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2-substituted thiazole-4-yl-containing aminophenol oxygroup zinc complex as well as preparation method and application of 2-substituted thiazole-4-yl-containing aminophenol oxygroup zinc complex

A technology of aminophenoloxyzinc and aminophenol, which is applied in the field of aminophenoloxyzinc complexes, can solve the problems of low catalytic activity, no stereoselectivity, and needs to be further deepened

Active Publication Date: 2021-08-17
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 2014, Du's research team combined a series of β-diimine-like zinc complexes derived from ortho-substituted oxazoles, which catalyzed the polymerization of rac-LA to obtain multi-block isotactic polylactide (P m =0.77-0.91), the highest isotactic selectivity P m =0.91, but the catalytic activity is very low (ACS MacroLett.2014,3,689)
In 2016, the Williams research group designed and synthesized a series of macrocyclic dinuclear zinc complexes, which have very high activity for catalyzing racemic lactide, TOF=60000h -1 , but no stereoselectivity (Angew.Chem.Int.Ed.2016,128,1-7)
Although there are currently some zinc catalysts that can achieve high activity and isotactic selective ring-opening polymerization of racemic lactide, their performance is still not ideal
Therefore, the research and development of catalysts with high activity, high isotactic selectivity, and good tolerance to impurities for lactide ring-opening polymerization still needs to be further deepened.

Method used

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  • 2-substituted thiazole-4-yl-containing aminophenol oxygroup zinc complex as well as preparation method and application of 2-substituted thiazole-4-yl-containing aminophenol oxygroup zinc complex
  • 2-substituted thiazole-4-yl-containing aminophenol oxygroup zinc complex as well as preparation method and application of 2-substituted thiazole-4-yl-containing aminophenol oxygroup zinc complex
  • 2-substituted thiazole-4-yl-containing aminophenol oxygroup zinc complex as well as preparation method and application of 2-substituted thiazole-4-yl-containing aminophenol oxygroup zinc complex

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] Ligand L 1 Synthesis of H:

[0046] (1) Synthesis of N-[(2-phenylthiazol-4-yl)methyl]n-hexylamine

[0047]

[0048] Dissolve 2-phenyl-4-chloromethylthiazole (10.7mmol, 2.24g) in 30mL dry DMF, add n-hexylamine (107mmol, 14mL), and finally add anhydrous K 2 CO 3 (11.8mmol, 1.63g), the reaction was stirred overnight. Quench the reaction with water, extract with ethyl acetate, wash the organic phase with saturated brine, then dry with anhydrous sodium sulfate, spin off the solvent to obtain a yellow oily mixture, and remove excess n-hexylamine under reduced pressure at 110°C / 8mmHg to obtain brown Crude product of red transparent oily liquid.

[0049] The purity is greater than 95%, and the yield is about 80%

[0050] (2) Ligand L 1 Synthesis of H

[0051] In a 100mL round bottom flask, add the above secondary amine (2.35g, about 8.56mmol), anhydrous K 2 CO 3 (1.3g, 9.4mmol), dissolved in 30mL DMF, added 2-bromomethyl-4-methyl-6-tritylphenol (4.2g, 9.0mmol), and ...

Embodiment 2

[0055] Ligand L 2 Synthesis of H

[0056] (1) Synthesis of N-[(2-phenylthiazol-4-yl)methyl]benzylamine

[0057]

[0058] Except that benzylamine (21.8mL, 200mmol), potassium carbonate (3.0g, 22mmol) and 2-phenyl-4-chloromethylthiazole (4.2g, 20mmol) were used as raw materials, other operating steps were the same as in Example 1. Excess benzylamine was removed under reduced pressure and heating (100° C. / 8 mmHg) to obtain 4.5 g of a brownish-red transparent liquid as a crude product with a purity greater than 95% and a yield of about 80%.

[0059] (2) Ligand L 2 Synthesis of H

[0060]N-[(2-phenylthiazol-4-yl)methyl]benzylamine (4.48g, about 16mmol), anhydrous potassium carbonate (2.43g, 17.6mmol) and 2-bromomethyl-4- Except for methyl-6-tritylphenol (7.54g, 17mmol), other operations were the same as in Example 1, and recrystallized from dichloromethane and methanol to obtain a white solid powder (5.9g, 57%).

[0061]

[0062] 1 H NMR (400MHz, CDCl 3 ):δ10.57(br s,1...

Embodiment 3

[0064] Ligand L 3 Synthesis of H

[0065] (1) Synthesis of N-[(2-tert-butylthiazol-4-yl)methyl]n-hexylamine

[0066]

[0067] Except that n-hexylamine (21.0 mL, 164 mmol), potassium carbonate (2.5 g, 18 mmol) and 2-tert-butyl-4-chloromethylthiazole (3.12 g, 16.4 mmol) were used as raw materials, other operating steps were the same as in Example 1. Excess n-hexylamine was removed under reduced pressure and heating (110° C. / 8 mmHg) to obtain 3.0 g of a brown-red transparent oil with a purity of more than 95% and a yield of about 71%.

[0068] (2) Ligand L 3 Synthesis of H

[0069] In addition to raw materials, N-[(2-tert-butylthiazol-4-yl)methyl]n-hexylamine (3.0g, about 11.7mmol), anhydrous potassium carbonate (1.8g, 12.9mmol) and 2-bromomethyl -Except for 4-methyl-6-tritylphenol (5.3g, 12.0mmol), other operations were the same as in Example 1, and recrystallized from petroleum ether and methanol to obtain a white solid (5.2g, 73%).

[0070]

[0071] 1 H NMR (400MHz...

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Abstract

The invention discloses a 2-substituted thiazole-4-yl-containing aminophenol oxygroup zinc complex as well as a preparation method and application of the 2-substituted thiazole-4-yl-containing aminophenol oxygroup zinc complex in catalysis of lactone ring opening polymerization. The preparation method comprises the following steps: directly reacting a neutral ligand with a metal raw material compound in an organic medium, and then filtering, concentrating and recrystallizing to obtain a target compound. The 2-substituted thiazole-4-yl-containing aminophenol oxygroup zinc complex provided by the invention is an efficient lactone ring-opening polymerization catalyst, and can be used for catalyzing the polymerization reaction of lactide and other lactones; particularly, the complex has a good catalytic effect on racemic lactide polymerization. The complex has the obvious advantages that the raw materials are easy to obtain, the synthesis route is simple, the product yield is high, the catalytic activity and stereoselectivity are high, a high-regularity and high-molecular-weight polyester material can be obtained, and the requirements of industrial departments can be met. The structural formula is shown in the specification.

Description

technical field [0001] The present invention relates to a class of 2-substituted thiazol-4-yl aminophenoxy zinc complexes and the application of such complexes in lactone polymerization. Background technique [0002] Polymer materials are widely used in all aspects of production and life due to their superior physical and mechanical properties, low price, safety and reliability. However, polyolefin materials, the most widely used polymer materials, cannot be biodegraded, causing serious pollution problems. In addition, the extensive use of polyolefin materials has accelerated the consumption of non-renewable petroleum resources. As a biodegradable polymer material, polylactide (also known as polylactic acid) has renewable raw materials, and the material itself has excellent physical, mechanical and processing properties. It is considered to have the most potential in disposable products, packaging industry, fiber Replace petroleum-based polymers in fields such as industry ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D277/28C07F7/10C08G63/83C08G63/08C08G64/30
CPCC07D277/28C07F7/10C08G63/83C08G63/823C08G63/08C08G64/30
Inventor 马海燕邵猛
Owner EAST CHINA UNIV OF SCI & TECH
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