UBC Theses and Dissertations
Photochemistry of cis, cis-cyclodeca-3,8-diene-1,6-dione Lungle, Melvin Leroy
In order to extend the study of medium-sized ring compounds, cis,cis-cyclodeca-3,8-diene-l,6-dione was synthesized by known methods and photolyzed. By monitoring the photolysis by glpc and tlc, it was evident that the initial photochemical reaction of cis , cis-cyclodeca -3 ,8-diene-1,6-dione was photoisotnerization to cis , trans-cyclodeca-3,8-diene-1,6-dione, which then underwent intramolecular cycloaddition in a second photochemical step to give cis, anti, cis-tricyclo[188.8.131.52²,⁶]-decane-4,9-dione. To show that the observed photoproduct was formed primarily by a secondary photolytic reaction, the cis, trans-cyclodeca-3 ,8-diene-1,6-dione was photolyzed to give cis, anti, cis-tricyclo[184.108.40.206²,⁶] decane-4,9-dione as the only product. Further evidence in support of the two-step reaction hypothesis was obtained by a kinetic study of the cis, cis-cyc1odeca-3,8-diene-1,6-dione photolysis. Two plausible mechanistic routes for the above photolysis are discussed in terms of the observed intermediate. These mechanistic pathways are then compared to the routes established for other β,ɤ- unsaturated ketone photolyses.
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