Similar salan monophenol ligand metal complexes as well as preparation method and application thereof

A technology of complexes and monophenols, applied in the preparation of organic compounds, preparation of amino hydroxyl compounds, magnesium organic compounds, etc., can solve the problem of insufficient activity, low activity, inability to coordinate monomers and non-selectivity of insertion, etc. problems, to achieve the effect of convenient preparation, high catalytic activity and stable properties

Inactive Publication Date: 2012-08-01
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The following year, Chisholm et al. reported that β-diimine calcium complexes (Inorg.Chem., 2004, 43, 6717) had higher ring-opening polymerization activity for rac-LA in THF at room temperature, but obtained random PLA
In 2006, Bochmann reported that the use of dianion dinuclear calcium complexes (Daltons.2006, 340) has good controllability for the ring-opening polymerization of caprolactone, but the activity is low
In 2007, Lin found that the Schiff base dinuclear calcium complex (Polymer, 2007, 48, 2257) can catalyze the ring-opening polymerization of L-LA in the presence of benzyl alcohol, but the activity is not high enough
[0007] In summary, the zinc, magnesium, and calcium complexes reported so far have high catalytic activity for the ring-opening polymerization of lactide and caprolactone, but the ligands cannot effectively form a stable ring-opening polymerization around the metal center. Chiral coordination environment without selectivity for monomer coordination and insertion, resulting in random or heterotactic polymers

Method used

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  • Similar salan monophenol ligand metal complexes as well as preparation method and application thereof
  • Similar salan monophenol ligand metal complexes as well as preparation method and application thereof
  • Similar salan monophenol ligand metal complexes as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] synthetic ligand L1

[0041]

[0042] Add 2.72g of 2-methoxybenzaldehyde, 20mL of anhydrous methanol, and 1.94g of N,N'-dimethylethylenediamine into a 100mL three-necked flask, and heat to reflux for 24h. Add 1.52g of sodium borohydride, heat to 50°C, add water to it, extract with dichloromethane, combine the organic phases, and dry with anhydrous magnesium sulfate, remove the solvent to obtain a light yellow viscous liquid, add 20mL of anhydrous Toluene and 1.34g dry KOH were added dropwise to a toluene solution of 5.12g 3,5-dichloro-2-benzylbromophenol, refluxed at 70°C, filtered to remove KOH, and the crude product was separated by column chromatography on silica gel to obtain ligand L1 (2.49 g, 22.07%).

[0043] 1 H NMR (CDCl 3 , 400MHz): δ7.32 (dd, 1H, J 1 =7.2Hz,J 2 =1.6Hz, ArH), 7.26-7.21(m, 2H, ArH), 6.90(td, 1H, J 1 =7.2Hz,J 2 =0.8Hz, ArH), 6.87-6.83(m, 2H, ArH), 3.78(s, 3H, OCH 3 ), 3.62(s, 2H, Ar-CH 2 N), 3.57(s, 2H, NCH 2 -Ar), 2.69-2.64 (m, 2H,...

Embodiment 2

[0045] Synthetic Ligand L2

[0046]

[0047] Add 2.72g of 2-methoxybenzaldehyde, 20mL of anhydrous methanol, and 1.94g of N,N'-dimethylethylenediamine into a 100mL three-necked flask, and heat to reflux for 24h. Add 1.52g of sodium borohydride, heat to 50°C, add water to it, extract with dichloromethane, combine the organic phases, and dry with anhydrous magnesium sulfate, remove the solvent to obtain a light yellow viscous liquid, add 20mL of anhydrous Toluene and 1.34g dry KOH were added dropwise to a toluene solution of 6.05g 3,5-dichloro-2-benzylbromophenol, refluxed at 70°C, filtered to remove KOH, and the crude product was separated by column chromatography on silica gel to obtain ligand L2 (1.94 g, 22.07%).

