Synthesis method and application of near-infrared light response anthraquinone polymer
By synthesizing near-infrared light-responsive anthraquinone polymer, the problem of the existing anthraquinone-based heterophase photocatalyst absorption spectrum is solved, the spectrum is expanded to the near-infrared region, which enhances its application potential in the fields of green synthesis and biomedicine, and demonstrates high selective cyanation reaction capabilities.
Patent Information
- Application Number
- CN202510299332.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-13
- Publication Date
- 2025-06-06
AI Technical Summary
The absorption spectrum of existing anthraquinone-based heterophase photocatalysts is mainly concentrated in the visible light region, making it difficult to absorb near-infrared light, limiting its application potential in the fields of green synthesis and biomedicine.
By synthesizing a near-infrared light-responsive anthraquinone polymer, anthraquinone polymer with absorption spectrum reaching the near-infrared region was prepared by using materials such as 2,6-dibromoanthraquinone, homotrivinylbenzene, palladium acetate, 1,1'-diphenylphosphino-ferrocene, triethylamine and N,N-dimethylformamide.
The near-infrared light response of anthraquinone polymer was realized, the absorption spectrum was expanded to the near-infrared region, and its application potential in green synthesis and biomedicine fields was enhanced, and the high selective reaction capability was demonstrated by catalyzing the cyanation of α-amino C(sp3)-H bonds.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of organic polymer compounds, and in particular to a synthesis method and application of a near-infrared light-responsive anthraquinone polymer. Background Art
[0002] Anthraquinone compounds have a wide range of visible light absorption and can activate molecular oxygen (O 2 ) has great prospects in the field of anthraquinone. In addition, anthraquinone also has excellent redox stability and reactivity. The unique redox elasticity allows anthraquinone and anthraquinone to be mutually converted through a two-electron / proton transfer pathway, thereby achieving H 2 O 2 Therefore, constructing anthraquinone compounds into heterogeneous photocatalysts has attracted widespread attention from chemists.
[0003] At present, the absorption spectrum of anthraquinone-based heterogeneous photocatalysts can basically only reach the visible light region, and few can reach the near-infrared region. Ultraviolet light or visible light only accounts for 5% and 43% of solar radiation, respectively, while near-infrared light accounts for about 50% of the solar spectrum and has excellent penetration performance, which has great application potential in the fields of green synthesis and biomedicine. Summary of the invention
[0004] The purpose of the present invention is to provide a synthesis method of a near-infrared light-responsive anthraquinone polymer and its application, aiming at synthesizing a polymer whose absorption spectrum can reach the near-infrared region.
[0005] To achieve the above object, in a first aspect, the present invention provides a method for synthesizing a near-infrared light-responsive anthraquinone polymer, comprising the following steps:
[0006] Obtain 2,6-dibromoanthraquinone, trivinylbenzene, palladium acetate, 1,1'-diphenylphosphino-ferrocene, triethylamine and N,N-dimethylformamide;
[0007] Add the 2,6-dibromoanthraquinone, the mesitylenetrivinylbenzene, the palladium acetate, the 1,1'-diphenylphosphino-ferrocene, the triethylamine and the N,N-dimethylformamide into a round-bottom flask under nitrogen;
[0008] The round-bottom flask was heated to 130° C. and refluxed for 48 hours to obtain an anthraquinone polymer.
[0009] Among them, the 2,6-dibromoanthraquinone is 1.0 mmol, the trivinylbenzene is 2.0 mmol, the molar percentage of palladium acetate is 10, the molar percentage of 1,1'-diphenylphosphino-ferrocene is 10, the triethylamine is 4.0 mmol, and the N,N-dimethylformamide is 5 ml.
[0010] In a second aspect, the present invention further provides an application of a near-infrared light-responsive anthraquinone polymer, wherein the anthraquinone polymer is prepared by the synthesis method of the near-infrared light-responsive anthraquinone polymer as described in the first aspect above, including the preparation of α-aminonitrile compounds.
[0011] Wherein, the preparation method of the α-aminonitrile compound comprises the following steps:
[0012] Amine, trimethylsilyl cyanide, catalyst and methanol were placed in a dry quartz tube and the reaction mixture was stirred under 15 W light irradiation of 760 nm LEDs for 8 h. When the reaction was completed, it was monitored by thin layer chromatography. The solution was filtered and washed with ethyl acetate. The filtrate was evaporated under vacuum and the crude product was directly purified by silica gel column chromatography to obtain α-amino nitrile compounds.
[0013] Among them, the amine is 0.2 mmol, the trimethylsilyl cyanide is 0.4 mmol, the catalyst is 10 mg, and the methanol is 2 ml.
