Cross-linked polystyrene microsphere immobilized tetramethylpiperidine nitroxide free radical catalyst and its preparation and application method

A technology of tetramethylpiperidine nitroxide radical and cross-linked polystyrene, which is applied in the preparation of carbon-based compounds, chemical instruments and methods, preparation of organic compounds, etc. development and other issues to achieve the effect of improving thermal stability and facilitating separation

Inactive Publication Date: 2018-08-24
ZHONGBEI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, most of the currently used TEMPO catalysts are homogeneous catalysts. Although they have the advantages of high catalytic activity, they also have disadvantages such as difficult recovery and recycling of catalysts and difficult separation of product systems, which seriously restrict the development of this catalytic system.

Method used

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  • Cross-linked polystyrene microsphere immobilized tetramethylpiperidine nitroxide free radical catalyst and its preparation and application method
  • Cross-linked polystyrene microsphere immobilized tetramethylpiperidine nitroxide free radical catalyst and its preparation and application method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Example 1: In a four-neck flask, add 2.0 g of CPS microspheres and place them in 20 mL of chloroform, soak for 12 hours to fully swell the microspheres, add 2.6 g of AlCl 3 ; Use a constant pressure dropping funnel to slowly add 13 mL of chloroform solution dissolved with 2.2 mL of chlorobutyryl chloride dropwise, heat up to 75°C, react at a constant temperature for 5 hours, filter, wash the product microspheres with dilute hydrochloric acid, 1,4-dioxane and ethanol The microspheres were washed repeatedly, and then washed with distilled water until there was no chloride ion in the washing liquid, and dried in vacuum to constant weight to obtain the chlorobutyrylated microspheres CB-CPS. The bonding amount of chlorobutyryl on the surface of microsphere CB-CPS is 2.9 mmol / g.

[0022] In a four-neck flask, add 1.0 g of microspheres CB-CPS and 21 mL of DMF, soak for 12 h to fully swell the microspheres; weigh 2.1 g of 4-OH-TEMPO, dissolve it with 30 mL of DMF, add it to the...

Embodiment 2

[0023] Example 2: In a four-necked flask, add 1.9 g of CPS microspheres and place them in 22 mL of carbon tetrachloride, soak for 12 hours to fully swell the microspheres, add 2.6 g of SnCl 4 ; Use a constant pressure dropping funnel to slowly add 10 mL of carbon tetrachloride solution dissolved with 2.2 mL of chlorobutyryl chloride dropwise, raise the temperature to 75°C, react at a constant temperature for 5 hours, filter, wash the product microspheres with dilute hydrochloric acid, and 1,4-dioxane The microspheres were repeatedly washed with ring and ethanol, and then washed with distilled water until there was no chloride ion in the washing liquid, and dried in vacuum to constant weight to obtain the chlorobutyrylated microspheres CB-CPS. The bonding amount of chlorobutyryl groups on the surface of microspheres CB-CPS is 0.9 mmol / g.

[0024] In a four-necked flask, add 1.0 g of microspheres CB-CPS and 23 mL of dimethyl sulfoxide, soak for 12 hours to fully swell the micros...

Embodiment 3

[0025]Example 3: In a four-neck flask, add 2.1 g of CPS microspheres and place them in 25 mL of 1,4-dioxane, soak for 12 hours to fully swell the microspheres, add 2.4 g of AlCl 3 ; Slowly add 11 mL of 1,4-dioxane solution with 2.1 mL of chlorobutyryl chloride dropwise with a constant pressure dropping funnel, heat up to 70°C, react at constant temperature for 4 hours, filter, and wash the product microspheres with dilute sulfuric acid, 1,4 - Wash the microspheres with dioxane and ethanol several times, then wash them with distilled water until there is no chloride ion in the washing solution, and dry them in vacuum to constant weight to obtain the chlorobutyrylated microspheres CB-CPS. The bonding amount of chlorobutyryl on the surface of microsphere CB-CPS is 1.6 mmol / g.

[0026] In a four-neck flask, add 1.0 g of microspheres CB-CPS and 25 mL of N,N-dimethylacetamide, soak for 12 h to fully swell the microspheres; weigh 1.9 g of 4-OH-TEMPO, and use 32 mL of N, After dissol...

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Abstract

The invention specifically relates to a cross-linked polystyrene microsphere immobilized tetramethylpiperidine nitroxide radical catalyst and preparation and application methods thereof, belonging to the technical field of heterogeneous nitroxide radical catalysis. The catalyst and the preparation and application methods thereof in the invention overcome the problems that a tetramethylpiperidine nitroxide radical catalyst is difficult to recover and to cyclically use, product systems are hard to separate, etc. in the prior art. The preparation method for the catalyst comprises the following steps: with chlorobutyryl chloride (CBC) as a reagent, allowing the surface of a microsphere (CPS) to undergone a Friedel-Crafts acylation reaction under the catalysis of Lewis acid so as to prepare chlorobutyrylated microsphere CB-CPS; and subjecting the chlorobutyrylated microsphere CB-CPS and 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical (4-OH-TEMPO) to nucleophilic substitution so as to prepare the heterogeneous catalyst TEMPO / CPS. According to the invention, immobilization of TEMPO is realized and homogeneous catalytic oxidation is changed into polyphase catalytic oxidation, so thermal stability of the catalyst is improved, the catalyst can be easily separated from reaction mediums and is thus repeatedly used, and the catalyst is allowed to have novel catalysis characteristics, such as higher activity and selectivity.

Description

technical field [0001] The invention belongs to the technical field of heterogeneous nitrogen oxide free radical catalysis, in particular to a cross-linked polystyrene microsphere immobilized tetramethylpiperidine nitrogen oxide free radical catalyst and its preparation and application method. The catalyst is heterogeneous Catalyst, which is used to catalyze the oxidation of alcohols with molecular oxygen. Background technique [0002] In organic synthesis, the selective oxidation of alcohols to corresponding aldehydes or ketones is the most widely used large class of functional group conversion reactions, and occupies a very important position in fine chemical production. Traditional oxidation methods use stoichiometric strong inorganic oxidants such as CrO 3 and MnO 2 etc., but this method not only has high production costs, but more importantly, the synthesis process is often accompanied by the generation of a large amount of hazardous waste, which causes serious pollut...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/06C07C45/38C07C47/232C07C45/39C07C49/78
Inventor 王蕊欣高保娇谢美娜门吉英董婷婷王晓刚
Owner ZHONGBEI UNIV
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