ALKYLTHIOSUBSTITUTED BIS(BENZENE-1,2-DITH IOLATO)ZINCATES, BENZENE-1,2-DITHIOLES, AND BENZENE-1,2-DITHIOLATES - EDUCTS FOR DIBENZO[C,G](1,2,5,6)TETRATHIOCINS, AND BENZO[C](1,2,3)TRITHIOLES - INVESTIGATIONS ON BENZODITHIETES AND ORTHO-DITHIOBENZOCHINONES

Using benzenehexathiolate 1 it is possible to synthesize alkylthio-sub stituted benzo-1,3-dithiole-2-thiones 2, or -ones 3 and benzo-di(1,3-d ithiole-2-thiones) 4, or -ones 5, resp., which were cleaved under basi c conditions. The generated benzene-1,2-dithiolates 7 were isolated as benzenedithiolato zincates 8, benzene-1,2-dithioles 11, and benzene-1 -thiole-2-thiolates 10. Dibenzo[c,g](1,2,5,6)-tetrathiocins 9 were syn thesized by oxidation of 7 or 8 in good yields. For the per(methylthio )-substituted tetrathiocin 9a the twist conformation was proved by x-r ay structure analysis. The tetrathiocin 9a was probably formed via the orthodithiobenzoquinone 13a. Photolysis of 3a at room temperature in solution led to 9a and tetrakis(methylthio)benzo[c] (1,2,3)trithiole 1 2a as the main product, which was also formed by irradiation of 9a. Th e trithioles 12 were formed from 8 by reaction with sulfur dichloride. 12a was investigated by x-ray structure analysis. ortho-Dithiobenzoqu inone 13c can be claimed as an intermediate upon irradiation of benzo- 1,3-dithiol-2-one 3c in an argon matrix at 10 K. Depending on the wave length the equilibrium lies either on the side of dithiobenzoquinone 1 3c or benzodithiete 14c. The same is true for system 15/16, which can be reached by flash vacuum pyrolysis of 3c.