Abstract
Flash thermolysis of dimethyl 3-oxatricyclo[3.2.2.02,4]nona-6,8-diene-6,7-dicarboxylate (the oxide of barrellene-2,3-dicarboxylic acid dimethyl ester) (2) at 700 °C gave methyl isocoumarin-7-carboxylate (3) as a major component of the thermolysate. The rearrangement is discussed in terms of sigmatropic shifts in cycloheptatrienes and their norcaradiene tautomers.

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