Tetranuclear copper complex, preparation method and application of tetranuclear copper complex in gas-phase amination catalysis of tetrahydrofuran

Abstract

The invention discloses a tetranuclear copper complex, a preparation method and application of the tetranuclear copper complex in gas-phase amination catalysis of tetrahydrofuran, and relates to the field of pyrrolidine catalysts.The chemical formula of the tetranuclear copper complex is [Cu(L)(ClO4)(H2O)](dioxane)1.5, wherein L represents a 2,3,5,6-tetrachloro-1,4-di(imidazole-1-carbonyl)benzene ligand, ClO4 represents a nitrate anion, and dioxane represents 1,4-dioxane.The copper complex with a tetranuclear cage-shaped structure is obtained by adopting copperperchlorate hydrate and the organic ligand 2,3,5,6-tetrachloro-1,4-di(imidazole-1-carbonyl)benzene in blend solvent of 1,4-dioxane and methyl alcohol under the closed condition through a thermal reaction.The tetranuclear copper complex is applied to ammoniation of tetrahydrofuran and ammonia to prepare pyrrolidine.Accordingly, the technological process is simple; a catalyst is convenient to prepare, and the reproducibility is good; the conversion rate of tetrahydrofuran reaches 83%, and the selectivity of pyrrolidine reaches 95%.

Description

technical field [0001] The invention relates to the field of tetrahydropyrrole catalysts, in particular to a tetranuclear copper complex, a preparation method thereof and the application of catalytic tetrahydrofuran gas phase amination. Background technique [0002] Tetrahydropyrrole, also known as pyrrolidine, English name Tetrahydropyrrole or Pyrrolidine, molecular formula C 4 h 9 N, boiling point 87°C, density 0.852gcm –3 , as a cyclic secondary amine, pK b =2.9, it has general amine properties and has extremely wide uses in many aspects. In the field of drug synthesis, there are many kinds of drugs directly having a tetrahydropyrrole structure in the structure, such as buflomedil for treating cerebrovascular disorders, dexmorphilamide tartrate with analgesic function, and procyclone for anti-parkinsonia The anti-infective drug pirromid, the local anesthetic pirrocaine, the depression drug fenprofen and so on. In addition, tetrahydropyrrole is also widely used in the...

AI Technical Summary

Problems solved by technology

The catalyst for the cyclization reaction is expensive, and some methods have long synthetic routes, many by-products, and low yields, which do not have the value of actual industrial operation

Using tetrahydrofuran and ammonia as raw materials, tetrahydropyrrole is prepared by gas-phase catalytic method, which has low raw material cost. This synthetic route is used in production, but there are still some problems, such as the catalyst used has low conversion rate and low selectivity.

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