Chiral imine phenol oxyl zinc and magnesium compound as well as preparation method and application thereof

A technology of imine phenoxy zinc and magnesium compounds, which is applied in the direction of magnesium organic compounds, zinc organic compounds, chemical instruments and methods, etc., and can solve the problems of few catalysts and low selectivity

Inactive Publication Date: 2014-06-18
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 is active against racemic lactide, but the selectivity is very low (Organometallics, 2009 ,28,1309)
As an environmentally friendly polymer, people tend to use complexes of biocompatible metals (zinc, magnesium, etc.) when synthesizing polylactide, but so far, complexes of zinc, magnesium, etc. For cyclopolymerization catalysts, racemic lactide only shows high heterotactic selectivity, and catalysts with high isotactic selectivity have rarely been reported.

Method used

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  • Chiral imine phenol oxyl zinc and magnesium compound as well as preparation method and application thereof
  • Chiral imine phenol oxyl zinc and magnesium compound as well as preparation method and application thereof
  • Chiral imine phenol oxyl zinc and magnesium compound as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] Synthesis of Ligand L1

[0047] Add 1.65 g of 3-isopropyl salicylaldehyde, 30 mL of absolute ethanol, and 1.35 g of (S)-1-ethyl-2-aminomethyltetrahydropyrrole into a 100 mL eggplant-shaped bottle, and heat to reflux for 24 hours. Dry over anhydrous magnesium sulfate, remove the solvent and excess low-boiling reactants to obtain a yellow viscous liquid. The pure product was obtained without further workup (2.51g, 91.6%).

[0048]

[0049] 1 H NMR (CDCl 3 ,400MHz):δ13.86(s,1H),8.36(s,1H),7.25(d,J=6.4Hz,1H),7.09(d,J=2.4Hz,1H),3.74(ddd,J= 11.8,4.1,0.9Hz,1H),3.36(dd,J=11.8,8.8Hz,1H),3.07(sept,1H),3.01–2.90(m,2H),2.56(dt,J=8.9,6.6Hz ,1H),2.01–1.77(m,2H),1.76–1.69(m,2H),1.45(s,9H),1.31(s,9H),1.15(d,J=6.5Hz,3H),1.05( d,J=6.4Hz,3H). 13 C{ 1 H}NMR (CDCl 3 For C 17 h 26 N 2 O:C,74.41;H,9.55;N,10.21.Found:C,74.54;H,9.69;N,10.15%.

Embodiment 2

[0051] Synthesis of Ligand L2

[0052] Add 2.34g of 3,5-di-tert-butyl salicylaldehyde, 30mL of absolute ethanol, and 1.60g of (S)-1-butyl-2-aminomethyltetrahydropyrrole into a 100mL eggplant-shaped bottle, and heat to reflux for 24 hours . Dry over anhydrous magnesium sulfate, remove the solvent and excess low-boiling raw materials to obtain a yellow viscous liquid (3.58g, 96.1%).

[0053]

[0054] 1 H NMR (CDCl 3,400MHz):δ13.86(s,1H),8.36(s,1H),7.37(d,J=2.4Hz,1H),7.09(d,J=2.4Hz,1H),3.81(dd,J= 11.7,4.6Hz,1H),3.41(dd,J=11.7,7.8Hz,1H),3.21–3.12(m,1H),2.82(ddd,J=11.7,9.5,6.9Hz,1H),2.75–2.65 (m,1H),2.27(ddd,J=11.8,9.2,5.4Hz,0H),2.23–2.17(m,2H),1.96(ddd,J=16.1,12.1,8.2Hz,1H),1.85–1.78 (m,1H),1.78–1.70(m,2H),1.69–1.60(m,1H),1.57–1.46(m,2H),1.44(s,9H),1.31(s,9H),0.90(t ,J=7.3Hz,3H). 13 C{ 1 H}NMR (CDCl 3 For C 24 h 39 N 2 O:C,77.58;H,10.58;N,7.54.Found:C,77.26;H,10.76;N,7.48%.

