| The first synthetically useful ortho-substituted SF 5-benzene was synthesized by the oxidative fluorination of the corresponding ortho-fluoro phenyl disulfide according to the Sheppard procedure shown in equation 1. The reactivity of the active halogen was demonstrated with the subsequent nucleophilic substitutions to generate a number of novel ortho-substituted SF5-benzenes. Other active halogens were exploited in order to afford compounds that could possibly find use as herbicides, pesticides, fungicides, or other agricultural chemicals. The synthesis of 1-chloro-2-nitro-4-pentafluorosulfanylbenzene was also made from the corresponding disulfide, similarly to equation 1. The reactivity of 1-chloro-2-nitro-4-pentafluorosulfanylbenzene was demonstrated with a series of nucleophiles in order to expand the variety of compounds available for use in agricultural compounds. Compounds analogous to that of TreflanRTM were generated so that direct comparison of the efficacy of the SF5 derivative could be made to that of the more often employed CF3 derivative. Those analogs are all synthetically derived from the same starting SF5-benzene, namely 1-chloro-2,6-dinitro-4-pentafluorosulfanylbenzene, again involving the nucleophilic aromatic substitution of the active chlorine atom.*; The last SF5-benzene used to expand the variety of agricultural compounds (1-chloro-2,6-dinitro-4-pentafluorosulfanylbenzene) is very similar to a known highly energetic compound, trinitrochlorobenzene (TNCB), and is easily converted into compounds analogous to trinitroanisole and picric acid. Through the synthesis of these compounds, the usefulness of replacing a nitro group with an SF5 group in the field of explosives can be explored.; The use of additivity parameters to predict the chemical shifts of carbon atoms in 13C NMR was explored and the parameters inherent to the SF5 group were tabulated. Trends specific to the SF5 group in the mass spectra used to characterize the different compounds synthesized in this dissertation were highlighted and tabulated as well. And finally, the role of copper in the Sheppard synthesis was elucidated through the use of alternate coinage metal catalysts (Ag, Au) and X-ray photoelectron spectroscopy (XPS) of the adsorbed species on the surface of the coinage metal catalyst.; *Please refer to dissertation for diagram. |
