阅读说明：本技术 一种非均相催化剂Cu@COF-Me-M及其制备方法和应用 (Heterogeneous catalyst Cu @ COF-Me-M and preparation method and application thereof ) 是由 董育斌 阚璇 王建成 牛相龙 尚金燕 乔华 于 2021-01-18 设计创作，主要内容包括：本发明具体涉及一种非均相催化剂Cu@COF-Me-M及其制备方法和应用。现有非均相催化剂存在扩散速度慢,并且制备难度较大。本发明提供了一种非均相催化剂Cu@COF-Me-M,采用式Ⅰ所示化合物、三甲酰间苯三酚作为原料,加入均三甲苯、二甲基亚砜及乙酸反应体系中加热反应降至室温,即得共价有机框架COF-Me-M,与氯化铜反应后得到所述Cu@COF-Me-M,该非均相催化剂可有效的催化三组分偶联反应。该非均相催化剂制备工艺更加简单,用量少并且催化效率高,回收方便,应用于工业化生产具有重要意义。(The invention particularly relates to a heterogeneous catalyst Cu @ COF-Me-M and a preparation method and application thereof. The existing heterogeneous catalyst has slow diffusion speed and higher preparation difficulty. The invention provides a heterogeneous catalyst Cu @ COF-Me-M, which is prepared by taking a compound shown in a formula I and tri-benzoyl phloroglucinol as raw materials, adding mesitylene, dimethyl sulfoxide and acetic acid into a reaction system, heating for reaction, cooling to room temperature to obtain a covalent organic framework COF-Me-M, and reacting with copper chloride to obtain the Cu @ COF-Me-M. The heterogeneous catalyst is simpler in preparation process, less in dosage, high in catalysis efficiency and convenient to recover, and has important significance in application to industrial production.)

1. A compound selected from compounds having the structure shown in formula i or pharmaceutically acceptable salts, solvates, and hydrates thereof:

2. the method for preparing the compound of claim 1, wherein the compound of formula I is obtained by synthesizing an intermediate product A from 2, 5-dibromotoluene and 4-methoxycarbonylphenylboronic acid, and reacting the intermediate product A with hydrazine hydrate, wherein the structure of the intermediate product A is shown as the following formula II:

3. the method for preparing the compound according to claim 2, which comprises the following steps:

(1) heating and separating a product in a 1, 4-dioxane solution by taking 2, 5-dibromotoluene and 4-methoxycarbonylphenylboronic acid as raw materials, cesium fluoride as alkali and tetrakis (triphenylphosphine palladium) as a catalyst to obtain an intermediate product A;

(2) and (3) reacting the intermediate product A with hydrazine hydrate, and reacting by using methanol as a solvent to obtain the compound shown in the formula I.

4. The method for preparing the compound according to claim 3, wherein the heating temperature in step (1) is 85 to 95 ℃; specifically, the temperature is 90 ℃;

or, the separation product is separated by a column chromatography mode;

or the molar ratio of the 2, 5-dibromotoluene to the 4-methoxycarbonylphenylboronic acid to the cesium fluoride is 0.8-1.2: 2-2.5: 3.5-4.5; specifically, the molar ratio of the 2, 5-dibromotoluene to the 4-methoxycarbonylphenylboronic acid to the cesium fluoride is 1.0:2.4: 4.0.

5. The method for preparing the compound according to claim 3, wherein in the step (2), the molar ratio of the intermediate product A to the hydrazine hydrate is 1.2-1.8: 12-13; specifically, the molar ratio of the intermediate product A to the hydrazine hydrate is 1.6: 12.8.

6. A heterogeneous catalyst Cu @ COF-Me-M is prepared by the following steps: adding the compound of claim 1 and trimethyolrophenol into a solvent system, and heating to react to obtain a covalent organic framework COF-Me-M; and adding the COF-Me-M into an organic solution of copper chloride to react to obtain the Cu @ COF-Me-M.

