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Benzothiazole ring substituted aminophenoxy zinc complex, and preparation method and application thereof

A technology of aminophenoloxyzinc and benzothiazole rings, which is applied in the field of aminophenoloxyzinc complexes, can solve the problems of catalyst sensitivity, no stereoselectivity, and low catalyst activity, and achieve stable properties and high isotactic stereo Effect of selectivity and high catalytic activity

Pending Publication Date: 2020-07-03
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In 2011, the β-monophosphine imide zinc complex reported by Wang Zhongxia's group showed high catalytic activity for the polymerization of racemic lactide, but only random polymers were obtained (Organometallics, 2011, 30, 4364-4373)
In 2014, the Du group reported zinc complexes based on chiral aminooxazolines with high isotactic stereoselectivity for the polymerization of racemic lactide P m =0.90, the melting point of the obtained polymer reaches T m =214°C, but the catalyst activity is very low (ACS Macro Lett.2014,3,689)
In 2016, the Williams group designed and synthesized a macrocyclic dinuclear zinc complex that can completely polymerize 1000 equivalents of racemic lactide within 1 min, TOF = 60000h -1 , but no stereoselectivity (Angew.Chem.Int.Ed.2016,128,1-7)
[0005] People have made great breakthroughs in the research of catalytic racemic lactide polymerization, but it is still very challenging to design and synthesize catalysts with high activity and high isotactic selectivity.
At present, although individual zinc complexes show high isotactic selectivity for the ring-opening polymerization of racemic lactide, the catalyst is sensitive to water, oxygen and impurities.

Method used

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  • Benzothiazole ring substituted aminophenoxy zinc complex, and preparation method and application thereof
  • Benzothiazole ring substituted aminophenoxy zinc complex, and preparation method and application thereof
  • Benzothiazole ring substituted aminophenoxy zinc complex, and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] Synthesis of Ligand L1:

[0044] (1) Synthesis of N-[(benzothiazol-2-yl)-methyl]cyclohexylamine

[0045]

[0046] Under the protection of inert gas, add cyclohexylamine (24.5mmol, 2.43g) and anhydrous K 2 CO 3 (2.94mmol, 0.41g), was added dropwise a solution of 2-chloromethylbenzothiazole (2.45mmol, 0.45g) in 50mL of N,N-dimethylformamide from a constant pressure dropping funnel, and reacted for 8h. Quenched with water, extracted with dichloromethane, washed with saturated brine and washed with anhydrous MgSO 4 Dry, filter, and distill off the solvent under reduced pressure to obtain a yellow viscous liquid, and distill off unreacted cyclohexylamine at 90°C / 1mmHg. The main product point was analyzed by TLC, and it was directly used in the next reaction, and the yield was about 80% according to the H NMR spectrum.

[0047] (2) Synthesis of Ligand L1

[0048] Add N-[(benzothiazol-2-yl)-methyl]cyclohexylamine (5mmol, 1.23g), anhydrous potassium carbonate (5.5mmol, ...

Embodiment 2

[0052] Synthesis of Ligand L2

[0053] (1) Synthesis of N-[(benzothiazol-2-yl)-methyl]benzylamine

[0054]

[0055] Except that benzylamine (16.07g, 150mmol), potassium carbonate (2.28g, 16.5mmol) and 2-chloromethylbenzothiazole (2.75g, 15mmol) were used as raw materials, other operating steps were the same as in Example 1. An orange-red oil was obtained.

[0056] (2) Synthesis of Ligand L2

[0057] N-[(benzothiazol-2-yl)-methyl]benzylamine (14mmol, 3.56g), anhydrous potassium carbonate (15.4mmol, 2.13g) and 2-bromomethyl-4-methyl -Except for 6-tritylphenol (14mmol, 6.34g), other operations were the same as in Example 1 (5.50g, 64%).

