Synthesis, Stability, and Spectroscopic and Electronic Properties of Three Benzocyclohepta[a]azulenylium Ions1

Novel π-systems, three benzocyclohepta[a]azulenylium ions, 7a − c, are synthesized, and their stability and properties have been characterized in terms of the position of the benzo-annulation and compared with those of the parent cyclohepta[a]azulenylium ion 4. Benzocyclohepta[6,7-a]azulenylium ion (7a) (pK R + = 7.3, E red = −0.567 V vs Ag/Ag+) and benzocyclohepta[6,5-a]azulenylium ion (7b) (pK R + = 5.1, E red = −0.482 V vs Ag/Ag+), which are annulated with benzene on the position having a high bond order of 4, are not appreciably destabilized compared with cyclohepta[a]azulenylium ion (4) (pK R + = 7.3, E red = −0.458 V vs Ag/Ag+). On the other hand, benzocyclohepta[7,6-a]azulenylium ion (7c) (pK R + = 1.6, E red = −0.197 V vs Ag/Ag+) is considerably destabilized, probably due to enhanced contribution of the quinoid structure of the benzene ring, which is annulated on the position having a low bond order of the cyclohepta[a]azulenylium ion moiety. Furthermore, the cations 7a and 7b are more stable than 12,13-dihydrobenzocyclohepta[7,6-a]azulenylium ion (25) (pK R + = 4.8, E red = −0.513 V vs Ag/Ag+), which is a dihydrogenated compound of 7a, while 7c is less stable than 25. These features are reflected in the considerable red shift of the longest absorption maximum of the electronic spectrum of 7c, as compared with those of 4, 7a, and 7b, and in the chemical shifts of the protons and their coupling constants of the 1H NMR spectra. Furthermore, the 1H NMR spectra and electronic spectra of 5H-benzocyclohepta[6,7-a]azulen-5-one (8a) and 7H-benzocyclohepta[6,5-a]azulen-7-one (8b) in acidic media have also been studied to clarify the spectral characteristics similar to those of 7a and 7b.