Novel perylene diimide coordination polymer as well as preparation method and application thereof
By preparing a novel perylene diimide coordination polymer as a photocatalyst, the problems of metal residue and environmental unfriendliness in the conversion of arylacetic acid to arylformaldehyde have been solved, achieving efficient and low-cost catalytic conversion with promising application prospects.
Patent Information
- Application Number
- CN202511774451.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-28
- Publication Date
- 2026-02-24
AI Technical Summary
Existing catalysts for the conversion of arylacetic acid to arylformaldehyde have metal residues, high costs, or are environmentally unfriendly. Furthermore, existing methods are not atom-economical and lack green and efficient catalysts.
A novel perylene diimide coordination polymer was prepared by heating isophthalic acid, N,N'-bis(4-pyridinemethyl)-1,6,7,12-tetrachloroperylene diimide and zinc salt in an organic solvent, using it as a photocatalyst for the photocatalytic conversion of arylacetic acid to arylformaldehyde.
It provides photocatalytic activity with high conversion rate and high chemical stability, is simple to operate and low in cost, and is suitable for large-scale production. Moreover, the perylene diimide coordination polymer is stable in solution at 100℃ and has good heat resistance.
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Figure CN121554762A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of coordination polymer technology, and particularly relates to a novel perylene diimide coordination polymer, its preparation method, and its application. Background Technology
[0002] Arylformaldehyde ketone derivatives are important chemical raw materials and organic synthesis intermediates. Traditional preparation methods, such as hydrolysis of chlorinated aromatics, toluene oxidation, aryl methanol oxidation, hydrogenation reduction of arylformic acid, and indirect electro-oxidation, generally suffer from drawbacks including cumbersome synthesis steps, high raw material costs, low reaction selectivity and efficiency, the need for inert atmosphere protection, and environmental unfriendliness, thus limiting the application of these compounds. Among these methods, the direct oxidative decarboxylation of arylacetic acid to prepare arylformaldehyde is a highly atom-economical route, but its core challenge lies in developing efficient and highly selective catalysts.
[0003] Currently, research in this field mainly relies on metal catalysts (such as copper-iron complexes) or noble metals (such as palladium). While these systems are effective, they suffer from problems such as metal residues, high costs, or environmental unfriendliness. Furthermore, organic catalytic methods using stoichiometric oxidants (such as persulfates) (e.g., DDQ) have been reported, but their atom economy is poor. Therefore, developing green catalysts to achieve the direct oxidative decarboxylation of arylacetic acid to arylformaldehyde derivatives has become a hot topic in chemical research. However, there are no reports in the existing technology regarding the use of perylene diimide-based coordination polymers as photocatalysts. Summary of the Invention
[0004] To address the aforementioned technical problems, this invention proposes a novel perylene diimide coordination polymer, its preparation method, and its applications.
[0005] To achieve the above objectives, the present invention provides the following technical solution:
[0006] This invention provides a novel perylene diimide coordination polymer, the chemical formula of which is C0. 44 H 20 C l4 N4O8Zn.
[0007] Furthermore, the novel perylene diimide coordination polymer belongs to the monoclinic crystal system, with space group P21 / n and unit cell parameters of: a=12.07260(10)Å, α=90°, b=32.7923(3)Å, β=107.9710(10)°, c=13.21850(10)Å, γ=90°.
[0008] This invention provides a method for preparing a novel perylene diimide coordination polymer as described above, comprising the following steps: dissolving isophthalic acid, N,N'-bis(4-pyridylmethyl)-1,6,7,12-tetrachloroperylene diimide and zinc salt in an organic solvent and heating the mixture to react, followed by cooling to obtain the novel perylene diimide coordination polymer.
[0009] Furthermore, the molar ratio of isophthalic acid, N,N'-bis(4-pyridylmethyl)-1,6,7,12-tetrachloroperylene diimide and zinc salt is 2:1:(2~4).
[0010] Furthermore, the zinc salt is selected from zinc nitrate hexahydrate.
[0011] Furthermore, the organic solvent is selected from N,N-dimethylformamide.
[0012] Furthermore, the temperature of the heating reaction is 80~95℃, and the heating reaction time is 24~48h.
[0013] Furthermore, the cooling rate is 5~10℃ / min.
[0014] This invention provides an application of the novel perylene diimide coordination polymer as described above in the photocatalytic preparation of arylformaldehyde derivatives from arylaceous acid and its derivatives.
[0015] Furthermore, the amount of the novel perylene diimide coordination polymer is 0.2 mol.
[0016] Compared with the prior art, the present invention has the following advantages and technical effects:
[0017] (1) The novel perylene diimide coordination polymer provided by the present invention has good thermal and chemical stability. It can be stably stored for 24 hours in aqueous solution, acetonitrile solution or N,N-dimethylformamide solution at 100℃, and its heat resistance under nitrogen atmosphere is up to 300℃.
[0018] (2) The novel perylene diimide coordination polymer provided by the present invention has the characteristics of high conversion rate and high chemical stability as a photocatalyst. It has extremely high photocatalytic activity for the conversion of arylacetic acid to aryl formaldehyde derivatives. Moreover, the amount used is low (only 0.2 mol%). The photocatalytic reaction is simple to operate, the reaction conditions are mild, and it has good practical value and application prospects.
[0019] (3) The preparation method of the novel perylene diimide coordination polymer provided by the present invention is simple and convenient to operate, has low requirements for synthesis equipment, low cost, readily available raw materials, mild reaction conditions, and can be produced on a large scale. The prepared novel perylene diimide coordination polymer has high yield and good purity. Attached Figure Description
[0020] 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 undue limitation of the invention. In the drawings:
[0021] Figure 1 The image shows the single-crystal structure of the novel perylene diimide coordination polymer prepared in Example 1.
