Oxidation of (Z,Z)-1,4-Diaminobuta-1,3-diene-1,4-dithiolates and Related Precursors − Alternatives For 1,2-Dithiin Formation

✍ Scribed by Werner Schroth; Roland Spitzner; Michael Felicetti; Christoph Wagner; Clemens Bruhn

• Publisher: John Wiley and Sons
• Year: 2000
• Tongue: English
• Weight: 262 KB
• Volume: 2000
• Category: Article
• ISSN: 1434-193X
• DOI: 10.1002/1099-0690(200009)2000:17<3093::aid-ejoc3093>3.0.co;2-k

✦ Synopsis

Oxidation of the title compounds, in contrast to that of ''normal'' (Z,Z)-buta-1,3-diene-1,4-dithiolates, does not lead to the formation of 1,2-dithiins. Thus, the aliphatic diaminodithiolates 7 and 8 were converted into the (E)-2-butenedithioamides 12 and 15 as a result of resonance stabilization of the thiocarbonyl group. On the other hand, the 3,3Ј-biindole-2,2Ј-dithiolate 9, the aromatic counterpart of 8, undergoes disulfide formation with preservation of aromaticity in the hetarene rings and yields the 1,2-dithiin dimer 31 with a 12membered ring structure. In this instance, the formation of the expected (E)-3,3Ј-biindolinylidene-2,2Ј-dithione 29 (a thioxo analogue of isoindigo) does not take place, paralleling