Kinetics of Bromine#Magnesium Exchange Reactions in Substituted Bromobenzenes

The Journal of Organic Chemistry, 2009, 74 (7), 2760-2764 published on 12.03.2009
The Journal of Organic Chemistry
Competition experiments have been performed to determine the relative reactivities of substituted bromobenzenes, bromonaphthalenes, and 9-bromoanthracene toward i-PrMgCl · LiCl in THF at 0 °C. The rates of the bromine-magnesium exchange reactions are accelerated by electron-acceptor substituents, the activating efficiency of which increases in the order para < meta , ortho. The activation free enthalpies of the bromine-magnesium exchange reactions correlate fairly (r2 ) 0.83) with the proton affinities of analogously substituted aryllithiums (slope 0.8). The kinetics of two representative bromoarenes with i-PrMgCl · LiCl were found to be first-order in both bromoarene and i-PrMgCl · LiCl. Combination of the resulting second-order rate constants with the krel values from competition experiments allowed us to calculate reaction times for the bromine-magnesium exchange reactions of a large variety of bromoarenes.
TU München