Synthesis of Benzo(1,2:4,5)dicycloheptene-1,9-dione via 6,7,12,13-Tetrahydro-7,12-methano-3H-cycloheptacyclodecene-3,14-dione and Its Protonation Behavior.

概要

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6,7,12,13-Tetrahydro-7,12-methano-3<I>H</I>-cycloheptacyclodecene-3,14-dione has been synthesized starting from the [4+6]-cycloaddition product of the reaction of 3,4-bis(methylene)-7,7-dibromobicyclo-[4.1.0]heptane with tropone. The adducts were transformed to their epoxides, which were treated with trifluoroacetic acid to give the 3,14-dione. This was transformed to benzo[1,2:4,5]dicycloheptene-1,9-dione, bis(tropono)benzene, by two different methods: (1) by heating it with trichloroacetic acid and DDQ in toluene or (2) through bromination followed by heating in DMF. The 1,9-dione is protonated in coned sulfuric acid to give bis(hydroxytropylium) dication, while it is protonated mainly (>80%) on the C-9 carbonyl oxygen and less (<40%) on the C-1 carbonyl oxygen in deuteriochloroform containing trifluoroacetic acid.
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