An amino-functionalized metal organic framework material and its preparation method and application
By preparing amino functional metal organic framework materials (NH2-MOF), the problems of multi-step conditions in the existing 4H-pyra-bean compound synthesis method, toxic solvent and transition metal use, realized high-efficiency and clean 4H- Pyanic compound synthesis.
Patent Information
- Application Number
- CN202410270170.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-03-11
- Publication Date
- 2025-01-28
- Estimated Expiration
- 2044-03-11
AI Technical Summary
The existing 4H-pyran compound synthesis methods have problems such as multi-step condition dependence, the use of toxic organic solvents or transition metal-containing catalysts, cumbersome post-processing procedures, high reaction time and low yields.
By preparing amino-functional metal organic framework materials (NH2-MOF), water is used as a reaction solvent to achieve clean and efficient synthesis of 4H-pyrarotic compounds. The material reacts in water through salt and bromine -containing organic ligands, and then reacts with organic amine and tetrazopylcellium bromide in alkaline solutions to form an amino -functional MOF.
The high conversion rate, selectivity and low reaction time of the 4H-pyra-beanized compounds are fully avoided, and the use of toxic solvents and transition metals is completely avoided, and post-processing procedures are simplified.
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Figure CN118146528B_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of organic catalyst synthesis, and specifically relates to an amino-functionalized metal organic framework material and a preparation method and application thereof. Background Art
[0002] In the production of bulk chemicals, traditional environmentally unacceptable processes have been largely replaced by cleaner synthetic processes, such as in the field of organocatalysis, because organocatalysis has significant advantages over traditional metal catalysis, such as: easy access, easy preparation, robust, cheap, non-toxic, novel, efficient, highly selective, and inert to moisture and oxygen (no need for harsh reaction conditions such as inert atmosphere, anhydrous solvents, etc.). More importantly, due to the absence of transition metals, organocatalytic methods seem to be more promising for the preparation of compounds that are intolerant to metal contamination, especially drugs. Therefore, organocatalysts have made valuable contributions to green chemistry.
[0003] 4H-pyran compounds have a wide range of biological and pharmacological activities, and can be used in a variety of applications such as emetic, anti-HIV, anti-tumor, anti-cancer, anticoagulant, anti-Lezheimer's, antibacterial, anti-malarial, diuretic, antispasmodic, anti-leukemia, anti-hyperglycemic and anti-lipid activities. They are also playing an increasingly important role in the fields of agrochemicals, cosmetics and pigment industries. Among the existing methods for synthesizing 4H-pyran compounds, the most direct method is the three-component cascade reaction of aldehydes, malononitrile and various enolizable CH activated acidic compounds. This reaction often uses homogeneous catalysts such as 2,2,2-trifluoroethanol, hexadecyldimethylbenzyl ammonium bromide, rare earth perfluorooctanoic acid, β-cyclodextrin-glycerol, urea, potassium phosphate, 3-butyl-1-methylimidazolium hexafluorophosphate, RuBr2(PPh3)4, squaramide, methanesulfonic acid, p-dimethylaminopyridine, etc. Although these reported protocols have certain advantages of their own, they still suffer from many disadvantages, such as reliance on multi-step conditions, use of toxic organic solvents or catalysts containing transition metals, tedious post-treatment procedures, high reaction times and low yields. Summary of the invention
[0004] The purpose of the present invention is to provide an amino-functionalized metal organic framework material and a preparation method and application thereof. The newly synthesized amino-functionalized metal organic framework material reduces the synthesis requirements of 4H-pyran compounds, and only water is used as the reaction solvent, and the conversion rate of raw materials in the synthesis process is high and the selectivity is strong.
[0005] To achieve the above object, the present invention provides the following technical solutions:
[0006] One of the technical solutions of the present invention is to provide a method for preparing an amino-functionalized metal organic framework material, comprising the following steps:
[0007] The zirconium salt and the bromine-containing organic ligand are co-dissolved in water, and reacted after adding acid to obtain Br-MOF; the Br-MOF and the organic amine tetrapropylammonium bromide are added to an alkaline solution, and an amino-functionalized metal organic framework material (NH2-MOF) is obtained after reaction.