[0048] 1 H NMR (CDCl 3 , 400MHz): δ7.36(d, 1H, J=7.6Hz, ArH), 7.21(t, 1H, J=7.6Hz, ArH), 7.19(s, 1H, ArH), 6.91(t, 1H, J =8.0Hz, ArH), 6.84(d, 1H, J=8.0Hz, ArH), 6.80(s, 1H, ArH), 3.78(s, 3H, OCH 3 ), 3.68(s, 2H, Ar-CH 2 -N), 3.53(s, 2H, N-CH 2 -Ar), 2.61...

Embodiment 3

[0050] synthetic ligand L3

[0051]

[0052] Add 2.72g of 2-methoxybenzaldehyde, 20mL of anhydrous methanol, and 1.94g of N,N'-dimethylethylenediamine into a 100mL three-necked flask, and heat to reflux for 24h. Add 1.52g of sodium borohydride, heat to 50°C, add water to it, extract with dichloromethane, combine the organic phases, and dry with anhydrous magnesium sulfate, remove the solvent to obtain a light yellow viscous liquid, add 20mL of anhydrous Toluene and 1.34g dry KOH were added dropwise to a toluene solution of 8.81g 3,5-dicumyl-2-benzylbromophenol, refluxed at 70°C, KOH was removed by filtration, and the crude product was separated by column chromatography on silica gel to obtain the ligand L3 (4.96 g, 45.07%).

[0053] 1 H NMR (CDCl 3 , 400MHz): δ7.28-7.29(m, 5H, ArH), 7.17-7.25(m, 7H, ArH), 7.12(t, 1H, J=6.4Hz, ArH), 6.92(t, 1H, J= 7.4Hz, ArH), 6.86(d, 1H, J=8.0Hz, ArH), 6.73(s, 1H, ArH), 3.78(s, 3H, OCH 3 ), 3.57(s, 2H, Ar-CH 2 -N), 3.45(s, 2H, N-CH 2...

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Abstract

The invention discloses zinc, magnesium and calcium complexes of monophenol ligands with similar salan-structures as well as a preparation method thereof and the application in lactone ring-opening polymerization. The preparation method comprises the steps as follows: the similar salan-monophenol ligands react with zinc, magnesium and calcium metallo-organic compounds, and then target products are collected from reaction coarse products. The zinc, magnesium and calcium complexes comprise asymmetrical multidentate amino monophenol oxygroup ligands with the similar salan-structures, are effective lactone ring-opening polymerization catalysts, and can be used for ring-opening polymerization of lactide, caprolactone and the like. The multidentate monophenol oxygroup zinc, magnesium and calcium complexes have the very obvious advantages as follows: raw materials are easy to get, the synthetic route is simple, separation and purification are easy, and the performance is stable relatively; meanwhile, high catalytic activity is achieved; in addition, polylactone that is obtained through catalysis has higher molecular weight, and the requirements of industrial sectors can be satisfied. The structure of the zinc, magnesium and calcium complexes has the following general formula.

Description

technical field [0001] The invention relates to a class of metal zinc, magnesium and calcium complexes containing salan-like structure monophenolic ligands and their synthesis, as well as the application of the complexes in ring-opening polymerization of lactones. Background technique [0002] Since the 1970s, it was discovered that polyester materials have many advantages comparable to polyolefin products, as well as the biocompatibility and degradability that polyolefin products do not have. Polyester materials have been synthesized, produced and Significant progress has been made in the processing of degradable polyesters, which are gradually finding applications in medicine, agriculture, and daily necessities. In the current field of polyester research, polylactide, polycaprolactone and their copolymers are relatively more studied, with the advantages of biodegradability, excellent biocompatibility, plasticity, and easy processing and molding. Considered as the most pro...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C217/58C07C213/02C07F19/00C07F3/06C07F3/02C07F3/04C08G63/08C08G63/83
Inventor 马海燕宋绍迪杨漾张星宇
Owner EAST CHINA UNIV OF SCI & TECH
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