7. The heterogeneous catalyst Cu @ COF-Me-M according to claim 6, wherein the molar ratio of the compound according to claim 1 to tricresyl is from 0.04 to 0.05: 0.02 to 0.04; further, 0.045: 0.03;

or, the solvent system comprises mesitylene, dimethyl sulfoxide and acetic acid; further, in the mixed solvent system of mesitylene, dimethyl sulfoxide and acetic acid, the volume ratio of the mesitylene, the dimethyl sulfoxide and the acetic acid is 1.3-1.8: 0.3-1.5: 0.54-0.6; furthermore, the volume ratio of the mesitylene to the dimethyl sulfoxide to the acetic acid is 1.6:0.4: 0.5;

or the parameters of the heating reaction are as follows: keeping the temperature of the mixture constant for 70-75 hours at the temperature of 55-65 ℃; further, the heating reaction comprises the following specific steps: adding the compound of claim 1 and trimesic phloroglucinol into a mixed solvent of mesitylene and dimethyl sulfoxide, stirring for dissolving, adding acetic acid into a reaction system, stirring for 72 hours at the temperature of 60 ℃, and cooling to room temperature to obtain the covalent organic framework COF-Me-M.

8. The heterogeneous catalyst Cu @ COF-Me-M according to claim 6, wherein the molar ratio of the COF-Me-M to copper chloride is 1: 3-4; further, the molar ratio of COF-Me-M to copper chloride is 1: 3.6;

alternatively, the organic solution of copper chloride is an acetonitrile solution including, but not limited to, copper chloride.

9. The heterogeneous catalyst Cu @ COF-Me-M according to claim 6, wherein the COF-Me-M is prepared by adding an organic solution of copper chloride under stirring at room temperature and purifying to obtain the Cu @ COF-Me-M;

or, the room temperature is 15-25 ℃;

or, the purification mode is as follows: and centrifuging the reaction product to obtain a solid part, sequentially cleaning the solid part by adopting the organic reagent and acetone, and drying to obtain the Cu @ COF-Me-M.

10. Use of the heterogeneous catalyst Cu @ COF-Me-M according to any one of claims 6 to 9 as a catalyst for a three-component coupling reaction;

preferably, the three-component coupling reaction is as follows:

further, the heterogeneous catalyst Cu @ COF-Me-M is applied to catalyzing three-phase coupling reaction of phenylacetylene, dichloromethane and diethylamine, and the reaction comprises the following specific steps: uniformly mixing phenylacetylene, dichloromethane, diethylamine, 1, 8-diazabicycloundecene-7-ene and Cu @ COF-Me-M, and heating and stirring the mixture at 75-85 ℃ for reaction to obtain a corresponding product; wherein the molar ratio of phenylacetylene, dichloromethane, diethylamine, 1, 8-diazabicycloundecen-7-ene, Cu @ COF-Me-M is 3:5:5:6: 0.04.

Technical Field

The invention belongs to the technical field of COF catalysts, and particularly relates to a heterogeneous catalyst Cu @ COF-Me-M, a preparation method of the heterogeneous catalyst and application of the heterogeneous catalyst in catalysis of three-component coupling reaction.

Background

The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.

A Covalent Organic Framework (COF) is a hot point of recent research, and compared with a traditional porous material, a COFs material has a pore structure with a specific size and uniformly distributed inside, and the stability of the COFs material in an acid-base environment is far higher than that of other porous materials. Therefore, the application of COFs as crystalline porous materials in catalysis has great advantages. In the field of catalysts, when the catalyst and the reactant are in different phases, heterogeneous catalysis, i.e., heterogeneous catalysis, is known. The heterogeneous catalyst is presented in the reaction of different phases and used as an essential material in the phase transfer catalytic synthesis technology, so that the heterogeneous catalyst not only has good catalytic effect and catalytic efficiency, but also can be conveniently separated from a reaction system after the reaction is finished, and the cyclic utilization is realized.

Nevertheless, the following problems still exist with current heterogeneous catalysts: (1) since in heterogeneous catalytic reactions the catalyst is out of phase with the reaction system, the two are contacted and then undergo a series of very complex diffusion processes. The reactants first diffuse to the catalyst surface and then continue to diffuse within the catalyst's interstices until they react upon reaching the active sites on the catalyst. The reaction products are separated from the catalyst by a series of diffusion processes. This results in a heterogeneously catalyzed reaction at a lower rate than a homogeneously catalyzed reaction. (2) Heterogeneous catalysts require very high stability for the production process and are also more complex to prepare than homogeneous catalysts. After being put into production, the catalyst also has more problems than homogeneous catalysts. This results in a very high technical and time investment for developing a heterogeneous catalyst. In view of the above, the inventors believe that the search for a novel phase transfer catalytic material with high catalytic efficiency and simple preparation becomes a scientific problem to be solved in the development of heterogeneous phase transfer catalysts.

