Scalable synthesis of quaterrylene: solution-phase 1H NMR spectroscopy of its oxidative dication.

Quaterrylene is prepared in a single reaction and high yield by Scholl-type coupling of perylene, utilizing trifluoromethanesulfonic acid as catalyst and DDQ or molecular oxygen as oxidant. Dissolution in 1 M triflic acid/dichloroethane with sonication yields the aromatic quaterrylene oxidative dication, which is characterized by its (1)H NMR spectrum.

A computational model for the dimerization of allene.

Computations at the CCSD(T)/6-311+G(d,p)//B3LYP/6-311+G(d,p) level of theory support long-held beliefs that allene dimerization to 1,2-dimethylenecyclobutane proceeds through diradical intermediates rather than a concerted (π)2(s) + (π)2(a) mechanism. Two diastereomeric transition states with orthogonal and skew geometries have been located for C2-C2 dimerization of allene, with predicted barriers of 34.5 and 40.

Phenyl shifts in substituted arenes via ipso arenium ions.

The isomerization of substituted arenes through ipso arenium ions is an important and general molecular rearrangement that leads to interconversions of constitutional isomers. We show here that the superacid trifluoromethanesulfonic acid (TfOH), ca. 1 M in dichloroethane (DCE), provides reliable catalytic reaction conditions for these rearrangements, easily applied at ambient temperature, reflux (84 °C), or in a microwave reactor for higher temperatures.