[0014] The invention discloses a method for synthesizing a near-infrared light-responsive anthraquinone polymer. The method comprises the following steps: obtaining 2,6-dibromoanthraquinone, trivinylbenzene, palladium acetate, 1,1'-diphenylphosphino-ferrocene, triethylamine and N,N-dimethylformamide; adding the 2,6-dibromoanthraquinone, trivinylbenzene, palladium acetate, 1,1'-diphenylphosphino-ferrocene, triethylamine and N,N-dimethylformamide into a round-bottom flask under nitrogen; heating the round-bottom flask to 130° C. and refluxing for 48 hours to obtain an anthraquinone polymer. The method synthesizes a class of vinyl-linked anthraquinone polymers (AQ-TVB-CPPs) through a simple Mizoroki-Heck reaction. The absorption spectrum of the AQ-TVB-CPPs can reach the near-infrared region and can be used for near-infrared photocatalysis of α-amino C (sp 3 )-H bonds for highly selective cyanation. BRIEF DESCRIPTION OF THE DRAWINGS
[0015] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.
[0016] Figure 1 This is the synthetic route of 1AQ-TVB-CPPs.
[0017] Figure 2a It is the Fourier infrared spectra of AQ-TVB-CPPs and 2,6-DBAQ.
[0018] Figure 2b This is the solid-state H NMR spectrum of AQ-TVB-CPPs.
[0019] Figure 2c is the scanning electron microscopy image of AQ-TVB-CPPs.
[0020] Figure 2d is the powder X-ray diffraction pattern of AQ-TVB-CPPs.
[0021] Figure 2e It is the nitrogen adsorption-desorption curve and pore size distribution curve (insert) of AQ-TVB-CPPs.
[0022] Figure 2f It is the thermogravimetric analysis curve of AQ-TVB-CPPs.
[0023] Figure 3a The graph is the UV-visible diffuse reflectance effect spectrum and the calculated AQ-TVB-CPPs optical band gap (inset).
[0024] Figure 3b It is the Mott-Schottky curve of AQ-TVB-CPPs in 0.1 mol / L sodium sulfate solution (pH=7) at test frequencies of 1000, 1500 and 2000 Hz.
[0025] Figure 3c This is the band structure diagram of AQ-TVB-CPPs.
[0026] Figure 3d is the Nyquist plot of AQ-TVB-CPPs.
[0027] Figure 3e This is the photocurrent test diagram of AQ-TVB-CPPs.
[0028] Figure 3f It is the time-resolved fluorescence spectrum of AQ-TVB-CPPs.
[0029] Figure 4 The present invention provides a flow chart of a method for synthesizing a near-infrared light-responsive anthraquinone polymer.
[0030] Figure 5 The general formula of AQ-TVB-CPPs for synthesizing α-amino nitrile is shown in Figure 1. 1 =H, alkyl, aromatic, etc., R 2 =H, alkyl, aromatic, etc., R 3 It is an alkyl group, an aromatic group, etc.
[0031] Figure 6 This is a characterization diagram of 2-phenyl-1,2,3,4-tetrahydroisoquinoline-1-carbonitrile.
[0032] Figure 7 This is a characterization diagram of 2-(((1H-indol-3-yl)methyl)(methyl)amino)acetonitrile.
[0033] Figure 8 This is a characterization diagram of 2-phenyl-2-(anilino)acetonitrile.
[0034] Fig. 9 This is a characterization diagram of 2-amino-2-phenylacetonitrile. DETAILED DESCRIPTION
[0035] Embodiments of the present invention are described in detail below, examples of which are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present invention, and should not be construed as limiting the present invention.
[0036] See also Figures 1 to 4 In a first aspect, the present invention provides a method for synthesizing a near-infrared light-responsive anthraquinone polymer, comprising the following steps:
[0037] S1 obtains 2,6-dibromoanthraquinone, trivinylbenzene, palladium acetate, 1,1'-diphenylphosphino-ferrocene, triethylamine and N,N-dimethylformamide;
[0038] S2, under nitrogen, adding the 2,6-dibromoanthraquinone, the trivinylbenzene, the palladium acetate, the 1,1'-diphenylphosphino-ferrocene, the triethylamine and the N,N-dimethylformamide into a round-bottom flask;
[0039] In an embodiment of the present invention, the 2,6-dibromoanthraquinone is 1.0 mmol, the isotrivinylbenzene is 2.0 mmol, the molar percentage of palladium acetate is 10, the molar percentage of 1,1'-diphenylphosphino-ferrocene is 10, the triethylamine is 4.0 mmol, and the N,N-dimethylformamide is 5 ml.
