2,2-bipyridine as a ligand,1,2-dichloroethane as a solv-ent,and sodium acetate as a base to explore fluoroalkylation of non-activated terminal olefins.After that,in order to obtain the optimum reaction conditions,numerous reaction were conducted using different solvents,temperatures,and catalysts.And then,22 substrates of two types were synthesized.