Reactions of N-sulfinylanilines with norbornene and norbornadiene result in the Diels-Alder adducts of benzo-ortho-thiazine structure, which was confirmed by the NMR, IR spectroscopy and XRD analysis. In all cases the diene added to the norbornenes bicyclic system at the side of the endo-methylene bridge. The methyl group of meta-N-sulfinyl toluidine directs the norbornene entry into the para-position.