[0008] Preferably, the molar ratio of the zirconium element in the zirconium salt to the bromine-containing organic ligand is 1:1; the molar ratio of the zirconium element in the zirconium salt to the acid is 1:6-8.
[0009] Preferably, the bromine-containing organic ligand is 2-bromosuccinic acid or 2-bromoglutaric acid; the acid is formic acid or acetic acid; and the organic amine is propylamine or n-butylamine.
[0010] When the bromine-containing organic ligand is 2-bromosuccinic acid or 2-bromoglutaric acid, the prepared MOF is more likely to graft organic amines into the MOF, and the resulting amino-functionalized MOF has stronger alkalinity and better catalytic effect.
[0011] Compared with other bromine-containing organic ligands, such as MOF materials made with bromoterephthalic acid, bromine atoms are more difficult to replace, and the resulting amino-functionalized MOF has weaker alkalinity.
[0012] Preferably, the reaction temperature of the zirconium salt and the bromine-containing organic ligand is 85-100° C. and the reaction time is 4-6 h.
[0013] Preferably, the ratio of the added amounts of Br-MOF, organic amine and tetrapropylammonium bromide is 1 g: 3~6 mmol: 0.06 g.
[0014] Preferably, the alkali solution is a 10 wt.% sodium bicarbonate solution.
[0015] Preferably, the reaction temperature of the Br-MOF, ethylenediamine and tetrapropylammonium bromide is 60° C. and the reaction time is 10 h.
[0016] The second technical solution of the present invention is to provide an amino-functionalized metal-organic framework material prepared by the preparation method of the above-mentioned amino-functionalized metal-organic framework material.
[0017] The third technical solution of the present invention is to provide an application of the above-mentioned amino-functionalized metal organic framework material in the catalytic synthesis of 4H-pyran compounds.
[0018] The beneficial technical effects of the present invention are as follows:
[0019] The present invention prepares an amino-functionalized metal organic framework material by amino-functionalizing the synthesized Br-MOF. The material is used as a catalyst for synthesizing 4H-pyran compounds, thereby realizing clean and efficient synthesis of 4H-pyran compounds. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] Figure 1 This is the XRD pattern of Br-MOF synthesized in Example 1.
[0021] Figure 2 This is the infrared spectra of Br-MOF and NH2-MOF synthesized in Example 1.
[0022] Figure 3 This is the nitrogen adsorption-desorption isotherm diagram of the Br-MOF synthesized in Example 1.
[0023] Figure 4 This is the nitrogen adsorption-desorption isotherm diagram of the NH2-MOF synthesized in Example 1. DETAILED DESCRIPTION
[0024] Now, various exemplary embodiments of the present invention are described in detail, and this detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics and embodiments of the present invention. It should be understood that the terms described in the present invention are only for describing specific embodiments and are not used to limit the present invention.
[0025] In addition, for the numerical range in the present invention, it is understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.
[0026] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the invention pertains. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention.
[0027] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.
[0028] Example 1
[0029] (1) Preparation of Br-MOF
[0030] 0.446 g (2 mmol) ZrCl4 and 0.394 g (2 mmol) 2-bromosuccinic acid were placed in a polytetrafluoroethylene-lined reactor, and then 4 mL of deionized water was added. Ultrasonication was performed for 3 min to fully dissolve the solid. 0.45 mL (12 mmol) formic acid was added to the above solution and stirred at room temperature for 5 min. Finally, the solution was placed in an oven at 85 °C for 4 h. After centrifugation, washing and drying, a white solid Br-MOF was obtained.
[0031] (2) Preparation of NH2-MOF
[0032] First, 0.5 g Br-MOF and 0.12 mL propylamine (1.5 mmol) were added to the reaction tube in sequence, followed by 0.030 g tetrapropylammonium bromide and 5 mL 10 wt.% sodium bicarbonate solution. The mixture was reacted at 60 °C for 10 h, and then centrifuged, washed and dried to obtain white solid NH2-MOF.
