Chiral polyacid-based metal organic framework material and preparing method and application thereof

An organic framework and metal-based technology, applied in the field of chiral polyacid-based metal-organic framework materials and their preparation, can solve the problems of high risk, toxicity, and process cost, and achieve atomic economy, greening, good performance, and three-dimensional structure. stable effect

Active Publication Date: 2019-05-21
HENAN UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although the above homogeneous chiral catalysis has the characteristics of high efficiency, high enantioselectivity and mild reaction conditions, but in order to realize the industrial application of these catalytic reactions, the serious problem of recycling expensive catalysts must first be solved, and these catalytic systems It is mainly based on the thermal catalytic reaction process, which requires organic peracids and organic peroxides as oxidants, and has disadvantages such as high process cost, corrosion, danger, toxicity, serious environmental pollution and harsh reaction conditions.

Method used

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  • Chiral polyacid-based metal organic framework material and preparing method and application thereof
  • Chiral polyacid-based metal organic framework material and preparing method and application thereof
  • Chiral polyacid-based metal organic framework material and preparing method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] The chemical formula of the chiral polyacid-based metal-organic framework material in this example is: C 74 h 101 B 2 Zn 2 N 22 o 84 W 24 , recorded as ZnW-DPNDI-PYIs, according to the material chirality and recorded as ZnW-DPNDI-PYI1 and ZnW-DPNDI-PYI2.

[0028] The preparation method of ZnW-DPNDI-PYI1 in this example is as follows: Weigh 45mg and 0.15mmol of Zn(NO 3 ) 2 ·6H 2 O, 157.8 mg, 0.05 mmol of K 5 [BW 12 o 40 ]·5H 2 O, 23.4mg, 0.15mmol of DPNDI and 24.5mg, 0.1mmol of L-BCIP in a small glass bottle, add 4.0mL of distilled water, 2.0mL of methanol to dissolve, stir overnight to obtain a suspension solution, transfer the suspension solution Put it into a 25mL autoclave, put it into an oven, heat it to 120°C and react for five days, take out the reaction product after cooling to room temperature, and wash it repeatedly with distilled water to obtain white-yellow rod-shaped crystal ZnW-DPNDI-PYI1, the ZnW-DPNDI- The yield of PYI1 was 60%;

[0029] The...

Embodiment 2

[0038] This embodiment is substrate with styrene, O 2 As an oxidant, add 0.1% mol of ZnW-DPNDI-PYI1 or ZnW-DPNDI-PYI2, and react for 12 hours under visible light irradiation to realize the heterogeneous asymmetric catalytic olefin epoxidation reaction. The reaction equation is as follows Figure 6 As shown, the reaction conditions and reaction results are shown in Table 1, the selective oxidation yield of styrene reaches 92%, and is converted into product styrene oxide, while the ee value is as high as 45%, and the substrate can be extended to styrene derivatives, Such as 4-chlorostyrene, 2-chlorostyrene, 4-methylstyrene.

Embodiment 3

[0040] Select multiple substrates as in table 1 to carry out catalytic oxidation reaction, wherein select 3,5-di-tert-butyl-4-vinylbiphenyl (i.e. tert-butylstyrene in table 1) as substrate, when with Under the same conditions of Example 2, the yield of the asymmetric catalytic epoxidation reaction is less than 10%. We speculate that this is because the substrate is too bulky to enter the pores of ZnW-DPNDI-PYI1 for reaction, and only a small amount of substrate is adsorbed on the surface of ZnW-DPNDI-PYI1 for reaction. This phenomenon not only reflects the advantages of POMOFs shape-selective catalysis, but also proves that the asymmetric catalytic epoxidation reaction in this experiment does occur in the pores of POMOFs. result of the action.

[0041] Table 1 Conversion and selectivity of aryl olefin epoxidation

[0042]

[0043]

[0044] The reaction equation in Table 1 can be passed Figure 6 Reaction conditions: substrate olefin 5mmol, ZnW-DPNDI-PYI1 (10mg, 12.5μmol...

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Abstract

The invention provides a chiral polyacid-based metal organic framework material. The chemical formula of the polyacid-based metal organic framework material is C74H101B2Zn2N22O84W24, and is recorded as ZnW-DPNDI-PYI1 and ZnW-DPNDI-PYI2 according to the chirality, wherein the DPNDI is N,N'-bi(4-picoline) naphthalimide and serves as a bridging ligand and a photosensitizer, and the PYI is L-pyrrolidine-2-imidazole and serves as a chiral ligand and an electron donor; crystals belong to a monoclinic system, and both the space group of the ZnW-DPNDI-PYI1 and the space group of the ZnW-DPNDI-PYI2 areP2(1). The chiral polyacid-based metal organic framework material is a multifunctional inorganic porous material, and has an asymmetric photocatalytic oxidation technology, and in the technology, a photocatalyst is driven by visible light to be an excited state, then the excited-state photocatalyst and substrates are subjected to an oxidation-reduction reaction, and therefore reactions of relatedfree radical types are completed.

Description

technical field [0001] The invention belongs to the technical field of preparation of polyoxometalate functional materials, and in particular relates to a chiral polyacid-based metal-organic framework material and its preparation method and application. Background technique [0002] Epoxy compounds are important intermediates and chemical raw materials for organic synthesis. During the "Eleventh Five-Year Plan", my country's propylene oxide industry is booming, and China has become the world's largest producer and seller of propylene oxide. In 2010, the production capacity reached 1.545 million tons, and the output was 1.4376 million tons. With the large demand for polyether polyol industry, high-quality electronic products, and aerospace product manufacturing, the demand for propylene oxide products in my country is still developing rapidly. It is predicted that the consumption will soon reach 2.756 million tons by 2020. In particular, optically active epoxides are importan...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22C07D301/04C07D301/08C07D303/08C07D303/22
Inventor 韩秋霞马鹏涛李杰何佳宸司晨
Owner HENAN UNIVERSITY
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