873958-08-8Relevant academic research and scientific papers
So2-extrusion of an 8-thiabicylo[3.2.1]octa-2,6-diene 8,8-dioxide and rearrangement of the resulting cycloheptatriene
Takayama, Jun,Sugihara, Yoshiaki,Nakayama, Juzo
, p. 132 - 137 (2005)
The reaction of 3,4-di-tert-butylthio-phene 1-oxide (8) with tetrachlorocyclopropene provided 6,7-di-tert-butyl-2,3,4,4-tetrachloro-8-thia- bicylo[3.2.1]-octa-2,6-diene 8-oxide (10), which was oxidized to the corresponding 8,8-dioxide 16 by m-chloroperbenzoic acid. The thermolysis of 16 in refluxing chlorobenzene, xylene, or octane gave 5-tert-butyl-1,2-dichloro-3- [(1,1-dichloro-2,2-dimethyl)propyl]benzene (18) with extrusion of SO2 and 2-tert-butyl-4,5,6-trichloro-9,9-dimethylbicyclo[5.2.0]nona-1,3,5-triene (19) with extrusion of SO2 and HCl in 73-78% combined yields. On the other hand, the thermolysis of 16 in the presence of triethylamine gave 19 as the sole product in 98% yield. A mechanism that involves the initial formation of 4,5-di-tert-butyl-1,2,7,7-tetrachlorocycloheptatriene (17) is proposed to explain the observed products.
