3,6-Bis(p-dimethylaminophenyl)-1,2-dithiin versus 3,4-Bis(p-dimethylaminophenyl)-1,2-dithiete – A Mechanistic Probe for the Photoinduced Behavior of the 1,2-Dithiin System©
✍ Scribed by Werner Schroth; Roland Spitzner; Clemens Bruhn
- Publisher
- John Wiley and Sons
- Year
- 1998
- Tongue
- English
- Weight
- 304 KB
- Volume
- 1998
- Category
- Article
- ISSN
- 1434-193X
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✦ Synopsis
Whereas 3,4-bis(p-dimethylaminophenyl)-1,2-dithiete ( 18) is are suggested as key intermediates. X-ray crystallography of the disulfide 31 obtained from the main product 30 in equilibrium with its ring-opened valence isomer 19/19Ј, which can also exist as a solid, the analogously disubstituted unequivocally confirms the structure. The synthesis of 20 is based on the nucleophilic addition of 1,1-dimethyl-1,2-dithiin 20 is stable when protected from light, but on exposure to light undergoes immediate ring transformation ethanethiol to 1,4-bis(p-dimethylaminophenyl)butadiyne (23a) with ensuing functional group conversion. An efficient to 2,5-bis(p-dimethylaminophenyl)thiophene-3-thiol (30). To a lesser extent, it also undergoes sulfur extrusion to form 2,5-variant of this method using ethoxycarbonylsulfenyl chloride as a deprotecting reagent is described, leading to the bis(p-dimethylaminophenyl)thiophene ( 29). The ring-opened valence isomer 21/21Ј and dihydrothiophene episulfide 28 synthesis of 3,6-diphenyl-1,2-dithiin ( 27).