CN111303442B - Nitroxide-free-radical-functionalized three-dimensional covalent organic framework material and preparation method thereof - Google Patents
Nitroxide-free-radical-functionalized three-dimensional covalent organic framework material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nitroxide radical functionalized three-dimensional covalent organic framework material and a preparation method thereof, belonging to the field of functionalized three-dimensional covalent organic framework (3D COFs) materials, the method firstly prepares 4, 7-di (4-aldehyde phenyl) -2,2,6, 6-tetramethylpiperidine-N-oxyl (TEMPO-TPDA) containing TEMPO functional groups, and then constructs the TEMPO functionalized three-dimensional covalent organic framework material (JUC-700) with tetra (4-aminophenyl) methane and tetra (4-aminophenyl) methane through Schiff base reaction by taking the TEMPO functional groups as construction units. The material obtained by the invention is determined to have good crystallinity by PXRD, and the EPR characterization also proves that TEMPO stably exists in the material.
Description
Technical Field
The invention belongs to the field of functionalized three-dimensional covalent organic framework (3D COFs) materials, and particularly relates to synthesis of a nitroxide radical (TEMPO) functionalized three-dimensional covalent organic framework material.
Background
Covalent organic framework materials (COFs), a novel crystalline organic porous polymer, are mainly formed by reversible reactions of various organic building units. Since the first report by Yaghi task group in 2005, COFs are receiving wide attention from material scientists, and it can be said that the appearance of COFs materials is a milestone for the development of crystalline organic porous materials. The constituent elements of the Covalent Organic Frameworks (COFs) are light elements such as (C, H, O, N and B), so that the material has high specific surface area and low density and has potential application in gas storage. Compared with MOFs and other amorphous organic porous polymers, COFs not only has a determined crystal structure, but also has greatly improved stability, and the application of the COFs in various fields is expanded. COFs are mainly classified into two-dimensional (2D COFs) and three-dimensional (3D COFs) structures, but 3D COFs are relatively slow to develop due to synthesis difficulty. Especially, the design synthesis and application of the functionalized 3D COFs are still greatly limited.
Tetramethylpiperidine nitroxide (TEMPO) is a very stable N-oxyl radical. It is often used as a radical scavenger, antioxidant and catalyst and has been studied in various fields. In organic synthetic chemistry, TEMPO can be used as an oxidizing agent to selectively oxidize primary alcohols to aldehydes and secondary alcohols to ketones. The TEMPO is fixed on certain carriers to form heterogeneous catalysts, so that the catalysts can be recycled and the products are easy to separate. At present, 2D COFs containing TEMPO functional groups are obtained by a post-modification method, and generally damage to the crystallinity of materials and uneven distribution of the functional groups. TEMPO-functionalized 3D COFs have not been reported.
Disclosure of Invention
In order to solve the problems of difficult synthesis of functionalized three-dimensional covalent organic framework materials and the like in the prior art, the invention firstly synthesizes an aldehyde derivative with a TEMPO functional group, and then successfully synthesizes 3D COFs of nitroxide free radicals (TEMPO) as a building unit, which is named JUC-700.
The technical scheme of the invention is realized by the following modes:
a nitroxide radical (TEMPO) functionalized three-dimensional covalent organic framework material is an organic framework structure formed by reacting 4- (3 ', 5 ' -bis (4 ' -aldehyde phenyl) benzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl and tetra (4-aminophenyl) methane through Schiff base, and the structural formula is as follows:
further, the chemical structural formula of the 4- (3 ', 5 ' -bis (4 ' -formylphenyl) benzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl (TEMPO-TPDA) is shown as follows:
a preparation method of a nitroxide radical (TEMPO) functionalized three-dimensional covalent organic framework material comprises the following specific steps:
adding a tetrahedron construction unit tetra (4-aminophenyl) methane and 4- (3 ', 5 ' -di (4 ' -aldehyde phenyl) benzamido) -2,2,6, 6-tetramethylpiperidine-N-oxygen free radical into a glass tube, adding an organic solvent, carrying out ultrasonic mixing uniformly, adding a catalyst acetic acid aqueous solution, putting the glass tube into liquid nitrogen for freezing, vacuumizing, carrying out flame sealing, and finally putting into an oven for heating to obtain the nitroxide radical (TEMPO) functionalized three-dimensional covalent organic framework material (JUC-700).