[0058]

[0059] 1 H NMR (400MHz, CDCl 3 ,298K):δ9.49(s,1H,OH),7.97(d, 3 J=8.1Hz,1H,ArH),7.85(d, 3 J=7.9Hz,1H,ArH),7.54–7.44(m,1H,ArH),7.40(m, 3 J=11.2Hz,1H,ArH),7.29–7.17(m,15H,ArH),7.13(t, 3 J=6.8Hz, 3H, ArH), 7.04(m, 3 J=14.0,10.5Hz,2H,ArH),6.92(s,1H,ArH),6.84(s,1H,ArH),3.89(s,2H,ArCH 2 ),3.86(s,2H,NCH 2 C=N),3.60(s,2H,PhCH ...

Embodiment 3

[0061] Synthesis of Ligand L3

[0062] (1) Synthesis of N-[(benzothiazol-2-yl)-methyl]n-hexylamine

[0063]

[0064] Except that n-hexylamine (15.18g, 150mmol), potassium carbonate (2.28g, 16.5mmol) and 2-chloromethylbenzothiazole (2.75g, 15mmol) were used as raw materials, other operating steps were the same as in Example 1. An orange-red oil was obtained.

[0065] (2) Synthesis of Ligand L3

[0066] In addition to raw materials, N-[(benzothiazol-2-yl)-methyl]n-hexylamine (13.85mmol, 3.44g), anhydrous potassium carbonate (16mmol, 2.21g) and 2-bromomethyl-4-methyl - Except for 6-tritylphenol (13.85mmol, 6.14g), other operations were the same as in Example 1 (6.30g, 73%).

[0067]

[0068] 1 H NMR (400MHz, CDCl 3 ,298K):δ9.45(s,1H,OH),7.96(d, 3 J=7.9Hz,1H,ArH),7.84(d, 3 J=7.6Hz,1H,ArH),7.51–7.43(m,1H,ArH),7.40(m, 3 J=11.1Hz,1H,ArH),7.24–7.14(m,12H,ArH),7.10(m, 3 J=9.2Hz, 3H, ArH), 6.92(d, 4 J=1.6Hz,1H,ArH),6.83(s,1H,ArH),3.91(s,2H,ArCH 2 ),3.84(s,2H,NCH 2 C=N)...

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Abstract

The invention discloses a benzothiazole ring substituted aminophenoxy zinc complex, a preparation method thereof, and an application of the benzothiazole ring substituted aminophenoxy zinc complex inhigh-activity and high-selectivity catalysis of lactone ring opening polymerization. The preparation method comprises the following steps: directly reacting a neutral ligand with a metal raw materialcompound in an organic medium, filtering, concentrating, and recrystallizing to obtain the target compound. The benzothiazole ring substituted aminophenoxy zinc complex disclosed by the invention is an efficient lactone ring opening polymerization catalyst and can be used for catalyzing a polymerization reaction of lactide and other lactones; and especially for racemic lactide, polylactide with high isotacticity can be obtained. The benzothiazole ring substituted aminophenoxy zinc complex has the very obvious following advantages: the raw materials are easy to obtain, the synthesis route is simple, the product yield is high, the catalytic activity and stereoselectivity are very 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 benzothiazole ring substituted aminophenoxy zinc complexes and the application of such complexes in lactone polymerization. Background technique [0002] Petroleum-based materials cause serious environmental pollution due to their difficulty in biodegradation, and limited petroleum resources do not conform to the strategy of sustainable development. Aliphatic polyester materials have the advantages of degradability and biocompatibility. Among them, polylactic acid, as a new type of green material, not only has the above advantages, but also its raw materials are renewable and realize its carbon cycle in nature, which is recognized Environmentally friendly green polymer materials have been widely used in medicine, medical treatment and food packaging and other fields. With the advancement of science and technology, new requirements and uses have been put forward for the performance of polylactic acid material...

Claims

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Application Information

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IPC IPC(8): C07D277/64C07F3/06C07F7/10B01J31/22C08G63/83C08G63/08
CPCC07D277/64C07F3/003C07F7/10B01J31/2217C08G63/83C08G63/08C08G63/823
Inventor 马海燕蒋旭敏
Owner EAST CHINA UNIV OF SCI & TECH
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