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(1R, 2R)-1, 2-diphenylethylenediamine grafted metal-organic framework catalyst, and preparation method and applications thereof

A technology of diphenylethylenediamine and metal-organic framework, which is applied to the metal-organic framework structure catalyst and its preparation of grafted-1,2-diphenylethylenediamine, asymmetric catalytic synthesis of (S)-warfarin In the field of application, it can solve the problems of difficult catalyst recovery and poor selectivity, and achieve good thermal and chemical stability, high efficiency and stability, and high specific surface area.

Inactive Publication Date: 2013-12-11
ZHEJIANG NORMAL UNIVERSITY
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0013] Based on the problems of difficult catalyst recovery and poor selectivity in the existing production process, the present invention provides a novel catalyst for the production process of asymmetric catalytic synthesis of (S)-warfarin, the catalyst can be recycled, and the operation simple and low cost

Method used

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  • (1R, 2R)-1, 2-diphenylethylenediamine grafted metal-organic framework catalyst, and preparation method and applications thereof
  • (1R, 2R)-1, 2-diphenylethylenediamine grafted metal-organic framework catalyst, and preparation method and applications thereof
  • (1R, 2R)-1, 2-diphenylethylenediamine grafted metal-organic framework catalyst, and preparation method and applications thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Dehydrate 0.5g of MIL-101 in vacuum at 150°C for 12h. After cooling to room temperature, quickly pour the dehydrated MIL-101 into anhydrous toluene (30mL), 3.0mmol of 1,2-diphenylethyl The diamine was refluxed and stirred at 110oC for 12h, filtered and washed with ethanol, and dried at room temperature to obtain the grafted catalyst CDMIL.

[0030] figure 1 Shown is the infrared spectrum of CDMIL. It can be seen from the figure that there are 3023cm -1 ,3028cm -1 Amino absorption peak.

[0031] figure 2Shown is the CDMIL powder diffraction pattern. It can be seen from the figure that compared with the material MIL-101 material, the basic skeleton of the material exists.

[0032] image 3 Shown is the CDMIL thermogravimetric analysis plot. It can be seen from the figure that the material is relatively stable at 0-250°C.

[0033] Figure 4 Shown is the SEM image of CDMIL. It can be seen from the figure that the morphology of the material is relatively regular....

Embodiment 2

[0035]

[0036] Put 4-hydroxycoumarin (1.62g, 10mmol), benzylidene acetone (2.20g, 15mmol), catalyst CDMIL (1.20g) and 50mL tetrahydrofuran into a 100mL test tube, and stir at 10°C for 96h. The catalyst was separated by centrifugation (400r / min, 10min), and after removing THF under reduced pressure, the column layer was carried out with a mixture of petroleum ether and ethyl acetate (the volume ratio of petroleum ether and ethyl acetate was 3:1) Analysis gave 2.8g of (S)-warfarin 3aa. Compared with traditional methods, there is no literature report that can produce gram-scale warfarin in the (S) configuration.

[0037] The structure of chiral warfarin 3aa obtained above was identified by nuclear magnetic resonance and high-resolution mass spectrometry (as shown in Figure 5(a), and Figure 5(b)). Proton NMR spectrum: (400MHz, CDCl 3 )δ7.97–7.86(m,1H),7.84–7.76(m,1H),7.60–7.52(m,1H),7.51–7.44(m,1H),7.38–7.16(m,14H),4.71( d,J=9.7Hz,0.2H),4.41–4.22(m,1H),4.15(td,J=11.1,7.1Hz,...

Embodiment 3

[0040] The first catalysis: put 4-hydroxycoumarin (1.62g, 10mmol), benzylidene acetone (2.20g, 15mmol), catalyst CDMIL (1.20g) and 50mL tetrahydrofuran in a 100mL test tube, and stir at 10°C for 96h. The catalyst was separated by centrifugation (400r / min, 10min), and after removing THF under reduced pressure, the column layer was carried out with a mixture of petroleum ether and ethyl acetate (the volume ratio of petroleum ether and ethyl acetate was 3:1) (S)-warfarin 3aa was obtained by analysis. The yield and enantioselectivity are shown in Table 1. The HPLC chromatogram is shown in Fig. 6(c).

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Abstract

The invention discloses a (1R, 2R)-1, 2-diphenylethylenediamine grafted metal-organic framework catalyst, wherein MIL-101 is used as a metal-organic framework material. The (1R, 2R)-1, 2-diphenylethylenediamine grafted metal-organic framework catalyst can be prepared by following steps: MIL-101 is subjected to vacuum dehydration for 12h at a temperature of 150 DEG C, and then is cooled to room temperature; the dehydrated MIL-101 is added into methylbenzene rapidly, and then (1R, 2R)-1, 2-diphenylethylenediamine is added into the mixture; and the mixture is subjected to refluxing and stirring for 12h at a temperature of 110 DEG C, filtered, washed with ethanol, and dried at room temperature so as to obtain the (1R, 2R)-1, 2-diphenylethylenediamine grafted metal-organic framework catalyst. The (1R, 2R)-1, 2-diphenylethylenediamine grafted metal-organic framework catalyst is friendly to the environment, and possesses high performance and stability; and reaction conditions are mild. The invention also discloses applications of the (1R, 2R)-1, 2-diphenylethylenediamine grafted metal-organic framework catalyst in asymmetric synthese of (S)-warfarin.

Description

technical field [0001] The invention belongs to the field of chemical synthesis, and in particular relates to a metal-organic framework catalyst grafted with (1R,2R)-1,2-diphenylethylenediamine and a preparation method thereof, and a method for asymmetrically catalytically synthesizing (S)-Hua Applied in farin. Background technique [0002] MIL-101 is a metal-organic framework (MOFs) material with good stability. The material can remain stable after being exposed to the air for several months, and can maintain a complete structure even in different hot solvents. MIL-101 is a supertetrahedral secondary structural unit composed of carboxylic acid ligands BDC and trinuclear Cr(Ⅲ) octahedral clusters linked in order, and then formed a three-dimensional space network structure through rigid BDC ligand links. The skeleton contains two mesoporous cages, which are respectively composed of 12 pentahedrons and polygons with 16 faces. pentagonal windows and The hexagonal windows a...

Claims

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Application Information

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IPC IPC(8): B01J31/22C07D311/56
Inventor 谢建武朱伟东钟依均郭志伟石涛
Owner ZHEJIANG NORMAL UNIVERSITY
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