Supported catalyst as well as preparation method and application thereof
The development of supported catalysts has solved the problems of high cost and difficulty in recycling photocatalysts, enabling the efficient and low-cost synthesis of juglone compounds and improving light energy utilization efficiency and catalytic reaction rate.
Patent Information
- Application Number
- CN202410549958.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-05-06
- Publication Date
- 2025-11-07
AI Technical Summary
Existing photocatalysts are expensive, have short lifespans, and absorb only a single wavelength, making it difficult to efficiently utilize light energy. Furthermore, homogeneous catalysts are difficult to separate and recover, and the chemical synthesis of juglone compounds suffers from problems such as long reaction steps, low yields, and difficulties in purification.
Develop supported catalysts by combining compounds modified with chromophores of specific structures with a support to form heterogeneous catalysts. Synthesize naphthoquinone by photocatalytic oxidation of naphthol and improve light energy utilization efficiency by utilizing the 300-600 nm spectral band.
This method enables the preparation of juglone compounds with high selectivity, high yield, and low catalyst usage, thereby improving light energy utilization efficiency and catalytic reaction rate.
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Figure CN120904160A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to a supported catalyst and a preparation method and application thereof. BACKGROUND
[0002] Juglone exists in the immature epicarp (green skin) of Juglans regia and its homologues, Juglans nigra, and has hemostatic and antibacterial activities. It has also been used to treat eczema, psoriasis and tinea. Studies have shown that juglone has anticancer activity on various tumor models in vivo and has significant cytotoxicity on different cancer cell lines. Naphthoquinone compounds derived from juglone as a precursor also have the effects of anti-tumor, anti-inflammatory and antibacterial.
[0003] Due to many problems in extraction from natural plant materials, such as low content of juglone in crops such as Juglans regia and Carya cathayensis, technical difficulties and high cost in concentration and purification, which cannot meet the market demand. Therefore, the currently marketed juglone compounds are mainly derived from chemical synthesis methods: 5,8-dihydroxy-1-tetrahydronaphthalene ketone intermediate synthesis method, naphthalene nitration oxidation synthesis method, naphthalene sulfonation oxidation synthesis method, ozone regeneration chromium acid oxidation method, etc. However, the above methods all have problems such as long reaction steps, low reaction yield, purification difficulty, large amount of oxidizing agent used, and introduction of a large amount of heavy metal oxidizing agent. Therefore, developing a new type of low-consumption and environmentally friendly synthesis method of juglone compounds has good application prospect.
[0004] In recent years, a photocatalytic oxidation method has been developed, which uses naphthol compounds as raw materials, triplet photosensitizers as photocatalysts, light as the driving force for the reaction, and singlet oxygen with high oxidation ability generated by light excitation of the photosensitizer as the oxidizing agent, to achieve high conversion of naphthol and high yield of naphthoquinone. The existing photosensitizers that can be used for photocatalysis are mostly homogeneous catalysts of porphyrin noble metal complexes. Such catalysts have high cost, short triplet state lifetime and single absorption wavelength, which is not conducive to the progress of the catalytic reaction and the effective use of light energy. Moreover, compared with heterogeneous catalysts, homogeneous photocatalysts are difficult to separate from the reaction mixture and recycle. SUMMARY
[0005] To solve the above problems, the present application provides a supported catalyst and a preparation method and application thereof.
[0006] In a first aspect of the present application, a compound of formula I is provided,
[0007]
[0008] wherein R1 is selected from a chromophore A having absorption in the 400-500 nm wavelength range or a C1-C6 alkyl group having a chromophore A having absorption in the 400-500 nm wavelength range, and the chromophore A is selected from C6-C 30fused ring heteroaryl;
[0009] R2is selected from deuterium, halogen, C1-C6alkyl, C1-C6alkoxy, C1-C6haloalkyl, nitro, cyano, phenyl, pyridyl, benzyl, m is 0, 1, 2 or 3;
[0010] R3is selected from C1-C6alkyl;
[0011] R4is selected from H, halogen, C1-C6alkyl, C1-C6alkoxy, C1-C6haloalkyl, nitro, cyano, phenyl, pyridyl, benzyl.
