Abstract: | X‐Ray‐diffraction analysis of tBu2CN SCl ( 4b ) revealed an almost linear CNS unit with an SN bond order of ca. 1.9 (Fig. 1), in agreement with the structure of a 1‐thia‐2‐azoniaallene chloride. With SCl2 and SbCl5, compound 4b was transformed into the imidosulfurous dichloride 6 (Scheme 2). With morpholine, compounds 4b and 6 afforded the sulfenamide 7 and the aminosulfonium salt 8 , respectively. The (diarylmethylene)amidosulfenyl chlorides 4g , h , i reacted with SbCl5 to give SbCl salts of the 1,2‐benzisothiazoles 9a , b , d , most likely via 1‐thia‐2‐azoniaallene intermediates 2 (Scheme 3). |