Study On Novel Reactions Of Amines With In Situ Generated Thiocarbonyl Fluoride As Well As Derivative Reactions Of Products

Nitrogen,sulfur,and fluorine elements exist widely in pharmaceuticals and biological active compounds.A series of novel reactions of amines with in situ generated thiocarbonyl fluoride as well as the derivative reactions were developed,providing novel avenues for efficient synthesis of a variety of compounds containing nitrogen,sulfur,or fluorine from safe and easily available starting materials.In the first part of the thesis,an efficient cascade reaction of propargyl amines with AgSCF₃ and KBr was developed,affording allenyl thiocyanates at room temperature in high yields.This transformation proceeds through in situ formation of isothiocyanate intermediates,followed by[3,3’]-sigmatropic rearrangement.The resulting allenyl thiocyanates bearing3-（electro-donating phenyl）substitutions without isolation can then be reacted with di-tert-butyl peroxide and AgSCF₃ under reflux to generate novel allenyl trifluoromethylthioether compounds in moderate to good yields via a“one-pot”three-step process.In the second part of the thesis,reactions of thiocarbonyl fluoride derived from cheap,readily available and widely used TMSCF₃,elemental sulfur and KF with secondary amines and primary amines at room temperature in THF provided a wide variety of thiocarbamoyl fluorides and isothiocyanates in moderate to excellent yields,respectively.The two reactions show broad substrate scope and good functional group tolerance.Moreover,AgSCF₃ reacts with secondary/primary amines under KBr at room temperature,affording quantitative thiocarbamoyl fluorides/isothiocyanates,which feature late-stage application.In the third part of the thesis,a derivative reaction of thiocarbamoyl fluorides was developed.Under potassium persulfate,ammonium chloride,carbonate,4（?）molecular sieve and CoBr₂ as catalyst in acetonitrile,thiocarbamoyl fluorides react with H₂O to afford benzo[d]thiazol-2（3H）-one derivatives in moderate to good yields with good functional group tolerance.This novel cascade reaction involves dehydrogenative oxidative coupling of C-H bond with C-S bond in an economic way.