CN114381006B - Covalent organic framework material BM-SO with acid-base dual functions 3 H, preparation method and application thereof - Google Patents
Covalent organic framework material BM-SO with acid-base dual functions 3 H, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a covalent organic framework material BM-SO with acid-base dual functions 3 H, a preparation method and application thereof, wherein the material has a structure shown as a formula (I), and the preparation method comprises the following steps: firstly, synthesizing a covalent organic framework material BM of benzimidazolyl under the catalysis of a photocatalyst; then BM and 1, 3-propane sultone are subjected to ring-opening N atom alkylation reaction to obtain a covalent organic framework material BM-SO 3 H. The material has a benzimidazole and propane sulfonic acid structure, so that the material has the acid-base double functions. With BM-SO 3 H is a heterogeneous catalyst, and catalyzes the Knoevenagel condensation reaction of the series decarboxylated aldehyde, and the yield can reach 95-99%. Heterogeneous catalyst BM-SO 3 H shows excellent catalytic performance, thermal stability and recycling performance, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of chemical engineering, and particularly relates to a covalent organic framework material BM-SO with acid-base double functions 3 H, and a preparation method and application thereof.
Background
Many homogeneous catalysts are used in cascades requiring concerted catalysis by acid-base functionalities. However, the homogeneous catalytic system is cumbersome in product separation and the catalyst is difficult to reuse, which causes a problem of increased cost. In addition, the activity of the bifunctional acid-base catalyst is easily deactivated in the homogeneous reaction medium due to acid-base neutralization. Therefore, solid heterogeneous bifunctional acid-base catalysts, in which acidic and basic functional groups are immobilized at different positions in a solid matrix, are receiving increasing attention for one-pot cascade reactions. To date, acid-base bifunctional catalytic sites with synergistic effects on silica, heteropolyacids, metal-organic frameworks, metal oxides, graphene oxide and covalent organic polymers have been used in cascades of reactions.
Among the C-C bond coupling reactions, the Knoevenagel condensation reaction is a very important reaction for human name. The traditional industrial application mainly adopts a homogeneous catalyst to catalyze the Knoevenagel condensation reaction, so that the problems of complicated catalyst separation and difficult reutilization exist. The heterogeneous catalyst prepared by adopting the heterogeneous catalysis method through immobilizing the functional groups on the material easy to recover has both economy and greenness. However, the prior heterogeneous catalyst has the phenomena of poor cycle performance caused by insufficient catalyst loading, unstable loading and the like in the research. Therefore, the application of the covalent organic framework material with large specific surface area, strong binding capacity with the catalyst and good cycle performance to catalyze the C-C bond coupling reaction has become a development trend.
Covalent organic framework materials (COFs) are an emerging class of materials that are based on the precise organization of light atoms into two-or three-dimensional porous crystalline structures connected by strong covalent bonds, with predictable control over the topology and porosity of the composition. Although applications of covalent organic framework materials in relation to gas adsorption and storage have been explored, the appropriate introduction of new functional blocks has opened up new potential uses, as advanced materials, including applications in catalysis, drug delivery, sensing, etc. However, most of the current methods for synthesizing COFs adopt a solvothermal method, which requires a high-temperature mixed solvent system.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a covalent organic framework material BM-SO with acid-base bifunctional 3 The benzimidazole structure is introduced into a covalent organic framework material and is modified by 1, 3-propane sultone to ensure that the benzimidazole structure retains unmodified alkalescent groups and sulfonic acidAnd (3) chemically modifying the modified acidic group. The method is applied to acid-base synergistic heterogeneous catalysis to catalyze Knoevenagel condensation reaction of series decarboxylated aldehyde. The synthesis method does not use the traditional solvothermal method to synthesize the covalent organic framework material, only needs reaction at room temperature, adopts a single solvent system, improves the synthesis condition, is simple, low in cost, green and environment-friendly, and has good catalytic performance and reusability when being used as a catalyst subsequently.
