Through-space or proximate 19F,19F and 19F,1H spin–spin coupling constants in some benzenesulfonyl fluoride derivatives

Abstract

The analysis of the fluorine and proton magnetic resonance spectra of 2,4,6-trimethylbenzenesulfonyl fluoride and of 2,5-difluorobenzenesulfonyl fluoride yields the signs and magnitudes of the spin–spin coupling constants containing a through-space component. The coupling between the fluorine nucleus and the methyl protons over five bonds is +1.9 Hz, opposite in sign to the −3.1 Hz observed for the corresponding coupling in 2,6-dimethylbenzoyl fluoride. The difference of 5 Hz is possibly a consequence of the different conformational preference of the SO2F and COF substituents. The coupling over four bonds between the fluorine nucleus on the side chain and that on the ring is +11.6 Hz in 2,5-difluorobenzenesulfonyl fluoride. It is argued that this value indicates a preference of the S—F bond for a plane lying, on average, nearly perpendicular to the benzene ring. Similar indications are noted for pentafluorobenzenesulfonyl fluoride and for pentafluorobenzenesulfinyl fluoride.