Disclosure of Invention

The invention provides a three-component catalyst based on a covalent organic framework structure in the previous research, and further provides a catalyst with simpler preparation process and good catalytic efficiency aiming at the previous research results.

Based on the technical effects, the invention provides the following technical scheme:

in a first aspect, the present invention provides a compound selected from compounds having the structure shown in formula i:

the second aspect of the present invention provides a preparation method of the compound of the first aspect, wherein the preparation method comprises synthesizing an intermediate product a from 2, 5-dibromotoluene and 4-methoxycarbonylphenylboronic acid as raw materials, and reacting the intermediate product a with hydrazine hydrate to obtain the compound of formula i, wherein the structure of the intermediate product a is shown in the following formula ii:

preferably, the preparation method comprises the following specific steps:

(1) heating and separating a product in a 1, 4-dioxane solution by taking 2, 5-dibromotoluene and 4-methoxycarbonylphenylboronic acid as raw materials, cesium fluoride as alkali and tetrakis (triphenylphosphine palladium) as a catalyst to obtain an intermediate product A;

(2) and (3) reacting the intermediate product A with hydrazine hydrate, and reacting by using methanol as a solvent to obtain the compound shown in the formula I.

In the research idea of the invention, the compound is used as a connection structure of a COF material, the preparation method of the compound is simpler and more convenient than the preparation method of a ligand in the previous scheme, and high temperature and toxic reagents are not needed in the preparation process.

In a third aspect of the invention, a heterogeneous catalyst Cu @ COF-Me-M is provided, and the preparation method of the heterogeneous catalyst is as follows: adding the compound of the first aspect and tricresyl into a solvent system, and heating for reaction to obtain a covalent organic framework COF-Me-M; and adding the COF-Me-M into an organic solution of copper chloride to react to obtain the Cu @ COF-Me-M.

In a fourth aspect of the invention, the heterogeneous catalyst Cu @ COF-Me-M in the third aspect is used as a three-component coupling reaction catalyst.

Preferably, the three-component coupling reaction is as follows:

in the three-component coupling reaction, aiming at various compounds meeting the general formula, the heterogeneous catalyst Cu @ COF-Me-M can achieve a good catalytic effect, the yield reaches 99%, and the catalyst is used in the reaction in a very small amount, so that the three-component coupling reaction has an important economic significance in meeting the coupling reaction of the general formula in industrial production.

The beneficial effects of one or more technical schemes are as follows:

(1) the heterogeneous catalyst provided by the invention has the advantages of low preparation reaction temperature, high reaction yield and reduced energy consumption.

(2) The heterogeneous catalyst provided by the invention is applied to the three-component coupling reaction, heterogeneous catalysis is realized, and the catalyst is convenient to recover after the reaction is finished. And when the catalyst is applied to the reaction, the dosage of the catalyst is small, the reaction yield is high, and the production cost is effectively reduced.

(3) The heterogeneous catalyst provided by the method has the advantages of simple preparation method, low cost, strong practicability and easy popularization.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.

FIG. 1 is a drawing of organic ligand L in example 1¹HNMR；

FIG. 2 is an infrared spectrum of an organic ligand L in example 1;

FIG. 3 is an IR spectrum of COF-Me-M in example 2;

FIG. 4 is a PXRD spectrum of COF-Me-M in example 2;

FIG. 5 is an IR spectrum of Cu @ COF-Me-M in example 2;

FIG. 6 is a PXRD spectrum of Cu @ COF-Me-M in example 2.

Detailed Description

It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.

As described in the background art, the heterogeneous catalyst has the defects of slow diffusion speed of a reaction system and difficult preparation process. In order to solve the above technical problems, the inventors have further studied on the heterogeneous catalyst provided in the previous research, and have provided a heterogeneous catalyst with a more simplified preparation process, which has a good catalytic effect for catalyzing a three-component coupling reaction.

