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Metal organic frame based on pyridine oxide ligand, and preparation method and application thereof

A metal-organic framework, pyridine oxidation technology, applied in the directions of organic chemistry methods, preparation of organic compounds, chemical instruments and methods, etc., can solve the problems of cumbersome preparation steps, unrecoverable, poor stability, etc., and achieves cost reduction, easy recovery, good stability

Inactive Publication Date: 2017-05-10
SHANDONG NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] However, the existing metal-organic frameworks as a Lewis acid catalyst have problems such as poor stability, cumbersome preparation steps, low activity, and non-recyclability.

Method used

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  • Metal organic frame based on pyridine oxide ligand, and preparation method and application thereof
  • Metal organic frame based on pyridine oxide ligand, and preparation method and application thereof
  • Metal organic frame based on pyridine oxide ligand, and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0055] Embodiment 1: Preparation of oxidized pyridine ligand L

[0056] Concrete preparation steps are as follows:

[0057] (1) In a 250mL single-necked bottle, dissolve 3,5-dibromopyridine (3.2g, 13.5mmol) in 50mL THF, add m-chloroperoxybenzoic acid (6.88g, 40mmol), stir at room temperature for 48 hours, and the reaction ends Then add 30mL saturated aqueous sodium carbonate solution, let stand to separate layers, and use 2×50mL CH for the aqueous phase 2 Cl 2 Extract, combine the organic phase and wash with anhydrous Na 2 SO 4 Drying, silica gel column chromatography (CH2 Cl 2 ) to obtain 1.53 g of light white solid, namely 3,5-dibromopyridine-N-oxide, with a yield of 44.1%. 1 H NMR (300MHz, DMSO, 25°C, TMS): δ=8.60(s, 2H, -C 5 h 3 NBr 2 ),7.97(s,1H,-C 5 h 3 NBr 2 ).

[0058]

[0059] (2)N 2 Under protection, 3,5-dibromopyridine-N-oxide (2.53g, 10.0mmol), 4-pyridineboronic acid (2.95g, 24.0mmol), tetrakistriphenylphosphine palladium (1.16g, 1.0mmol), Anhydrou...

Embodiment 2

[0062] Embodiment 2: the synthesis of Zn-MOF

[0063] At room temperature, the ZnBr 2 (2.2mg, 0.01mmol) was dissolved in methanol (2mL) to obtain ZnBr 2 methanol solution, L (2.4 mg, 0.01 mmol) was dissolved in CH 2 Cl 2 solution (2mL), the methanol solution was slowly spread over CH 2 Cl 2 On the solution, a colorless single crystal was obtained after standing for three days.

[0064] By infrared spectrogram (IR), thermogravimetric analysis spectrogram (TGA) has characterized this compound, and the results are shown in image 3 , Figure 4 .

[0065] Zn-MOF single crystal structure such as Figure 5 shown.

[0066] Depend on Figure 5 It can be seen that Zn-MOF is monoclinic and belongs to the P2(1) / n space group. There is only one kind of Zn(II) center in Zn-MOF, which is in (ZnN 2 Br 2 ) in the coordination environment, the nitrogen atom coordinated with it is from the end group pyridine of the ligand L, and the lengths of the Zn-N bonds are respectively with...

experiment example 3

[0069] Experimental Example 3: Formation of benzaldehyde and malononitrile condensation reaction

[0070] At room temperature, add benzaldehyde (1mmol) and malononitrile (1.2mmol) into a 2mL glass bottle, after stirring for 5 minutes, add the catalyst Zn-MOF (19mg, 4% (mol), based on the amount of benzaldehyde) , continue to stir for 6 hours, and track the reaction with gas chromatography. After the reaction, quickly centrifuge. The solid after centrifugation is the catalyst Zn-MOF for the catalytic reaction. The catalyst is recovered and directly put into the next cycle reaction. According to the above conditions, the catalyst is used 5 cycles, the reaction solution calculates the productive rate by gas chromatography, and the catalytic effect is as shown in table 2, and the catalyst of recovery is characterized by PXRD, as Image 6 shown.

[0071] Table 2 Yield and TOF value of 5 cycles of Zn-MOF catalyzed Knoevenagel condensation reaction

[0072]

[0073] a: The yield...

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Abstract

The invention discloses a metal organic frame based on a pyridine oxide ligand, and a preparation method and application thereof. The structural formula of the metal organic frame Zn-MOF is (ZnLBr2)n, wherein L refers to the pyridine oxide ligand L with the structural formula shown as below, and n refers to a non-zero natural number. A preparation method of the pyridine oxide ligand L includes (1), preparing 3, 5-dihalogenated pyridine into 3, 5-dihalogenated pyridine-N-oxide; (2), subjecting the 3, 5-dihalogenated pyridine-N-oxide to Suzuki reaction to obtain the pyridine oxide ligand L. According to the preparation method of the metal organic frame based on the pyridine oxide ligand, ZnBr2 liquor is laid on pyridine oxide ligand L liquor, and standing is performed to obtain a colorless monocrystal, namely the metal organic frame Zn-MOF. When the metal organic frame serves as a catalyst, reaction temperature is mild, reaction time is short, activity is high, catalyst consumption is low, the catalyst is easy to recycle, catalyst utilization rate is increased, and cost is reduced.

Description

technical field [0001] The invention belongs to the technical field of catalyst preparation, and in particular relates to a metal-organic framework based on an oxidized pyridine ligand, a preparation method and an application. Background technique [0002] The dehydration condensation reaction of aldehydes or ketones with active methylene compounds to form carbon-carbon double bonds is called Knoevenagel condensation reaction. This kind of reaction can directly synthesize a large number of useful compounds, and has a wide range of applications in many fields such as industry, agriculture, pharmacy, and biological science. Knoevenagel condensation reaction generally uses Lewis acid or base as catalyst, and weak base (amine, pyridine, etc.) can also be used as catalyst, and the reaction is carried out in a homogeneous or heterogeneous environment. Generally, it takes a long time and the yield is low. . [0003] Metal-Organic Frameworks (MOFs) are a class of organic-inorganic...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D213/89C07F3/06B01J31/22C07C253/30C07C255/34
CPCB01J31/1691B01J31/1815B01J2231/4205B01J2531/0205B01J2531/26C07B2200/13C07C253/30C07D213/89C07F3/003C07C255/34Y02P20/584
Inventor 董育斌杨嘉时程军妍
Owner SHANDONG NORMAL UNIV
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