[0033] Example 2
[0034] (1) 0.446 g (2 mmol) ZrCl4 and 0.422 g (2 mmol) 2-bromoglutaric acid were placed in a polytetrafluoroethylene-lined reactor, and then 4 mL of deionized water was added. Ultrasonication was performed for 3 min to fully dissolve the solid. Then 0.80 mL (14 mmol) acetic acid was added to the above solution and stirred at room temperature for 5 min. Finally, the solution was placed in an oven at 100 °C for 4 h. After centrifugation, washing and drying, a white solid Br-MOF was obtained.
[0035] (2) Preparation of NH2-MOF
[0036] First, 0.5 g Br-MOF and 0.16 mL propylamine (2 mmol) were added to the reaction tube in sequence, followed by 0.030 g tetrapropylammonium bromide and 5 mL 10 wt.% sodium bicarbonate solution. The mixture was reacted at 60 °C for 10 h, and then centrifuged, washed and dried to obtain white solid NH2-MOF.
[0037] Example 3
[0038] (1) 0.446 g (2 mmol) ZrCl4 and 0.422 g (2 mmol) 2-bromoglutaric acid were placed in a polytetrafluoroethylene-lined reactor, and then 4 mL of deionized water was added. Ultrasonication was performed for 3 min to fully dissolve the solid. Then 0.60 mL (16 mmol) formic acid was added to the above solution and stirred at room temperature for 5 min. Finally, the solution was placed in an oven at 90 °C for 5 h. After centrifugation, washing and drying, a white solid Br-MOF was obtained.
[0039] (2) Preparation of NH2-MOF
[0040] First, 0.5 g Br-MOF and 0.25 mL butylamine (2.5 mmol) were added to the reaction tube in sequence, followed by 0.030 g tetrapropylammonium bromide and 5 mL 10 wt.% sodium bicarbonate solution. The mixture was reacted at 60 °C for 10 h, and then centrifuged, washed and dried to obtain white solid NH2-MOF.
[0041] Example 4
[0042] 0.446 g (2 mmol) ZrCl4 and 0.394 g (2 mmol) 2-bromosuccinic acid were placed in a polytetrafluoroethylene-lined reactor, and then 4 mL of deionized water was added. Ultrasonication was performed for 3 min to fully dissolve the solid. Then 0.69 mL (12 mmol) acetic acid was added to the above solution and stirred at room temperature for 5 min. Finally, the solution was placed in an oven at 85 °C for 6 h. After centrifugation, washing and drying, a white solid Br-MOF was obtained.
[0043] (2) Preparation of NH2-MOF
[0044] First, 0.5 g Br-MOF and 0.30 mL butylamine (3 mmol) were added to the reaction tube in sequence, and then 0.030 g tetrapropylammonium bromide and 5 mL 10 wt.% sodium bicarbonate solution were added, and the mixture was reacted at 60 °C for 10 h. Finally, white solid NH2-MOF was obtained after centrifugation, washing and drying.
[0045] Example 5
[0046] (1) 0.446 g zirconium chloride was dissolved in DMF, and then 0.490 g 2-bromoterephthalic acid was added. After ultrasonic treatment for a certain period of time, it was hydrothermal at 120 °C for 24 h. Finally, it was centrifuged, washed with water and ethanol for multiple times, and then dried in a vacuum oven overnight to obtain Br-Ph-MOF.
[0047] (2) Preparation of NH2-MOF
[0048] First, 0.5 g Br-Ph-MOF and 0.12 mL propylamine (1.5 mmol) were added to the reaction tube in sequence, followed by 0.030 g tetrapropylammonium bromide and 5 mL 10 wt.% sodium bicarbonate solution. The mixture was reacted at 60 °C for 10 h, and then centrifuged, washed and dried to obtain white solid NH2-Ph-MOF.
[0049] The XRD pattern of Br-MOF synthesized in Example 1 is shown in Figure 1 .from Figure 1 It can be seen that the synthesized Br-MOF has a MOF structure.
[0050] The infrared spectra of Br-MOF and NH2-MOF synthesized in Example 1 are shown in Figure 2 .from Figure 2 It can be seen that the Br-MOF sample has a -1 The infrared absorption peak of C-Br bond appeared, which further proved that 2-bromosuccinic acid reacted with zirconium chloride to form an organic framework compound. -1 The C-Br bond absorption peak disappears, while the absorption peak at 1280 cm -1 A new absorption peak appeared, which corresponded to the absorption peak of the CN bond, indicating that the amino group had been successfully grafted onto the MOF material.
