Synthesis of 1,6‑, 2,7‑, 3,8‑, and 4,9-Isomers of Didodecyl[1]benzothieno[3,2‑<i>b</i>][1]benzothiophenes

The synthesis of 1,6-, 2,7-, 3,8-, and 4,9-isomers of dibromo- and didodecyl[1]­benzothieno­[3,2-b]­[1]­benzothiophenes, via the stilbene pathway, is described. Starting from the synthesis of bromo-2-(methylthio)­benzaldehydes, a series of functionalization, McMurry coupling, and finalising cyclization reactions were explored. The stereochemistry of the cyclization mechanism was investigated. Using this methodology didodecyl[1]­benzothieno­[3,2-b]­[1]­benzothiophenes were formed in overall yields of 5–32%.