Desulfonation-fluorination of thiuram disulfides, [R2NC(S)S]2 and silver dithiocarbamates, Ag[SC(S)NR2] (R = CH3, CH3Ch2, C6H5CH2), with silver(I) fluoride, AgF -: A simple access to diorgano(trifluoromethyl)amines, R2NCF3, and thiocarbamoyl fluorides, R2NC(S)F

AgF and [R2NC(S)S](2) (R = CH3, CH3CH2, C6H5CH2), selectively react at room temperature in the stoichiometric ratio of 1:1 to give the corresponding N,N-diorganothiocarbamoyl fluorides, R2NC(S)F, AgSC(S)NR2 and elemental sulfur. Under comparable conditions in a ratio >3:1 both reactants selectively yield diorgano(trifluoromethyl)amines, R2NCF3, AgSC(S)NR2, Ag2S and elemental sulfur. At stoichiometry 6.1, R2NCF3, Ag2S besides elemental sulfur are formed. By analogy, thiocarbarnoyl fluorides and silver dithiocarbamates react with AEF yielding selectively the corresponding trifluoromethylamines. (C) 2001 Elsevier Science B.V. All rights reserved.