The Application Of Arylglyoxals Involved Multicomponent Reaction For The Construction Ofaza-heterocycles

This paper consists of four parts.The first part briefly describes the synthetic progress of tandem reaction and arylglyoxals, proposes the topic basis, meaning, innovation and research methods of [2,6]naphthyridine derivatives, [1,7]naphthyridine derivatives, [1,3]diazocane derivatives, pyrazoloazole derivatives and pyrazolooxazine derivatives.The second part introduces a novel A2B2 type cascade reaction, namely using the aminopyrazole and arylglyoxal monohydrate as raw materials, under the conditions of n-butyric acid microwave irradiation, tandem constructed unprecedented dipyrazolo-[2,6]naphthyridine skeleton. The structure of the target products are complex, reflecting the products of multi-component reaction have the characteristics of structural complexity plenty. Provides a more efficient synthesis of these compounds, gives a more space to develop the pharmacological activity and the biological activity of these compounds.The third part describes when we use strong Br?nsted acid such as p-toluenesulfonate instead of weak Br?nsted acid such as n-butyric acid to expand the diversity of acid, the reaction under microwave irradiation conditions accidentally got [1,7] naphthyridine derivatives. And by adjusting the C-3 position substituent group of methyl-5-aminopyrazole, selectively generating an another product of [1,3] diazocine derivatives. Meanwhile, the reaction have highly chemicalselectivity, regioselectivity and stereoselectivity, only water is the byproduct and subsequent processing is convenient, in line with the environment friendly requirements of green chemistry.The fourth part describes when changing the feed ratio of aminopyrazole and arylglyoxal monohydrate will generate different products. When the feed ratio of aminopyrazole and arylglyoxal monohydrate were 2:1, generate pyrazoloazole derivatives. When the feed ratio of aminopyrazole and arylglyoxal monohydrate were 1:2, generate pyrazolooxazine derivatives. This reaction has the advantage of short reaction time, high yield and regioselectivity, easy operation, avoid the tedious separation process.Full summary can draw this conclusion: selection of different acid catalysis will generate different products, control aminopyrazole substituent at C-3 will generate different products, control the feed ratio of aminopyrazole and arylglyoxal monohydrate will produce different products.Structures of the products were confirmed by IR and 1H NMR, 13 C NMR characterization, high resolution mass spectrometry and single-crystal X-ray diffraction confirmed, while the reaction made possible reaction mechanism.We builded a series of structural complexity and diversity of aza-heterocyclic skeleton, efficient synthesis of the five categories, 84 heterocyclic compounds, explored the selectivity of the tandem reaction, established a number of specific synthesis of heterocyclic compounds, developed the series of chemical reactions and enriched the content of green synthetic chemistry.