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Polycarboxylic acid organic ligand based on NHPI functionalization and synthesis method of ligand

A technology of organic ligands and polycarboxylic acids, applied in chemical instruments and methods, organic compound/hydride/coordination complex catalysts, organic chemistry, etc., can solve NHPI leakage, difficult to achieve catalytic effect, and poor reusability problems such as improved product purity, excellent reusability, and good molecular oxygen oxidation performance

Active Publication Date: 2019-04-12
TONGJI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, this method cannot completely confine NHPI in its pores, and NHPI will continue to leak during the catalysis process, resulting in poor reusability and difficulty in achieving the target catalytic effect.

Method used

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  • Polycarboxylic acid organic ligand based on NHPI functionalization and synthesis method of ligand
  • Polycarboxylic acid organic ligand based on NHPI functionalization and synthesis method of ligand
  • Polycarboxylic acid organic ligand based on NHPI functionalization and synthesis method of ligand

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] N-hydroxyphthalimide (NHPI)-modified polycarboxylic acid organic ligand (a): 4,4'-(2-hydroxy-1,3-dioxoisoindoline-4, 7-diyl) dibenzoic acid (referred to as H 2 L N-OH ) The specific structure is as follows:

[0034]

[0035] h 2 L N-OH The reaction formula of the synthetic method is as follows:

[0036]

[0037] Preparation of polycarboxylic acid organic ligands (a) based on NHPI functionalization: in N 2Add 6.3mmol of 1,4-dibromo-2,3-dimethylbenzene, 14.1mmol of 4-methylphenylboronic acid, 25.6mmol of sodium carbonate, 0.2mmol of tetraphenylphosphopalladium, and 30ml of toluene to a 100ml three-necked flask under protection. , 6ml of deionized water, and then replaced with nitrogen three times, and then heated to 90°C with an oil bath under magnetic stirring, and reacted for 6h. After the reaction, wash with water, extract, dry and remove the organic solvent under reduced pressure. The product is separated by column chromatography (petroleum ether) with a y...

Embodiment 2

[0043] N-hydroxyphthalimide (NHPI) modified polycarboxylic acid organic ligand (b): 5,5'-(2-hydroxy-1,3-dioxoisoindoline-4,7 -diyl) diisophthalic acid (referred to as H 4 L N-OH ) The specific structure is as follows:

[0044]

[0045] h 4 L N-OH The reaction formula of the synthetic method is as follows:

[0046]

[0047] Preparation of polycarboxylic acid organic ligands (b) based on NHPI functionalization: in N 2 Add 6.3mmol of 1,4-dibromo-2,3-dimethylbenzene, 13.5mmol of 3,5-dimethylphenylboronic acid, 25.6mmol of potassium carbonate, and 0.2mmol of tetrakistriphenylphosphopalladium to a 100ml three-necked flask under protection. , 30ml of 1,4-dioxane, 6ml of deionized water, and replaced with nitrogen three times, then heated to 90°C with an oil bath under magnetic stirring, and reacted for 6h. After the reaction, wash with water, extract, dry and remove the organic solvent under reduced pressure. The product is separated by column chromatography (petroleum et...

Embodiment 3

[0053] Weigh the ligand (a), ZrCl according to the molar ratio of 1:1.2:25 4 , Benzoic acid in a glass bottle, then add N,N'-dimethylformamide (DMF) solution, ultrasonic for 15 minutes to clarify the solution, and then place the solution in a constant temperature oven at 85°C for 3 days to obtain a white powder Precipitation, the obtained white powder precipitate was washed with DMF, soaked in acetone for 2 days, and activated in vacuum at 100° C. for 8 hours. The crystal yield calculated based on the ligand was about 65%. The PXRD test results show that the obtained white powder has good crystallinity. The SEM scanning results show that the obtained white powder has a regular octahedral structure with uniform size. The BET test results show that the specific surface area of ​​the obtained material is 2557.8386m 2 .g -1 , thus proving that the target metal organic framework material MOFs (UiO-68-nhpi) was successfully prepared. Then using the obtained MOFs (UiO-68-nhpi) as a...

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Abstract

The present invention relates to a polycarboxylic acid organic ligand based on NHPI functionalization and a synthesis method, and belongs to the technical field of organic chemical synthesis. A multi-methyl-containing terphenyl compound is obtained by conducting coupling reaction on 1,4-dibromo-2,3-dimethylbenzene and a phenylboronic acid having methyl at 4-position or 3- and 5-position of a phenyl ring under catalyst of palladium, then methyl is oxidized by potassium permanganate under conditions of 100 DEG C by taking pyridine and water as a solvent so as to generate a multi-carboxylic acidterphenyl structure, then the multi-carboxylic acid terphenyl structure and hydroxylamine hydrochloride are directly heated and refluxed in a pyridine solution for 3 hours, cooling is carried out, rotary evaporation is carried out for solvent removal, water and hydrochloric acid are added for adjusting the pH to be 1 for precipitating a large amount of precipitate, centrifugal treatment, water washing and drying are carried out, so that a relatively pure target product with high yield is obtained. compared with a conventional technology, the method is simple in technology, and the product purity is high. An MOFs material prepared by the organic ligand has wide application prospects because of excellent catalysis efficiency up to 90%-99%, recyclability and other comprehensive performance.

Description

technical field [0001] The invention relates to a polycarboxylic acid organic ligand based on NHPI functionalization. The invention further relates to a synthesis method of the polycarboxylic acid ligand, which belongs to the technical field of organic chemical synthesis. Background technique [0002] In recent years, the application of N-hydroxyphthalimide (NHPI) and its analogues in organic oxidation reactions has attracted great attention. They are widely used as electrochemical oxidation substrates or catalysts in the oxidation reactions of aromatics, alkanes, alkenes, alkynes, alcohols, ethers, amides and acetals. Especially when supplemented with transition metal salts, it can realize the catalytic oxidation of many organic compounds under normal pressure and mild conditions of 25-100°C, and is an ideal green oxidant. However, as a homogeneous small-molecule catalyst, N-hydroxyphthalimide (NHPI) has the same problems as other small-molecule catalysts that it cannot be...

Claims

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Application Information

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IPC IPC(8): C07D209/48C08G83/00B01J31/22
CPCB01J31/2243B01J2231/70B01J2531/16B01J2531/48C07D209/48C08G83/008
Inventor 李良春梁干孙成美
Owner TONGJI UNIV
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