The invention is realized by the following technical scheme:
covalent organic framework material BM-SO with acid-base dual functions 3 H, has a structure as shown in formula (I):
covalent organic framework material BM-SO with acid-base dual functions 3 The preparation method of H comprises the following steps:
step 1) synthesis of a benzimidazolyl-based covalent organic framework material BM: aldehyde monomers and ammonia monomers are reacted for 24 hours at room temperature with 470nm blue light by taking xanthene compounds as a photocatalyst in an organic solvent according to the molar ratio of 2:3, a product is obtained by centrifugation, and then the product is repeatedly washed by water and ethanol and dried in vacuum to obtain the BM;
step 2) covalent organic framework material BM-SO with acid-base dual function 3 H synthesis: dispersing the BM prepared in the step 1) in an ethanol solution, adding 0.5eq of 1, 3-propane sultone, stirring for 3-6 h at room temperature, filtering, washing and drying to obtain the covalent organic framework material BM-SO with acid-base dual functions 3 H。
Preferably, the aldehyde monomer in step 1) is 1,3, 5-tri (p-formylphenyl) benzene, and the ammonia monomer is 1,2,4, 5-benzene tetramine tetrahydrochloride.
Preferably, the organic solvent in step 1) is one of N, N-dimethylformamide, dimethyl sulfoxide and methanol.
Preferably, the xanthene compound in the step 1) is one of fluorescein, sodium fluorescein and 5-azido fluorescein, and the addition amount is 3 mol%.
Covalent organic framework material BM-SO with acid-base dual functions 3 The application of H in catalyzing the Knoevenagel condensation reaction of the series decarboxylated aldehyde.
Preferably, BM-SO is added 3 H is directly added into a reaction system to be used as a catalyst for the Knoevenagel condensation reaction of the series decarboxylated aldehyde, and the catalytic reaction equation is shown as a formula (II):
in the formula (II), R is one of hydrogen atom, bromine atom, chlorine atom, methyl, methoxyl, nitryl, fluorine atom, trifluoromethyl and phenyl; r 1 Is a cyano group; r 2 Is one of cyano and ethyl acetate;
the method comprises the following specific steps:
adding various substitutes of benzaldehyde dimethyl acetal, malononitrile or ethyl cyanoacetate, and catalyst BM-SO into container 3 H and a solvent react for 5-6 hours at 50-60 ℃, after the reaction is finished, the reaction product is filtered and separated, a filter cake is the catalyst and can be recycled by washing, the filtrate is extracted by ethyl acetate firstly, and then the product is obtained by silica gel column chromatography purification, and the eluent is ethyl acetate and petroleum ether.
Preferably, the solvent is one of water, ethanol, toluene, dimethyl sulfoxide and N, N-dimethylformamide.
The invention has the following beneficial effects:
(1) the covalent organic framework material BM based on the benzimidazolyl group is simple in synthesis method, good in thermal stability, high in specific surface area and the like.
(2) The acid-base double compound of the inventionFunctional covalent organic framework materials BM-SO 3 The preparation method of the H is simple, the material has the acid-base concerted catalysis function due to the specific properties of the material when the material is used as a heterogeneous catalyst to participate in the Knoevenagel condensation reaction of the series decarboxylated aldehyde, and the covalent organic framework material is an insoluble solid, so that the catalyst has the property of recycling, is easy to recycle, has better thermal stability, higher catalysis efficiency and recyclability, is mild in catalysis condition, and is easy to separate from a product.
Drawings
FIG. 1 shows BM and BM-SO 3 H infrared spectrogram;
FIG. 2 shows BM-SO 3 Transmission electron micrograph of H: (a) on the 0.5 μm scale, (b) on the 200nm scale;
FIG. 3 shows BM-SO 3 Scanning electron micrograph H: (a) on the scale of 1 μm, (b) on the scale of 200 nm;
FIG. 4 shows BM and BM-SO 3 H thermogravimetric analysis;
FIG. 5 shows BM-SO 3 A nitrogen adsorption-desorption curve chart of H;
FIG. 6 shows BM-SO 3 Bar graph of the yield of the Knoevenagel condensation reaction of H-catalyzed series decarboxylated aldehydes versus the number of cycles of catalysis.
Detailed Description
The present invention is further described with reference to the accompanying drawings and specific embodiments, which are implemented on the premise of the technical solution of the present invention and give detailed implementation procedures, but the scope of the present invention is not limited to the following embodiments.
Example 1
Covalent organic framework material BM-SO with acid-base dual functions 3 H, has a structure as shown in formula (I):
covalent organic framework material BM-SO with acid-base dual functions 3 The preparation method of H comprises the following specific steps:
(1) synthesis of 1,3, 5-tris (p-formylphenyl) benzene (TFPB)
Into a 100mL round bottom flask were charged 251mg of 1,3, 5-tribromobenzene, 553mg of 4-formylphenylboronic acid, 530mg of potassium carbonate and 10mg of Pd (pph) 3 ) 2 Cl 2 Then, 40mL of ethanol was added, and the reaction was refluxed at 80 ℃ for 8 hours. After the reaction is finished, potassium carbonate and catalyst Pd (pph) are removed by filtration 3 ) 2 Cl 2 Collecting the filtrate, concentrating, and performing column chromatography to obtain the trisubstituted product 1,3, 5-tri (p-formylphenyl) benzene as white solid.
