Convenient One-step Construction Of Yne-functionalized Primary Aryl Amine Through Benzyne Intermediate From Tetraynes

Aromatic ring structure in material and drug molecules can be seen everywhere. In consequence, at the request of highly efficient and environmental protection, it is particularly important to develop a series of new method of synthesis of aromatic amine compounds.System studied in the absence of catalyst in this artcle, Using organic small molecule hexamethylene tetramine directly with various substituents (-CH3,-Cl,-OCH3,-F) tetraynes derivatives were generated benzyne intermediates.After C-N coupling activation,the aryl amine products can be constructed by convenient one-step. Due to the conditions of optimized cyclization, the reaction can be more easily occured under the condition of100℃and no using any catalyst. As well the substituent of electronic effect on product yield has certain influence.In this reaction, the electronic effect of substituents may also influence the yield of product, when the temperature is below70℃,the reaction is difficult to happen; and also when the reaction temperature higher than120℃, the yield of the product has a little change. Means of IR, NMR, Mass spectrometry were applied to identified structures, and the two representative compounds were also carried out X-ray single crystal diffraction analysis. The reaction starting materials is simple easy, simple synthesis method, high substrate applicability and higher rate. Because the aromatic primary amine is a very versatile organic chemical raw materials, so the reaction is expected to be widely used at the development of high efficiency, environmental protection material.