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Immobilized bichiral ligand metal complex and synthetic method and application thereof

A metal complex, chiral technology, applied in organic chemistry methods, chemical instruments and methods, organic compounds/hydrides/coordination complex catalysts, etc., can solve problems such as high cost, inability to use hydrogen peroxide, fire, etc. Achieve the effect of easy regeneration, simple and easy immobilization method, and easy separation

Active Publication Date: 2014-12-31
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 synthetic method and application thereof
  • Immobilized bichiral ligand metal complex and synthetic method and application thereof
  • Immobilized bichiral ligand metal complex and synthetic method and application thereof

Examples

Experimental program
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Effect test

example 1

[0037] Example 1. Preparation of L-type immobilized bimanual ligand

[0038] Soak 50 grams of D311 macroporous anion exchange resin with 500ml 1mol / L NaOH overnight, filter, and wash thoroughly with purified water to pH 7.5, 80 0 Dry at C for 5 hours, take 1 gram of dry resin, and measure its exchange equivalent to 7.5 mmol / g.

[0039] Add 10g of the above dry D311 resin, 50ml of toluene, 90mmol L-type methyl mandelic acid (14.9g) into the reaction flask, heat it to reflux at 110°C for 10 hours, cool to room temperature, filter, and wash with 150ml of toluene. 0 C was dried for 5 hours to obtain 20 g of L-type immobilized bimanual ligand, the content of L-type mandelic acid amide unit was 3.85 mmol / g. The structural formula of the L-type immobilized bimanual ligand is:

[0040]

example 2

[0041] Example 2. Preparation of D-type immobilized bimanual ligand

[0042] Add 10 grams of the above dry D311 resin, 50ml xylene, 80mmol D-mandelic acid methyl ester (13.3g) into the reaction flask, heat it to reflux at 120°C for 5 hours, cool to room temperature, filter, wash with 150ml xylene, 90 0 C was dried for 5 hours to obtain 20 g of D-type immobilized bimanual ligand, the content of D-mandelic acid amide unit was 3.85 mmol / g. The structural formula of the L-type immobilized bimanual ligand is:

[0043]

[0044] 2. Preparation of immobilized bimanual ligand metal complex

[0045] Example 1: Preparation of L-type or D-type immobilized bimanual ligand titanium complex

[0046] Add 20g of L-type or D-type immobilized bimanual ligand, 100ml of chlorobenzene, 38.5mmol (10.9g) of isopropyl titanate, 85 to the reaction flask 0 C react for 2 hours, cool to room temperature, filter, wash with 50ml methanol, 70 0 C was dried for 5 hours to obtain 26.3 grams of L-type or D-type i...

example 3

[0055] Example 3. Preparation of L-type or D-type immobilized two-handed ligand tungsten complex

[0056] Add 20g of L-type or D-type immobilized bimanual ligand, 100ml of isopropanol, 3g of triethylamine to the reaction flask, and cool to 0 0 C, 38.5mmol (14.6g) of tungsten hexachloride solution (50ml) in chloroform was added dropwise to control the temperature of 10-15 0 C, slowly warm up to 45 after dropping 0 C react for 2 hours, cool to room temperature, add 5ml water, stir for half an hour, filter, wash with 50ml isopropanol, 50ml 0 C was dried for 8 hours to obtain 28.2 grams of L-type or D-type immobilized bimanual ligand tungsten complex. The structural formula of the L-type immobilized bimanual ligand tungsten complex is:

[0057]

[0058] The structural formula of D-type immobilized bimanual ligand tungsten complex is:

[0059]

[0060] The chiral ligand unit (L-type or D-mandelic acid amide unit) of the immobilized bimanual ligand forms a complex with a molar r...

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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 present invention relates to a method for synthesizing a metal complex and its application in asymmetric synthesis, especially its application in catalyzing the asymmetric epoxidation of olefins by 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 and so on. [0003] In order to achieve asymmetric epoxidation, people designed and synthesized many chiral ligands and their metal complexes. In 1980, K. Barry Sharpless used D / L diethyl tartrate and titanate to react to prepare a catalyst, using organic Peroxide, such as TBHP, acts as an oxidant to cause asymmetric epoxidation of allyl alcohol and achieve a high ee value. In 1990, Jacobsen developed a class of chiral ligands called salen, which can catalyze the asymmetric epoxidation of non-functiona...

Claims

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Application Information

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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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