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Immobilized bichiral ligand metal complex and its synthesis method and application

A technology of chiral ligands and tungsten complexes, applied in organic chemistry methods, chemical instruments and methods, organic compounds/hydrides/coordination complex catalysts, etc., can solve the problems of high cost, ignition, and complex synthesis of jacobsen catalysts and other problems, to achieve the effect of easy separation and easy regeneration

Active Publication Date: 2017-02-22
SHAYANG QINJIANG CHEM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] There are certain shortcomings in the above catalytic systems: the Sharpless catalyst is only effective for allyl alcohol, and the reaction needs to be strictly anhydrous, the synthesis of jacobsen catalyst is complicated, and the chirality of Shi Hongchang et al. Butyllithium is used in the synthesis of pyridyl alcohol, which is costly and easy to catch fire
[0007] The present invention has analyzed the catalyzer of Park, thinks that there is only one chiral ligand in its structure, can only provide two coordinations, although cheap and easy to get, However, there are also catalysts that are not resistant to water, hydrogen peroxide cannot be used as an oxidant, and the catalyst can only be effective once

Method used

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  • Immobilized bichiral ligand metal complex and its synthesis method and application
  • Immobilized bichiral ligand metal complex and its synthesis method and application
  • Immobilized bichiral ligand metal complex and its synthesis method and application

Examples

Experimental program
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Effect test

example 1

[0046] Example 1. Preparation of L-type immobilized bichiral ligands

[0047] Soak 50 grams of D311 macroporous anion exchange resin with 500ml 1mol / L NaOH overnight, filter, fully wash with purified water to pH 7.5, dry at 80°C for 5 hours, take 1 gram of dry resin, and measure its exchange equivalent as 7.5 mmol / g.

[0048] Add 10g of the above dry D311 resin, 50ml of toluene, 90mmol L-type methyl mandelate (14.9g) to the reaction bottle, heat at 110°C and reflux for 10 hours, cool to room temperature, filter, wash with 150ml of toluene, and dry at 80°C for 5 hours , to obtain 20 g of L-type immobilized bichiral ligands, whose L-type mandelic acid amide unit content is 3.85 mmol / g. The structural formula of the immobilized L-type chiral ligand is:

[0049] .

example 2

[0050] Example 2. Preparation of immobilized D-type chiral ligand

[0051] Add 10g of the above dry D311 resin, 50ml xylene, 80mmol D-methyl mandelate (13.3g) to the reaction bottle, heat at 120°C and reflux for 5 hours, cool to room temperature, filter, wash with 150ml xylene, and dry at 90°C After 5 hours, 20 g of immobilized D-type chiral ligands were obtained, and the content of D-mandelic acid amide units was 3.85 mmol / g. The structural formula of the immobilized D-type chiral ligand is:

[0052] .

[0053] 2. Preparation of immobilized chiral ligand metal complexes

[0054] Example 1: Preparation of immobilized L-type or D-type chiral ligand titanium complex

[0055] Add 20g of immobilized L-type or D-type chiral ligands, 100ml of chlorobenzene, 38.5mmol of isopropyl titanate (10.9g) into the reaction flask, react at 85°C for 2 hours, cool to room temperature, filter, and wash with 50ml of methanol , and dried at 70° C. for 5 hours to obtain 26.3 g of immobilized L...

example 3

[0066] Example 3, Preparation of immobilized L-type or D-type chiral ligand tungsten complexes

[0067] Add 20 grams of immobilized L-type or D-type chiral ligands, 100ml of isopropanol, and 3 grams of triethylamine into the reaction flask, cool to 0°C, add dropwise 38.5 mmol (14.6 grams) of tungsten hexachloride in chloroform ( 50ml) to control the dropping temperature at 10-15°C, after the dropwise addition, slowly raise the temperature to 45°C for 2 hours, cool to room temperature, add 5ml of water, stir for half an hour, filter, wash with 50ml of isopropanol, and dry at 50°C for 8 hours. 28.2 g of immobilized L-type or D-type chiral ligand tungsten complexes were obtained.

[0068] The structural formula of the immobilized L-type chiral ligand tungsten complex is:

[0069]

[0070] The structural formula of the immobilized D-type chiral ligand tungsten complex is:

[0071]

[0072] The chiral ligand unit (L-type or D-mandelic acid amide unit) on the immobilized chi...

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Abstract

The invention discloses an immobilized chiral ligand for production of a bichiral ligand complex and a synthetic method thereof, and is characterized in that the molecular structural formulas of L type and D type solid supported chiral ligands are shown in the specification; the immobilized chiral ligand has the following advantages: the immobilization method is simple; the immobilized chiral ligand can be applied to a variety of asymmetric synthesis objectives, a produced immobilized chiral ligand complex catalyst is easy to separate, and a disabled immobilized chiral ligand complex catalyst is easy to regenerate.

Description

technical field [0001] The invention relates to a synthesis method of a metal complex and its application in asymmetric synthesis, especially the application in the asymmetric epoxidation of olefins by catalyzing hydrogen peroxide. Background technique [0002] Chiral ligands and their metal complexes are widely used in asymmetric synthesis, such as asymmetric oxidation, asymmetric epoxidation, asymmetric hydrogenation, asymmetric addition, asymmetric Mannich reaction, etc. [0003] In order to achieve asymmetric epoxidation, people designed and synthesized many chiral ligands and their metal complexes. In 1980, K. Barry Sharpless prepared a catalyst by reacting D / L diethyl tartrate with titanate, using organic Peroxides such as TBHP are used as oxidizing agents to asymmetrically epoxidize allyl alcohol and obtain high ee values. In 1990, Jacobsen developed a class of chiral ligands called salen, which can catalyze the asymmetric epoxidation of non-functionalized alkenes af...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/22B01J31/40C07B53/00C07F9/655C07D301/12C07D303/48
CPCY02P20/584
Inventor 丁勇李斌许友兵张华锋
Owner SHAYANG QINJIANG CHEM
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