Chiral amino phenoxyl zinc and magnesium compound, and preparation method and application thereof

A technology of aminophenol oxyzinc and magnesium compounds, applied in the field of magnesium compounds and chiral aminophenoloxyzinc, which can solve the problems of high heterotactic selectivity and low selectivity

Inactive Publication Date: 2014-05-14
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 2009, Mehrkhodavandi combined a tridentate Schiff base ligand zinc ethyl complex containing chiral cyclohexanediamine structure, which has activity for racemic lactide, but the selectivity is very low (Organometallics, 2009 , 28, 1309)
As an environment-friendly polymer, people tend to use biocompatible metal complexes (zinc, magnesium, etc.) when synthesizing polylactide, but so far, zinc, magnesium, etc. Cyclopolymerization catalysts, racemic lactide only show high heteroselectivity, catalysts with high isotactic selectivity have not been reported

Method used

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  • Chiral amino phenoxyl zinc and magnesium compound, and preparation method and application thereof
  • Chiral amino phenoxyl zinc and magnesium compound, and preparation method and application thereof
  • Chiral amino phenoxyl zinc and magnesium compound, and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] Synthesis of Ligand L1

[0047] Add 1.22 g of benzaldehyde, 30 mL of absolute ethanol, and 1.28 g of (S)-1-ethyl-2-aminomethyltetrahydropyrrole into a 100 mL eggplant-shaped bottle, and heat to reflux for 24 hours. Add 0.76 g of sodium borohydride, stir for 3 hours, pour into water, extract the organic phase with dichloromethane, dry over anhydrous magnesium sulfate, and remove the solvent to obtain a light yellow viscous liquid. Add 30 mL of absolute ethanol, 0.6 g of paraformaldehyde, and 1.63 g of 2,4-dichlorophenol, and heat to reflux for 12 hours. The crude product was separated by column chromatography on silica gel to obtain red liquid L1 (2.32 g, 59.0%).

[0048]

[0049] 1 H NMR (400MHz, CDCl 3 ): δ7.22(m, 6H), 6.83(d, 4 J=2.4Hz), 3.84(d, 2 J=14.0Hz, 1H), 3.65(d, 2 J=13.0Hz, 1H), 3.53(d, 2 J=14.0Hz, 1H), 3.39(d, 2 J=13.0Hz, 1H), 3.06(m, 1H), 2.80-2.70(m, 1H), 2.60-2.50(m, 2H), 2.60-2.50(m, 1H), 2.21-2.08(m, 2H) , 2.01-1.94(m, 1H), 1.71-1.63(m, 2H), ...

Embodiment 2

[0051] Synthesis of Ligand L2

[0052] Add 1.22 g of benzaldehyde, 30 mL of absolute ethanol, and 1.28 g of (S)-1-ethyl-2-aminomethyltetrahydropyrrole into a 100 mL eggplant-shaped bottle, and heat to reflux for 24 hours. Add 0.76 g of sodium borohydride, stir for 3 hours, pour into water, extract the organic phase with dichloromethane, dry over anhydrous magnesium sulfate, and remove the solvent to obtain a light yellow viscous liquid. Add 30 mL of absolute ethanol, 0.6 g of paraformaldehyde, and 2.06 g of 2,4-di-tert-butylphenol, and heat to reflux for 12 hours. The crude product was separated by column chromatography on silica gel to obtain a colorless transparent liquid L2 (1.95 g, 44.7%).

[0053]

[0054] 1 H NMR (400MHz, CDCl 3 ): δ10.55(s, 1H), 7.35-7.23(m, 5H), 7.18(s, 1H), 6.85(s, 1H), 3.97(d, J=13.4Hz, 1H), 3.75(d, J=13.0Hz, 1H), 3.51(d, 2 J=13.4Hz, 1H), 3.37(d, 2J=13.0Hz, 1H), 3.09-3.02(m, 1H), 2.71-2.63(m, 1H), 2.50-2.38(m, 3H), 2.11-2.01(m, 1H), 2.03-1.8...

Embodiment 3

[0056] Synthesis of Ligand L3

[0057] Add 1.22 g of benzaldehyde, 30 mL of absolute ethanol, and 1.28 g of (S)-1-ethyl-2-aminomethyltetrahydropyrrole into a 100 mL eggplant-shaped bottle, and heat to reflux for 24 hours. Add 0.76 g of sodium borohydride, stir for 3 hours, cool to room temperature, pour into water, extract the organic phase with dichloromethane, dry over anhydrous magnesium sulfate, and remove the solvent to obtain a light yellow viscous liquid. Add 30 mL of absolute ethanol, 0.6 g of paraformaldehyde, and 3.30 g of 2,4-dicumylphenol, and heat to reflux for 12 hours. The crude product was separated by column chromatography on silica gel to obtain light brown liquid L3 (3.41 g, 60.9%).

[0058]

[0059] 1 H NMR (400MHz, CDCl 3 ): δ7.16(d, J=12.6Hz, 17H), 6.66(d, J=1.8Hz, 1H), 3.80(d, 2 J=13.6Hz, 1H), 3.46(d, 2 J=13.8Hz, 1H), 3.33(d, 2 J=13.6Hz, 1H), 3.13(d, 2 J=12.8Hz), 2.97-2.86(m, 1H), 2.55(dq, J=14.7, 7.3Hz, 1H), 2.28(dt, J=15.7, 7.9Hz, 3H), 2.01-1...

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Abstract

The invention discloses a chiral amino phenoxyl zinc and magnesium compound, a preparation method of the chiral amino phenoxyl zinc and magnesium compound, and application of the chiral amino phenoxyl zinc and magnesium compound in ring opening polymerization of catalytic lactone with high activity and high selectivity. The preparation method comprises the following steps: directly reacting a neutral ligand with a metal raw material compound in an organic medium; performing filtration, concentration and re-crystallization to obtain a target compound. The chiral amino phenoxyl zinc and magnesium compound is an efficient lactone ring opening polymerization and can be applied to polymerization reaction of catalytic lactide and the like; particularly, high-isotacticity or high-heterotacticity polylactic acid can be obtained for racemization lactide. The chiral amino phenoxyl zinc and magnesium compound has the obvious advantages that raw materials are easily obtained; a synthetic route is simple; high product yield, high catalytic activity and high stereo selectivity are realized; a high-regularity and high-molecular-weight polymer material can be obtained; requirements of industrial departments can be met. A structural formula is shown as (img file='DSA00000897420700011.TIF' wi='860'he='608' / ).

Description

technical field [0001] The invention relates to a class of chiral aminophenol oxy zinc and magnesium compounds and the application of such compounds in lactone polymerization. Background technique [0002] As a class of polymers that can replace traditional polymer materials (polyolefins), aliphatic polyesters have attracted extensive attention due to their good biocompatibility and degradability. Aliphatic polyesters that have been extensively studied include polylactic acid, polycaprolactone, and polybutyrolactone. Among them, polylactic acid can be degraded by microorganisms in nature and participate in the carbon cycle of nature, which is an environmentally friendly polymer. The biocompatibility and excellent processability of polylactic acid make it the most promising aliphatic polyester, which is mainly used in industrial and agricultural production and biomedicine (such as slow-release materials for drugs, medical suture materials, etc.). In recent years, polylactic...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D207/09C07F7/10C07F19/00C08G63/83C08G63/08
CPCC07D207/09C07F3/003C07F7/0812C07F7/10C08G63/08C08G63/823C08G63/83
Inventor 马海燕王号兵
Owner EAST CHINA UNIV OF SCI & TECH
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