Studies On Application Of Organosulfonyl Fluorides In Synthetic Organic Chemistry

Recently,fluorinated organic compounds have received a great deal of attention, due to their potential biological activity and wide application as new types of organic materials and reagents.The application of fluorine as a leaving group was mainly focused on the preparation of aryl sulfone and aryl sulfonate through the reactions of two type of nucleophilic reagents,carbanions and oxygen anions,with organosulfonyl fluorides.However,the reaction of organosulfonyl fluorides and other nucleophilic reagents,such as HOO^- and RCOO^-,have been rarely reported so far.In this paper, the studies on the appliction of organosulfonyl fluoride reagents,p-toluenesulfonyl fluoride and poly(per)fluoroalkanesulfonyl fluoride,which are commercially available in synthetic organic chemistry has been carried out.The specific contents have been described in three chapters and are as follows:In chapter one,the in situ preparation methods and their application in organic synthesis of organic peroxy-sulfonic acid were reviewed.In chapter two,the epoxidation of a variety of olefins with p-toluenesulfonic peracid in situ generated from p-TolSO₂F/H₂O₂/OH^- system was investigated.First, the effect of temperature,solvents and bases on the epoxidation was studied. Second,under the optimized conditions,the epoxidation of a variety of olefins using this system was studied.Our experimental results showed that p-toluenesulfonic peracid in situ generated is a good epoxidation reagent and it is very suitable for the epoxidation of electron-rich olefins.Last,the possible mechanism of epoxidation of p-TolSO₂F/H₂O₂/OH^- system with olefins was presented.In chapter three,the application of perfluorobutanesulfonyl fluoride as a new kind of condensation agent for anhydridization of carboxylic acids was investigated. First of all,we optimized the reaction conditions using p-methoxybenzoic acid as a substrate and then under the optimized conditions,we investigated the anhydridization of several aromatic carboxylic acids.Results showed that nonafluorobutanesulf only fluoride can also be relatively efficiently used as a class of condensing agent for the anhydridization of some aromatic carboxylic acids.