Embodiment 3

[0056] Synthesis of Ligand L3

[0057] Add 3.58 g of 3,5-dicumyl salicylaldehyde, 30 mL of absolute ethanol, and 1.60 g of (S)-1-butyl-2-aminomethyltetrahydropyrrole into a 100 mL eggplant-shaped bottle, and heat to reflux for 24 hours. Dry over anhydrous magnesium sulfate, remove the solvent and low-boiling raw materials to obtain a yellow viscous liquid (4.71g, 94.8%).

[0058]

[0059] 1 H NMR (CDCl 3 ,400MHz):δ13.45(s,1H),8.21(s,1H),7.31(d,J=2.4Hz,1H),7.28(s,1H),7.27(s,1H),7.26(s, 1H),7.23(s,1H),7.21(s,1H),7.19(d,J=4.6Hz,3H),7.16(d,J=1.9Hz,1H),7.10(d,J=6.8Hz, 1H),7.00(d,J=2.3Hz,1H),3.64(dd,J=11.7,4.7Hz,1H),3.27(dd,J=11.7,7.7Hz,1H),3.09(td,J=6.5 ,3.1Hz,1H),2.73–2.64(m,1H),2.63–2.53(m,1H),2.22–2.10(m,2H),1.82(dd,J=12.3,8.1Hz,1H),1.69( s,6H),1.66(s,3H),1.64(s,3H),1.55–1.44(m,2H),1.40(ddd,J=10.0,7.6,3.6Hz,2H),1.30–1.24(m, 2H),0.85(t,J=7.3Hz,3H). 13 C{ 1 H}NMR (CDCl 3 ,100MHz):165.9,157.9,150.8,150.7,139.3,136.0,128.8,128.0,127.7,126.7,125.6,125.0,118.0,64.4,64.4,55....

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Abstract

The invention discloses a chiral imine phenol oxyl zinc and magnesium compound as well as a preparation method and application thereof to catalyzing lactone to carry out ring opening polymerization. The preparation method comprises the following steps: directly enabling a neutral ligand to react with a metal raw material compound in an organic medium; then carrying out steps of filtering, pumping and re-crystallizing to obtain a target compound. The chiral imine phenol oxyl zinc and magnesium compound is an efficient lactone ring opening polymerization catalyst and can be used for polymerization reactions of catalytic lactide, epsilon-caprolactone and the like; particularly, polylactic acid with high miscellaneous normal degree can be obtained aiming at racemized lactide. The chiral imine phenol oxyl zinc and magnesium compound disclosed by the invention has the very obvious advantages that raw materials are easily available, a synthetic route is simple and the yield of a target product is high; the chiral imine phenol oxyl zinc and magnesium compound has high catalytic activity; polylactide with high molecular weight and narrow molecular weight distribution can be obtained and the requirements of industrial departments can be met. The structural formula is as shown in the specification.

Description

technical field [0001] The invention relates to a class of chiral imine phenoxy 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 polyolefin materials, aliphatic polyesters have good biocompatibility and degradability, and the raw materials are derived from renewable resources, so they have received extensive attention. Among the aliphatic polyesters that have been extensively studied at present, polylactic acid is particularly attractive. On the one hand, its raw material lactic acid can be fermented from crops such as corn, and on the other hand, polylactic acid can be degraded by microorganisms in nature and participate in the carbon cycle of nature. It is an environment-friendly polymer. The excellent processability of polylactic acid makes it the aliphatic polyester with the most development potential, and it has broad application prospects in t...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D207/09C07F7/10C07F3/06C07F3/02C08G63/08C08G63/83
CPCC07D207/09C07F3/003C07F7/10C08G63/08C08G63/823C08G63/83
Inventor 马海燕王号兵杨漾
Owner EAST CHINA UNIV OF SCI & TECH
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