As part of an investigation into new synthetic routes to poly(peri-naphthalene), the synthesis and cycloaromatization of tetraethynylbiphenyls is described. The temperature-dependent cyclization of biphenyls containing unsubstituted alkynes provides the desired perylene in good yield.
The substituents at the peri positions of dehydro[14]annulenes 1 have a dramatic effect on the stability of these macrocycles, and lead to derivatives that are stable even at elevated temperatures (up to 190°C).
The cover picture shows the influence of high pressure on the Heck cross-coupling reaction. As reflected by its generally accepted mechanism, this palladium-catalyzed reaction proceeds in a number of distinctly different steps, some of which ought to be retarded by high pressure. Yet, the overall effect leads to a significant acceleration, and the reaction has a negative volume of activation. The kinetic parameters were determined by monitoring the reaction in a massive metal cylinder Ϫ as seen in the background Ϫ by on-line FT-IR spectroscopy. Details are discussed in the article by A. de Meijere et al. on p. 2375 ff.
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