(2) Synthesis of benzimidazolyl-based covalent organic framework materials BM
Into a 250mL round-bottomed flask was charged 100mL of N, N-dimethylformamide, and then 1,3, 5-tris (p-formylphenyl) benzene (192mg, 0.5mmol) and 1,2,4, 5-benzenetetraamine tetrahydrochloride (208 mg, 0.75mmol) were sequentially added to the round-bottomed flask, and 6mg of photocatalyst a (sodium fluorescein) was added to react at room temperature with 470nm blue light for 24 hours. After the reaction is finished, the product is washed by water and ethanol for 3 times respectively, and then is dried in vacuum at 100 ℃ for 12 hours to obtain yellow powder, namely the target product BM, with the yield of about 83 percent.
(3) Benzimidazolyl-based covalent organic framework material BM-SO with acid-base bifunctional function 3 Synthesis of H
Dispersing 100mg of BM in 50mL of ethanol in a 100mL round-bottom flask to form a suspension, adding 20mg of 1, 3-propane sultone, stirring at room temperature for 3-6 h, filtering, washing and drying to obtain a target product BM-SO 3 H, yield 90%.
For the above synthesized covalent organic framework material BM based on benzimidazolyl group and the acid having benzimidazolyl groupBase bifunctional covalent organic framework materials BM-SO 3 And H, performing characterization.
As shown in FIG. 1, BM and BM-SO 3 H infrared spectrogram, covalent organic framework material BM-SO after sulfonation modification 3 The infrared passing comparison of H and the covalent organic framework material BM which is not modified by sulfonation can find that 2960cm -1 The absorption peak at (A) still shows that the covalent organic framework material after sulfonation still has a-NH structure, that the weak alkalinity still remains, and at 1042cm -1 A new absorption peak appears, which is-SO 3 Stretching vibration of H, which indicates successful attachment of the sulfonic acid group, thereby confirming BM-SO 3 And H is successfully synthesized.
FIG. 2 and FIG. 3 are BM-SO, respectively 3 The transmission electron microscope image and the scanning electron microscope image of H show that BM-SO 3 H is a spherical stacked sheet which is closely arranged and has a size between the mesopores and the macropores.
FIG. 4 shows BM and BM-SO 3 H, the change trend of the two materials is basically consistent: there is a loss rate of about 8% at around 100 ℃ due to the loss of adsorbed water. Then the weight is basically not lost when the temperature is about 250 ℃, the decomposition is started from about 250 ℃, and BM-SO is obtained after sulfonic acid modification 3 The H weight loss was slightly less than the unmodified BM. BM-SO modified by sulfonic acid at about 450 deg.C 3 H initially showed a large loss, essentially corresponding to that of unmodified BM (about 25%), from 450 ℃ to 800 ℃ the loss of both materials was essentially identical, at 800 ℃ the loss of both materials was about 40%, both materials retained about 60% by weight, showing that BM and BM-SO are present in combination 3 H has good thermal stability, thereby ensuring BM-SO 3 H has good stability when being used as a heterogeneous catalyst in the application process.
Shown as BM-SO in FIG. 5 3 The nitrogen adsorption-desorption curve chart of H shows BM-SO 3 H has a large specific surface area.
Example 2
BM-SO prepared in example 1 3 H participates in series decarboxylation of aldehyde Kno as a heterogeneous catalystThe evenagel condensation reaction is shown as a formula (II), and the method comprises the following specific steps:
(1) benzaldehyde dimethyl acetal (0.152g, 1mmol), malononitrile (0.07 g, 1.05mmol) and 1 mol% BM-SO were added to the reaction flask respectively 3 H (0.005g) and water (5mL) were stirred at 60 ℃ for 5H. After the reaction is finished, filter cake (namely catalyst BM-SO) is separated and recovered by filtration 3 H) Extracting the filtrate with ethyl acetate to obtain an organic layer, purifying by silica gel column chromatography to obtain a product, wherein the eluent is ethyl acetate and petroleum ether, and calculating the product yield.