[0022] Figure 2 Two-dimensional structure diagram of the novel perylene diimide coordination polymer prepared in Example 1;
[0023] Figure 3 The XRD pattern of the novel perylene diimide coordination polymer prepared in Example 1;
[0024] Figure 4 Thermogravimetric curve of the novel perylene diimide coordination polymer prepared in Example 1;
[0025] Figure 5 XRD patterns of the novel perylene diimide coordination polymer prepared in Example 1 after immersion in different solutions at 100°C for 24 h;
[0026] Figure 6 The XRD pattern of the novel perylene diimide coordination polymer prepared in Example 2;
[0027] Figure 7 The cyclic photocatalytic yield diagram shows the photocatalytic synthesis of 2-methoxybenzaldehyde from the novel perylene diimide coordination polymer prepared in Example 2.
[0028] Figure 8 The image shows the XRD patterns of the novel perylene diimide coordination polymer prepared in Example 2 before and after recycling. Detailed Implementation
[0029] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0030] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
[0031] This invention provides a novel perylene diimide coordination polymer, the chemical formula of which is C0. 44 H20 C l4 N4O8Zn.
[0032] In a preferred embodiment, the novel perylene diimide coordination polymer belongs to the monoclinic crystal system, space group P21 / n, and has unit cell parameters of: a=12.07260(10)Å, α=90°, b=32.7923(3)Å, β=107.9710(10)°, c=13.21850(10)Å, γ=90°.
[0033] This invention provides a method for preparing a novel perylene diimide coordination polymer as described above, comprising the following steps: dissolving isophthalic acid, N,N'-bis(4-pyridylmethyl)-1,6,7,12-tetrachloroperylene diimide and zinc salt in an organic solvent and heating the mixture to react, followed by cooling to obtain the novel perylene diimide coordination polymer.
[0034] In a preferred embodiment, the molar ratio of isophthalic acid, N,N'-bis(4-pyridylmethyl)-1,6,7,12-tetrachloroperylene diimide and zinc salt is 2:1:(2~4); the zinc salt is selected from zinc nitrate hexahydrate.
[0035] In a preferred embodiment, the structural formula of the isophthalic acid is as follows: The structural formula of the N,N'-bis(4-pyridinemethyl)-1,6,7,12-tetrachloroperylene diimide is as follows: .
[0036] In a preferred embodiment, the organic solvent is selected from N,N-dimethylformamide.
[0037] In a preferred embodiment, the temperature of the heating reaction is 80~95℃, more preferably 80~90℃; the heating reaction time is 24~48h, more preferably 24~36h.
[0038] In a preferred embodiment, the cooling rate is 5~10℃ / min, more preferably 5~8℃ / min; the cooling is to cool to room temperature.
[0039] In a preferred embodiment, the cooling process further includes steps of filtration, washing, and drying; the washing reagent is selected from N,N-dimethylformamide; the drying is vacuum drying, and the drying time is 5 hours.
[0040] This invention provides an application of the novel perylene diimide coordination polymer as described above in the photocatalytic preparation of arylformaldehyde derivatives from arylaceous acid and its derivatives.
[0041] In a preferred embodiment, the amount of the novel perylene diimide coordination polymer is 0.2 mol.
[0042] In a preferred embodiment, the application of the novel perylene diimide coordination polymer in the photocatalytic preparation of aryl formaldehyde derivatives from aryl acetic acid derivatives includes the following steps: dissolving aryl acetic acid or aryl acetic acid derivatives in acetonitrile, then adding the novel perylene diimide coordination polymer, copper trifluoromethanesulfonate, and 1,1,3,3-tetramethylguanidine to obtain a mixed solution; stirring the mixture under blue light irradiation, and after post-treatment, obtaining aryl formaldehyde and its derivatives.
[0043] In a preferred embodiment, the molar ratio of the arylacetic acid or arylacetic acid derivative, copper trifluoromethanesulfonate, and 1,1,3,3-tetramethylguanidine is 4:1:12.
[0044] In a preferred embodiment, the structural formula of 1,1,3,3-tetramethylguanidine is as follows: .
[0045] In a preferred embodiment, the power of the blue light is 50W and the wavelength of the blue light is 460nm.
[0046] In a preferred embodiment, the stirring reaction is carried out at room temperature for 24 hours.
[0047] In a preferred embodiment, the post-processing specifically involves: adding water and dichloromethane to the reaction solution obtained by stirring to obtain an aqueous phase and an oil phase; after separation, extracting the aqueous phase with dichloromethane 3-4 times; combining all the dichloromethane and concentrating under reduced pressure to obtain a crude product; and separating the crude product by column chromatography to obtain the aryl formaldehyde and its derivatives.
[0048] In a preferred embodiment, the eluent for column chromatography separation is a mixed solvent of petroleum ether and ethyl acetate, wherein the volume ratio of petroleum ether to ethyl acetate is 20:1.
[0049] In a preferred embodiment, the yield of the aryl formaldehyde and its derivatives is 85-91%.
[0050] In a preferred embodiment, the structural formula of the arylacetic acid derivative is as follows: , where R 1 =H, 2-OMe, 3-OMe, 4-OMe, 4-CH3, 4-tBu, 4-F, 4-Cl or 4-Br.
[0051] In a preferred embodiment, when the raw material is an arylacetic acid derivative, the chemical reaction equation for preparing the arylformaldehyde derivative from the arylacetic acid derivative is as follows:
[0052] .
[0053] In this embodiment of the invention, room temperature refers to "25±2℃".
[0054] Unless otherwise specified, all raw materials used in the embodiments of this invention were purchased through commercial channels.
[0055] In the following examples and comparative examples, isophthalic acid, N,N'-bis(4-pyridylmethyl)-1,6,7,12-tetrachloroperylene diimide, zinc nitrate hexahydrate, N,N-dimethylformamide, arylaceous acid and its derivatives, copper trifluoromethanesulfonate, 1,1,3,3-tetramethylguanidine, petroleum ether and ethyl acetate were all of analytical grade.
