Dicyclopentaheptalene (Azupyrene) Chemistry. Jutz Synthesis Byproducts. Synthesis and Thermal Isomerization of 1-Methylazupyrene

Article abstract of DOI:10.1021/jo00365a020

The Jutz synthesis of azupyrene (4) has been found to form chloro-, methyl-, and dimethylazupyrene byproducts in the final step.Perchlorate and methoxide ions were shown to cause the chlorination and methylation, respectively.Temperature control at 200-205 deg C reduced the chlorination and the use of ethoxide virtually eliminated the alkylation. 1-Methylazupyrene (7) was synthesized.The termal isomerization of 7 to methylpyrenes was carried out and the products were found to be those predicted by certain of the mechanisms proposed for the azulene to naphthalene isomerization.