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Pentaerythritol-immobilized quinine catalyst as well as preparation method and application thereof

A technology for pentaerythritol and pentaerythritol benzene sulfonate is applied in the field of pentaerythritol-supported quinine catalyst and preparation thereof, can solve the problems of slow reaction speed, reduced catalytic activity and stereoselectivity, etc., and achieves high yield and simple synthesis route , the effect of constant catalytic activity

Active Publication Date: 2018-01-09
东营睿港招商服务有限责任公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, this method of catalyst immobilization also has limitations. The main one is that when a homogeneous catalyst is immobilized on an insoluble polymer, its catalytic activity and stereoselectivity are often reduced to a large extent. The reaction is carried out in the phase, and the reaction rate is generally slower than that of the homogeneous reaction due to mass transfer.

Method used

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  • Pentaerythritol-immobilized quinine catalyst as well as preparation method and application thereof
  • Pentaerythritol-immobilized quinine catalyst as well as preparation method and application thereof
  • Pentaerythritol-immobilized quinine catalyst as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] The preparation of the quinine catalyst supported by pentaerythritol:

[0023] Add 2.04g (10.7mmol) of p-toluenesulfonyl chloride into a 250mL reaction flask, add 13mL of dry pyridine, stir at room temperature until all the solids are dissolved, cool the system to about 5°C in an ice bath, and add 0.34g (2.5 mmol) monopentaerythritol, stirred at room temperature for 8h. Add 50mL of water to the system, react for 2h, filter with suction, wash the solid with water, dissolve in dichloromethane, and precipitate with methanol to obtain 1.45g of pentaerythritol sulfonate in the form of white powder, with a yield of 78%. Mp: 148.5-150°C.

[0024] With 752mg (1mmol) pentaerythritol sulfonate, 546mg (4.4mmol) p-hydroxybenzyl alcohol and 1.43g (4.4mmol) Cs 2 CO 3 Add to 10mL dry DMF, react at 60°C for 24h, filter, evaporate the solvent under reduced pressure, add 10mL CH 2 Cl 2 Dissolved, washed with saturated brine, dried, concentrated, and purified by column chromatography...

Embodiment 2

[0028] (1R,2S )-1-phenyl-2-benzoyloxirane preparation:

[0029] Add 500mg (2.4mmol) styryl benzophenone, 53mg (0.024mmol) pentaerythritol-supported quinine and 0.03mL Span-20 into 7mL diisopropyl ether, stir, and add 30% H 2 o 2 (2.7mL, 24mmol) and 50% KOH (0.27mL, 2.4mmol) aqueous solution, stirred vigorously, reacted at room temperature for 4h, concentrated under reduced pressure to half of the original volume, added diethyl ether, precipitated, filtered, washed with diethyl ether, and dried in vacuo , Recover the catalyst, the recovery rate is 97%. The filtrate was washed with water, dried, filtered, concentrated under reduced pressure, and purified by column chromatography to obtain (1R,2S )-1-phenyl-2-benzoyloxirane. Yield: 95%, ee: 99.5%.

Embodiment 3

[0031] ( 1R,2S )-1-(2'-fluorophenyl)-2-benzoyloxirane preparation:

[0032] Replace 500mg (2.4mmol) styryl benzophenone with 542mg (2.4mmol) 2-fluorostyryl benzophenone, replace 0.03mL Span-20 with 0.03mL Tween-20, other operations are the same as in Example 2, get( 1R,2S )-1-(2’-fluorophenyl)-2-benzoyloxirane, yield 97%, ee: 99.7%.

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Abstract

The invention discloses a pentaerythritol-immobilized quinine catalyst as well as a preparation method and application thereof. The structure of the pentaerythritol-immobilized quinine catalyst is asshown in a formula (I). The preparation method of the pentaerythritol-immobilized quinine catalyst comprises the following steps of a, enabling pentaerythritol to react with para-toluene sulfochlorideto prepare pentaerythritol besilate; afterwards, reacting with p-hydroxybenzyl alcohol in an alkaline condition to prepare an intermediate (1); b, under the action of pyridine, enabling the intermediate (1) to react with phosphorus tribromide, so as to prepare an intermediate (2); c, enabling the intermediate (2) to react with quinine, so as to prepare the pentaerythritol-immobilized quinine catalyst. The pentaerythritol-immobilized quinine catalyst can be applied to the asymmetric epoxidation reaction of chalcone, and the catalyst is separated and purified simply, and can be repeatedly recycled. The formula (I) is shown in the description.

Description

technical field [0001] The invention relates to the field of catalytic organic synthesis, in particular to a pentaerythritol immobilized quinine catalyst and its preparation method and application. Background technique [0002] Cinchona alkaloids are used as chiral catalysts, ligands, NMR recognition reagents, etc., all of which are directly related to asymmetric synthesis. In fact, many important asymmetric syntheses can be realized by using naginina alkaloids as ligands, catalysts or acceptors. In recent years, polymer-supported cinchona alkaloids have received more and more attention based on people's requirements for catalyst recovery and recycling. [0003] The immobilization of the catalyst can be achieved by covalently linking the homogeneous catalyst on the insoluble polymer carrier. The advantages of this method are obvious: since the catalyst is immobilized on the insoluble polymer carrier, the separation of the catalyst and the reaction system can be achieved by...

Claims

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Application Information

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IPC IPC(8): B01J31/02C07D519/00C07D301/12C07D303/32
Inventor 张宝华张冀男史兰香刘斯婕
Owner 东营睿港招商服务有限责任公司
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