[0056] Example 1
[0057] A method for preparing a novel perylene diimide coordination polymer:
[0058] 0.2 mmol of isophthalic acid, 0.1 mmol of N,N'-bis(4-pyridylmethyl)-1,6,7,12-tetrachloroperylene diimide, and 0.2 mmol of zinc nitrate hexahydrate were added to 5 mL of N,N-dimethylformamide. The mixture was stirred for 10 min at room temperature in air. The solution was then transferred to a 10 mL Teflon high-pressure reactor and heated to 80 °C in an oven for 48 h. After the reaction was completed, the mixture was cooled to room temperature at a rate of 10 °C / h. After filtration, washing with N,N-dimethylformamide, and vacuum drying at 50 °C for 5 h, red crystals were obtained, which were the novel perylene diimide coordination polymer with a yield of 85%. Subsequently, the obtained novel perylene diimide coordination polymer was ground and passed through a 100-mesh sieve for later use.
[0059] The X-ray single-crystal diffraction data of the novel perylene diimide coordination polymer in Example 1 are shown in Table 1.
[0060] Table 1
[0061]
[0062] Figure 1 This is a single-crystal structure diagram of the novel perylene diimide coordination polymer prepared in Example 1. From... Figure 1 As can be seen, in the novel perylene diimide coordination polymer prepared in Example 1, each zinc atom is coordinated with the carboxyl groups of two isophthalic acids and the pyridine nitrogen atoms of two N,N'-di(4-pyridinemethyl)-1,6,7,12-tetrachloroperylene diimide atoms to form a tetrahedral coordination configuration.
[0063] Figure 2 This is a two-dimensional structural diagram of the novel perylene diimide coordination polymer prepared in Example 1. From... Figure 2As can be seen, in the novel perylene diimide coordination polymer prepared in Example 1, the two pyridine nitrogen atoms of N,N'-bis(4-pyridinemethyl)-1,6,7,12-tetrachloroperylene diimide and the two carboxyl groups of isophthalic acid are coordinated with zinc atoms and interconnected to form a two-dimensional coordination polymer.
[0064] Figure 3 The image shows the XRD pattern of the novel perylene diimide coordination polymer prepared in Example 1. Figure 3 It can be seen that the characteristic peaks of the novel perylene diimide coordination polymer prepared in Example 1 are completely consistent with the positions of the characteristic peaks in the theoretical simulation, indicating that the structure of the synthesized novel perylene diimide coordination polymer is consistent with the simulated structure and is a pure phase.
[0065] The thermal stability of the novel perylene diimide coordination polymer prepared in Example 1 was characterized by thermogravimetric analysis. Specifically, the polymer was heated at a rate of 10 °C / min under a N2 atmosphere, and the thermogravimetric curves of the novel perylene diimide polymer were measured. The results are shown in [Figure number missing]. Figure 4 .
[0066] Figure 4 Thermogravimetric curve of the novel perylene diimide coordination polymer prepared in Example 1. From... Figure 4 It can be seen that approximately 6% weight loss occurs within the temperature range of room temperature to 120℃, indicating that the novel perylene diimide coordination polymer contains solvent molecules. After the solvent molecules evaporate, the product shows virtually no weight loss within the 120~300℃ range, demonstrating its stability and good thermal stability within this temperature range. Subsequently, continuous weight loss occurs within the 300~800℃ range, indicating that the product begins to decompose.
[0067] The novel perylene diimide coordination polymer prepared in Example 1 was immersed in aqueous solution, acetonitrile solution, and N,N-dimethylformamide solution in a high-pressure reactor, respectively, and heated to 100°C and held at that temperature for 24 hours. XRD analysis was then performed, and the results are shown below. Figure 5 .
[0068] Figure 5 XRD patterns of the novel perylene diimide coordination polymer prepared in Example 1 after immersion in different solutions at 100°C for 24 hours. Figure 5 It can be seen that after the novel perylene diimide coordination polymer prepared in Example 1 was immersed in aqueous solution, acetonitrile solution and N,N-dimethylformamide solution at 100℃ for 24 h, its XRD pattern was consistent with the theoretically simulated pattern. Figure 1 The result indicates that the structure of the coordination polymer did not change in the above solution, demonstrating good chemical stability.
[0069] Application Example 1
[0070] Example 1 describes the photocatalytic oxidative decarboxylation synthesis of arylformaldehyde derivatives 2a~2i from a novel perylene diimide coordination polymer:
[0071] (1) Synthesis of compound 2a
[0072] 0.002 mol phenylacetic acid 1a ( The compound 2a was dissolved in 5 mL of acetonitrile, and then 0.2 mol% of the novel perylene diimide coordination polymer prepared in Example 1, 0.0005 mol of copper trifluoromethanesulfonate, and 0.006 mol of 1,1,3,3-tetramethylguanidine were added to obtain a mixed solution. The mixed solution was placed at 10 cm from a 50 W blue LED light source and magnetically stirred for 24 h. After the reaction of phenylacetic acid 1a was complete, water and dichloromethane were added for dilution to obtain an aqueous phase and an oil phase. The aqueous phase was extracted three times with dichloromethane, 10 mL each time. The dichloromethane was combined and the solvent was dried to obtain a crude product. The crude product was separated by column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain compound 2a. The yield was 90%. The NMR spectral data for compound 2a are as follows: 1 H NMR (400 MHz, CDCl3): δ = 10.02 (s,1H), 7.91 (d, J = 8.0 Hz, 2H), 7.64-7.68 (m, 1H), 7.54-7.58 (m, 2H) ppm; 13 CNMR (100 MHz, CDCl3): δ = 192.6, 136.5, 134.5, 129.9, 129.1 ppm.
