REACTIONS OF POLYFLUOROAROMATIC IMIDOYL CHLORIDE DERIVATIVES WITH S-NUCLEOPHILIC REAGENTS

The interactions of N-pentafluorophenylcarbonimidoyl dichloride, N-pen tafluorophenylbenzimidoyl chloride and N-pentafluorophenyl (C-pentaflu orophenyl) imidoyl chloride with the S-nucleophilic reagents thiourea, sodium N,N-diethyldithiocarbamate, thiocarbonyl difluoride and bis(tr ifluoromethyl)trithiocarbonate in the presence of CsF or AgSCF3, or th iophenol and polyfluorinated thiophenols in the presence of anhydrous K2CO3, were studied. Reactions with charged S-nucleophiles and with S- nucleophiles in the presence of a base proceeded with preservation of the N=C multiple bond in the reaction products. By varying the reactio n conditions in the case of N-pentafluorophenylcarbonimidoyl dichlorid e it was possible to substitute one or two chlorines and obtain mono- or di-thioimidates. When C6F5 or SC6F5 groups were present at the C at om of the N=C multiple bond, preferential substitution of the para-flu orine atom occurred. Semiempirical PM3 calculation data were used to e xplain the direction of these reactions. N-Pentafluorophenylcarbonimid oyl dichloride reacted with sodium N,N-diethyldithiocarbamate or thiou rea to give pentafluorophenylisothiocyanate. Depending on the conditio ns of the reactions of polyfluorinated benzimidoyl chlorides with thio urea, N-pentafluorophenylthioamides and 2-aryl-4,5,6,7-tetrafluorobenz othiazoles were formed. An attempt to produce SCF3 derivatives from Ag SCF3 was unsuccessful.