The reactions of dimethyl 2,5-bis(diazo)-3,4-dikentoadipate with aromatic and heteroaromatic compounds

Heating the title compound with benzene provides a mixture of dimethyl 1,3-dihydroxynaphthalene-2,4-dicarboxylate and 3-carbomethoxy-4-hydroxy-5-phenylpyrone which rearranges on melting to the aforementioned naphthalene derivative. The initial substitution reaction appears to proceed through an intermediary pyronyl cation. The scope of this potential ring annelation reaction has been investigated for a range of aromatic and heteroaromatic compounds. Heating with basic substrates converts the bisdazo compound into dimethyl 4-hydroxypyrazole-3,5-dicarboxylate, while heating with isopropanol yields dimethyl 4,5-dihydroxypyridazine-3,6-dicarboxylate.