The chemical structure of organic molecules and materials, which are applied in organic electronic devices such as organic light emitting diodes, solar cells, or batteries, determines their performance to a great extent. Therefore, structure-property relationships are a vital basis for the optimal design of organic semiconductors. In this respect, there is a great interest in the development of novel -conjugated polycyclic molecules such as acenes, phenacenes, or nanographenes. Corresponding heteroacenes, which contain heteroatoms such as nitrogen or sulfur represent encouraging alternatives to the pure hydrocarbons, because electronic properties are tunable and chemical stability is typically increased. One of the most prominent example is represented by benzo[1,2-b:4,5-b′]dithiophene 1, which was very successfully implemented as synthon in a multitude of oligomeric and polymeric materials for efficient organic solar cells. However, it was found that benzodithiophenes undergo photooxidative degradation at the 4-and 8-position. As it is known for acenes, in particular pentacene, introduction of nitrogens into the conjugated -system lower the HOMO energy level without influencing the planarity of the molecule. Consequently, N-heteroacenes are more air-stable and possess higher electron transport efficiency. In this respect, Hayashi et al. could show by quantum chemical calculations that the introduction of nitrogen(s) in syn-and anti-benzodithiophene 1 and 2, represented in dithienopyridines 3 and 4 and in syn-and anti-dithienopyrazine 5 and 6 leads to a continuous decrease of both, the HOMO and the LUMO energy level (Figure ). We use the denomination "anti" and "syn" in order to represent regiochemical relationships in the triacenes. "Anti" means that the sulfur atoms of the fused thiophene rings are "on opposite sides" of a reference line/plane in the molecule, in contrast to "syn" which means "on the same side". The synthetic realization of the basic benzodithiophenes 1 and 2 is long known since the 1950 th and various methods have been developed over the years. In the case of N-heterotriacenes 3-6 typically substituted derivatives were prepared by different synthetic strategies and only preparation of the basic syn-derivative, dithieno[3, 2-b:2',3'-e]pyridine 3, was described by Outurquin et al. whereby the other unsubstituted heterotriacenes 4-6 are not literature-known up to now.