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A kind of polycarboxylic acid organic ligand and synthetic method based on ndhpi modification

A technology of organic ligands and polycarboxylic acids, applied in the field of polycarboxylic acid organic ligands, can solve the problems of low catalytic activity, unfavorable reusability of MOFs materials, high reaction temperature, etc., and achieve wide application prospects, excellent catalytic efficiency and Recyclability and the effect of improving purity

Active Publication Date: 2021-02-26
TONGJI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, compared with the symmetrical structure of NDHPI, NHPI only contains a single active site that can generate nitroxide radicals, and its catalytic activity is relatively low. Therefore, in practical applications, for NHPI-functionalized ligands The amount of MOFs materials is larger, and the reaction temperature is higher and the reaction time is longer, which is extremely unfavorable for the reusability of MOFs materials.

Method used

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  • A kind of polycarboxylic acid organic ligand and synthetic method based on ndhpi modification
  • A kind of polycarboxylic acid organic ligand and synthetic method based on ndhpi modification
  • A kind of polycarboxylic acid organic ligand and synthetic method based on ndhpi modification

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] Polycarboxylic acid organic ligand (a) based on N,N′-dihydroxypyromellitic imide (NDHPI): 4,4’-(2,6-dihydroxy-1,3,5,7- Tetraoxo 1,2,3,5,6,7-hexahydropyrrolo[3,4-F]isoindole-4,8-diyl)dibenzoic acid (referred to as H 2 L 2N-OH ) The specific structure is as follows:

[0035]

[0036] h 2 L 2N-OH The reaction formula of the synthetic method is as follows:

[0037]

[0038] Preparation of polycarboxylic acid organic ligand (a) based on N,N′-dihydroxypyromellitic acid imide (NDHPI): in N 2 Add 6.5mmol3,6-dibromotetramethylbenzene, 13mmol4-methylphenylboronic acid, 26mmol sodium carbonate, 0.2mmol tetrakistriphenylphosphopalladium, 30ml1,4-dioxane, 5.9ml Deionized water was replaced with nitrogen three times, and then heated to 100° C. in an oil bath under magnetic stirring, and reacted for 8 hours. After the reaction was completed, it was allowed to stand at room temperature, and then the solid powder precipitated from the reaction solution was suction-filtered a...

Embodiment 2

[0044] N,N′-dihydroxypyromellitic acid imide modified polycarboxylic acid organic ligand (b): 5,5’-(2,6-dihydroxy-1,3,5,7-tetraoxo 1 ,2,3,5,6,7-hexahydropyrrolo[3,4-F]isoindole-4,8-diyl)diisophthalic acid (referred to as H 4 L 2N-OH ) The specific structure is as follows:

[0045]

[0046] h 4 L 2N-OH The reaction formula of the synthetic method is as follows:

[0047]

[0048] Preparation of polycarboxylic acid organic ligand (b) based on N,N′-dihydroxypyromellitic acid imide modification: in N 2 Add 6.5mmol 3,6-dibromotetramethylbenzene, 13mmol 3,5-dimethylphenylboronic acid, 26mmol sodium carbonate, 0.2mmol tetrakistriphenylphosphopalladium, 30ml 1,4-dioxane to a 100ml three-necked flask under protection , 5.9ml of deionized water, and then replaced with nitrogen three times, and then heated to 120°C with an oil bath under magnetic stirring, and reacted for 12h. After the reaction was completed, it was allowed to stand at room temperature, and then the solid pow...

Embodiment 3

[0054] Weigh the ligand (a), ZrCl according to the molar ratio of 1:1.2:30 4 , Benzoic acid in a glass bottle, then add N,N'-dimethylformamide (DMF) solution and a drop of deionized water, ultrasonic for 10 minutes to clarify the solution, and then place the solution in a constant temperature oven at 70°C for reaction 2 days, then raise the temperature to 85°C for one day, and finally raise the temperature to 100°C to react for 2 days. After the reaction stops, the white powder precipitate obtained is washed with DMF and then soaked in acetone for 3 days. It is activated under vacuum at 120°C for 12 hours. Calculated based on the ligand The crystal yield is about 76%. PXRD test results show that the obtained white powder has good crystallinity, SEM scanning results show that the obtained white powder is a nano-scale regular octahedral structure with uniform size, and BET test results show that the specific surface area of ​​the obtained material is 1470.2046m 2 .g -1 , thus ...

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Abstract

The invention relates to a polycarboxylic acid organic ligand based on NDHPI modification and a synthesis method. It belongs to the technical field of organic chemical synthesis. Through palladium catalyzed coupling of 3,6-dibromotetramethylbenzene with phenylboronic acid with a methyl group at the 4 or 3,5 positions on the benzene ring to obtain polymethyl terphenyl compounds, then use pyridine and water as solvents Under the condition of 90-110°C, use potassium permanganate to oxidize the methyl group to form the structure of polycarboxylic acid terphenyl, then directly react it with hydroxylamine hydrochloride in pyridine solution at 100°C for 5 hours, spin off the solvent after cooling, add Water and hydrochloric acid are adjusted to PH = 1, and a large amount of precipitates can be precipitated. After centrifugation, washing with water and drying, a relatively pure target product can be obtained with a high yield. Compared with the traditional technique, the technique of the invention is simple and the product has high purity. The MOFs material prepared by the present invention has a wide application prospect in the field of catalysis because of its excellent catalytic efficiency as high as 94%-99%, recyclability and other comprehensive properties.

Description

technical field [0001] The invention relates to a polycarboxylic acid organic ligand modified based on NDHPI. 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] NDHPI is the abbreviation of N,N'-dihydroxypyromellitic acid imide. As an electrochemical oxidation substrate or catalyst, it is widely used in the oxidation reactions of aromatics, alkanes, alkenes, alkynes, alcohols, ethers, amides and acetals. It is an ideal green oxidant. Tetraacid imine (NDHPI), because of its simple preparation process, two-site active groups and high activity catalytic properties, NDHPI has been widely concerned and applied in the field of molecular oxygen oxidation. However, as homogeneous small molecule catalysts, N,N'-dihydroxypyromellitic acid imide (NDHPI) and its analogs and N-hydroxyphthalimide (NHPI) and its analogs, they are also Like other small mole...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D487/04B01J31/22
Inventor 李良春梁干刘昌伟
Owner TONGJI UNIV
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