[0073] (2) Synthesis of compound 2b
[0074] 0.002 mol of 2-methoxyphenylacetic acid 1b ( The compound 2b was dissolved in 5 mL of acetonitrile, and then 0.2 mol% of the novel perylene diimide coordination polymer prepared in Example 1, 0.0005 mol of copper trifluoromethanesulfonate, and 0.006 mol of 1,1,3,3-tetramethylguanidine were added to obtain a mixed solution. The mixed solution was placed at 10 cm from a 50 W blue LED light source and magnetically stirred for 24 h. After the reaction of 2-methoxyphenylacetic acid 1b was complete, water and dichloromethane were added for dilution to obtain an aqueous phase and an oil phase. The aqueous phase was extracted three times with dichloromethane, 10 mL each time. The dichloromethane was combined and the solvent was dried to obtain a crude product. The crude product was separated by column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain compound 2b. The yield was 86%. The NMR spectral data for compound 2b are as follows: 1 H NMR (400MHz, CDCl3) δ = 10.47 (s, 1H), 7.82 (d, J = 7.64 Hz, 1H), 7.55 (td, J = 8.64,1.36 Hz, 1H), 7.01 (q, J = 7.48 Hz, 2H), 3.92 (s, 3H) ppm; 13 C NMR (100 MHz, CDCl3) δ = 190.0, 161.8, 136.0, 128.5, 124.8, 120.7, 111.6, 55.6 ppm.
[0075] (3) Synthesis of compound 2c
[0076] 0.002 mol 3-methoxyphenylacetic acid 1c ( The compound 2c was dissolved in 5 mL of acetonitrile, and then 0.2 mol% of the novel perylene diimide coordination polymer prepared in Example 1, 0.0005 mol of copper trifluoromethanesulfonate, and 0.006 mol of 1,1,3,3-tetramethylguanidine were added to obtain a mixed solution. The mixed solution was placed at 10 cm from a 50 W blue LED light source and magnetically stirred for 24 h. After the reaction of 3-methoxyphenylacetic acid 1c was complete, water and dichloromethane were added for dilution to obtain an aqueous phase and an oil phase. After separation, the aqueous phase was extracted three times with dichloromethane, 10 mL each time. The dichloromethane was combined and the solvent was dried to obtain a crude product. The crude product was separated by column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain compound 2c. The yield was 88%. The NMR spectral data for compound 2c are as follows: 1 H NMR (400 MHz, CDCl3) δ = 9.97 (s, 1H), 7.45 (d, J = 6.28 Hz, 2H), 7.39 (d, J =2.04 Hz, 1H), 7.17-7.19 (m, 1H), 3.86 (s, 3H) ppm; 13 C NMR (100 MHz, CDCl3) δ192.3, 160.1, 137.8, 130.1, 123.6, 121.6, 112.0, 55.5 ppm.
[0077] (4) Synthesis of compound 2d
[0078] 0.002 mol of 4-methoxyphenylacetic acid for 1 day ( Dissolved in 5 mL of acetonitrile, then 0.2 mol% of the novel perylene diimide coordination polymer prepared in Example 1, 0.0005 mol of copper trifluoromethanesulfonate, and 0.006 mol of 1,1,3,3-tetramethylguanidine were added to obtain a mixed solution. The above mixed solution was transferred to a 50W blue LED light source at 10 cm, irradiated, and magnetically stirred for 24 h. After the reaction of 1d of 4-methoxyphenylacetic acid was complete, water and dichloromethane were added for dilution to obtain an aqueous phase and an oil phase. After separation, the aqueous phase was extracted three times with dichloromethane, 10 mL each time. The dichloromethane was combined and the solvent was dried to obtain the crude product. The crude product was separated by column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain compound 2d ( The yield was 91%. The NMR spectral data for compound 2d are as follows: 1 H NMR(400 MHz, CDCl3) δ = 9.88 (s, 1H), 7.84 (d, J = 8.80 Hz, 2H), 7.01 (d, J =8.72 Hz, 2H), 3.89(s, 3H) ppm; 13 C NMR (100 MHz, CDCl3) δ 190.9, 164.6, 132.0,130.0, 114.3, 55.6 ppm.
[0079] (5) Synthesis of compound 2e
[0080] 0.002 mol 4-methylphenylacetic acid 1e ( The compound 2e was dissolved in 5 mL of acetonitrile, and then 0.2 mol% of the novel perylene diimide coordination polymer prepared in Example 1, 0.0005 mol of copper trifluoromethanesulfonate, and 0.006 mol of 1,1,3,3-tetramethylguanidine were added to obtain a mixed solution. The mixed solution was placed at 10 cm from a 50 W blue LED light source and magnetically stirred for 24 h. After the reaction of 4-methylphenylacetic acid 1e was complete, water and dichloromethane were added for dilution to obtain an aqueous phase and an oil phase. The aqueous phase was extracted three times with dichloromethane, 10 mL each time. The dichloromethane was combined and the solvent was dried to obtain a crude product. The crude product was separated by column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain compound 2e. The yield was 90%. The NMR spectral data for compound 2e are as follows: 1H NMR (400MHz, CDCl3) δ = 9.96 (s, 1H), 7.78 (d, J = 7.96 Hz, 1H), 7.23 (s, 1H), 6.84 (d, J = 7.92 Hz, 1H), 5.99 (s, 2H) ppm; 13 C NMR (100 MHz, Chloroform-d) δ192.1, 145.6, 134.2, 129.9, 129.8, 21.9 ppm.
[0081] (6) Synthesis of compound 2f
[0082] 0.002 mol of 4-tert-butylphenylacetic acid 1f ( Dissolve 4-tert-butylphenylacetic acid 1f in 5 mL of acetonitrile, then add 0.2 mol% of the novel perylene diimide coordination polymer prepared in Example 1, 0.0005 mol of copper trifluoromethanesulfonate and 0.006 mol of 1,1,3,3-tetramethylguanidine to obtain a mixed solution; transfer the above mixed solution to a 50W blue LED light source at 10 cm, irradiate and magnetically stir for 24 h, after the reaction of 4-tert-butylphenylacetic acid 1f is complete, add water and dichloromethane for dilution to obtain an aqueous phase and an oil phase, separate the liquid and extract the aqueous phase three times with dichloromethane, 10 mL each time, combine the dichloromethane and dry the solvent to obtain the crude product; separate the crude product by column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain compound 2f ( The yield was 86%. The NMR spectral data for compound 2f are as follows: 1 H NMR (400 MHz, CDCl3) δ = 9.98 (s, 1H), 7.82 (d, J = 8.48 Hz, 2H), 7.55 (d, J =8.36 Hz, 2H), 1.35 (s, 9H) ppm; 13 C NMR (100 MHz, CDCl3) δ 192.1, 158.5,134.1, 129.7, 126.0, 35.4, 31.1 ppm.