[0040] S3: heating the round-bottom flask to 130° C. and refluxing for 48 hours to obtain an anthraquinone polymer.
[0041] Characterization of anthraquinone polymers: In the Fourier transform infrared spectrum of AQ-TVB-CPPs, a sharp signal at the reciprocal of 732 cm was observed to disappear in the vibration of the C-Br bond in 2,6-DBAQ ( Figure 2a It is noteworthy that the characteristic C=O peak is well preserved in the FTIR spectrum of AQ-TVB-CPPs, indicating the successful incorporation of anthraquinone O 2 Reduction of active sites.
[0042] To further prove the success of the polymerization, solid-state nuclear magnetic resonance (S-NMR) was performed on AQ-TVB-CPPs. The results showed that the typical signal at 6.95 parts per million belonged to Ph-CH=CH( Figure 2b ). At the same time, this observation excludes the presence of Ph-CH=CH in the 1,3,5-trivinylbenzene linker framework. 2 The possibility of AQ-TVB-CPPs. The signals at 8.13-8.25 ppm can be attributed to the hydrogens of c and d in the aromatic skeleton of 2,6-DBAQ. In addition, the signal at 7.28 ppm can be attributed to the hydrogens of e in the aromatic skeleton of 2,6-DBAQ. The above characterization results provide overwhelming evidence for the successful construction of AQ-TVB-CPPs. Scanning electron microscopy determined that AQ-TVB-CPPs have an irregular morphology ( Figure 2c ), which was also confirmed by powder X-ray diffraction analysis ( Figure 2d The porous properties of AQ-TVB-CPPs have been characterized by nitrogen physical adsorption analysis ( Figure 2e ). From the nitrogen adsorption-desorption curve, it can be seen that the surface area of AQ-TVB-CPPs is 45.8 m2 / g, and the pore size distribution ranges from 0.83 to 1.31 nm ( Figure 2e Thermogravimetric analysis curves show that AQ-TVB-CPPs have good thermal stability, retaining 80% of their weight at around 630°C ( Figure 2f ).
[0043] Optical and electronic properties of AQ-TVB-CPPs. Figure 3a As shown, AQ-TVB-CPPs exhibit a broad absorption band spanning the entire UV-visible and near-infrared regions, which is a result of extended π conjugation. The optical band gap is calculated to be 1.63 electron volts based on the optical band gap curve. Mott-Schottky electrochemical measurements determined the flat band potential to be -0.85 electron volts (relative to silver chloride electrode), close to the bottom of the conduction band (CB) of AQ-TVB-CPPs ( Figure 3b ). According to the conduction band and band gap, the valence band (VB) of AQ-TVB-CPPs is 1 electron volt (relative to silver chloride electrode). Therefore, the energy band structure of AQ-TVB-CPPs is summarized in Figure 3c Subsequent electrochemical impedance spectroscopy and photocurrent tests showed that AQ-TVB-CPPs had a relatively small radius and obvious photocurrent response under near-infrared light irradiation, indicating the feasibility of photoinduced charge separation and transfer (Figure 3, de). Finally, time-resolved fluorescence decay spectroscopy showed that the average lifetime of AQ-TVB-CPPs was 6.01 nanoseconds ( Figure 3f ).
[0044] See also Figure 5-Figure 9In a second aspect, the present invention further provides an application of a near-infrared light-responsive anthraquinone polymer, an anthraquinone polymer prepared by the synthesis method of the near-infrared light-responsive anthraquinone polymer as described in the first aspect above, including the preparation of α-aminonitrile compounds.
[0045] α-Aminonitriles are an important class of compounds that act as intermediates in organic transformations and natural products and can be used to synthesize nitrogen-containing biologically active compounds such as α-amino acids, alkaloids, and heterocycles. 3 )-H bond cyanation is an ideal method for the synthesis of α-amino nitrile. Therefore, we used AQ-TVB-CPPs in this reaction under 760 nm LEDs light to achieve the synthesis of α-amino C(sp 3 )-H bond cyanation, and this method is not only applicable to tertiary amines, but also to primary amines and secondary amines.
[0046] The preparation method of the α-aminonitrile compound comprises the following steps:
[0047] Amine, trimethylsilyl cyanide, catalyst and methanol were placed in a dry quartz tube and the reaction mixture was stirred under 15 W light irradiation of 760 nm LEDs for 8 h. When the reaction was completed, it was monitored by thin layer chromatography. The solution was filtered and washed with ethyl acetate. The filtrate was evaporated under vacuum and the crude product was directly purified by silica gel column chromatography to obtain α-amino nitrile compounds.
