Pyrimidyl-penta-phenylbenzenes have been synthesized by Diels–Alder addition of phenylethynylpyrimidines and tetraphenylcyclopentadienones under microwave irradiation. Scholl reactions of these compounds led to two types of hetero polyaromatic hydrocarbons: (a) partial cyclization by creation of two C–C bonds ortho to the pyrimidine nitrogen atoms gave substituted tribenzo[e,gh,j]perimidine (N-1/3HSB) in high yields; (b) when the position 2 of the pyrimidine ring was substituted by a tert-butyl group, the Scholl reaction was complete and provided the first example of a diaza-hexa-peri-benzocoronene.