New 4-Pentafluorosulfanyl and 4-Perfluoroalkylthio Derivatives of 1-Chloro-2-nitro- and 1-Chloro-2,6-dinitrobenzenes.

Abstract New 4-pentafluorosulfanyl and 4-perfluoroalkylthio derivatives of 1-chloro-2-nitrobenzene and 1-chloro-2,6-dinitrobenzene were prepared from the corresponding bis(4-chloro-3-nitrophenyl)disulfide and bis(4-chloro-3,5-dinitrophenyl)disulfide, respectively. The SF 5 derivatives were obtained by fluorination of the disulfides with AgF 2 according to Sheppard’s method, while perfluoroalkylation was carried out by means of thermolytic reactions with xenon(II) bis(perfluoroalkylcarboxylates). The introduction of fluorine-containing, electron-withdrawing substituents into the aromatic ring (in the presence of other deactivating groups) reinforces the activation of the halogen substituent towards nucleophilic attack. Several nucleophilic substitution reactions have been carried out with these compounds, and as a result, some N - and S -containing groups were introduced in the benzene ring. For example, the previously unknown SF 5 , CF 3 S, and C 2 F 5 S analogues of trifluralin (Treflan ® ) were prepared and characterized. Additional synthetic possibilities for heterocyclic chemistry are presented on the basis of reactions of the new 1-chloro-2,6-dinitrobenzene derivatives with ethyl thioglycolate wherein fluorine-containing derivatives of benzothiazole N -oxide were obtained as the main products.