[0083] (7) Synthesis of compound 2g
[0084] 0.002 mol 1 g of 4-fluorophenylacetic acid ( Dissolve 4-fluorophenylacetic acid in 5 mL of acetonitrile, then add 0.2 mol% of the novel perylene diimide coordination polymer prepared in Example 1, 0.0005 mol of copper trifluoromethanesulfonate, and 0.006 mol of 1,1,3,3-tetramethylguanidine to obtain a mixed solution; transfer the above mixed solution to a 50W blue LED light source at 10 cm, irradiate and magnetically stir for 24 h, after 1 g of 4-fluorophenylacetic acid has reacted completely, add water and dichloromethane for dilution to obtain an aqueous phase and an oil phase, separate the liquid and extract the aqueous phase three times with dichloromethane, 10 mL each time, combine the dichloromethane and dry the solvent to obtain the crude product; separate the crude product by column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain 2 g of compound ( The yield was 85%. The NMR spectral data for 2g of compound were as follows: 1 H NMR (400 MHz, CDCl3) δ= 9.97 (s, 1H), 7.92 (q, J = 3.28 Hz, 2H), 7.22 (t, J = 8.52 Hz, 2H) ppm; 13 CNMR (100 MHz, CDCl3) δ 190.6, 167.8, 165.3, 132.9, 132.9, 132.2, 116.5, 116.3ppm.
[0085] (8) Synthesis of compound 2h
[0086] 0.002 mol 4-chlorophenylacetic acid for 1 h ( Dissolved in 5 mL of acetonitrile, then 0.2 mol% of the novel perylene diimide coordination polymer prepared in Example 1, 0.0005 mol of copper trifluoromethanesulfonate, and 0.006 mol of 1,1,3,3-tetramethylguanidine were added to obtain a mixed solution. The above mixed solution was transferred to a 50W blue LED light source at 10 cm, irradiated, and magnetically stirred for 24 h. After the reaction of 4-chlorophenylacetic acid was complete for 1 h, water and dichloromethane were added for dilution to obtain an aqueous phase and an oil phase. After separation, the aqueous phase was extracted three times with dichloromethane, 10 mL each time. The dichloromethane was combined and the solvent was dried to obtain the crude product. The crude product was separated by column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain compound 2 h ( The yield was 88%. The NMR spectral data of compound 2 h were as follows: 1 H NMR (400 MHz, CDCl3)δ = 9.91 (s, 1H), 7.76 (d, J = 8.36 Hz, 2H), 7.45 (d, J = 8.28 Hz, 2H) ppm; 13C NMR (100 MHz, CDCl3) δ 191.0, 141.0, 134.7, 131.0, 129.5 ppm.
[0087] (9) Synthesis of compound 2i
[0088] 0.002 mol 4-bromophenylacetic acid 1i ( Dissolve 4-bromophenylacetic acid 1i in 5 mL of acetonitrile, then add 0.2 mol% of the novel perylene diimide coordination polymer prepared in Example 1, 0.0005 mol of copper trifluoromethanesulfonate, and 0.006 mol of 1,1,3,3-tetramethylguanidine to obtain a mixed solution; transfer the above mixed solution to a 50W blue LED light source at 10 cm, irradiate and magnetically stir for 24 h, after the reaction of 4-bromophenylacetic acid 1i is complete, add water and dichloromethane for dilution to obtain an aqueous phase and an oil phase, separate the liquid and extract the aqueous phase three times with dichloromethane, 10 mL each time, combine the dichloromethane and dry the solvent to obtain the crude product; perform column chromatography separation of the obtained crude product with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain compound 2i ( The yield was 89%. The NMR spectral data for compound 2i are as follows: 1 H NMR (400 MHz, CDCl3) δ = 9.98 (s, 1H), 7.75 (d, J = 8.40 Hz, 2H), 7.69 (d, J = 8.32 Hz, 2H)ppm; 13 C NMR (100 MHz, CDCl3) δ 191.2, 135.0, 132.5, 131.0, 129.8 ppm.
[0089] Example 2
[0090] A method for preparing a novel perylene diimide coordination polymer:
[0091] 0.4 mmol of isophthalic acid, 0.2 mmol of N,N'-bis(4-pyridylmethyl)-1,6,7,12-tetrachloroperylene diimide, and 0.8 mmol of zinc nitrate hexahydrate were added to 10 mL of N,N-dimethylformamide. The mixture was stirred for 10 min at room temperature under air atmosphere. The solution was then transferred to a 15 mL Teflon high-pressure reactor and heated to 95 °C in an oven for 24 h. After the reaction was completed, the mixture was cooled to room temperature at a rate of 5 °C / h. After filtration, washing with N,N-dimethylformamide, and vacuum drying at 50 °C for 5 h, red crystals were obtained, which were the novel perylene diimide coordination polymer with a yield of 83%. Subsequently, the obtained novel perylene diimide coordination polymer was ground and passed through a 100-mesh sieve for later use.
[0092] Figure 6 The image shows the XRD pattern of the novel perylene diimide coordination polymer prepared in Example 2. Figure 6 It can be seen that the characteristic peaks of the novel perylene diimide coordination polymer prepared in Example 1 are completely consistent with the positions of the characteristic peaks in the theoretical simulation, indicating that the structure of the synthesized novel perylene diimide coordination polymer is consistent with the simulated structure and is a pure phase.
[0093] Application Example 2
[0094] Example 2: Photocatalytic oxidative decarboxylation of arylacetic acid to synthesize aryl formaldehyde derivatives 2a~2i using a novel perylene diimide coordination polymer.
