Studies on Heterocyclic Analogs of Azulene. VI. Cycloadditions of Styryl-substituted Aza Analogs of Azulene with Dimethyl Acetylenedicarboxylate

Abstract 8-[(E)-Styryl]-1-azaazulenes stereospecifically react with dimethyl acetylenedicarboxylate to form trans-7H-6a-azacyclobuta[j]cyclopent[cd]azulene (3), which undergoes thermal rearrangement into 3-[(E)-styryl]3H-2a-azacyclopent[cd]azulene and 3a,4-dihydro-3H-2a-azadicyclopent[cd, ij]azulene (7), or isomerization into 3H-2a-azacyclopenta[ef]heptalene by silica gel. Compound 7 is oxidized during the course of reaction to yield 11-oxo-2aH-7,10b-methano-2a-azacyclopenta[ab]cycloundecene, compound 3 forming 5a,6-dihydro-3H-2a-azadicyclopenta[ef, kl]heptalene upon reaction with acetylene. The formation of 3 could be accounted for in terms of a symmetry-allowed thermal [π2s+π2a+π6a] cycloaddition.