Synthesen und chemische Eigenschaften neuer «Donor-Akzeptor»-stabilisierter Molekülsysteme mit zentraler Bicyclo [4.4.1]undeca-l (10), 3,6,8-tetraen-2,5-diyliden-Gruppe

✍ Scribed by Richard Neidlein; Hartmut Zeiner

• Publisher: John Wiley and Sons
• Year: 1982
• Tongue: German
• Weight: 647 KB
• Volume: 65
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.19820650502

✦ Synopsis

Syntheses and Chemical Properties of New ‘Donor‐Acceptor’‐stahilized Molecular Systems with a Central Bicyclo[4.4.1] undeca‐l(10).3,6,8‐tetraene‐2,5‐diylidenc Group

The synthesis of X‐methyl‐2‐(5‐oxobicyclo[4.4.1]undeca‐l)10(,3,6,8‐tetraen‐2‐yliden)‐l,3‐benzodithiol (4) is described starting with the keto‐enol mixture 2 and 5‐methyl‐1,3‐benzodithiolium perchlorate. Under rearomatization of the central frame protonation of 4 yields the salt 4c. The reaction of 4 with dicyanoketene gives the ‘push‐pull‐substituted’ 5, and with 9‐carbonylfluorene the fulvalene derivative 7, which can be protonated by CF~3~CO~2~H at C(9″) to the salt 8. The reaction of 2‐methylthio‐l,3‐dithiolium jodide 9 with the keto‐enol mixture 2 yields 10, which, on protonation at the carbonyl group by CF~3~CO~2~H, gives the salt 11 under rearomatization. The spectral data of the new compounds 4, 4c, 5, 7, 8, 10 and 11 are reported and discussed.