[0095] (1) Synthesis of compound 2a
[0096] 0.004 mol phenylacetic acid 1a ( The compound 2a was dissolved in 10 mL of acetonitrile, and then 0.2 mol% of the novel perylene diimide coordination polymer prepared in Example 2, 0.001 mol of copper trifluoromethanesulfonate, and 0.012 mol of 1,1,3,3-tetramethylguanidine were added to obtain a mixed solution. The mixed solution was placed at 10 cm from a 50 W blue LED light source and magnetically stirred for 24 h. After the reaction of phenylacetic acid 1a was complete, water and dichloromethane were added for dilution to obtain an aqueous phase and an oil phase. The aqueous phase was extracted three times with dichloromethane, 10 mL each time. The dichloromethane was combined and the solvent was dried to obtain a crude product. The crude product was separated by column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain compound 2a. The yield was 88%. The NMR spectral data for compound 2a are as follows: 1 H NMR (400 MHz, CDCl3): δ = 10.02 (s,1H), 7.91 (d, J = 8.0 Hz, 2H), 7.64-7.68 (m, 1H), 7.54-7.58 (m, 2H) ppm; 13 CNMR (100 MHz, CDCl3): δ = 192.6, 136.5, 134.5, 129.9, 129.1 ppm.
[0097] (2) Synthesis of compound 2b
[0098] 0.004 mol of 2-methoxyphenylacetic acid 1b ( The compound 2b was dissolved in 10 mL of acetonitrile, and then 0.2 mol% of the novel perylene diimide coordination polymer prepared in Example 2, 0.001 mol of copper trifluoromethanesulfonate, and 0.012 mol of 1,1,3,3-tetramethylguanidine were added to obtain a mixed solution. The mixed solution was placed at 10 cm from a 50 W blue LED light source and magnetically stirred for 24 h. After the reaction of 2-methoxyphenylacetic acid 1b was complete, water and dichloromethane were added for dilution to obtain an aqueous phase and an oil phase. After separation, the aqueous phase was extracted three times with dichloromethane, 10 mL each time. The dichloromethane was combined and the solvent was dried to obtain a crude product. The crude product was separated by column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain compound 2b. The yield was 85%. The NMR spectral data for compound 2b are as follows: 1 H NMR (400 MHz, CDCl3) δ = 10.47 (s, 1H), 7.82 (d, J = 7.64 Hz, 1H), 7.55 (td, J = 8.64, 1.36Hz, 1H), 7.01 (q, J = 7.48 Hz, 2H), 3.92 (s, 3H)ppm; 13 C NMR (100 MHz, CDCl3)δ = 190.0, 161.8, 136.0, 128.5, 124.8, 120.7, 111.6, 55.6 ppm.
[0099] (3) Synthesis of compound 2c
[0100] 0.004 mol 3-methoxyphenylacetic acid 1c ( The compound 2c was dissolved in 10 mL of acetonitrile, and then 0.2 mol% of the novel perylene diimide coordination polymer prepared in Example 2, 0.001 mol of copper trifluoromethanesulfonate, and 0.012 mol of 1,1,3,3-tetramethylguanidine were added to obtain a mixed solution. The mixed solution was placed at 10 cm from a 50 W blue LED light source and magnetically stirred for 24 h. After the reaction of 3-methoxyphenylacetic acid 1c was complete, water and dichloromethane were added for dilution to obtain an aqueous phase and an oil phase. After separation, the aqueous phase was extracted three times with dichloromethane, 10 mL each time. The dichloromethane was combined and the solvent was dried to obtain the crude product. The crude product was separated by column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain compound 2c. The yield was 87%. The NMR spectral data for compound 2c are as follows: 1H NMR (400 MHz, CDCl3) δ = 9.97 (s, 1H), 7.45 (d, J = 6.28 Hz, 2H), 7.39 (d, J =2.04 Hz, 1H), 7.17-7.19 (m, 1H), 3.86 (s, 3H) ppm; 13 C NMR (100 MHz, CDCl3) δ192.3, 160.1, 137.8, 130.1, 123.6, 121.6, 112.0, 55.5 ppm.
[0101] (4) Synthesis of compound 2d
[0102] 0.004 mol of 4-methoxyphenylacetic acid for 1 day ( Dissolved in 10 mL of acetonitrile, then 0.2 mol% of the novel perylene diimide coordination polymer prepared in Example 2, 0.001 mol of copper trifluoromethanesulfonate, and 0.012 mol of 1,1,3,3-tetramethylguanidine were added to obtain a mixed solution. The above mixed solution was transferred to a 50W blue LED light source at 10 cm, irradiated, and magnetically stirred for 24 h. After the reaction of 4-methoxyphenylacetic acid 1d was complete, water and dichloromethane were added for dilution to obtain an aqueous phase and an oil phase. After separation, the aqueous phase was extracted three times with dichloromethane, 10 mL each time. The dichloromethane was combined and the solvent was dried to obtain the crude product. The crude product was separated by column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain compound 2d ( The yield was 91%. The NMR spectral data for compound 2d are as follows: 1 H NMR(400 MHz, CDCl3) δ = 9.88 (s, 1H), 7.84 (d, J = 8.80 Hz, 2H), 7.01 (d, J =8.72 Hz, 2H), 3.89(s, 3H) ppm; 13 C NMR (100 MHz, CDCl3) δ 190.9, 164.6, 132.0,130.0, 114.3, 55.6 ppm.
