(S)-BNDE-TAPB-PA-COF polymer as well as preparation method and application thereof
By preparing (S)-BNDE-TAPB-PA-COF polymer, the stability problem of COFs under acidic conditions and the insufficient reactivity of chiral phosphoric acid catalysts were solved, and the hydrophosphonylation reaction of aniline, aldehyde and diethyl phosphite was achieved with high efficiency, improving the yield and enantioselectivity.
Patent Information
- Application Number
- CN202511313556.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-15
- Publication Date
- 2025-12-12
AI Technical Summary
Covalent organic frameworks (COFs) have poor stability under acidic conditions, which limits their application range. Chiral phosphoric acid catalysts have low reactivity, low enantioselectivity and are difficult to recover. Existing catalysts also have heterogeneity problems.
Using (S)-BINOLDE-DA as a new monomer, (S)-BNDE-TAPB-PA-COF polymers were synthesized via a solvothermal method with 1,3,5-tris(4-aminophenyl)benzene and phosphorous acid to form highly stable COF materials with Brønsted acid sites, which can be used to catalyze the hydrophosphonylation reaction of aniline, aldehydes and diethyl phosphite.
The crystallinity and stability of the material were improved, and high-yield catalytic reactions were achieved, especially in heterogeneous catalysis for substrates with different substituents, with a yield of 86%, demonstrating the advantage of enantioselectivity.
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Figure CN121108438A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of porous organic polymer materials technology, and in particular to a (S)-BNDE-TAPB-PA-COF polymer and its preparation method and application. Background Technology
[0002] The information disclosed in the background section of this invention is intended only to enhance the understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.
[0003] Covalent organic frameworks (COFs) are a novel type of multifunctional crystalline organic catalyst constructed from organic monomers through strong covalent bonds. COFs possess advantages such as periodic network structures, well-defined structures, regular pores, and strong designability, and are considered a promising catalyst support. However, the inherent reversibility of COFs leads to poor stability under acidic conditions, which severely limits their application range.
[0004] Enantiomeric phosphine oxides, as a class of organic compounds with both biological functions and synthetic value, have wide applications in pharmaceuticals, coordination chemistry, and asymmetric catalysis. The synthesis of complex enantiomer-rich α-aminophosphine oxides, in particular, has attracted considerable attention. Chiral phosphoric acid catalysts, with their unique dual-active-site structure—a Brønsted acid active site (OH) and a Lewis base active site (P=O)—can effectively activate basic substrates, exhibiting significant catalytic advantages. However, they still suffer from problems such as low reactivity, limited enantioselectivity control for specific substrates, and the difficulty in separating and recycling homogeneous catalysts. Summary of the Invention
[0005] In view of this, the present invention provides a (S)-BNDE-TAPB-PA-COF polymer, its preparation method and application.
[0006] To achieve the above objectives, the present invention is implemented through the following technical solution: In a first aspect, the present invention provides a (S)-BNDE-TAPB-PA-COF polymer, wherein the (S)-BNDE-TAPB-PA-COF polymer uses the structure shown in formula (Ⅰ) as a repeating unit: Equation (Ⅰ).
[0007] The (S)-BNDE-TAPB-PA-COF polymer is a COF polymer containing phosphorous acid.
[0008] In a second aspect, the present invention provides a method for preparing the (S)-BNDE-TAPB-PA-COF polymer described in the first aspect, comprising the following steps: The ligand (S)-BINOLDE-DA, 1,3,5-tris(4-aminophenyl)benzene and phosphorous acid were dispersed in an organic solvent, and a catalyst was added to carry out a solvothermal reaction to obtain the (S)-BNDE-TAPB-PA-COF polymer.
[0009] Preferably, the catalyst is acetic acid.
[0010] Preferably, the organic solvent is a mixed solution of mesitylene and ethanol, wherein the volume ratio of mesitylene to ethanol is (0.8~1.2):(0.8~1.2), more preferably 1:1.
[0011] Preferably, the molar ratio of (S)-BINOLDE-DA, 1,3,5-tris(4-aminophenyl)benzene and phosphorous acid is (8.8~9.2):(5.8~6.2):(1.8~2.2), more preferably 9:6:2.
[0012] Preferably, the concentration of phosphorous acid in the organic solvent solution is 53.909~57.909 mmol / L, more preferably 55.909 mmol / L.