[0012] In a second aspect of the present application, there is provided a compound according to formula II:
[0013]
[0014] wherein: R1is selected from a chromophore A having an absorption in the 400-500 nm wavelength band or a C1-C6alkyl group having a chromophore A having an absorption in the 400-500 nm wavelength band, and said chromophore A is selected from a C6-C 30 fused ring heteroaryl;
[0015] R5is selected from a chromophore B having an absorption in the 300-400 nm wavelength band;
[0016] each R2is the same or different and is independently selected from deuterium, halogen, C1-C6alkyl, C1-C6alkoxy, C1-C6haloalkyl, nitro, cyano, phenyl, pyridyl, benzyl; m is 0, 1, 2 or 3;
[0017] each R3is the same or different and is independently selected from C1-C6alkyl;
[0018] each R4is the same or different and is independently selected from H, halogen, C1-C6alkyl, C1-C6alkoxy, C1-C6haloalkyl, nitro, cyano, phenyl, pyridyl, benzyl.
[0019] According to some embodiments of the compound of the present application, said R5is selected from an anthracene group with or without a substituent, said substituent being one or more of methyl, ethyl, propyl, isopropyl, butyl, nitro, cyano, hydroxyl, thiol, carbonyl, phenyl.
[0020] According to some embodiments of the compound of the present application, said chromophore A is selected from one or more of a perylenetetracarboxylic diimide group, a rhodamine group, a fluoroboropyrrole group, with or without a substituent, said substituent being one or more of butyl, isobutyl, phenyl, C1-C6alkyl-substituted phenyl, naphthyl, phenothiazinyl, phenoxazinyl, diphenylamino, styryl, diethylaminostyryl.
[0021] According to some embodiments of the compound of the present application, R5 is selected from anthracene group with or without substituent, preferably the substituent is phenyl, and / or, R1 is selected from C1-C3 alkyl with perylenetetracarboxylic diimide or C1-C3 alkyl with perylenetetracarboxylic diimide with substituent, preferably R1 is ethyl with perylenetetracarboxylic diimide.
[0022] According to some embodiments of the compound of the present application, the compound of formula I has the following structure:
[0023]
[0024] According to some embodiments of the compound of the present application, the compound of formula II has the following structure:
[0025]
[0026]
[0027] According to a third aspect of the present application, there is provided a supported catalyst, comprising a support and a structure of formula a linked to the support:
[0028]
[0029] wherein: R1 is selected from a chromophore A having absorption in the wavelength range of 400-500 nm or a C1-C6 alkyl group with a chromophore A having absorption in the wavelength range of 400-500 nm, and the chromophore A is selected from C6-C 30 fused ring heteroaryl;
[0030] R5 is selected from a chromophore B having absorption in the wavelength range of 300-400 nm;
[0031] R2, R4 and m are as defined in the compound of the first and second aspects of the present application;
[0032] L is propyl;
[0033] " " indicates the site of attachment to the support.
[0034] According to some embodiments of the catalyst of the present application, R5 is selected from anthracene group with or without substituent, the substituent is one or more of methyl, ethyl, propyl, isopropyl, butyl, nitro, cyano, hydroxyl, thiol, carbonyl, phenyl.
[0035] According to some embodiments of the preparation method of the present application, the chromophore A is selected from one or more of a substituted or unsubstituted perylenetetracarboxylic diimide group, a rhodamine group, and a boron-dipyrromethene group; the substituent is one or more of a butyl group, an isobutyl group, a phenyl group, a C1-C6 alkyl-substituted phenyl group, a naphthyl group, a phenothiazine group, a phenoxazine group, a diphenylamine group, a styryl group, and a diethylaminostyryl group.
[0036] According to a fourth aspect of the present application, there is provided a method for preparing the compound of the first aspect of the present application, comprising the following steps: performing a first reaction of intermediate 3 with an azide compound containing a chromophore A having an absorption in a wavelength range of 400-500 nm to generate a compound of formula I;
[0037] The structural formula of intermediate 3 is as follows:
[0038]
[0039] wherein: R2 is selected from deuterium, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, nitro, cyano, phenyl, pyridyl, and benzyl;
[0040] m is 0, 1, 2, or 3;
[0041] R3 is selected from C1-C6 alkyl;
[0042] R4 is H.
[0043] According to some embodiments of the preparation method of the present application, the conditions of the first reaction include: performing the first reaction of a first solvent, intermediate 3, and the azide compound under the action of a first catalyst, and performing solid-liquid separation on the first reaction liquid to obtain the compound of formula I.
[0044] According to some embodiments of the preparation method of the present application, the chromophore A is selected from one or more of a perylenetetracarboxylic diimide group, a rhodamine group, and a boron-dipyrromethene group.
