Reactions involving di-trans-[12]annulenes

The low temperature complete dehydrohalogenation of pentabromocyclododecene (C12H17Br5) with potassium tert-butoxide in THF followed by exposure to potassium metal leads to the formation of the anion radical of 1,5-di-trans-12]annulene, which loses hydrogen and undergoes ring closure to form the anion radical of 11,12-dihydro-8]annuleno-6]annulene. This product can, in turn, be isolated as its neutral molecule via reoxidation with iodine. A 12]annulene obtained via the dimerization of 1,5-hexadiyne in the presence of 18-crown-6 and potassium tert-butoxide undergoes ring closure, with concomitant loss of hydrogen, to yield the heptalene anion radical. It follows that the heptalene anion radical precursor was the 1,7-di-trans isomer of 12]annulene.