[0013] Preferably, the molar ratio of phosphorous acid to catalyst is 1:(8~12), more preferably 1:10.
[0014] Preferably, the temperature of the solvothermal reaction is 110~130 ℃, more preferably 120 ℃; the time of the solvothermal reaction is 96~144 h, more preferably 120 h.
[0015] A novel (S)-BNDE-TAPB-PA-COF was synthesized using ligand (S)-BINOLDE-DA, 1,3,5-tris(4-aminophenyl)benzene, and phosphorous acid as starting materials via a bottom-up synthetic strategy. (S)-BNDE-TAPB-PA-COF abandons the traditional imine bond structure, instead employing a CN bond containing phosphorous acid. The rigid framework and C2 symmetry provided by the binaphthyl group not only result in high structural tunability but also significantly improved stability, effectively overcoming the stability defects of imine-bonded CCOFs. Furthermore, the phosphorous acid in this material acts as a Brønsted acidic site, catalyzing the phospha-Mannich reaction, providing a new pathway for synthesizing α-aminophosphine oxide molecules with NC(sp3)-P structural units of significant application value.
[0016] Thirdly, the present invention provides the application of the (S)-BNDE-TAPB-PA-COF polymer described in the first aspect and / or the (S)-BNDE-TAPB-PA-COF polymer prepared by the preparation method described in the second aspect as a catalyst.
[0017] Preferably, the application includes the catalytic hydrophosphonylation of substituted or unsubstituted anilines, aldehydes, and diethyl phosphite.
[0018] Preferably, the substituents in the substituted aniline are alkyl, methoxy, halogen, or nitro groups; and the aldehyde compounds are benzaldehyde, naphthaldehyde, or anthracene formaldehyde.
[0019] Fourthly, the present invention provides a method for the phosphonylation reaction of substituted or unsubstituted aniline, aldehyde compounds and diethyl phosphite, comprising the following steps: The substituted or unsubstituted aniline, aldehyde compounds, diethyl phosphite, and the above-mentioned (S)-BNDE-TAPB-PA-COF polymer are dissolved in an organic solvent and reacted at 0-5°C to obtain the product.
[0020] Preferably, the substituents in the substituted aniline are alkyl, methoxy, halogen, or nitro groups; and the aldehyde compounds are benzaldehyde, naphthaldehyde, or anthracene formaldehyde.
[0021] Preferably, the organic solvent is at least one of tetrahydrofuran, toluene, chloroform, acetonitrile, or methanol, more preferably tetrahydrofuran.
[0022] Preferably, the reaction time is 116-120 h, more preferably 120 h.
[0023] Preferably, the ratio of aniline, benzaldehyde, diethyl phosphite, (S)-BNDE-TAPB-PA-COF polymer, and organic solvent is (0.05~0.10 mmol):(0.05~0.10 mmol):(0.05~0.10 mmol):(0.01~0.05 mmol):(1-5 mL), more preferably (0.06~0.07 mmol):(0.06~0.07 mmol):(0.06~0.07 mmol):(0.01~0.02 mmol):(1-2 mL); most preferably (0.0625 mmol):(0.0625 mmol):(0.0625 mmol):(0.0124 mmol):(1 mL).
[0024] The (S)-BNDE-TAPB-PA-COF material provided by this invention also possesses Brønsted acid active sites and has been used for asymmetric catalytic reactions of amines, aldehydes, and diethyl phosphite. The optimal conditions were tetrahydrofuran as solvent, 0°C as reaction temperature, 2 mmol% catalyst dosage, and 5 days as reaction time. Under these conditions, the material exhibited catalytic activity for aniline substrates with different substituents. Although insufficient crystallinity of the CCOF material can affect yield and enantioselectivity due to pore blockage and reduced chiral confinement effects, (S)-BNDE-TAPB-PA-COF, with its unique active site distribution and structural characteristics, still provides an innovative route for the green and efficient synthesis of α-aminophosphine oxides, demonstrating potential application value in catalytic reactions.
[0025] Compared with the prior art, the present invention has achieved the following beneficial effects: (1) In this invention, (S)-BINOLDE-DA is used as a new monomer to replace conventional aldehyde monomers and 1,3,5-tris(4-aminophenyl)benzene and phosphorous acid to synthesize a highly stable COF polymer (S)-BNDE-TAPB-PA-COF with acidic sites by a solvothermal method.
