Electron Donor‐Acceptor Compounds, 45 Syntheses of [2.2]‐, [3.3]‐, and [4.4]Paracyclophanes with 1,2,4,5‐Tetracyanobenzene Units as Electron Acceptors

[2.2]Paracyclophanes 1–4 containing tetracyanobenzene (TCNB) units opposite to different electron donor components have been synthesized via the corresponding substituted dithia[3.3]paracyclophanes 8, 10, 12 , and 14 . For the pyrolysis of the disulfones 9, 11, 13 , and 15 derived therefrom, due to the very low volatility of these compounds, a modification of the conventional pyrolysis method had to be used. – The syntheses of [3.3]paracyclophanes 16–18 via the dithia[4.4]paracyclophanes 19, 21 , and 23 and the corresponding disulfones 20, 22 , and 24 are described. [4.4]Paracyclophanes 32 and 33 were prepared from the respective dithia[5.5]paracyclophanes 34 and 36 by pyrolysis of the disulfones 35 and 37 . – As cyclisation components for the synthesis of the mentioned dithiaparacyclophanes several new 1,4‐bis(mercaptoalkyl)benzenes with electron‐donating substituents were prepared as was the TCNB derivative 5 .