Oxazoline ring-containing amino tocopheroxyl zinc/magnesium complexes and preparation method and application thereof

A kind of aminophenoloxyzinc, oxazoline-containing technology, applied in magnesium organic compounds, zinc organic compounds, organic chemistry and other directions, can solve the problems of low selectivity, reduced catalytic activity and the like

Active Publication Date: 2016-01-13
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 a chiral cyclohexanediamine structure, which has activity for racemic lactide, but the selectivity is very low (Organometallics, 2009 ,28,1309)
In 2013, Otero reported a chiral heteroscorpion-type zinc complex containing a phenocene ligand, which obtained a moderately isotactic polymer (P m =0.77) (Organometallics, 2013, 32, 3437)
At present, although individual zinc complexes show high isotactic selectivity to racemic lactide, their catalytic activity is much lower than that of general zinc complexes; while magnesium complexes catalyze the polymerization of racemic lactide to obtain only Polylactide with high heterotactic or partial isotactic tendency

Method used

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  • Oxazoline ring-containing amino tocopheroxyl zinc/magnesium complexes and preparation method and application thereof
  • Oxazoline ring-containing amino tocopheroxyl zinc/magnesium complexes and preparation method and application thereof
  • Oxazoline ring-containing amino tocopheroxyl zinc/magnesium complexes and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0052] Synthesis of Ligand L1:

[0053] (1) Synthesis of N-[(4R)-2-methylene-4-phenyloxazoline]benzylamine

[0054]

[0055] Add benzylamine (8.21g, 76.6mmol) and potassium carbonate (1.17g, 8.47mmol) in the reaction flask, (4R)-2-chloromethyl-4-phenyl-2-oxazoline (1.50g, 7.66mmol ) and 25mLN,N-dimethylformamide, reacted for 12 hours. The solvent and unreacted benzylamine were distilled off under reduced pressure to obtain an orange-red oil. It is directly used in the next reaction, and the yield is calculated at 80%.

[0056] (2) Synthesis of Ligand L1

[0057]N-[(4R)-2-methylene-4-phenyloxazoline]benzylamine (2.23g, 6.70mmol), potassium carbonate (1.39g, 9.84mmol), 2-bromomethyl -4,6-dichlorophenol (2.55g, 9.96mmol) and 20mL N,N-dimethylformamide were reacted at room temperature for 2 hours. Add water to quench the reaction, extract with ethyl acetate, combine the organic phases, dry over anhydrous magnesium sulfate, filter, evaporate the solvent under reduced pressu...

Embodiment 2

[0061] Synthesis of Ligand L2

[0062] N-[(4R)-2-methylene-4-phenyloxazoline]benzylamine (1.50g, 4.51mmol), potassium carbonate (0.856g, 6.19mmol) and 2-bromomethyl- Except for 4,6-di-tert-butylphenol (1.11g, 3.71mmol), other operating steps were the same as in Example 1. Separation and purification by column chromatography gave light yellow foam L2 (1.01 g, 56%).

[0063]

[0064] 1 HNMR (CDCl 3 ,400MHz,298K):δ10.12(s,1H,OH),7.37–7.25(m,11H,ArH),6.91(d,1H, 4 J=2.4Hz, ArH), 5.23 (pesudot, 1H, 3 J=9.2Hz,CH 2 O),4.63(dd,1H, 3 J=8.4Hz, 2 J=10.4Hz,CH 2 O),4.12(t,1H, 3 J=8.4Hz, CHN), 4.00(s, 2H, ArCH 2 ),3.76(s,2H,PhCH 2 ),3.44(ddd,2H, 4 J=0.8Hz, 2 J=15.6Hz, 2 J=16.0Hz, NCH 2 C=N),1.46(s,9H,C(CH 3 ) 3 ),1.29(s,9H,C(CH 3 ) 3 ). 13 CNMR (CDCl 3 ,100MHz,298K):δ165.4,154.1,142.0,140.8,137.1,136.0,129.7,128.9,128.6,127.7,126.7,124.4,123.4,121.3,74.7,69.7,58.8,57.5,13.4,34.8,35. 29.8. Anal. Calcd. ForC 32 h 40 N 2 o 2 : C, 79.30; H, 8.32; N, 5.78. Found: C, 7...

Embodiment 3

[0066] Synthesis of Ligand L3

[0067] N-[(4R)-2-methylene-4-phenyloxazoline]benzylamine (4.95g, 14.9mmol), potassium carbonate (2.80g, 20.3mmol) and 2-bromomethyl- Except for 4,6-dicumylphenol (12.98g, calculated based on a yield of 50%, the actual raw material content is about 10.38g, 15.3mmol), the other operating steps are the same as in Example 1. Separation and purification by column chromatography gave light yellow foam L3 (2.12g, 23.4%).

[0068]

[0069] 1 HNMR (CDCl 3 ,400MHz,298K):δ9.79(s,1H,OH),7.34–7.11(m,19H,ArH),6.97-6.95(m,2H,ArH),6.79(d,1H, 4 J=2.0Hz, ArH), 5.15 (pesudot, 1H, 3 J=9.2Hz,CH 2 O),4.53(dd,1H, 3 J=8.4Hz, 2 J=10.4Hz,CH 2 O),4.02(t,1H, 3 J=8.4Hz, CHN), 3.84(s, 2H, ArCH 2 ),3.55(d,2H, 4 J=1.6Hz, PhCH 2 ),3.27(s,2H,NCH 2 C=N),1.69(s,12H,PhC(CH 3 ) 2 ). 13 CNMR (CDCl 3 ,100MHz,298K):δ165.0,153.6,151.6,151.5,142.0,140.2,136.8,135.5,130.0,128.8,128.5,128.0,127.8,127.6,127.5,126.9,126.6,126.5,125.5,125.8 121.5, 74.5, 69.5, 58.5, 56.5, ...

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Abstract

The invention discloses oxazoline ring-containing amino tocopheroxyl zinc / magnesium complexes and a preparation method and an application thereof in high-activity and high-selectivity catalysis of lactone ring-opening polymerization. The preparation method includes the following steps: directly carrying out a reaction of a neutral ligand with a metal raw material compound in an organic medium, carrying out filtration, concentration and recrystallization steps to obtain the target compounds. The oxazoline ring-containing amino tocopheroxyl zinc / magnesium complexes are efficient lactone ring-opening polymerization catalysts, and can be used for catalyzing a polymerization reaction of lactones such as lactide; especially for rac-lactide, higher-isotacticity polylactic acid can be obtained. The oxazoline ring-containing amino tocopheroxyl zinc / magnesium complexes have quite obvious advantages that raw materials are easily available, the synthetic route is simple, the product yield is high, and the complexes have quite high catalytic activity and stereoselectivity, can obtain higher-isotacticity high-molecular-weight polyester materials, and can meet the needs of industrial departments. The complexes have the structural formula described in the description.

Description

technical field [0001] The invention relates to a class of oxazoline ring-containing aminophenoxyzinc and magnesium complexes and the application of the complexes in lactone polymerization. Background technique [0002] As a class of polymers that can replace traditional polyolefin materials, 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 in 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.). Lactide with low raw mat...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F3/06C07F3/02C07D263/10C07D263/56C07D263/52C08G63/08C08G63/83
Inventor 马海燕阚超胡建文
Owner EAST CHINA UNIV OF SCI & TECH
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