[0103] (5) Synthesis of compound 2e
[0104] 0.004 mol 4-methylphenylacetic acid 1e ( The compound 2e was dissolved in 10 mL of acetonitrile, and then 0.2 mol% of the novel perylene diimide coordination polymer prepared in Example 2, 0.001 mol of copper trifluoromethanesulfonate, and 0.012 mol of 1,1,3,3-tetramethylguanidine were added to obtain a mixed solution. The mixed solution was placed at 10 cm from a 50 W blue LED light source and magnetically stirred for 24 h. After the reaction of 4-methylphenylacetic acid 1e was complete, water and dichloromethane were added for dilution to obtain an aqueous phase and an oil phase. The aqueous phase was extracted three times with dichloromethane, 10 mL each time. The dichloromethane was combined and the solvent was dried to obtain a crude product. The crude product was separated by column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain compound 2e. The yield was 91%. The NMR spectral data for compound 2e are as follows: 1 H NMR (400MHz, CDCl3) δ = 9.96 (s, 1H), 7.78 (d, J = 7.96 Hz, 1H), 7.23 (s, 1H), 6.84 (d, J = 7.92 Hz, 1H), 5.99 (s, 2H) ppm; 13 C NMR (100 MHz, Chloroform-d) δ192.1, 145.6, 134.2, 129.9, 129.8, 21.9 ppm.
[0105] (6) Synthesis of compound 2f
[0106] 0.004 mol of 4-tert-butylphenylacetic acid 1f ( Dissolve 4-tert-butylphenylacetic acid 1f in 10 mL of acetonitrile, then add 0.2 mol% of the novel perylene diimide coordination polymer prepared in Example 2, 0.001 mol of copper trifluoromethanesulfonate and 0.012 mol of 1,1,3,3-tetramethylguanidine to obtain a mixed solution; transfer the above mixed solution to a 50W blue LED light source at 10 cm, irradiate and magnetically stir for 24 h, after the reaction of 4-tert-butylphenylacetic acid 1f is complete, add water and dichloromethane for dilution to obtain an aqueous phase and an oil phase, separate the liquid and extract the aqueous phase three times with dichloromethane, 10 mL each time, combine the dichloromethane and dry the solvent to obtain the crude product; separate the crude product by column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain compound 2f ( The yield was 87%. The NMR spectral data for compound 2f are as follows: 1H NMR (400 MHz, CDCl3) δ = 9.98 (s, 1H), 7.82 (d, J = 8.48 Hz, 2H), 7.55 (d, J =8.36 Hz, 2H), 1.35 (s, 9H) ppm; 13 C NMR (100 MHz, CDCl3) δ 192.1, 158.5,134.1, 129.7, 126.0, 35.4, 31.1 ppm.
[0107] (7) Synthesis of compound 2g
[0108] 0.004 mol 1 g of 4-fluorophenylacetic acid ( Dissolve 1 g of 4-fluorophenylacetic acid in 10 mL of acetonitrile, then add 0.2 mol% of the novel perylene diimide coordination polymer prepared in Example 2, 0.001 mol of copper trifluoromethanesulfonate, and 0.012 mol of 1,1,3,3-tetramethylguanidine to obtain a mixed solution; transfer the above mixed solution to a 50W blue LED light source at 10 cm, irradiate and magnetically stir for 24 h, after 1 g of 4-fluorophenylacetic acid has reacted completely, add water and dichloromethane for dilution to obtain an aqueous phase and an oil phase, separate the liquid and extract the aqueous phase three times with dichloromethane, 10 mL each time, combine the dichloromethane and dry the solvent to obtain the crude product; perform column chromatography separation of the obtained crude product with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain 2 g of compound ( The yield was 89%. The NMR spectral data of 2g of compound were... 1 H NMR (400 MHz, CDCl3) δ =9.97 (s, 1H), 7.92 (q, J = 3.28 Hz, 2H), 7.22 (t, J = 8.52 Hz, 2H) ppm; 13 CNMR (100 MHz, CDCl3) δ 190.6, 167.8, 165.3, 132.9, 132.9, 132.2, 116.5, 116.3ppm.
[0109] (8) Synthesis of compound 2h
[0110] 0.004 mol of 4-chlorophenylacetic acid was added for 1 hour. Dissolved in 10 mL of acetonitrile, then 0.2 mol% of the novel perylene diimide coordination polymer prepared in Example 2, 0.001 mol of copper trifluoromethanesulfonate, and 0.012 mol of 1,1,3,3-tetramethylguanidine were added to obtain a mixed solution. The above mixed solution was transferred to a 50W blue LED light source at 10 cm, irradiated, and magnetically stirred for 24 h. After the reaction of 4-chlorophenylacetic acid was complete for 1 h, water and dichloromethane were added for dilution to obtain an aqueous phase and an oil phase. After separation, the aqueous phase was extracted three times with dichloromethane, 10 mL each time. The dichloromethane was combined and the solvent was dried to obtain the crude product. The crude product was separated by column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain compound 2 h ( The yield was 89%. The NMR spectral data of compound 2 h were as follows: 1 H NMR (400MHz, CDCl3) δ = 9.91 (s, 1H), 7.76 (d, J = 8.36 Hz, 2H), 7.45 (d, J = 8.28Hz, 2H) ppm; 13 C NMR (100 MHz, CDCl3) δ 191.0, 141.0, 134.7, 131.0, 129.5 ppm.
[0111] (9) Synthesis of compound 2i
[0112] 0.004 mol 4-bromophenylacetic acid 1i ( Dissolve 4-bromophenylacetic acid 1i in 10 mL of acetonitrile, then add 0.2 mol% of the novel perylene diimide coordination polymer prepared in Example 2, 0.001 mol of copper trifluoromethanesulfonate and 0.012 mol of 1,1,3,3-tetramethylguanidine to obtain a mixed solution; transfer the above mixed solution to a 50W blue LED light source at 10 cm, irradiate and magnetically stir for 24 h, after the reaction of 4-bromophenylacetic acid 1i is complete, add water and dichloromethane for dilution to obtain an aqueous phase and an oil phase, separate the liquid and extract the aqueous phase three times with dichloromethane, 10 mL each time, combine the dichloromethane and dry the solvent to obtain the crude product; perform column chromatography separation of the obtained crude product with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain compound 2i ( The yield was 90%. The NMR spectral data for compound 2i were... 1 H NMR (400 MHz, CDCl3) δ = 9.98 (s, 1H), 7.75 (d, J = 8.40 Hz, 2H), 7.69 (d, J = 8.32 Hz, 2H)ppm; 13C NMR (100 MHz, CDCl3) δ 191.2, 135.0, 132.5, 131.0, 129.8 ppm.