In a first aspect, the present invention provides a compound selected from compounds having the structure shown in formula i:

the second aspect of the present invention provides a preparation method of the compound of the first aspect, wherein the preparation method comprises synthesizing an intermediate product a from 2, 5-dibromotoluene and 4-methoxycarbonylphenylboronic acid as raw materials, and reacting the intermediate product a with hydrazine hydrate to obtain the compound of formula i, wherein the structure of the intermediate product a is shown in the following formula ii:

preferably, the preparation method comprises the following specific steps:

(1) heating and separating a product in a 1, 4-dioxane solution by taking 2, 5-dibromotoluene and 4-methoxycarbonylphenylboronic acid as raw materials, cesium fluoride as alkali and tetrakis (triphenylphosphine palladium) as a catalyst to obtain an intermediate product A;

(2) and (3) reacting the intermediate product A with hydrazine hydrate, and reacting by using methanol as a solvent to obtain the compound shown in the formula I.

Further, in the step (1), the heating temperature is 85-95 ℃; further, it is 90 ℃.

Further, in the step (1), the separation product is separated by column chromatography, in a specific embodiment, the separation product is separated by silica gel column chromatography, and the solvent is removed by reduced pressure distillation to obtain the intermediate product a.

Further, in the step (1), the molar ratio of the 2, 5-dibromotoluene to the 4-methoxycarbonylphenylboronic acid to the cesium fluoride is 0.8-1.2: 2-2.5: 3.5-4.5.

In some embodiments of the invention, the molar ratio of 2, 5-dibromotoluene, 4-methoxycarbonylphenylboronic acid and cesium fluoride is 1.0:2.4: 4.0.

Further, in the step (2), the molar ratio of the intermediate product A to hydrazine hydrate is 1.2-1.8: 12-13.

In some embodiments of the invention, the molar ratio of intermediate a to hydrazine hydrate is 1.6: 12.8.

In a third aspect of the invention, a heterogeneous catalyst Cu @ COF-Me-M is provided, and the preparation method of the heterogeneous catalyst is as follows: adding the compound of the first aspect and tricresyl into a solvent system, and heating for reaction to obtain a covalent organic framework COF-Me-M; and adding the COF-Me-M into an organic solution of copper chloride to react to obtain the Cu @ COF-Me-M.

Preferably, the molar ratio of the compound of the first aspect to the phloroglucinol is 0.04-0.05: 0.02 to 0.04; further, it was 0.045: 0.03.

Preferably, the solvent system comprises mesitylene, dimethyl sulfoxide and acetic acid.

Further, in the mixed solvent system of mesitylene, dimethyl sulfoxide and acetic acid (6M), the volume ratio of the mesitylene, the dimethyl sulfoxide and the acetic acid is 1.3-1.8: 0.3-1.5: 0.54-0.6.

In some embodiments of the invention, the volume ratio of mesitylene, dimethyl sulfoxide, and acetic acid is 1.6:0.4: 0.5.

Preferably, the parameters of the heating reaction are as follows: keeping the temperature constant at 55-65 ℃ for 70-75 hours.

In some embodiments of the above preferred embodiments, the heating reaction comprises the following steps: adding the compound and the tri-methy-phloroglucinol into a mixed solvent of mesitylene and dimethyl sulfoxide, stirring and dissolving, adding acetic acid into a reaction system, stirring for 72 hours at the temperature of 60 ℃, and cooling the reaction to room temperature to obtain the covalent organic framework COF-Me-M.

Preferably, the molar ratio of COF-Me-M to copper chloride is 1: 3-4; further, the molar ratio of COF-Me-M to copper chloride is 1: 3.6.

Preferably, the organic solution of copper chloride is an acetonitrile solution or methanol including but not limited to copper chloride.

Preferably, the COF-Me-M is prepared by adding the COF-Me-M into an organic solution of copper chloride and stirring at room temperature, and the Cu @ COF-Me-M is obtained after purification.

Further, the room temperature is 15-25 ℃.

Further, the purification mode is as follows: and centrifuging the reaction product to obtain a solid part, sequentially cleaning the solid part by adopting the organic reagent and acetone, and drying to obtain the Cu @ COF-Me-M.

In a fourth aspect of the invention, the heterogeneous catalyst Cu @ COF-Me-M in the third aspect is used as a three-component coupling reaction catalyst.

Preferably, the three-component coupling reaction is as follows:

further, Ar-is one of phenyl, chlorphenyl, hydroxymethyl phenyl, formylphenyl, biphenyl and tolyl.