Furthermore, the mole ratio of the tetrahedron construction unit tetra (4-aminophenyl) methane to 4- (3 ', 5 ' -bis (4 ' -aldehyde phenyl) benzamide) -2,2,6, 6-tetramethylpiperidine-N-oxyl is 1: 0.8-1; the optimum molar ratio is 1: 1.
Further, the organic solvent is a mixed solvent of 1-butanol and o-dichlorobenzene, and the mixing volume ratio is 1: 1-1.5; the optimal ratio is 1: 1.
Further, the concentration of the acetic acid aqueous solution is 3-6M; the optimum concentration is 6M.
Further, the heating temperature is 120-140 ℃, and the reaction time is 3-7 days; the optimum reaction temperature and time were 120 ℃ and 5 days.
Further, the 4- (3 ', 5 ' -bis (4 ' -formylphenyl) benzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl is prepared by the following method:
reacting 4- (3 ', 5 ' -dibromobenzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl, 4-aldehyde phenylboronic acid, tetrakis (triphenylphosphine) palladium, [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, cesium carbonate and cesium fluoride in anhydrous tetrahydrofuran and water at 70-75 ℃, extracting with dichloromethane after the reaction is finished, washing with brine, drying with anhydrous sodium sulfate, spin-drying to remove the solvent, and purifying; the purification is to extract, wash and dry the mixture after reaction by using ethyl acetate and normal hexane as developing agent columns for separation and purification.
Further, the molar ratio of 4- (3 ', 5 ' -dibromobenzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl, 4-carboxaldehyde benzeneboronic acid, tetrakis (triphenylphosphine) palladium, [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, cesium carbonate and cesium fluoride is 1:2-3:0.03-0.05:0.1-0.2:3-5:0.5-0.8, preferably 1:2.3:0.03:0.1:3: 0.5.
Further, the volume ratio of the tetrahydrofuran to the water is 20: 1; stirring at 75 deg.C for 24 h.
Further, the 4- (3 ', 5' -dibromobenzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl is prepared by taking 2, 5-dibromobenzoic acid as an initiator, and performing acyl chlorination and amidation with 4-amino-2, 2,6, 6-tetramethylpiperidine-N-oxyl;
the method comprises the following specific steps: dissolving 2, 5-dibromobenzoic acid in thionyl chloride, and refluxing at 80 ℃; after the reaction is finished, cooling to room temperature, removing the residual thionyl chloride by spin drying, dissolving the thionyl chloride in anhydrous dichloromethane, placing the anhydrous dichloromethane in a constant-pressure dropping funnel, dropping the anhydrous dichloromethane and triethylamine mixed solution into the anhydrous dichloromethane and triethylamine mixed solution at 0 ℃, continuing to react at room temperature after the dropping is finished, after the reaction is finished, extracting the mixture by dichloromethane, washing brine, drying anhydrous sodium sulfate, removing the solvent by spin drying, and purifying to obtain the 4- (3 ', 5' -dibromobenzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl shown in the chemical formula (I):
the purification is to extract, wash and dry the mixture after reaction by using ethyl acetate and normal hexane as developing agent columns for separation and purification.
Further, the volume ratio of the mass of the 2, 5-dibromobenzoic acid to the volume of the thionyl chloride is 4:15, the reaction conditions are that reflux is carried out for 3 hours at 80 ℃, the volume of dichloromethane is 40mL, and the reaction time is 48 hours.
Compared with the prior art, the invention has the following advantages:
(1) the invention synthesizes a building unit 4- (3 ', 5 ' -di (4 ' -aldehyde phenyl) benzamido) -2,2,6, 6-tetramethyl piperidine-N-oxygen free radical containing nitroxide free radical (TEMPO) by a bottom-up method for the first time;
(2) the three-dimensional covalent organic framework material with nitroxide free radical (TEMPO) functionalization is synthesized for the first time;
(3) compared with a nitroxide radical (TEMPO) functionalized two-dimensional covalent organic framework material synthesized by a post-modification method, the bottom-up functionalization method avoids the damage of post-modification to the material.
