Nanogel modified by ionic liquid and loaded with chiral catalyst and preparing method and application thereof

A chiral catalyst, ionic liquid technology, applied in chemical instruments and methods, preparation of organic compounds, catalysts for physical/chemical processes, etc., can solve the problems of difficult recovery of homogeneous reactions and expensive chiral catalysts, and improve catalytic activity. , the effect of adjustable size and high conversion rate

Inactive Publication Date: 2015-12-09
HENAN NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0002] Chiral catalysts exhibit high activity, high enantioselectivity, high conversion and mild reaction conditions in organic synthesis reactions, especially in asymmetric catalysis, but chiral catalysts are relatively expensive. In the previous catalytic system, it was a homogeneous reaction and it was difficult to recover. Therefore, the use of polymer-loaded chiral catalysis with hydrophobic and hydrophilic parts is a better solution.

Method used

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  • Nanogel modified by ionic liquid and loaded with chiral catalyst and preparing method and application thereof
  • Nanogel modified by ionic liquid and loaded with chiral catalyst and preparing method and application thereof
  • Nanogel modified by ionic liquid and loaded with chiral catalyst and preparing method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Preparation of O-methacryloyl-L-hydroxyproline chiral monomer:

[0022] (1) Preparation of O-methacryloyl-L-hydroxyproline hydrochloride:

[0023] Add 30mL of trifluoroacetic acid into a 100mL round-bottomed flask, add 6g of L-hydroxyproline in batches in an ice-water bath, stir and react at room temperature for 3 hours, and wait until the L-hydroxyproline is completely dissolved, then place in an ice-water bath Add 9.6mL of newly prepared methacryloyl chloride, react at room temperature for 3 hours, stir magnetically, slowly add cold diethyl ether dropwise to the reaction bottle, a white substance will precipitate, filter it with suction and wash it with diethyl ether three times, and dry the product in a drying oven to obtain a white powder shape substance.

[0024] (2) Preparation of O-methacryloyl-L-hydroxyproline:

[0025] Weigh 3.97g of O-methacryloyl-L-hydroxyproline hydrochloride and add it to a 250mL round bottom flask, add 4.4mL triethylamine, 100mL dichloro...

Embodiment 2

[0029] Preparation of proline derivative monomer:

[0030] Preparation of chiral monomer N-p-vinylbenzenesulfonyl-L-prolineamide: add 85mL tetrahydrofuran, 2.50g L-proline, 1.23g p-vinylbenzenesulfonamide, 3.52g 4-dimethylamino Pyridine and 5.04g of dicyclohexylcarbodiimide, stirred at room temperature for 48h, then added 8g of protonated Amberlyst-15, 20mL of ethyl acetate, and continued to stir for 5h, a large amount of white precipitate was produced, and the precipitate was filtered off with a silica gel column, acetic acid After washing with ethyl ester, the resulting solution was concentrated by rotary evaporation, precipitated twice in ether, filtered, dried under vacuum at 30°C, and weighed to obtain 0.7334 g of the product, with a yield of 30%.

[0031] Preparation of proline derivative nanogels:

[0032] Weigh the chiral monomer N-p-vinylbenzenesulfonyl-L-prolinamide (0.2mmol, 0.056g), imidazole ionic liquid (n=7 and X=Br - ) (0.1005mmol, 0.02163g), sodium dodecylsu...

Embodiment 3

[0034] Add the nanogel ball of the load chiral catalyst that the embodiment 1 that adds the amount of substrate p-nitrobenzaldehyde 20% as catalyst 4.9mg, 0.1mmol p-nitrobenzaldehyde, 1mL cyclohexanone and 1 mL DMF / H 2 O (v / v, 95 / 5), reacted at room temperature for 48 hours, and tracked the reaction to the end point by thin-layer chromatography. After the reaction was completed, centrifuged, the supernatant was extracted three times with ethyl acetate (3×10mL), and the organic phases were combined. MgSO 4 Drying, suction filtration, concentration, CDCl 3The conversion rate was calculated by solvent proton nuclear magnetic resonance spectroscopy. The measured conversion rate was 99%, and the anti / syn was 95 / 5. The pure product was obtained by column chromatography (petroleum ether: ethyl acetate = 4:1), and was passed through AD- H chiral column separation chiral substance, high performance liquid chromatography (HPLC) records ee value to be 95%, and reaction equation is as f...

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Abstract

The invention discloses nanogel modified by ionic liquid and loaded with a chiral catalyst and a preparing method and application thereof. The nanogel is characterized in that polymerization of functional monomers, a crosslinking agent, sodium dodecyl sulfate, chiral monomers and the imidazolium ionic liquid is initiated by initiator ammonium persulfate in solvent water to form a crosslinking copolymer, and the nanogel modified by the ionic liquid and loaded with the chiral catalyst is obtained through dialysis. The invention further discloses the preparing method of the nanogel modified by the ionic liquid and loaded with the chiral catalyst and application of the nanogel to an asymmetric Aldol reaction. The ionic liquid is introduced into preparation of chiral nanometer hydrogel, and a simple and effective path is provided for preparing a novel chiral catalyst which is high in catalytic activity and selectiveness, easy to separate, capable of being used repeatedly in an aqueous solution.

Description

technical field [0001] The invention belongs to the technical field of synthesis of polymer chiral catalysts, and in particular relates to an ionic liquid-modified nanogel loaded with chiral catalysts, a preparation method and application thereof. Background technique [0002] Chiral catalysts have the characteristics of high activity, high enantioselectivity, high conversion and mild reaction conditions in organic synthesis reactions, especially in asymmetric catalysis, but chiral catalysts are relatively expensive. In the previous catalytic system, it was a homogeneous reaction and it was difficult to recover. Therefore, the use of polymer-loaded chiral catalysis with hydrophobic and hydrophilic parts is a better solution. [0003] Nanogels have unique advantages, such as non-toxicity, adjustable size, large specific surface area and internal network structure, so nanogels can be used as nanoreactors to effectively support metal catalysts, and their special network structu...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F220/06C08F222/14C08F222/38C08F212/14C08F220/34C08F226/06B01J31/06C08J3/075C07C201/12C07C205/45
CPCY02P20/54
Inventor 李新娟吕春娜贾献彬胡志国朱双营
Owner HENAN NORMAL UNIV
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