ULLMANN CONDENSATION REACTION OF HALOANTHRAQUINONE DERIVATIVES WITH AMINES IN APROTIC-SOLVENTS .4. KINETIC STUDIES OF THE CONDENSATION WITH ETHYLENEDIAMINE

In the Ullmann condensation of bromoanthraquinones (AQBr) with ethylenediamine using copper (I) bromide as a catalyst, the reaction rate decreased with time which has been interpreted in terms of the formation of the ineffective copper(II) species. The kinetic investigation showed the reaction rate to be first order both for the copper(I) species and AQBr. After prolonged reaction the copper(I) species was quantitatively converted to the copper (II) species, the copper (II) species appearing to have little catalytic activity due to strong coordination with ethylenediamine. The reactivities of the haloanthraquinones were dependent on the ease of coordination with Cu(I) and the rate of Cu(II) formation. The mechanism, including the reaction between Gu(AQBr) and ethylenediamine, has been proposed and discussed.