(2) Catalyst BM-SO recovered in the reaction 3 And H, washing with ethanol, centrifuging, drying in vacuum, carrying out next cyclic catalysis under the same condition, carrying out catalytic reaction for 10 times in a cyclic manner, and calculating the yield of each product.
Subjecting BM-SO to 3 H yield of product obtained by 10 times of cyclic catalytic reaction in the condensation reaction of serially-connected decarboxylated aldehyde Knoevenagel is prepared into a bar graph of yield and cyclic catalytic times as shown in figure 6, and as can be seen from figure 6, the benzimidazolyl-based covalent organic framework material BM-SO with acid-base bifunctional prepared in example 1 3 H has good catalytic performance and reusability.
Comparative example 1
(1) Catalyst CBAP-1 (EDA-SO) 3 H) Preparation of
In a 250mL round bottom flask equipped with a condenser were placed 1,3, 5-triphenylbenzene (10mmol, 3.06g), terephthaloyl chloride (15mmol, 3.05g), anhydrous AlCl 3 (15mmol, 2.00g) and dichloromethane DCM (180 mL). The mixture was refluxed for 12h to give a dark brown solid powder and the precipitate was filtered and washed sequentially with DCM, methanol and water. The product was further purified in a soxhlet extractor for 10h, the catalyst was completely removed with water, and dried under vacuum at 130 ℃ for 12h to obtain solvent-free CBAP-1. CBAP-1(1.00g) was then added to a solution of ethylenediamine (2mL in 40mL of methanol) and refluxed for 15 h. After cooling to room temperature, slowlyAdding NaBH 4 (about 2.00g) and the mixture was stirred at room temperature for 10 h. The solid mixture was then filtered and washed with methanol and water, in order, and dried at 130 ℃ to give 1.18g of CBAP-1 (EDA). 1.00g of CBAP-1(EDA) was then placed in 40mL of dry DCM and cooled to 5 ℃ with stirring in an ice bath for 10 min. Chlorosulfonic acid (0.10mL), dissolved in 5mL DCM, was then added dropwise to the CBAP-1(EDA) suspension over 5min, and the resulting mixture was stirred at room temperature for 2 h. Finally, the mixture was poured into ice-cold water (200mL), the solid phase was filtered, washed with distilled water (100 mL. times.3), and dried at 110 ℃ to give 1.04g of CBAP-1 (EDA-SO) 3 H)。
(2)CBAP-1(EDA-SO 3 H) Participating in Knoevenagel condensation reaction of series decarboxylated aldehyde as a catalyst
Benzaldehyde dimethyl acetal (1mmol), malononitrile (1.05mmol) and CBAP-1 (EDA-SO) were put into a reaction tube equipped with a condenser 3 H) (20mg), toluene (4mL) and H 2 O (1 mL). The reaction mixture was kept at 70 ℃ for 80min under magnetic stirring. Then purifying by silica gel column chromatography to obtain the product, and calculating the yield.
Comparative example 2
(1) Preparation of catalyst Zr (IV) -UiO-67
ZrCl 4 (34.5mg, 0.15mmol) and 2,2 '-diamino- [1,1' -biphenyl]-4,4' -dicarboxylic acid (41mg, 0.15mmol) was mixed in a molar ratio of 1:1 in a glass tube. Then, 2mL of N, N-Dimethylformamide (DMF) and glacial acetic acid (257. mu.L, 4.5mmol) were added thereto. The total reaction mixture was sonicated for 15 min and heated at 120 ℃ for 24h on a preheated block heater. After 24h, the reaction mixture was cooled to room temperature. The yellow precipitate was collected by filtration, washed several times with acetone, and dried in a vacuum oven at 60 ℃ for 4h to give Zr (IV) -UiO-67.
(2) Zr (IV) -UiO-67 as a catalyst participates in Knoevenagel condensation reaction of series decarboxylated aldehyde
A50 mL round-bottomed flask was charged with benzaldehyde dimethyl acetal (1mmol), malononitrile (1.05mmol), Zr (IV) -UiO-67(15mg) and ethanol (4mL) and reacted at 60 ℃ for 10 hours. Then purifying by silica gel column chromatography to obtain the product, and calculating the yield.