[0045] According to some embodiments of the preparation method of the present application, the first solvent is selected from at least one of chloroform, dichloromethane, methanol, ethanol, isopropanol, and water, and is preferably chloroform, ethanol, and water.
[0046] According to some embodiments of the preparation method of the present application, the first catalyst is selected from at least one of triethylamine, copper sulfate, and sodium ascorbate.
[0047] According to some embodiments of the preparation method of the present application, the first catalyst is a mixture of triethylamine, copper sulfate, and sodium ascorbate.
[0048] According to some embodiments of the preparation method of the present application, the first catalyst is a mixture of triethylamine, copper sulfate and sodium ascorbate in a molar ratio of 1:0.57:1.42.
[0049] According to some embodiments of the preparation method of the present application, the temperature of the first reaction is 20-30℃ (such as: 20℃, 22℃, 25℃, 28℃, 30℃).
[0050] According to some embodiments of the preparation method of the present application, the time of the first reaction is 12-36h (such as: 12h, 15h, 18h, 20h, 26h, 30h, 32h, 36h).
[0051] According to some embodiments of the preparation method of the present application, the molar ratio of the intermediate 3 to the azide compound is (1-3):1 (such as: 1:1, 1.2:1, 1.8:1, 2:1, 2.3:1, 2.6:1, 3:1).
[0052] In a fifth aspect of the present application, a preparation method of the compound of the second aspect of the present application is provided, comprising the following steps: performing a second reaction of the intermediate 4 and the compound of formula I to generate the compound of formula II.
[0053] The structure of the intermediate 4 is as follows:
[0054]
[0055] wherein R5 is selected from a chromophore B having absorption in the wavelength range of 300-400 nm; preferably, R5 is selected from an anthracene group with or without a substituent, and the substituent is one or more of methyl, ethyl, propyl, isopropyl, butyl, nitro, cyano, hydroxyl, thiol, carbonyl, phenyl;
[0056] R2 is selected from deuterium, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, nitro, cyano, phenyl, pyridyl, benzyl;
[0057] m is 0, 1, 2 or 3;
[0058] R3 is selected from C1-C6 alkyl;
[0059] R4 is selected from H, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, nitro, cyano, phenyl, pyridyl, benzyl.
[0060] According to some embodiments of the preparation method of the present application, the conditions of the second reaction include: mixing the second solvent, the intermediate 4, the compound of formula I and formic acid to perform the second reaction, and then performing solid-liquid separation on the second reaction solution to obtain the compound of formula II.
[0061] According to some embodiments of the preparation method of the present application, the second solvent is selected from one or more of benzene, toluene, xylene, n-butanol, isobutanol, tert-butanol; preferably, n-butanol and toluene.
[0062] According to some embodiments of the preparation method of the present application, the temperature of the second reaction is 80-120℃ (such as: 80℃, 100℃, 120℃).
[0063] According to some embodiments of the preparation method of the present application, the time of the second reaction is 0.5-6h (0.5h, 1h, 1.3h, 2h, 3h, 4h, 5h, 6h).
[0064] According to some embodiments of the preparation method of the present application, the molar ratio of the intermediate 4 and the compound of formula I is (3:1)-(0.5:1), such as 3:1, 3:2, 1:1, 1:2, and the molar ratio of the intermediate 4 and squaric acid is (3:1)-(0.5:1), such as 3:1, 3:2, 1:1, 1:2.
[0065] According to some embodiments of the preparation method of the present application, the molar ratio of the intermediate 4 and the compound of formula I is 1:1.
[0066] According to some embodiments of the preparation method of the present application, the molar ratio of the intermediate 4 and squaric acid is 1:1.
[0067] According to a sixth aspect of the present application, there is provided a preparation method of the catalyst of the third aspect of the present application, comprising the following steps: carrying out a third reaction of a compound of formula II and a modified carrier modified by a modifier to generate the catalyst, wherein the modifier is NH2-L-Si(OR)3, L is selected from C1-C6 alkyl, and R is selected from C1-C6 alkyl.
[0068] According to some embodiments of the preparation method of the present application, the conditions of the third reaction comprise: mixing a third solvent, the compound of formula II, and the carrier to carry out the third reaction, and solid-liquid separating the third reaction liquid to obtain the catalyst.
