Methylenecyclopropane Rearrangement as a Probe for Free Radical Substituent Effects. sigma (*) Values for Potent Radical-Stabilizing Nitrogen-Containing Substituents.

A series of nitrogen-containing 2-aryl-3,3-dimethylmethylenecyclopropanes have been prepared and rearrangement rates to the corresponding 2-arylisopropylidenecyclopropanes have been measured. These rates are dependent on the nature of the nitrogen-containing group in the para-position of the aryl group. Rearrangement rates have been used to calculate sigma (*) values, which are a measure of the radical stabilizing ability of the substituent. Groups such as p-N=N-Bu-t, p-CH=N-Bu-t, p-NH(2), p-CH=N-OH, and p-CH=N-OCH(3), are "good" radical stabilizers. We have also classified groups such as p-CH=N-NMe(2), p-N=N-Ph, p-N=N(O)-Bu-t, p-CH=N(O)-Bu-t, and p-CH=N-O(-) M(+), which have an extraordinarily large radical stabilizing effect, as "Super Stabilizers". These substituents stabilize the transition state of the methylenecyclopropane rearrangement by extensive spin delocalization. In the case of the latter three substituents, nitroxyl type stabilization is proposed. Density functional calculations (B3LYP/6-31G) have been carried out on a series of nitrogen-containing substituted benzylic radicals. Rates of the methylenecyclopropane rearrangement correlate with radical stabilization energies (DeltaE) determined from an isodesmic reaction of substituted benzylic radicals with toluene. These calculations confirm substantial spin delocalization onto the nitrogen-containing substituents on the para-position of the benzylic radical.