[0113] Application Example 3 (Cyclic Experiment)
[0114] The photocatalyst (a novel perylene diimide coordination polymer) from the photocatalytic synthesis of 2-methoxybenzaldehyde 2b in Application Example 2 was used to repeat three photocatalytic cycles under the same experimental conditions as the synthesis of compound 2b in Application Example 2 (the catalyst was collected by centrifugation after each reaction for the next reaction). The yield of 2-methoxybenzaldehyde 2b after each cycle was calculated. Simultaneously, the novel perylene diimide coordination polymer after the third photocatalytic cycle was characterized by X-ray powder diffraction. The results are shown in [Figure 1]. Figure 7 and Figure 8 .
[0115] Figure 7 The cyclic photocatalytic yield diagram shows the photocatalytic synthesis of 2-methoxybenzaldehyde using the novel perylene diimide coordination polymer prepared in Example 2. Figure 8 The images show the XRD patterns of the novel perylene diimide coordination polymer prepared in Example 2 before and after recycling. Figure 7 and Figure 8 As can be seen from the above, the photocatalytic activity of the novel perylene diimide coordination polymer prepared in Example 2 remained basically unchanged after three cycles of use, maintaining good photocatalytic activity. At the same time, the structure of the material also remained unchanged, indicating that the material has good photocatalytic stability and chemical stability.
[0116] Comparative Application Example 1
[0117] The synthesis of compound 2b in Application Example 2 is the same, except that the novel perylene diimide coordination polymer prepared in Example 2 is replaced with N,N'-bis(4-pyridylmethyl)-1,6,7,12-tetrachloroperylene diimide.
[0118] The structural formula of N,N'-bis(4-pyridylmethyl)-1,6,7,12-tetrachloroperylene diimide is as follows:
[0119] .
[0120] The specific application method is as follows:
[0121] 0.004 mol of 2-methoxyphenylacetic acid 1b ( The compound was dissolved in 10 mL of acetonitrile, and then 0.2 mol% N,N'-bis(4-pyridylmethyl)-1,6,7,12-tetrachloroperylene diimide, 0.001 mol copper trifluoromethanesulfonate, and 0.012 mol 1,1,3,3-tetramethylguanidine were added to obtain a mixed solution. The mixed solution was placed at 10 cm from a 50W blue LED light source and magnetically stirred for 24 h. Then, water and dichloromethane were added for dilution to obtain an aqueous phase and an oil phase. The aqueous phase was extracted three times with dichloromethane, 10 mL each time. The dichloromethane was combined and the solvent was dried to obtain a crude product. The crude product was separated by column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain compound 2b. The yield was 5%.
[0122] Compared with the photocatalyst N,N'-bis(4-pyridylmethyl)-1,6,7,12-tetrachloroperylenediimide in Application Example 1, the yield of 2-methoxyphenylacetic acid decarboxylation to 2-methoxybenzaldehyde was significantly lower than that of the novel perylenediimide coordination polymers prepared in Examples 1 and 2. This indicates that the coordination of N,N'-bis(4-pyridylmethyl)-1,6,7,12-tetrachloroperylenediimide with zinc ions to form a coordination polymer can significantly improve its photocatalytic activity.
[0123] Comparative Application Example 2
[0124] The synthesis of compound 2b in Application Example 2 is the same, except that the novel perylene diimide coordination polymer prepared in Example 2 is replaced with isophthalic acid.
[0125] The results of nuclear magnetic resonance 1H NMR and column chromatography showed that 2-methoxybenzaldehyde 2b was not detected. This indicates that isophthalic acid cannot photocatalyze the conversion of 2-methoxyphenylacetic acid to 2-methoxybenzaldehyde.
[0126] In summary, the novel perylene diimide coordination polymer provided by this invention has the characteristics of high conversion rate and high chemical stability as a catalyst, and exhibits extremely high catalytic activity for the photocatalytic decarboxylation of arylacetic acid and its derivatives to arylformaldehyde and its derivatives.
[0127] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.
Claims
1. A novel perylene diimide coordination polymer, characterized in that, The chemical formula of the novel perylene diimide coordination polymer is C 44 H 20 C l4 N4O8Zn.
2. The novel perylene diimide coordination polymer according to claim 1, characterized in that, The novel perylene diimide coordination polymer belongs to the monoclinic crystal system, space group P21 / n, and has the following unit cell parameters: a=12.07260(10)Å, α=90°, b=32.7923(3)Å, β=107.9710(10)°, c=13.21850(10)Å, γ=90°.
3. A method for preparing the novel perylene diimide coordination polymer as described in any one of claims 1 to 2, characterized in that, The process includes the following steps: dissolving isophthalic acid, N,N'-bis(4-pyridylmethyl)-1,6,7,12-tetrachloroperylene diimide and zinc salt in an organic solvent and reacting them under heat, followed by cooling to obtain the novel perylene diimide coordination polymer.
4. The preparation method according to claim 3, characterized in that, The molar ratio of isophthalic acid, N,N'-bis(4-pyridylmethyl)-1,6,7,12-tetrachloroperylene diimide and zinc salt is 2:1:(2~4).
5. The preparation method according to claim 4, characterized in that, The zinc salt is selected from zinc nitrate hexahydrate.
6. The preparation method according to claim 3, characterized in that, The organic solvent is selected from N,N-dimethylformamide.
7. The preparation method according to claim 3, characterized in that, The heating reaction is carried out at a temperature of 80-95°C for 24-48 hours.
8. The preparation method according to claim 3, characterized in that, The cooling rate is 5~10℃ / min.
9. The application of a novel perylene diimide coordination polymer as described in any one of claims 1 to 2 in the photocatalytic preparation of arylformaldehyde derivatives from arylaceous acid and its derivatives.
10. The application according to claim 9, characterized in that, The amount of the novel perylene diimide coordination polymer used is 0.2 mol.