Département de chimie moléculaire

The addition of aniline{,} even in excess{,} to a solution of 1{,}3-dichloro-1{,}3-bis(dimethylamino)vinamidinium salt in the presence of triethylamine invariably leads to the formation of 2{,}4-bis(dimethylamino)quinoline. Conversely{,} delaying the addition of the base leads to the formation of 1{,}3-dimethylamino-N{,}N[prime or minute]-diphenylpropane-1{,}3-diimine{,} even when only a substoichiometric amount of aniline was used. A DFT study led to the consideration of factors that accounted for this reversal of reactivity. The role of a secondary orbital interaction in key transition states{,} as well as the role of solvent{,} is discussed.