Copper-Mediated Synthesis of Phthalocyanino-Fused Dehydro[12]- and [18]annulenes

• Published in: Journal of organic chemistry 2000-10, Vol.65 (21), p.6841-6846
• Main Authors: García-Frutos, Eva M, Fernández-Lázaro, Fernando, Maya, Eva M, Vázquez, Purificación, Torres, Tomás
• Format: Article
• Language: English
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo0006019

Cyclooligomeric phthalocyanines with the special feature of having a dehydroannulene core are described. Compounds 4a,b and 5a,b were prepared by an oxidative coupling mediated by copper from the corresponding diethynyl unsymmetrically substituted phthalocyanines 8a,b, which are easily accessible from the corresponding diiodo compounds 6a,b by a palladium−copper-catalyzed coupling. Appropriate conditions to selectively form cyclodimers and cyclotrimers using Glaser and Eglinton methodologies have been attempted. In this way, two compounds, 4a and 5b, each representative of a kind of oligomers, could be appropriately isolated and characterized by MALDI-MS. The UV−vis spectra of compounds 4a and 5b show a split Q-band shifted to the red with respect to the corresponding precursor 8a,b. This can be interpreted, in light of previous results, as a consequence of intramolecular electronic coupling between the Pc subunits. Extensive formation of aggregates in chloroform can be also inferred from the spectra. No significant differences could be observed in the spectra by comparison with that of the open-chain analogue 11, most probably due to a saturation phenomenon of the optical properties already pointed out in the literature for other alkynyl-linked open-chain dimers.