[0069] According to some embodiments of the preparation method of the present application, the third solvent is selected from tetrahydrofuran, dichloromethane, chloroform, toluene, dioxane, dimethylformamide, dimethylacetamide, or dimethyl sulfoxide, preferably dichloromethane.
[0070] According to some embodiments of the preparation method of the present application, the temperature of the third reaction is 20-30℃ (such as: 20℃, 22℃, 25℃, 28℃, 30℃).
[0071] According to some embodiments of the preparation method of the present application, the third reaction is performed for 12-24 hours (for example: 12 hours, 18 hours, 20 hours, 24 hours).
[0072] According to some embodiments of the preparation method of the present application, the mass ratio of the carrier to the compound of formula II is 1:(1-5) (for example: 1:1, 1:2, 1:3, 1:4, 1:5).
[0073] In a seventh aspect of the present application, the present application provides a use of the catalyst of the third aspect of the present application or the catalyst prepared by the preparation method of the sixth aspect of the present application in a photocatalytic reaction.
[0074] According to some embodiments of the use of the present application, the use is for synthesizing naphthoquinone compounds by photocatalytic oxidation of naphthol compounds.
[0075] According to some embodiments of the use of the present application, the naphthoquinone compound has the structure of general formula b2:
[0076]
[0077] wherein R3 is selected from hydroxyl, amino, nitro, methoxy.
[0078] The present application has the following beneficial effects: the supported catalyst of the present application can cover the light absorption spectrum band of 300-600 nm, improve the utilization efficiency of light energy, and realize the preparation of juglone compounds with high selectivity, high yield, low catalyst usage, and high reaction rate. BRIEF DESCRIPTION OF DRAWINGS
[0079] Figure 1 The UV absorption spectrum of the intermediate 5 according to the embodiments of the present application is shown in the following figure. DETAILED DESCRIPTION
[0080] In order to make the purpose, technical solutions and advantages of the present application clearer, the present application is further described in detail below with reference to the embodiments and the accompanying drawings. The specific embodiments described herein are only used to explain the present application and do not constitute any limitation on the present application. In addition, in the following description, the description of known structures and technologies is omitted to avoid unnecessary confusion of the concept of the present disclosure. Such structures and technologies are also described in many publications.
[0081] The drugs used in the embodiments of the present application are purchased from the National Pharmaceutical Group Chemical Reagent Co., Ltd. and Beijing Inokai Technology Co., Ltd. If not particularly limited, they are disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation method disclosed in the prior art. The nuclear magnetic resonance spectrometer used in the present application is purchased from Japan Electronics Corporation and Bruker Corporation.
[0082] Preparation of Intermediate 1:
[0083] The structural formula of Intermediate 1 is:
[0084]
[0085] The preparation method is:
[0086] 5-benzyloxyindole (111.5 mg, 0.5 mmol), methyl acrylate (51.6 mg, 0.6 mmol), KOH (28 mg, 0.5 mmol) and 2 mL of DMSO were added into a Schlenk flask, heated to 120°C for 20 h under a nitrogen atmosphere. After cooling to room temperature, 10 mL of deionized water was added, extracted with ethyl acetate for 3 times, removed the solvent, separated by silica gel column chromatography to obtain Intermediate 1 (139 mg, yield: 90%), with a molecular formula of C 19 H 19 NO3.
[0087] 1 H NMR (400 MHz, CDCl3) δ 7.88-7.86 (m, 1H), 7.50-7.48 (m, 1H), 7.45-7.41 (m, 1H), 7.38-7.34 (m, 2H), 7.30-7.28 (m, 2H), 7.25 (d, J = 4 Hz, 1H), 6.92-6.90 (m, 1H), 6.71-6.70 (m, 1H), 5.10 (s, 2H), 4.47 (t, J = 8 Hz, 2H), 3.75 (s, 3H), 2.86 (t, J = 8 Hz, 2H).
[0088] Preparation of Intermediate 2:
[0089] The structural formula of Intermediate 2 is:
[0090]
[0091] Intermediate 1 (309 mg, 1 mmol), 20% Pd / C (200 mg) and 10 mL of tetrahydrofuran were added into a Schlenk flask, reacted for 48 hours at room temperature (25°C) under a hydrogen atmosphere, the solid was removed by filtration, the filtrate was removed by solvent, separated by silica gel column chromatography to obtain Intermediate 2 (197 mg, yield: 90%), with a molecular formula of C 12 H 13 NO3.
