N-arylation method taking substituted adipic dihydrazide as ligand in aqueous phase system

Abstract

The invention provides an N-arylation method in an aqueous phase system, which is simple and convenient and environmentally friendly, and has mild reaction condition and economic process. The method comprises the following steps: taking aryl halide and amine as raw materials, and water as solvent, metallic copper, or oxide of copper, or cuprous salt or cupric salt as catalytic agent, and using adipic dihydrazide compound as a ligand to generate C-N coupling reaction; the reaction steps are as follows: adding catalyst, ligand, aryl halide, amine, alkali, surface active agent and water into a microwave reactor or a reaction vessel; reacting by stirring by adopting the mode of microwave assistant heating, or common heating bath heating or direct room temperature reaction; separating and purifying the reaction mixed liquor after the reaction is completed to obtain the N-arylation product. The method of the invention has the characteristics of simple operation, wide substrate application range, simple products which can be separated easily, high yield, economic process and environmental friendliness and the like, and takes water as solvent, has wide application range of the substrate, and has wide application prospects in preparation aspects of natural products, drugs and pesticides.

Description

technical field [0001] The invention relates to the technical field of chemistry, in particular to an N-arylation method. technical background [0002] Arylamines are an important class of compounds that widely exist in natural and non-natural products with physiological activities. The study of C-N bond formation reactions has been widely valued. [0003] The Ullmann reaction of carbon-nitrogen cross-coupling has a long history since it was first reported in 1903 (Ley, S.V.; Thomas, A.W. Angew. Chem. Int. Ed. 2003, 42, 5400 and related citations). Since this reaction is usually carried out in a polar solvent with a high boiling point, under the condition of high temperature, catalytic amount or equivalent amount of copper powder as a catalyst, the reaction time is long, the follow-up treatment of the reaction is difficult, and the reaction product is complex and difficult. The disadvantages such as low reaction yield. In 1983, Migita et al. first discovered the Pd-catalyz...

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Problems solved by technology

However, the above-mentioned reactions can only be carried out for specific compounds, so they cannot be widely used.

While Buchwald et al. reported Pd-catalyzed C-N bond formation in aqueous solution (Huang, X.; Anderson, K.W.; Zim, D.; Jiang, L.; Klapars, A.; Buchwald, S.L.J. Am. Chem. Soc. 2003, 125, 6653) is defective due to the cost of the catalytic system

The applicant once proposed patent applications 200610033067 and 200710026860, which overcome the shortcomings of the previous C-N coupling reaction method to a certain extent, but also have the disadvantage of excessive ligand usage

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