New synthesis of nitrogen-containing polyaryl compounds catalyzed by transitionmetal complexes and application to organic EL devices

1.我们观察到，当2-苯基吡啶和芳基卤化物在钌络合物催化剂和碱的存在下反应时，2-苯基吡啶苯环邻位发生直接芳化。经过深入研究，确定了该重要反应的最佳条件：配位叔膦的钌络合催化剂，其中以[η^6-C_6H_6RuCl_2]_2-4PPh_3催化剂的活性最好。以碳酸钾为碱，n -甲基吡咯烷为溶剂，反应温度120℃，反应时间20 ~ 40 h为最佳反应条件。吡啶基作为导向基团，通过配位钌中心，促进了邻位导向反应的发生，是反应发生的必然要求。然而吡啶基很难转化为其他官能团。发展易转换的定向组显得至关重要。我们利用亚胺基和恶唑基作为直接邻位芳基。这些基团很容易转化为其他官能团：亚胺基可转化为酮、醛、醇、胺，恶唑基可转化为羧酸、酯、酰胺。然后利用上述反应方法制备了几种含氮的聚芳基化合物，并研究了这些化合物作为有机电致发光器件的用途。它们是良好的电子传递材料，也是铱和铂配合物的良好配体，具有高效的磷光发光。

1.We observed that direct arylation of the ortho position in the benzene ring of 2-phenylpyridine took place when 2-phenylpyridine and aryl halides were reacted in the presence of a ruthenium complex catalyst and base. After intensive works, the best conditions were established for this important reaction as follows : Ruthenium complex catalysts coordinating tertiary phosphine, above all, [η^6-C_6H_6RuCl_2]_2-4PPh_3 showed the best performance in activity. The employment of potassium carbonate as base, N-methyl pyrrolidine as solvent, 120℃ as reaction temperature, 20-40 h as reaction time were found to be the best reaction conditions.2.Pyridyl group is inevitable for the reaction to occur as the directing group which facilitates the ortho directing reaction by coordinating the ruthenium center. However pyridyl group is hard to be converted into another functional group. Development of easily convertible directing group seems essential. We exploited imino and oxazoyl group as the directing group for the direct ortho arylation of the aromatic ring. These groups can easily be converted into other functional groups : Imino group can be converted into ketone, aldehyde, alcohol, amine, and oxazole group can be converted into carboxylic acid, ester, and amide.3.Then we prepared several nitrogen-containing polyaryl compounds utilizing above reaction method, and investigated the utility of these compounds as organic EL device. They were found to be good electron transporting material and also good ligand for iridium and platinum complexes with efficient phosphorescence luminescence.