Test example 1
In example 2, comparative example 1 and comparative example 2, BM-SO was used 3 H、CBAP-1(EDA-SO 3 H) And Zr (IV) -UiO-67 as a catalyst for the Knoevenagel condensation reaction of the series decarboxylated aldehydes are shown in Table 1 below:
TABLE 1 comparison of product yields
| Examples | Catalyst and process for preparing same | Solvent(s) | Temperature of | Time | Yield of |
| Example 2 | BM-SO 3 H | H 2 O | 60℃ | 5h | 99％ |
| Comparative example 1 | CBAP-1(EDA-SO 3 H) | |
70℃ | 80min | 84％ |
| Comparative example 2 | Zr(IV)-UiO-67 | |
60℃ | 4h | 98％ |
As can be seen from Table 1, the covalent organic framework material BM-SO with acid-base bifunctional of the present invention 3 The product yield of the H which is used as a catalyst to participate in the Knoevenagel condensation reaction of the series decarboxylated aldehyde is higher than that of CBAP-1 (EDA-SO) 3 H) And Zr (IV) -UiO-67, and the solvent used for the catalytic reaction of example 2 is H 2 O, more green and environment-friendly, has lower cost and is compared with CBAP-1 (EDA-SO) 3 H) And Zr (IV) -UiO-67, BM-SO 3 The H can be repeatedly used for multiple times, and has remarkable recycling property.
The above description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto. Any changes, simplifications or modifications made in accordance with the principles and spirit of the present invention should be construed as being included in the scope of the present invention.
Claims (8)
1. Covalent organic framework material BM-SO with acid-base dual functions 3 H, characterized in that the material BM-SO 3 H has the structure shown in formula (I):
2. the covalent organic framework material BM-SO of claim 1 having an acid-base bifunctional 3 The preparation method of H is characterized by comprising the following steps:
step 1) synthesis of covalent organic framework materials BM based on benzimidazolyl: aldehyde monomers and ammonia monomers react for 24 hours at room temperature with 470nm blue light by taking xanthene compounds as a photocatalyst in an organic solvent according to the molar ratio of 2:3, a product is obtained by centrifugation, and then the product is repeatedly washed by water and ethanol and is dried in vacuum to obtain the BM;
step 2) covalent organic framework material BM-SO with acid-base dual function 3 H synthesis: dispersing the BM prepared in the step 1) in an ethanol solution, adding 0.5eq of 1, 3-propane sultone, stirring for 3-6 h at room temperature, filtering, washing and drying to obtain the covalent organic framework material BM-SO with acid-base dual functions 3 H。
3. The acid-base bifunctional covalent organic framework material BM-SO of claim 2 3 The preparation method of H is characterized in that the aldehyde monomer in the step 1) is 1,3, 5-tri (p-formylphenyl) benzene, and the ammonia monomer is 1,2,4, 5-benzene tetramine tetrahydrochloride.
4. The acid-base bifunctional covalent organic framework material BM-SO of claim 2 3 The preparation method of H is characterized in that the organic solvent in the step 1) is one of N, N-dimethylformamide, dimethyl sulfoxide and methanol.
5. The acid-base bifunctional covalent organic framework material BM-SO of claim 2 3 The preparation method of H is characterized in that the xanthene compound in the step 1) is one of fluorescein, fluorescein sodium and 5-azido fluorescein, and the addition amount is 3 mol%.
6. The acid-base bifunctional covalent organic framework material BM-SO of claim 1 3 The application of H in catalyzing the Knoevenagel condensation reaction of the series decarboxylated aldehyde.
7. Use according to claim 6, wherein BM-SO is used 3 H is directly added into the reaction systemThe catalyst is used as a catalyst for Knoevenagel condensation reaction of series decarboxylated aldehyde, and the catalytic reaction equation is shown as a formula (II):
in the formula (II), R is one of hydrogen atom, bromine atom, chlorine atom, methyl, methoxyl, nitryl, fluorine atom, trifluoromethyl and phenyl; r 1 Is cyano; r 2 Is one of cyano and ethyl acetate;
the method comprises the following specific steps:
adding various substitutes of benzaldehyde dimethyl acetal, malononitrile or ethyl cyanoacetate, and catalyst BM-SO into container 3 H and a solvent react for 5-6 hours at 50-60 ℃, after the reaction is finished, the reaction product is filtered and separated, a filter cake is the catalyst and can be recycled by washing, the filtrate is extracted by ethyl acetate firstly, and then the product is obtained by silica gel column chromatography purification, and the eluent is ethyl acetate and petroleum ether.
8. The use according to claim 7, wherein the solvent is one of water, ethanol, toluene, dimethylsulfoxide, N-dimethylformamide.
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