[0092] 1H NMR (400 MHz, CDC13): δ = 7.33-7.22 (m, 2H), 6.86-6.56 (m, 3H), 4.10 (t, J = 8 Hz, 2H), 3.65 (s, 3H), 2.69 (t, J = 8 Hz, 2H).
[0093] Preparation of Intermediate 3:
[0094] The structural formula of Intermediate 3 is:
[0095]
[0096] Intermediate 2 (219 mg, 1 mmol), 3-bromopropynyl (177 mg, 1.5 mmol), K2CO3(207 mg, 1.5 mmol) and 10 mL DMF were added to a Schlenk flask, and reacted at 100°C for 8 hours under a nitrogen atmosphere. After cooling to room temperature, dichloromethane was added, and deionized water was washed 3 times. The organic layer was dried with anhydrous sodium sulfate, the solid was removed by filtration, the filtrate was removed from the solvent, and column chromatography on silica gel was performed to obtain Intermediate 3 (219 mg, yield: 85%), which has a molecular formula of C 15 H 15 NO3.
[0097] 1 H NMR (400 MHz, CDC13): δ = 7.33-7.22 (m, 2H), 6.86-6.56 (m, 3H), 4.10 (t, J = 8 Hz, 2H), 3.65 (s, 3H), 2.69 (t, J = 8 Hz, 2H).
[0098] Preparation of Intermediate 4
[0099] The structural formula of Intermediate 4 is:
[0100]
[0101] Intermediate 3 (334 mg, 1.3 mmol), 9-azidomethyl anthracene (233 mg, 1.0 mmol), and 30 mL of a mixed solvent CHCl3 / EtOH / H2O (10:0.8:0.8, v / v) were added to a Schlenk flask, 0.1 mL of triethylamine, CuSO4·5H2O (100 mg), and sodium ascorbate 200 mg were added under a nitrogen atmosphere, and reacted at room temperature for 12 hours. Dichloromethane was added, deionized water was washed 3 times, the organic layer was dried with anhydrous sodium sulfate, the solid was removed by filtration, the filtrate was removed from the solvent, and column chromatography on silica gel was performed to obtain Intermediate 4 (294 mg, yield: 60%), which has a molecular formula of C 30 H26 N4O3.
[0102] 1 H NMR (400 MHz, CDC13): δ = 8.30 (s, 1H), 8.03 (m, 4H), 7.64 (s, 1H), 7.63-7.42 (m, 4H), 7.35-7.28 (m, 2H), 7.18 (t, 1H), 6.90-6.88 (m, 1H), 6.57-6.55 (m, 1H), 5.85 (s, 2H), 4.70 (s, 2H), 4.12 (t, J = 8 Hz, 2H), 3.60 (s, 3H), 2.65 (t, J = 8 Hz, 2H).
[0103] Preparation of Intermediate 5
[0104] The structural formula of Intermediate 5 is:
[0105]
[0106] Intermediate 3 (334 mg, 1.3 mmol), N-azidopropyl peryleneboximide (404 mg, 1.0 mmol), and 30 mL of mixed solvent CHCl3 / EtOH / H2O (10:0.8:0.8, v / v) were added into a Schlenk flask, 0.1 mL of triethylamine, CuSO4·5H2O (100 mg), and sodium ascorbate 200 mg were added under nitrogen atmosphere, and the reaction was carried out at room temperature for 12 hours. Dichloromethane was added, and deionized water was washed for 3 times. The organic layer was dried with anhydrous sodium sulfate, and the solid was removed by filtration. The filtrate was removed from the solvent, and column chromatography was performed on silica gel to obtain Intermediate 5 (363 mg, yield: 55%), with a molecular formula of C 40 H 31 N5O5.
[0107] 1 H NMR (400 MHz, CDC13): δ = 8.52 (d, 2H), 8.22 (d, 2H), 8.10 (d, 2H), 7.87-7.85 (m, 3H), 7.58-7.54 (m, 2H), 7.32-7.27 (m, 2H), 7.16 (t, 1H), 6.95-6.92 (m, 1H), 6.59-6.56 (m, 1H), 4.74 (s, 2H), 4.30 (t, J = 8 Hz, 2H), 4.18 (t, J = 8 Hz, 2H), 4.10 (t, J = 8 Hz, 2H), 3.62 (s, 3H), 2.60 (t, J = 8 Hz, 2H), 2.26-2.20 (m, 2H).
