A kind of supported metal catalyst and its preparation method and application

Abstract

The invention provides a supported metal catalyst whose carrier is Al 2 o 3 , SiO 2 Or ZSM-5, the active components are Cu, Ni and Pd, and the total loading of active components Cu and Ni is 3~15wt.% of the carrier, and Pd is 0~1wt.% of the carrier. Using the supported metal as a catalyst and 1,4-butanediol and ammonia as raw materials, in H 2 Under a reducing atmosphere, 1-butylpyrrolidine, 1-(2-butene)pyrrolidine and 1-(3-butene)pyrrolidine were jointly prepared by using a one-pot reaction; the method is simple to operate and low in cost. The combined yield of the product is high, and the by-product of the reaction is water, which is economical, green and environmentally friendly.

Description

technical field [0001] The invention provides a preparation method of a supported metal catalyst, which is mainly used for catalytic joint preparation of 1-butylpyrrolidine, 1-(2-butene)pyrrolidine and 1-(3-butene)pyrrolidine, belonging to catalysts and chemical synthesis technology. Background technique [0002] 1-Butylpyrrolidine has a wide range of uses in the field of chemical industry, and can be used as a raw material for pharmaceutical intermediates, pesticides, dyes, and pyrrolidinium-based ionic liquids. Existing 1-butylpyrrolidine synthesis method mainly contains: Journalof Organometallic Chemistry, 373 (3), 343-52; 1989 reported a kind of RuCl 3 As a catalyst to catalyze tetrahydropyrrole and n-butanol to synthesize 1-butylpyrrolidine, the yield can reach 80%, but the raw material tetrahydropyrrole used in the reaction is expensive, and the catalyst is a noble metal, which limits its industrial application; Organic Reactions (Hoboken, NJ, United States), 71, 1-7...

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Problems solved by technology

Existing 1-butylpyrrolidine synthesis method mainly contains: Journalof Organometallic Chemistry, 373 (3), 343-52; 1989 reported a kind of RuCl 3 As a catalyst to catalyze tetrahydropyrrole and n-butanol to synthesize 1-butylpyrrolidine, the yield can reach 80%, but the raw material tetrahydropyrrole used in the reaction is expensive, and the catalyst is a noble metal, which limits its industrial application; Organic Reactions (Hoboken, NJ, United States), 71, 1-737; 2008 reported the route of reducing 1-butylpyrrolidone with 1-butylpyrrolidone, and the yield can reach 64%, but the reaction process needs to use Diphenylsilane is used as a reducing agent, and tetrahydrofuran is used as a solvent. Due to the use of a large amount of organic solvents, the reaction process is not green enough, and the prices of 1-butylpyrrolidone and reducing agent are all relatively high; European Journal of Inorganic Chemistry, (21), 3353- 3358; 2008 reported the method of obtaining 1-butylpyrrolidine by reducing 1-butylpyrrole, the yield of this method can reach 62%, but the reaction process of this method is complicated, several solvents need to be used, post-treatment is difficult, and The price of 1-butylpyrrole is also high, and the route is not economical enough; Synthetic Communications, 39(16), 2907-2916; 2009 and Synthesis, (3), 490-496; 2011 reported a synthesis of tetrahydropyrrole and n-butyraldehyde The method of 1-butylpyrrolidine, the reaction 1-butylpyrrolidine yield can reach more than 90%, but the reaction process uses NaBH 4 Reductant, after the reaction generates corrosive NaOH, needs to be treated with hydrochloric acid and generates a large amount of solid waste salt, the process is not green enough, in addition, the price of tetrahydropyrrole as a raw material is also high, which limits its industrial application; Journal of the American Chemical Society, 137(40), 12796-12799; 2015 reported a method for synthesizing 1-butylpyrrolidine with tetrahydropyrrole and 1-iodobutane as raw materials. The raw material tetrahydropyrrole of this method is expensive and not economical enough. And the by-product of the reaction is hydrogen iodide, serious pollution, difficult post-processing, difficult to achieve large-scale production

[0003] At present, there are very few reports about 1-(3-butene)pyrrolidine and 1-(2-butene)pyrrolidine, Tetrahedron Letters, 44(4), 667-670; 2003 reported that tetrahydropyrrole, formaldehyde, 3 -Bromopropene is used as a method for synthesizing 1-(3-butene)pyrrolidine as a raw material. The raw material of this method is complicated, the reaction by-product is HBr, and the process is not green enough; US 20050038068 and Industrial & Engineering Chemistry Research, 54(16), 4396- 4406; 2015 reported a method for synthesizing 1-(3-butene)pyrrolidine with tetrahydropyrrole and 4-bromobutanal as raw materials. Similarly, the method raw material tetrahydropyrrole is expensive, and the reaction will produce HBr, and the route is not enough Economical, the process is not green enough; Tetrahedron, 38 (3), 413-17; 1982 provides a kind of synthesis of 1-(2-butene) pyrrolidine with 2-pyrrolidinyl-but-2 enoic acid methyl ester as raw material method, the method yield is low, it is difficult to realize industrialization