The syntheses of 1,2-benzodithiino [5,4,3-cde][1,2]benzo-side product of the preparation of 15. It was transformed analogously to the preparation of 1 into 1,2-bis(3-dithiin-2,7-diamine (1) and dithio-bridged benzidine 2 have been achieved. The starting material for the synthesis of 1 ethylthiophenyl)diazane (28). The benzidine rearrangement of 28 in presence of HBF 4 at -30 Β°C afforded 4,4Π-diamino-was 1,3-diiodo-5-nitrobenzene (15) which was transformed by conventional means into 1,2-bis[3,5-bis(ethylthio)phenyl]-2,2Π-bis(ethylthio)biphenyl ( 29) in 49 % yield. Treatment of 29 with sodium in ammonia and work-up under aerobic diazane (19). The benzidine rearrangement of 19 in the presence of HBF 4 at -30 Β°C yielded 4,4Π-diamino-2,2Π,6,6Π-conditions yielded 2. Quantitative reduction of 2 to the thiol 29a could be achieved with LiAlH 4 . The reversible tetraethylthiobiphenyl (20) in 50 % yield. Treatment of 20 with sodium in ammonia and work-up in the presence of air electrochemical reduction of 1 on unmodified glassy carbon electrodes leads to a product to which the structure of 3 yielded 1. The latter compound could be reduced with LiAlH 4 to the tetrathiol 20a. The starting material for the was assigned. preparation of 2 was 3-chloro-1-iodo-5-nitrobenzene (23), a