Drawings
FIG. 1 is a powder X-ray diffraction pattern of synthesized JUC-700 of the present invention;
FIG. 2 is a Fourier infrared spectrum of a synthesized JUC-700 and raw material monomers according to the present invention;
FIG. 3 is a thermogravimetric analysis of the synthesized JUC-700 of the present invention;
FIG. 4 is an EPR diagram of JUC-700 synthesized by the present invention and a raw material monomer.
Detailed Description
The present invention will be described in detail with reference to the drawings and the detailed description, and the embodiments described herein are only for the purpose of illustrating and explaining the present invention, but are not to be construed as limiting the present invention.
Example 1
A nitroxide radical (TEMPO) functionalized three-dimensional covalent organic framework material is an organic framework structure formed by reacting 4- (3 ', 5 ' -bis (4 ' -aldehyde phenyl) benzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl and tetra (4-aminophenyl) methane through Schiff base, and the structural formula is as follows:
further, the chemical structural formula of the 4- (3 ', 5 ' -bis (4 ' -formylphenyl) benzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl (TEMPO-TPDA) is shown as follows:
a preparation method of a nitroxide radical (TEMPO) functionalized three-dimensional covalent organic framework material comprises the following specific steps:
(1) synthesis of 4- (3 ', 5' -dibromobenzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl:
2, 5-dibromobenzoic acid (8.06g) is dissolved in 32mL thionyl chloride, refluxed for 3h at 80 ℃, cooled to room temperature after the reaction is finished, and the residual thionyl chloride is removed by spin drying. This was dissolved in 40mL of dichloromethane and placed in a constant pressure dropping funnel. The resulting mixture was slowly dropped into a mixed solution containing 40mL of methylene chloride and 5mL of triethylamine at 0 ℃. After the dropwise addition, the reaction was continued at room temperature for 2 days, and after the completion of the reaction, the mixture was extracted with dichloromethane, washed with brine, dried over anhydrous sodium sulfate, and the solvent was removed by spin-drying. Separating with ethyl acetate and n-hexane (1:3) as developing agent. Thus, 4- (3 ', 5' -dibromobenzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl as a red solid (I) is obtained with a yield of 60 percent.
(2) Synthesis of 4- (3 ', 5' -bis (4 "-formylphenyl) benzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl (II):
4- (3 ', 5 ' -dibromobenzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl (3.45g), 4-aldehyde phenylboronic acid (3.6g), tetrakis (triphenylphosphine) palladium (0.3g) and [1,1' -bis (diphenylphosphino) ferrocene are mixed at 70-75 DEG C]Palladium dichloride (0.7g), cesium carbonate (8.0g) and cesium fluoride (0.7g) were dissolved in 80mL tetrahydrofuran and 4mL water in N2And reacting for 24 hours under protection. After the reaction is finished, dichloromethane is used for extraction, brine washing is carried out, anhydrous sodium sulfate is used for drying, the solvent is removed by spinning, andand (3) carrying out column layer separation by taking dichloromethane as a developing agent to obtain the 4- (3 ', 5 ' -bis (4 ' -aldehyde phenyl) benzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl with the yield of 50 percent.
(3) Synthesis of nitroxide radical (TEMPO) -functionalized three-dimensional covalent organic framework materials:
mixing tetra (4-phenylamino) methane (TAPM, (15mg) and 4- (3 ', 5 ' -bis (4 ' -formylphenyl) benzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl (TEMPO-TPDA, 35.5mg) in a mortar thoroughly and uniformly, adding into a glass tube, then slowly adding 0.5mL of 1, 2-o-dichlorobenzene, 0.5mL of 1-butanol and 0.1mL of acetic acid (6mol/L), pumping and inflating for three times under nitrogen atmosphere, then placing the glass tube into liquid nitrogen to freeze the reaction system, then blocking the glass tube under the flame of methane/oxygen, placing the prepared glass tube reaction system into an oven at 120 ℃ for 5 days after the cutting knife reaction is finished, opening the glass tube with glass, washing the product with N, N-dimethylformamide and acetone for three times respectively, then, a filtration treatment is performed. The solid product was dried in a vacuum oven at 80 ℃ for 2 hours to give the desired product as a tan color with a yield of 83%. The reaction formula is shown as the following formula.
