Dehydrobenzoannulenes

Recrystallization of 76 (R=H) from CH2CI2 provided crystals adequate for X-ray structural determination. The molecule was found to be saddle shaped with a phenyl ring at each vertex and nadir. The alkynyl bonds were found to be essentially linear and to possess a mean length of 1.194 A, typical for the length of triple bonds in free butadiyne. Although 76 is a dehydrobenzoannulene possessing a 4n TT-electron circuit, the nonplanarity of the macrocycle alleviated much of the strain associated with a flat structure and thus precluded the possibility of anti-aromatic ring currents. 

An alternative mode for dehydrobenzoannulene decomposition was recently reported by Vollhardt et al. [58]. Non-planar hybrid 81, prepared in low yield via cyclodimerization of known triyne 82 [Eq.(3)], reacted explosively at ca. 250°C to give a nearly pure carbon residue. Solvent extraction of the black powder failed to yield soluble materials such as fullerenes however, analysis of the residue by TEM showed formation of bucky onions and bucky tubes [59], in addition... 

Using similar methodology, macrocycle 126 was prepared, as well as the unusual monoene 127 [76]. Considerable debate in the literature over the last thirty years has focused on whether dehydrobenzoannulenes are able to sustain induced ring currents [5al. Although fusion of arenes to the annulenic core provides rigidity and stability, this also weakens the diatropicity/paratropicity of the macrocycle significantly. Until quite recently, the number of planar systems available for study was limited however, with the the addition of 123 and 126, the series of alkyne-linked, tribenzo-fused dehydroannulenes is complete from... 

More recent developments exploit the energy content of readily accessible cycloalkynes based on phenyl-alkynyl structural motives, albeit not always with fullerene formation in mind. For example, the strained dehydrobenzoannulene 4 [19] could be converted by light, heat (145 °C), or pressure (20000 psi) in a topochemical polymerization reaction typical for butadiynes to a deeply coloured polymer. A similar thermochemical behaviour (strongly exothermic transformation around 200 °C) was observed for compounds 5 and 6 [20]. However, none of the systems 4-6 shows any tendency to produce spherical forms of carbon under the conditions investigated. 

To study the aromatic character of dehydrobenzoannulenes by 1H NMR spectroscopy, it is desirable to replace one or more of the benzene rings in the above and related hydrocarbons... 

Haley M.M. It takes alkynes to make a world—new methods for dehydrobenzoannulene synthesis Synlett 557, 1998... 

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