[0026] (2) In this invention, (S)-BNDE-TAPB-PA-COF has higher crystallinity and stability (thermal stability up to 200℃); (S)-BNDE-TAPB-PA-COF, as a heterogeneous catalyst, has a yield of up to 86% in the phosphonylation reaction of aniline, benzaldehyde and diethyl phosphite. Attached Figure Description
[0027] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.
[0028] Figure 1 A scanning electron microscope image of the (S)-BNDE-TAPB-PA-COF polymer prepared in Example 1; Figure 2 Thermogravimetric image of the (S)-BNDE-TAPB-PA-COF polymer prepared in Example 1; Figure 3 The PXRD pattern of the (S)-BNDE-TAPB-PA-COF polymer prepared in Example 1; Figure 4 Infrared spectrum of the (S)-BNDE-TAPB-PA-COF polymer prepared in Example 1; Figure 5 The N2 adsorption diagram of the (S)-BNDE-TAPB-PA-COF polymer prepared in Example 1; Figure 6 The circular dichroism chromatogram of the (S)-BNDE-TAPB-PA-COF polymer prepared in Example 1 is shown. Detailed Implementation
[0029] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, 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 pertains.
[0030] The technical solution of the present invention will be further described below with reference to specific embodiments.
[0031] Example 1 Preparation of COF ((S)-BNDE-TAPB-PA-COF) polymer containing phosphorous acid: (S)-BINOLDE-DA (36.0 mg, 0.0581 mmol), 1,3,5-tris(4-aminophenyl)benzene (13.7 mg, 0.0388 mmol), and phosphorous acid (10.0 mg, 0.123 mmol) were weighed into a large-volume tube. A catalytic amount of acetic acid (6 mol / L, 200 μL) was added. The reaction solvent was a mixed solution of mesitylene and ethanol (volume ratio 1:1, 2 mL). After thorough mixing, the mixture was degassed three times using a freeze-pump-thaw cycle. The mixture was then placed in an oven and reacted for five days at 120 °C. After the reaction was complete, the solid in the large-volume tube was removed, washed completely with DMF, ethanol, and dichloromethane, and then dried under vacuum to obtain 32 mg of a gray solid, with a yield of 56%.
[0032] The (S)-BNDE-TAPB-PA-COF polymer prepared in this embodiment was characterized. Figure 1 This is a scanning electron microscope image of the (S)-BNDE-TAPB-PA-COF polymer. Figure 2 Thermogravimetric diagram of (S)-BNDE-TAPB-PA-COF polymer. Figure 3 The PXRD pattern of the (S)-BNDE-TAPB-PA-COF polymer is shown. Figure 4 The infrared spectrum of the (S)-BNDE-TAPB-PA-COF polymer. Figure 5 The N2 adsorption diagram is for the (S)-BNDE-TAPB-PA-COF polymer. Figure 6 The circular dichroism chromatogram for the (S)-BNDE-TAPB-PA-COF polymer. From... Figure 1 , Figure 3 and Figure 5As can be seen from this, the (S)-BNDE-TAPB-PA-COF polymer prepared in this embodiment has a porous structure. From... Figure 2 It can be seen that the (S)-BNDE-TAPB-PA-COF polymer exhibits high thermal stability. From... Figure 4 The molecular structure and chemical bonds of the (S)-BNDE-TAPB-PA-COF polymer can be observed. From... Figure 6 It can be seen that (S)-BNDE-TAPB-PA-COF has chiral characteristics.
[0033] Example 2 The (S)-BNDE-TAPB-PA-COF polymer prepared in Example 1 was used as a catalyst in the hydrophosphonylation reaction of aniline, benzaldehyde and diethyl phosphite.
[0034] The preparation process was as follows: Aniline (5.7 μL, 0.0625 mmol), benzaldehyde (6.4 μL, 0.0625 mmol), and diethyl phosphite (8.0 μL, 0.0625 mmol) were weighed into a reaction flask. 1 mL of tetrahydrofuran was added, and the mixture was reacted at 0 °C for five days. After the reaction was complete, (S)-BNDE-TAPB-PA-COF was separated by centrifugation. The product was analyzed in THF solution using gas chromatography (GC) to determine the reaction yield. After purification by thin-layer chromatography, the product was further processed using... 1 The product structure was determined by 1H NMR, and the ee value of the product was determined by HPLC (OD-H chiral column, n-hexane:isopropanol = 95:5, flow rate 0.4 mL / min, UV wavelength 254 nm).