[0048] In the embodiment of the present invention, the amine is 0.2 mmol, the trimethylsilyl cyanide is 0.4 mmol, the catalyst is 10 mg, and the methanol is 2 ml.
[0049] General method for the synthesis of α-amino nitrile:
[0050] Amine (0.2 mmol), trimethylsilyl cyanide (0.4 mmol), catalyst (10 mg) and methanol (2 ml) were placed in a dry quartz tube. The reaction mixture was stirred for 8 hours under 15 watts of light irradiation of 760 nm LEDs. When the reaction was complete (monitored by thin layer chromatography), the solution was filtered and washed with ethyl acetate. The filtrate was evaporated under vacuum. The crude product was directly purified by silica gel column chromatography (petroleum ether: ethyl acetate = 10: 1) to obtain the corresponding product.
[0051] Preparation and characterization of α-aminonitrile compounds:
[0052] Preparation and characterization of phenyl-1,2,3,4-tetrahydroisoquinoline-1-carbonitrile (a):
[0053] 2-phenyl-1,2,3,4-tetrahydroisoquinoline (0.2 mmol), trimethylsilyl cyanide (0.4 mmol), catalyst (10 mg) and methanol (2 ml) were placed in a dry quartz tube. The reaction mixture was stirred for 8 hours under 15 watts of light irradiation from 760 nm LEDs. When the reaction was complete (monitored by thin layer chromatography), the solution was filtered and washed with ethyl acetate. The filtrate was evaporated under vacuum. The crude product was directly purified by silica gel column chromatography (petroleum ether: ethyl acetate = 10: 1) to obtain the corresponding product.
[0054] Yellow oil; yield 95%, 44.5 mg; H NMR (500 MHz, deuterated chloroform) δ 7.41–7.38 (m, 2H), 7.36–7.30 (m, 3H), 7.29–7.27 (m, 1H), 7.13–7.11 (m, 2H), 7.07–7.04 (m, 1H), 5.55 (s, 1H), 3.82–3.78 (m, 1H), 3.54–3.49 (m, 1H), 3.22–3.15 (m, 1H), 3.02–2.97 (m, 1H). 13 CNMR carbon nuclear magnetic resonance spectrum (126 MHz, deuterated chloroform) δ 148.5, 134.7, 129.7, 129.7, 129.5, 128.9, 127.2, 127.0, 122.0, 117.9, 117.7, 53.3, 44.3, 28.6. High resolution mass-to-charge ratio: [M+H] + Calculated as [C 16 H 15 N 2 ] + 235.1230, found to be 235.1227.
[0055] Preparation and characterization of 2-(((1H-indol-3-yl)methyl)(methyl)amino)acetonitrile (b):
[0056] Phragmites australis (0.2 mmol), trimethylsilyl cyanide (0.4 mmol), catalyst (10 mg) and methanol (2 ml) were placed in a dry quartz tube. The reaction mixture was stirred for 8 hours under 15 watts of light irradiation of 760 nanometer LEDs. When the reaction was complete (monitored by thin layer chromatography), the solution was filtered and washed with ethyl acetate. The filtrate was evaporated under vacuum. The crude product was directly purified by silica gel column chromatography (dichloromethane: methanol = 10: 1) to obtain the product.
[0057] Yellow oil, yield 54%, 21.5 mg; H NMR (400 MHz, deuterated chloroform) δ8.18 (s, 1H), 7.75–7.73 (m, 1H), 7.39–7.37 (m, 1H), 7.26–7.21 (m, 1H), 7.18–7.13 (m, 2H), 3.82 (s, 2H), 3.46 (s, 2H), 2.51 (s, 3H). C NMR (101 MHz, deuterated chloroform) δ136.6127.3, 124.2, 122.6, 120.0, 119.6, 115.0, 111.8, 111.3, 51.3, 43.7, 42.5. High resolution mass-to-charge ratio: [M+H] + Calculated as [C 12 H 14 N 3 ] + 200.1182, found to be 200.1186.
[0058] Preparation and characterization of 2-phenyl-2-(anilino)acetonitrile (c):
[0059] N-benzylaniline (0.2 mmol), trimethylsilyl cyanide (0.4 mmol), catalyst (10 mg) and methanol (2 ml) were placed in a dry quartz tube. The reaction mixture was stirred for 8 hours under 15 watts of light irradiation of 760 nm LEDs. When the reaction was complete (monitored by thin layer chromatography), the solution was filtered and washed with ethyl acetate. The filtrate was evaporated under vacuum. The crude product was directly purified by silica gel column chromatography (petroleum ether: ethyl acetate = 10: 1) to obtain the corresponding product.
