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Ni (II)-based metal-organic framework and synthesis method and application thereof

A technology of metal-organic frameworks and organic ligands, applied in nickel-organic compounds, organic chemistry, organic compound/hydride/coordination complex catalysts, etc., can solve the problems of non-recyclable catalysts, long running time, strong toxicity, etc.

Inactive Publication Date: 2015-03-25
SHANDONG NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the use of MOFs to adsorb iodine to continue the catalytic reaction has not yet been discovered.
Especially for the silicocyanation reaction of benzaldehyde, the existing catalysts are generally organic solvents, which not only have strong toxicity and low catalytic efficiency, but also need to add other additives, the catalyst is not recyclable, the cost is too high, and the running time is too long.

Method used

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  • Ni (II)-based metal-organic framework and synthesis method and application thereof
  • Ni (II)-based metal-organic framework and synthesis method and application thereof
  • Ni (II)-based metal-organic framework and synthesis method and application thereof

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Experimental program
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Effect test

Embodiment 1

[0064] The synthesis route of the catalyst synthesized by the present invention is as follows:

[0065] 1. Preparation of Ligand L:

[0066]

[0067] At room temperature, 2,7-dibromofluorene (10.40g, 32mmol), tetrabutylammonium bromide (0.10g, 0.3mmol), methyl iodide (9.93g, 90mmol), and 10mL of 50% NaOH solution were added to 140mL of In DMSO, ultrasonic reaction (100W) was performed for 5 hours. After the reaction was completed, it was poured into 500mL water, stirred for 20min and left to stand for 1 hour, filtered with suction, and the filter cake was washed with 1% NaCl aqueous solution and dried to obtain 10.97g of a yellow solid. The yield was 97.40%.

[0068] N 2 Under protection, intermediate A (3.52g, 10mmol) 1,2,4-triazole (1,93g, 28mmol), cesium carbonate (13.03g, 40mmmol, cuprous iodide (0.762g, 4mmol) were placed in 100ml In the there-necked flask, 20mlDMF was used as solvent, heated to 120°C, tracked by TLC, poured into 300ml of water after the reaction ...

experiment example 1

[0076] Experimental Example 1 Benzaldehyde reacts with trimethylsilyl cyanide to generate 2-phenyl-2-(trimethylsilyloxy) acetonitrile

[0077] At room temperature, benzaldehyde (106mg, 1mmol) and trimethylsilyl cyanide (119mg, 1.2mmol) were added to a 25ml round bottom flask, and then 32.5mg (0.033mmol) of the catalyst Ni-MOF-3 was added, and the reaction was stirred. 1 After the HNMR tracking reaction, 1.5 ml of dichloromethane was added, and the catalyst was recovered by quick centrifugation, and the liquid was used to calculate the yield by GC-MS.

[0078] Purification of the product (2-phenyl-2-(trimethylsilyloxy)acetonitrile): evaporate the centrifuged liquid to dryness under reduced pressure, dissolve it in n-hexane, perform silica gel column chromatography (n-hexane:ethyl acetate=9:1 ) to obtain a colorless oily product. That 1 HNMR such as Figure 14 shown.

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Abstract

The invention relates to a Ni (II)-based metal-organic framework and a synthesis method and application thereof and belongs to the field of catalyst preparation. The synthesis method comprises the following steps: firstly, synthesizing a metal-organic framework Ni-MOF-1 through an organic ligand L, and then heating Ni-MOF-1 crystals at 100 DEG C for 4-6 hours, so as to prepare Ni-MOF-2; and finally, immersing the Ni-MOF-2 into a gas-phase atmosphere of iodine for 24 hours, so as to obtain a novel iodine-loaded catalyst Ni-MOF-3. The benzaldehyde silicon cyanation can be effectively catalyzed by the catalyst without need of a solvent reaction; and therefore, the harm to the environment caused by a toxic solvent is reduced, the reaction temperature is mild, reaction time is short, the catalyst consumption is low, and no other additives are used; and compared with free iodine, the metal-organic framework can be reused for over five times.

Description

technical field [0001] The invention belongs to the field of catalyst preparation, in particular to a Ni(II) metal-organic framework and its synthesis method and application. Background technique [0002] The application of supramolecular assemblies is the most important research hotspot in current supramolecular chemistry. MOFs, as porous functional materials, show great advantages in gas adsorption and gas adsorption of small organic molecules. Elemental iodine is a purple-black scaly crystal with metallic luster, easily soluble in organic solvents and sublimated. Iodine is an important raw material for the manufacture of various inorganic and organic iodine compounds. It is also one of the indispensable elements of the human body, animals and plants. It has a large atomic radius and multi-layer electronic structure, so that it has certain special properties, such as the ability to catalyze organic chemical reactions, so it has been valued by the organic chemistry commun...

Claims

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Application Information

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IPC IPC(8): C07D249/08C07F15/04B01J31/22C07F7/18
CPCB01J31/1691B01J2231/341B01J2531/0213B01J2531/847C07D249/08C07F7/188C07F15/045
Inventor 董育斌张小蒙刘启奎马建平
Owner SHANDONG NORMAL UNIV
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