As shown in fig. 1, by comparing the powder X-ray diffraction spectra of monomer TAPM and JUC-700 synthesized by the present invention, it can be confirmed that a nitroxide radical (TEMPO) functionalized three-dimensional covalent organic framework material is successfully synthesized by the method of the present invention;
as shown in FIG. 2, by comparing the Fourier infrared spectra of two monomers (TAPM and TEMPO-TPDA) and the synthesized JUC-700 of the present invention, the JUC-700 spectrum at 1608cm-1The formation of imine bonds is evidenced by the infrared absorption peak of (a).
As shown in FIG. 3, the slight weight loss of the JUC-700 before 400 ℃ is caused by the volatilization of the solvent, and the material begins to have obvious weight loss until about 400 ℃, which indicates that the thermal stability of the JUC-700 is good.
As shown in FIG. 4, EPR characterization of JUC-700 demonstrated that TEMPO free radicals in its framework were still stable.
Example 2
The steps (1) and (2) are the same as those in example 1,
(3) mixing tetra (4-phenylamino) methane (TAPM, (15mg) and 4- (3 ', 5 ' -bis (4 ' -formylphenyl) benzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl (TEMPO-TPDA, 35.5mg) in a mortar thoroughly and uniformly, adding into a glass tube, then slowly adding 0.5mL of 1, 2-o-dichlorobenzene, 0.75mL of 1-butanol and 0.1mL of acetic acid (3mol/L), pumping and inflating for three times under nitrogen atmosphere, then placing the glass tube into liquid nitrogen to freeze the reaction system, then blocking the glass tube under the flame of methane/oxygen, placing the prepared glass tube reaction system into an oven at 120 ℃ for 5 days after the reaction of a cutting knife, opening the glass tube with glass, washing the product with N, N-dimethylformamide and acetone for three times respectively, then, a filtration treatment is performed. The solid product was dried in a vacuum oven at 80 ℃ for 2 hours to give the desired product as tan in 80% yield. The resulting product was subjected to subsequent characterization after 2 days of acetone immersion.
Example 3
Mixing tetra (4-phenylamino) methane (TAPM, (15mg) and 4- (3 ', 5 ' -bis (4 ' -formylphenyl) benzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl (TEMPO-TPDA, 35.5mg) in a mortar thoroughly and uniformly, adding into a glass tube, then slowly adding 0.5mL of 1, 2-o-dichlorobenzene, 0.75mL of 1-butanol and 0.1mL of acetic acid (4mol/L), pumping and inflating for three times under nitrogen atmosphere, then placing the glass tube into liquid nitrogen to freeze the reaction system, then blocking the glass tube under the flame of methane/oxygen, placing the prepared glass tube reaction system into an oven at 140 ℃ for 3 days after the reaction of a cutting knife, opening the glass tube with glass, washing the product with N, N-dimethylformamide and acetone for three times respectively, then, a filtration treatment is performed. The solid product was dried in a vacuum oven at 80 ℃ for 2 hours to give the desired product as a tan color with a yield of 79%.
Claims (10)
1. A nitroxide radical functionalized three-dimensional covalent organic framework material is characterized in that the material is an organic framework structure formed by reacting 4- (3 ', 5' -di (4 '' -aldehyde phenyl) benzamido) -2,2,6, 6-tetramethyl piperidine-N-oxyl and tetra (4-aminophenyl) methane through Schiff base, and the structural formula is as follows:
JUC-700。
2. the nitroxide-functionalized three-dimensional covalent organic framework material of claim 1, wherein the 4- (3 ', 5' -bis (4 "-formylphenyl) benzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl (TEMPO-TPDA) has the following chemical formula:
(Ⅱ)。
3. the method for preparing the nitroxide-functionalized three-dimensional covalent organic framework material of claim 1, comprising the following steps:
adding a tetrahedron construction unit of tetra (4-aminophenyl) methane and 4- (3 ', 5' -di (4 '' -aldehyde phenyl) benzamido) -2,2,6, 6-tetramethylpiperidine-N-oxygen free radical into a glass tube, adding an organic solvent, uniformly mixing by ultrasonic, adding a catalyst of acetic acid aqueous solution, putting the glass tube into liquid nitrogen for freezing, vacuumizing, sealing the tube by flame, and finally putting the tube into an oven for heating to obtain the nitroxide functionalized three-dimensional covalent organic framework material (JUC-700).
