Anion radicals of Di-trans-[12]annulene and heptalene in a one-pot synthesis from a common fire retardant

Low temperature (-100 degreesC) dehydrohalogenation of 1,2,5,6,9,10-hexabromocyclododecane (a common fire retardant) with potassium tert-butoxide in THF followed by one-electron reduction yields the anion radical of the di-trans form of [12]annulene. This system yields a well-resolved EPR signal that reveals that most of the spin density resides on one side (the planar side) of the anion radical. Five of the carbons in this [12]annulene system are twisted from the plane of the remaining seven carbons, and the rate of rearrangement between the degenerate conformations is on the EPR time scale (k = 10(6)-10(7) s(-1)). Warming of the solution results in the formation of a sigma-bond between the two internal carbons, loss of molecular hydrogen, and consequent generation of the anion radical of heptalene. Tractable quantities of neutral heptalene can be obtained via the reoxidation of this anion radical with iodine.