Reactions of Amines with Zwitterionic Quinoneimines: Synthesis of New Anionic and Zwitterionic Quinonoids

Following the discovery of an unprecedented transamination reaction between primary alkylamines and a quinonoid molecule of the type [C6H2(- NHCH2R)(2)(- O)(2)] (1), obtained from commercially available diaminoresorcinol center dot 2HCl, we have extended this method to the use of primary arylamines, and found that, in contrast, secondary amines led to a different outcome. Whereas functionalized molecules of type 1, which are best described as 6 pi + 6 pi zwitterions, were obtained with aniline or 4-methoxyaniline, no transmination was observed with tBuNH(2) in ethanol. In water, however, a reaction took place, but it afforded instead salt 6a, which resulted from hydrolysis of the imine group and deprotonation. Under similar conditions, secondary amines led to comparable results. The cations associated with the anionic quinonoid are readily exchanged in the presence of a primary amine. Whereas for the transamination reaction basic amines react under mild conditions, slightly harsher conditions are needed for less basic an-lines such as piperidine, diisopropylamine, or diethylamine. Transamination reactions were also performed with bis(methylamino) quinoneimine 4c, which is more soluble in organic solvents than 3. This led to the first examples of quinonoidal zwitterions functionalized with different alkyl groups on the nitrogen atoms. A number of compounds were characterized by X-ray diffraction, which allowed a better understanding of their electronic situation, and in many cases, the presence of multiple hydrogen-bond donors and acceptors results in crystal packings dominated by these interactions. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)