4. The method of claim 3, wherein the tetrahedral building block comprises a mole ratio of tetrakis (4-aminophenyl) methane to 4- (3 ', 5' -bis (4 "-formylphenyl) benzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl of 1: 0.8-1.
5. The method for preparing the nitroxide radical functionalized three-dimensional covalent organic framework material as claimed in claim 3, wherein the organic solvent is a mixed solvent of 1-butanol and o-dichlorobenzene in a volume ratio of 1: 1-1.5.
6. The method of claim 3, wherein the concentration of the aqueous acetic acid solution is 3-6M.
7. The method as claimed in claim 3, wherein the heating temperature is 120-140 ℃ and the reaction time is 3-7 days.
8. The method of claim 3, wherein the 4- (3 ', 5' -bis (4 '' -formylphenyl) benzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl is prepared by the following steps:
reacting 4- (3 ', 5 ' -dibromobenzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl, 4-aldehyde phenylboronic acid, tetrakis (triphenylphosphine) palladium, [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, cesium carbonate and cesium fluoride in anhydrous tetrahydrofuran and water at 70-75 ℃, extracting with dichloromethane after the reaction is finished, washing with brine, drying with anhydrous sodium sulfate, spin-drying to remove the solvent, and purifying; the purification is to extract, wash and dry the mixture after reaction by using ethyl acetate and normal hexane as developing agent columns for separation and purification.
9. The method of claim 8, wherein the molar ratio of 4- (3 ', 5 ' -dibromobenzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl, 4-carboxaldehyde phenylboronic acid, tetrakis (triphenylphosphine) palladium, [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, cesium carbonate and cesium fluoride is 1:2-3:0.03-0.05:0.1-0.2:3-5: 0.5-0.8; the volume ratio of the tetrahydrofuran to the water is 20: 1; stirring at 75 deg.C for 24 h.
10. The method for preparing the nitroxide-functionalized three-dimensional covalent organic framework material of claim 8, wherein the 4- (3 ', 5' -dibromobenzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl is prepared by amidation of 2, 5-dibromobenzoic acid as an initiator with 4-amino-2, 2,6, 6-tetramethylpiperidine-N-oxyl after acyl chlorination;
the method comprises the following specific steps: dissolving 2, 5-dibromobenzoic acid in thionyl chloride, and refluxing at 80 ℃; after the reaction is finished, cooling to room temperature, spin-drying to remove the residual thionyl chloride, dissolving the thionyl chloride in anhydrous dichloromethane, placing the anhydrous dichloromethane in a constant-pressure dropping funnel, dropping the anhydrous dichloromethane and triethylamine mixed solution into the anhydrous dichloromethane and triethylamine mixed solution at the temperature of 0 ℃, continuing to react at room temperature after the dropping is finished, after the reaction is finished, extracting the mixture by dichloromethane, washing brine, drying by anhydrous sodium sulfate, spin-drying to remove the solvent, and purifying;
the purification is to extract, wash and dry the mixture after reaction by using ethyl acetate and normal hexane as developing agent columns for separation and purification; the volume ratio of the mass of the 2, 5-dibromobenzoic acid to the volume of the thionyl chloride is 8.06 g: 32mL, refluxing for 3h at 80 ℃, wherein the volume of dichloromethane is 40mL, and the reaction time is 48 h; then amidating with 4-amino-2, 2,6, 6-tetramethylpiperidine-N-oxyl to obtain 4- (3 ', 5' -dibromobenzamido) -2,2,6, 6-tetramethylpiperidine-N-oxyl shown as the chemical formula (I):
(Ⅰ)。
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