Synthesis Of Alkyl Trifluoromethyl Thloethers

Over the past several decades,organic molecules that contain a trifluoromethylthio group(-SCF3)have been an important class of compounds,due to their remarkable stability,electronegativity,and lipophilicity properties.These have found potential applications in a variety of areas,including pharmaceutical and agrochemical,as well as in advanced materials industries.Consequently,there has been an immense effort to develop novel methods and reagents to access this class of compounds.Alkyl trifluoromethyl sulfides have been involved in numerous synthetic applications,mainly devoted to the synthesis of bioactive molecules.Examples include trifluoromethylthioacetic acid and its deri,vatives,which serve as useful intermediates in the synthesis of the cephalosporin antibiotic cefazaflur.In this paper,a kind of nucleophilic trifluoromethylthiolation reagent was used to react with alkyl halides to produce alkyl trifluoromethyl thioethers through the trifluoromethylthiolation reaction.This reaction conditions are mild,proceeded smoothly with yields up to 99%.The reaction produts are easy to sparate.The thesis consists of three parts:Part I:Synthesis of trifluoromethylthiolation reagent[(bpy)CuSCF3].The reagent used copper salt as raw material is cheap,The reagent either in air or in solutin,to be have more stable.At the same time,the reagent can be react with benzyl bromide,allyl bromide,alpha cinnamom bormo ketones in mild conditions,high yields,and the products are single.Part II:According to a series of conditions explored,an optimal facile method was found in this paper,which is that under nitrogen protected and 110?,with acetonitrile as the solvent,the alkyl halides reacted with 1.2 equivalents[(bpy)CuSCF3]for 15 hours,and successfully proceeded to afford the corresponding products in good yields.Through the expansion of the substrate,it was found that lots of common functional groups.In an attempt to examine whether any radical intermediates are generated during trifluoromethylthiolation,the addition of a radical scavenger,cyclohexa-1,4-diene,under the potimized conditions.The reifluoromethylthiolated product was formed in similar yield both in the absence.Then,Subsequently,the intermediacy of alkyl radical was probed by reactions with a radical clock,such as(bromomethyl)cyclopropane and 6-bromo-1-hexene.No ring-opened or cyclized products were detected.These results indicate that radicals are not produced in this trifluoromethylthiolation.Given the good reactivity of alkyl tosylates,the mechanism of the present trifluoromethylthiolation might involve an SN2-type.Part ?:To further illustrate the synthetic potential of these alkyl trifluoromethyl thioethers,the subsequent oxidation was performed.the trifluoromethylthiolated compound underwent smooth oxidation with H2O2 in acetic acid to give the corresponding alkyl trifluoromethanesulfones in good yields.