Reactions of polyfluoroaromatic imidoyl chloride derivatives with S-nucleophilic reagents

Polyfluoroaromatic compounds with a NCClR group—a reactive type of polyfluoroarene

“…Investigation of the reactions of compounds 10, 19 and 57 with thiocarbonyl difluoride and its trimer in the presence of fluoride ion as sources of the CF 3 S À anion under different conditions showed that the reactions proceed with low degrees of conversion or do not proceed at all. In all the experiments, the major part of the substrate remains unchanged [64]. Thus, when 10 reacts with the CF 2 S monomer and CsF (in acetonitrile, À5 8C) or with the (CF 3 S) 2 C S trimer and CsF (in acetonitrile, 20 and 70 8C; in sulfolane, 20 and 100 8C), one or both chlorine atoms are replaced by the SCF 3 group, forming a mixture containing the product of monosubstitution and disubstitution; however, the substrate 10 remains the major component of the mixture.…”

“…Reactions of polyfluorinated imidoyl chlorides and carbonimidoyl dichlorides with thiophenols proceed in acetonitrile at room temperature in the presence of anhydrous K 2 CO 3 [64]. One or two chlorine atoms in imidoyl dichloride 10 may be replaced by a SAr group (compounds 104, Scheme 17) depending on the amount of the thiophenol compound and K 2 CO 3 present.…”

“…Reactions of polyfluoroaromatic imidoyl chlorides and carbonimidoyl dichlorides with different thiophenols, thiourea and sodium N,N-diethyldithiocarbamate were studied [64]. Two last S-nucleophiles contain additional heteroatomic centers and are promising for heterocyclic system formation.…”

“…It was established by quantum chemical calculations of substrates and their s-complexes with the C 6 H 5 S À and CF 3 S À anions [64] that for compounds 10 and 57 the energy gain in the formation of the s-complexes of C 6 H 5 S À and CF 3 S À anions addition at the imidoyl carbon atom is the major factor, leading to chlorine substitution. For compound 19, however, the reaction route depends on the maximal density of the LUMO in the para-position of the C-pentafluorophenyl ring.…”

Aromatic and heterocyclic perfluoroalkyl sulfides. Methods of preparation

“…Interestingly, the reaction of (CF 3 S) 2 C=S/CsF with C , N -bis(pentafluorophenyl) imidoyl chloride leads to introduction of the SCF 3 group into the pentafluorophenyl ring along with substitution of the imidoylic chlorine atom [112]. …”