[0035] The specific reaction equation is as follows:
[0036] Using THF as solvent, the reaction temperature was 0 °C, the amount of (S)-BNDE-TAPB-PA-COF catalyst was 2 mmol%, and the reaction time was 5 days. Under these conditions, (S)-BNDE-TAPB-PA-COF catalyzed the reaction of aniline with different substituents with benzaldehyde and diethyl phosphite. The corresponding reaction yields and ee values were recorded, as shown in Table 1.
[0037] Table 1. Substrate Expansion for (S)-BNDE-TAPB-PA-COF Catalytic Reactions
[0038] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.
Claims
1. A (S)-BNDE-TAPB-PA-COF polymer, characterized in that, The (S)-BNDE-TAPB-PA-COF polymer uses the structure shown in formula (Ⅰ) as a repeating unit: Equation (Ⅰ).
2. The method for preparing the (S)-BNDE-TAPB-PA-COF polymer as described in claim 1, characterized in that, Includes the following steps: The ligand (S)-BINOLDE-DA, 1,3,5-tris(4-aminophenyl)benzene and phosphorous acid were dispersed in an organic solvent, and a catalyst was added to carry out a solvothermal reaction to obtain the (S)-BNDE-TAPB-PA-COF polymer.
3. The preparation method according to claim 2, characterized in that, The catalyst is acetic acid; or, the organic solvent is a mixed solution of mesitylene and ethanol, wherein the volume ratio of mesitylene and ethanol is (0.8~1.2):(0.8~1.2), preferably 1:
1.
4. The preparation method according to claim 2, characterized in that, The molar ratio of (S)-BINOLDE-DA, 1,3,5-tris(4-aminophenyl)benzene, and phosphorous acid is (8.8~9.2):(5.8~6.2):(1.8~2.2), preferably 9:6:2; or, the concentration of phosphorous acid in the organic solvent solution is 53.909~57.909 mmol / L, preferably 55.909 mmol / L.
5. The preparation method according to claim 2, characterized in that, The molar ratio of phosphorous acid to catalyst is 1:(8~12), preferably 1:10; or, the temperature of the solvothermal reaction is 110~130 ℃, preferably 120 ℃; or, the time of the solvothermal reaction is 96~144 h, preferably 120 h.
6. The application of the (S)-BNDE-TAPB-PA-COF polymer as described in claim 1 as a catalyst.
7. The application as described in claim 1, characterized in that, The application includes the catalytic hydrophosphonylation reaction of substituted or unsubstituted anilines, aldehydes, and diethyl phosphite; preferably, the substituents in the substituted aniline are alkyl, methoxy, halogen, or nitro groups; and the aldehydes are benzaldehyde, naphthaldehyde, or anthracene formaldehyde.
8. A method for the catalytic hydrophosphonylation reaction of substituted or unsubstituted aniline, aldehyde compounds, and diethyl phosphite, characterized in that, Includes the following steps: The substituted or unsubstituted aniline, aldehyde compound, diethyl phosphite and the above-mentioned (S)-BNDE-TAPB-PA-COF polymer are dissolved in an organic solvent and reacted at 0-5°C to obtain the product.
9. The method as described in claim 8, characterized in that, The substituents in the substituted aniline are alkyl, methoxy, halogen, or nitro groups; the aldehyde compounds are benzaldehyde, naphthaldehyde, or anthracene formaldehyde. And / or, the organic solvent is at least one of tetrahydrofuran, toluene, chloroform, acetonitrile or methanol, preferably tetrahydrofuran; And / or, the reaction is carried out for 116-120 h, preferably 120 h.
10. The method as described in claim 8, characterized in that, The ratio of aniline, benzaldehyde, diethyl phosphite, (S)-BNDE-TAPB-PA-COF polymer, and organic solvent is (0.05~0.10 mmol):(0.05~0.10 mmol):(0.05~0.10 mmol):(0.01~0.05 mmol):(1-5 mL), preferably (0.06~0.07 mmol):(0.06~0.07 mmol):(0.06~0.07 mmol):(0.01~0.02 mmol):(1-2 mL).