[0051] The nitrogen adsorption-desorption isotherm of the Br-MOF synthesized in Example 1 is shown in Figure 3 ; The nitrogen adsorption-desorption isotherm of the synthesized NH2-MOF is shown in Figure 4 .
[0052] Depend on Figure 3 The specific surface area of the Br-MOF sample can be calculated to be 426 cm 2 / g, pore volume is 0.52 cm 3 / g.
[0053] Depend on Figure 4 The specific surface area of NH2-MOF can be calculated to be 165 cm 2 / g, compared with Br-MOF, the specific surface area is significantly reduced, which also shows that the amino group is successfully grafted into the MOF material.
[0054] Test the catalytic activity of NH2-MOF prepared in Example 1
[0055] Methods: 1 mmol benzaldehyde, 1.2 mmol malononitrile (excess), 1.2 mmol ethyl acetoacetate (excess), 0.010 g NH2-MOF (catalyst) and 3 mL water were added to a 10 mL round-bottom flask in sequence, and then refluxed at 95 °C for 1 h. After the reaction, the liquid after the reaction was extracted with ethanol, and the upper organic liquid was collected. Finally, the upper liquid was analyzed by gas chromatography. The conversion rate, selectivity and yield of the reaction were calculated based on the chromatographic results; among them, the conversion rate was calculated based on benzaldehyde.
[0056] The calculated results are: benzaldehyde conversion rate 96%; selectivity 100% (indicating that no other by-products are generated); yield 96% (yield = benzaldehyde conversion rate × selectivity).
[0057] The reaction equation of the above method is as follows:
[0058] .
[0059] Referring to the above method, the catalytic activity of the catalysts prepared in Examples 2-5 was tested. The test results are shown in Table 1.
[0060] Table 1
[0061] catalyst Benzaldehyde conversion rate Selectivity Yield Example 1 96% 100% 96% Example 2 94% 100% 94% Example 3 94% 100% 94% Example 4 93% 100% 93% Example 5 36% 100% 36%
[0062] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.
Claims
1. A method for preparing an amino-functionalized metal organic framework material, characterized in that: The following steps are involved: Dissolving zirconium salt and bromine-containing organic ligand in water, adding acid and reacting to obtain Br-MOF; adding the Br-MOF, organic amine and tetrapropylammonium bromide into an alkaline solution, and reacting to obtain an amino-functionalized metal organic framework material; The bromine-containing organic ligand is 2-bromosuccinic acid or 2-bromoglutaric acid; the acid is formic acid or acetic acid; the organic amine is propylamine or n-butylamine; The ratio of the added amounts of Br-MOF, organic amine and tetrapropylammonium bromide is 1 g: 3-6 mmol: 0.06 g.
2. The method for preparing an amino-functionalized metal organic framework material according to claim 1, characterized in that: The molar ratio of the zirconium element in the zirconium salt to the bromine-containing organic ligand is 1:1; the molar ratio of the zirconium element in the zirconium salt to the acid is 1:6-8.
3. The method for preparing an amino-functionalized metal organic framework material according to claim 1, characterized in that: The reaction temperature of the zirconium salt and the bromine-containing organic ligand is 85-100°C and the reaction time is 4-6 hours.
4. The method for preparing an amino-functionalized metal organic framework material according to claim 1, characterized in that: The alkali solution is a 10wt.% sodium bicarbonate solution.
5. The method for preparing an amino-functionalized metal organic framework material according to claim 1, characterized in that: The reaction temperature of the Br-MOF, the organic amine and tetrapropylammonium bromide is 60° C. and the reaction time is 10 h.
6. An amino-functionalized metal-organic framework material obtained by the method for preparing an amino-functionalized metal-organic framework material according to any one of claims 1 to 5.
7. The use of the amino-functionalized metal organic framework material according to claim 6 in catalytic synthesis of 4H-pyran compounds, characterized in that: The catalytic synthesis method of the 4H-pyran compounds is as follows: Benzaldehyde, malononitrile, ethyl acetoacetate, amino-functionalized metal organic framework and water are added in sequence and refluxed to obtain 4H-pyran compounds; The structural formula of the 4H-pyran compound is .