Further, R-is ethyl.

In a specific implementation manner of the preferable technical scheme, the heterogeneous catalyst Cu @ COF-Me-M is applied to catalyzing three-phase coupling reaction of phenylacetylene, dichloromethane and diethylamine, and the reaction comprises the following specific steps: uniformly mixing phenylacetylene, dichloromethane, diethylamine, 1, 8-diazabicycloundecene-7-ene and Cu @ COF-Me-M, and heating and stirring the mixture at 75-85 ℃ for reaction to obtain a corresponding product; wherein the molar ratio of phenylacetylene, dichloromethane, diethylamine, 1, 8-diazabicycloundecen-7-ene, Cu @ COF-Me-M is 3:5:5:6: 0.04.

The heterogeneous catalyst Cu @ COF-Me-M realizes heterogeneous catalysis in the catalysis of the three-component coupling reaction, and after the reaction is finished, the catalyst can be recovered by simple post-treatment modes such as centrifugation and filtration. In addition, in the reaction system, the heterogeneous catalyst Cu @ COF-Me-M is used in a small amount, and the catalytic yield can reach about 99 percent for various reactions conforming to the general formula.

In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.

Example 1: preparation of Compounds of formula I

In this example, a process for the preparation of a compound of formula i is provided, the specific preparation steps being as follows:

(1) under nitrogen, 4.33g (24mmol) of 4-methoxycarbonylphenylboronic acid and 6g (40mmol) of cesium fluoride were placed in a 250mL three-necked flask, and a mixed solution of 150mL of 1, 4-dioxane and 2.754mL (10mmol) of 2, 5-dibromotoluene was added, followed by addition of 1.6g of tetrakis (triphenylphosphine) palladium catalyst and reflux at 90 ℃ for 48 hours. After the reaction was complete, an orange solution was obtained with a black precipitate. The system was evaporated to dryness under reduced pressure and air dried, and then subjected to silica gel column chromatography (petroleum ether and dichloromethane) to obtain 3.0g of a white product with a yield of 82%.

(2) 1.0g of intermediate A was weighed out and added to 30mL of methanol, after dissolution, 0.775mL (12.8mmol) of hydrazine hydrate was added and the reaction was continued at room temperature for 12 h. The solvent was evaporated under reduced pressure, washed with ethanol and dried. 0.7g of a white solid was obtained in a yield of 70%.

The compounds prepared in this example were subjected to structural characterization, which¹HNMR, IR are shown in FIGS. 1 and 2, respectively.

Example 2 Synthesis of Cu @ COF-Me-M

(1)16.2mg (0.045mmoL) of the compound of example 1 and 6.3mg (0.03mmoL) of phloroglucinol are placed in a reaction flask and mesitylene: dimethyl sulfoxide: acetic acid (6M) was mixed with 16:4:5 (vol.) in a total of 2.5mL, and the mixture was kept at 60 ℃ for 3 days (72 h). Cooling to room temperature, centrifuging, taking out the precipitate, and drying in vacuum to obtain COF-Me-M.

(2) Copper chloride (6mg) was added to a 50mL round-bottom flask, dissolved in 20mL acetonitrile, and then 20mg COF was added and stirred at room temperature for 24h, after the reaction was completed, the mixture was centrifuged, washed with acetonitrile 3 times, then with acetone 3 times, and dried at 80 ℃ for 3h to obtain Cu @ COF-Me-M.

The polymer was characterized by IR, PXRD and the results are shown in figures 5 and 6, respectively.

Example 3:

phenylacetylene (0.3mmol, 30. mu.L), Cu @ COF-Me-M (0.004mmol,5mg), dichloromethane (0.5mmol,35ul), diethylamine (0.5mmol,62ul), 1, 8-diazabicycloundec-7-ene (0.6mmol,110ul) acetonitrile 2mL were added to a 5mL single neck round bottom flask, the reaction was stirred at constant temperature of 80 ℃ and followed by thin layer chromatography. After the reaction is finished, the reaction system is cooled to room temperature, the organic phase is quickly centrifuged, the catalyst is recovered and directly put into the next reaction, the yield of the organic phase is calculated through a gas chromatography test, and the catalytic effect is shown in table 1.

TABLE 1

Yield determination by GC

It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.