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A nitrogen-containing ligand hemicellulose-palladium catalyst and its preparation method and application

A technology of hemicellulose and palladium catalysts, applied in the field of catalysis, can solve the problems of complex preparation methods, cumbersome preparation process, and high cost, and achieve the effects of simple process, environment-friendly, and convenient operation

Active Publication Date: 2017-08-25
SOUTH CHINA UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Among them, polymer-supported metal catalysts have become a research hotspot due to their high catalytic activity and stereoselectivity, good stability and reusability, but currently such polymer-supported palladium catalysts are mostly made of synthetic polymers. carrier, the preparation process is cumbersome and the cost is high
The literature also reported the use of inorganic substances (such as carbon, metal oxides, zeolites, etc.) to support palladium to catalyze the Suzuki reaction, and achieved a good catalytic effect, but it still has the disadvantages of complicated preparation methods and high costs.

Method used

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  • A nitrogen-containing ligand hemicellulose-palladium catalyst and its preparation method and application
  • A nitrogen-containing ligand hemicellulose-palladium catalyst and its preparation method and application
  • A nitrogen-containing ligand hemicellulose-palladium catalyst and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] (1) Preparation of ethylenediamine-modified hemicellulose: Weigh 1.32g (about 0.01mol) of xylose hemicellulose into 8mL deionized water, swell at 85°C for 10min, slowly add 4mL sodium hydroxide solution dropwise (200g / L) alkalization for 30min to obtain hemicellulose alkali solution;

[0043] Weigh 2.40g (0.04mol) of ethylenediamine and 1.85g (0.02mol) of epichlorohydrin, stir at room temperature for 10min, add the above-mentioned hemicellulose alkali solution into the above-mentioned system, and react for 6h under stirring at room temperature. After the reaction, Precipitate with three times the volume of absolute ethanol, wash with absolute ethanol until the product is neutral, and vacuum-dry to constant weight to obtain light yellow ethylenediamine-modified hemicellulose (EDAH);

[0044] (2) Preparation of ethylenediamine-modified hemicellulose-palladium catalyst: Weigh 0.3g ethylenediamine-modified hemicellulose (EDAH) and 0.03g palladium acetate into 15mL absolute ...

Embodiment 2

[0047] (1) Preparation of o-phenanthroline modified hemicellulose: Weigh 0.11g (0.8mmol) carboxymethyl hemicellulose and 0.77g (4.0mmol) EDC·HCl and add 12mL deionized water (adjust pH with dilute hydrochloric acid =5.5), then activated at a temperature lower than 20°C for 15min, then added 0.46g (4.0mmol) NHS, stirred and continued to activate for 2h, then added 0.085g (0.4mmol) 1,10-phenanthroline -5-Amino, kept stirring at low temperature for 24 hours. After the reaction, precipitated with three times the volume of absolute ethanol, washed twice with absolute ethanol and ether, and dried in vacuum to constant weight to obtain the modified o-phenanthroline Hemicellulose (PACMH);

[0048] (2) Preparation of o-phenanthroline modified hemicellulose-palladium catalyst: Weigh 0.3g o-phenanthroline modified hemicellulose (PACMH) and 0.03g palladium acetate into 15mL absolute ethanol, react at 60°C After 12 hours, filter, wash with absolute ethanol and ether, and vacuum-dry to obt...

Embodiment 3

[0051] (1) Preparation of ethylenediamine-modified hemicellulose: Weigh 1.32g (about 0.01mol) of xylose hemicellulose into 8mL deionized water, swell at 85°C for 10min, slowly add 4mL sodium hydroxide solution dropwise (200g / L) alkalization for 30min to obtain hemicellulose alkali solution;

[0052] Weigh 2.40g (0.04mol) of ethylenediamine and 1.85g (0.02mol) of epichlorohydrin, stir at room temperature for 10min, add the above-mentioned hemicellulose alkali solution into the above-mentioned system, and react for 6h under stirring at room temperature. After the reaction, Precipitate with three times the volume of absolute ethanol, wash with absolute ethanol until the product is neutral, and vacuum-dry to constant weight to obtain light yellow ethylenediamine-modified hemicellulose (EDAH);

[0053] (2) Preparation of ethylenediamine-modified hemicellulose-palladium catalyst: Weigh 0.3g ethylenediamine-modified hemicellulose (EDAH) and 0.03g palladium acetate into 15mL absolute ...

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Abstract

The invention belongs to the technical field of catalysis, and discloses a nitrogenous ligand hemicelluloses-palladium catalyst as well as a preparation method and application thereof. The preparation method of the catalyst comprises the following steps of: adding ethylenediamine modified hemicelluloses or phenanthroline modified hemicelluloses and palladium salt to a solvent, performing a reaction for 4-24 hours at the temperature of 20-60 DEG C to obtain a reaction product, filtering the reaction product, washing the filtered reaction product, and drying the washed reaction product so as to obtain an ethylenediamine modified hemicelluloses-palladium catalyst or a phenanthroline modified hemicelluloses-palladium catalyst. The application process of the catalyst in a Suzuki coupled reaction comprises the following steps of: adding the ethylenediamine modified hemicelluloses-palladium catalyst or the phenanthroline modified hemicelluloses-palladium catalyst, halogeno benzene, arylboronic acid and alkali to a solvent, performing a reaction for 1-5 hours at room temperature to obtain new reaction products, filtering the new reaction products so as to remove the catalyst, performing reduced pressure distillation on filtrate so as to remove the solvent, and performing column chromatography purification so as to obtain a catalytic synthesis product. The catalyst disclosed by the invention has the advantages of being good in catalytic effect, convenient to separate and low in cost, and has favorable application prospects.

Description

technical field [0001] The invention belongs to the technical field of catalysis, and in particular relates to a nitrogen-containing ligand hemicellulose-palladium catalyst and a preparation method and application thereof. Background technique [0002] Since Suzuki et al. reported in 1981 that palladium-catalyzed organoboron compounds and halogenated hydrocarbons could undergo coupling reactions to prepare unsymmetrical biaryls under very mild conditions, the formation of Aryl-Aryl bonds has opened up a new field. Suzuki-Miyaura cross-coupling reaction is currently the most widely used method for the preparation of biaryl and its derivatives. Due to its strong substrate adaptability and functional group tolerance, it is often used in the synthesis of polyenes, styrene and biphenyl Derivatives of the reaction are applied in the synthesis of many natural products and organic materials. This reaction has a wide range of applications in pesticides, medicines, polymers, dyes and ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/06C07C43/205C07C41/30C07C49/784C07C45/68
Inventor 彭新文吴昌艳谭杰文梁炜光郑少波孙润仓
Owner SOUTH CHINA UNIV OF TECH
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