[0060] Colorless oil, yield 81%, 33.7 mg; H NMR (500 MHz, deuterated chloroform) δ7.63–7.61 (m, 2H), 7.50–7.45 (m, 3H), 7.31–7.26 (m, 2H), 6.94–6.90 (m, 1H), 6.81–6.78 (m, 2H), 5.45 (s, 1H), 4.06 (s, 1H). C NMR (126 MHz, deuterated chloroform) δ144.8, 134.1, 129.7, 129.7, 129.5, 127.4, 120.4, 118.3, 114.3, 50.4. High resolution mass-to-charge ratio: [M+H] + Calculated as [C 14 H 13 N 2 ] + 209.1073, found to be 209.1073.
[0061] Preparation and characterization of 2-amino-2-phenylacetonitrile (d):
[0062] Benzylamine (0.2 mmol), trimethylsilyl cyanide (0.4 mmol), catalyst (10 mg) and methanol (2 ml) were placed in a dry quartz tube. The reaction mixture was stirred for 8 hours under 15 watts of light irradiation of 760 nm LEDs. When the reaction was complete (monitored by thin layer chromatography), the solution was filtered and washed with ethyl acetate. The filtrate was evaporated under vacuum. The crude product was directly purified by silica gel column chromatography (petroleum ether: ethyl acetate = 20: 1) to obtain the corresponding product.
[0063] Colorless oil, yield 77%, 16.1 mg; H NMR (500 MHz, deuterated chloroform) δ7.55–7.53 (m, 2H), 7.44–7.39 (m, 3H), 4.92 (s, 1H), 1.94 (s, 1H). C NMR (126 MHz, deuterated chloroform) δ136.4, 129.2, 129.2, 126.8, 121.0, 47.4. High resolution mass-to-charge ratio: [M+H] + Calculated as [C 8 H 9 N 2 ] + 133.0760, found to be 133.0761.
[0064] The above disclosure is only a preferred embodiment of a method for synthesizing a near-infrared light-responsive anthraquinone polymer and its application of the present invention. Of course, this cannot be used to limit the scope of rights of the present invention. Ordinary technicians in this field can understand that all or part of the processes of the above embodiments and equivalent changes made according to the claims of the present invention are still within the scope of the invention.
Claims
1. A method for synthesizing a near-infrared light-responsive anthraquinone polymer, characterized in that: The following steps are involved: Obtain 2,6-dibromoanthraquinone, trivinylbenzene, palladium acetate, 1,1'-diphenylphosphino-ferrocene, triethylamine and N,N-dimethylformamide; Add the 2,6-dibromoanthraquinone, the mesitylenetrivinylbenzene, the palladium acetate, the 1,1'-diphenylphosphino-ferrocene, the triethylamine and the N,N-dimethylformamide into a round-bottom flask under nitrogen; The round-bottom flask was heated to 130° C. and refluxed for 48 hours to obtain an anthraquinone polymer.
2. The method for synthesizing a near-infrared light-responsive anthraquinone polymer according to claim 1, characterized in that: The 2,6-dibromoanthraquinone is 1.0 mmol, the isotrivinylbenzene is 2.0 mmol, the molar percentage of palladium acetate is 10, the molar percentage of 1,1'-diphenylphosphino-ferrocene is 10, the triethylamine is 4.0 mmol, and the N,N-dimethylformamide is 5 ml.
3. An application of a near-infrared light-responsive anthraquinone polymer, the anthraquinone polymer prepared by the method for synthesizing a near-infrared light-responsive anthraquinone polymer as claimed in any one of claims 1 to 2, characterized in that: Preparation of α-amino nitrile compounds.
4. Use of the near-infrared light-responsive anthraquinone polymer as claimed in claim 3, It is characterized by: The preparation method of the α-aminonitrile compound comprises the following steps: Amine, trimethylsilyl cyanide, catalyst and methanol were placed in a dry quartz tube and the reaction mixture was stirred under 15 W light irradiation of 760 nm LEDs for 8 h. When the reaction was completed, it was monitored by thin layer chromatography. The solution was filtered and washed with ethyl acetate. The filtrate was evaporated under vacuum and the crude product was directly purified by silica gel column chromatography to obtain α-amino nitrile compounds.
5. Use of the near-infrared light-responsive anthraquinone polymer as claimed in claim 4, It is characterized by: The amount of the amine is 0.2 mmol, the amount of the trimethylsilyl cyanide is 0.4 mmol, the amount of the catalyst is 10 mg, and the amount of the methanol is 2 ml.