n2 substituted 1,2,3-triazole ligand/cu(i) composite catalyst and its synthesis and application

Abstract

The invention relates to an N2 substituted 1,2,3-triazole ligand / Cu(I) composite catalyst, synthesis thereof, and applications thereof in reaction of an azide and a terminal alkyne. The synthesis of the composite catalyst comprises the following steps: (1) by a molar ratio of N2 substituted 1,2,3-triazole ligand to Cu(I) salt, which is equal to 1:0.5-1:3, weighing raw materials, selecting solvents, and mixing and stirring for 20-60 minutes at room temperature to separate out a large quantity of solids; (2) standing a reaction liquid obtained from the step (1) at normal temperature, filtering the reaction liquid to obtain a solid, and repeatedly washing the solid by methanol; and (3) vacuum drying the solids obtained from the step (2) for later use. The composite catalyst has the advantage of being simple to synthesize, stable in properties, and available for efficiently catalytic reaction in environments with oxygen and water. Catalysis can be performed just with a small quantity of N2 substituted 1,2,3-triazole ligand / Cu(I) salt composites; in addition, the composite catalyst is high in catalytic efficiency and universally applicable to synthesis of substrates containing special substituents.

Description

technical field [0001] The present invention relates to a class of ligands, catalysts and applications thereof, in particular to a class of N2-substituted 1,2,3-triazole ligand / Cu(I) composite catalysts and their synthesis and reaction between azide compounds and terminal alkynes in the application. Background technique [0002] The early synthesis of 1,2,3-triazoles was mainly based on the 1,3-dipolar Huisgen cycloaddition reaction of organic azides and terminal alkynes, but this reaction required an active group on the azide or alkyne group, At the same time, the reaction requires high temperature or high pressure, and the reaction time is long, the reaction selectivity is not high, and the yield is low, so the application of 1,2,3-triazole compounds is greatly limited. In 2002, Sharpless and Meldal respectively reported that Cu(I) can efficiently promote the Huisgen [3+2] cycloaddition reaction of terminal alkynes and azides, and this discovery promoted the development o...

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Problems solved by technology

[0003] (1) Cu(II) salt is reduced to produce Cu(I) to catalyze the synthesis of 1,2,3-triazole, namely CuSO 4 ·5H 2 O, Cu(OAc) 2 , CuSO 4 etc. can interact with copper metal or other reducing agents (sodium ascorbate) to produce Cu(I) compounds, and then play a catalytic role; but most of them are used in aqueous systems, and some water-sensitive groups need to be in organic solvents. At the same time, the post-reaction treatment process of this system is relatively complicated, and it is inconvenient to use for some systems with strict requirements (such as the fields of biochemistry and pharmaceutical research)

[0004] (2) Cu(0) is oxidized to produce Cu(I) to catalyze the synthesis of 1,2,3-triazole, that is, metal copper is reacted in some oxidants (CuSO 4 , FeCl 3 ) in the presence of Cu (I) catalytic reaction; but with metal copper and other catalytic systems compared with the need for a longer reaction time and a larger amount, which needs to improve the copper metal catalytic system

[0005] (3) Cu(I) salt catalyzes the synthesis of 1,2,3-triazole, that is, CuI, CuBr, CuCl, CuCN, CuOAc and other copper salts can be used for catalysis in a certain solvent system and can achieve good yields; However, Cu(I) salts are easily disproportionated or oxidized, and the reaction system catalyzed by Cu(I) salts requires the use of specific solvents and even the addition of alkalis, which limits its application.

At present, the research on the ligands used for Cu(I) catalysis is mainly based on polyamines, poly-1,2,3-triazole-substituted amines and other ligands with complex structures, which are not easy to synthesize and are limited in application.

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