[0108] Preparation of Intermediate 6
[0109] The structural formula of intermediate 6 is:
[0110]
[0111] Intermediate 4 (245 mg, 0.5 mmol), intermediate 5 (330 mg, 0.5 mmol), formic acid (57 mg, 0.5 mmol), and 30 mL mixed solvent n-butanol / toluene (1 / 1, v / v) were added into a Schlenk flask, refluxed for 2 hours under nitrogen atmosphere, cooled to room temperature, added with dichloromethane, removed the solvent, and separated by silica gel column chromatography to obtain intermediate 6 (270 mg, yield: 22%), with a molecular formula of C 74 H 55 N9O 10 .
[0112] 1 H NMR (400 MHz, CDCl3): δ = 8.96 (s, 1H), 8.46-8.43 (m, 3H), 8.20 (d, 2H), 8.10 (d, 2H), 8.05-7.99 (m, 4H), 7.87-7.85 (m, 4H), 7.65 (s, 1H), 7.55-7.42 (m, 8H), 7.24-7.21 (m, 1H), 7.10-6.93 (m, 3H), 5.80 (s, 2H), 5.30 (s, 4H), 4.43 (t, J = 8 Hz, 2H), 4.30-4.23 (m, 4H), 4.05 (t, J = 8 Hz, 2H), 3.66 (s, 3H), 3.64 (s, 3H), 2.98 (t, J = 8 Hz, 2H), 2.74 (t, J = 8 Hz, 2H), 2.25-2.21 (m, 2H).
[0113] IR: C=O stretching vibration: 1640 cm -1 .
[0114] The UV-visible absorption spectrum is shown in Figure 1 It can be seen from Figure 1 that the absorption of the compound can cover the spectral region from 300 nm to 600 nm.
[0115] Preparation of catalyst a1
[0116] The structural formula of a1 is:
[0117]
[0118] Intermediate 6 (245 mg, 0.2 mmol), 100 mg of aminopropyl triethoxysilane modified mesoporous material support T-40 and 30 mL of dichloromethane were added into a Schlenk flask, and the reaction was carried out at room temperature 25 °C under a nitrogen atmosphere until the absorbance of the solution no longer changed. The filter cake was obtained by filtration, dichloromethane was added to wash the filter cake, and after drying, a dark purple powder catalyst a1 was obtained.
[0119] IR: C=0 stretching vibration: 1642 cm -1 ; Si-O stretching vibration: 1085 cm -1 Elemental analysis showed that the loading rate of catalyst a1 was 6%, as shown in Table 1.
[0120] Table 1 Elemental analysis results
[0121] Sample N(％) C(％) H(％) Load ratio (%) T40 - 0.25 2.21 0 a1 0.709 4.56 2.37 6
[0122] Preparation of catalyst a2
[0123] The structural formula of a2 is:
[0124]
[0125] In the preparation of intermediate 6, N-diisopropylbenzene was used to replace ethyl substituted perylene diimide instead of perylene monoimide, and intermediate 6 was obtained by reaction ， .
[0126] Different from catalyst a1, intermediate 6 ， (292 mg, 0.2 mmol) was used as a reactant instead of intermediate 6, 100 mg of aminopropyl triethoxysilane modified mesoporous material support T-40 and 30 mL of dichloromethane were added into a Schlenk flask, and the reaction was carried out at room temperature 25 °C under a nitrogen atmosphere until the absorbance of the solution no longer changed. The filter cake was obtained by filtration, dichloromethane was added to wash the filter cake, and after drying, a dark purple powder catalyst a2 was obtained.
[0127] IR: C=0 stretching vibration: 1640 cm -1 ; Si-O stretching vibration: 1088 cm -1 Elemental analysis showed that the loading rate of catalyst a2 was 7%.
[0128] Preparation of catalyst a3
[0129] The structural formula of a3 is:
[0130]
[0131] In the preparation of intermediate 6, 9-phenylanthracene was used to replace anthracene, and intermediate 6 was obtained by reaction
[0132] Different from catalyst a1, intermediate 6 (260 mg, 0.2 mmol) was used instead of intermediate 6 as the reactant, 100 mg of aminopropyl triethoxysilane modified mesoporous material carrier T-40 and 30 mL of dichloromethane were added into a Schlenk flask, and the reaction was carried out at room temperature 25 °C under a nitrogen atmosphere until the absorbance of the solution no longer changed. The filter cake was obtained by filtration, dichloromethane was added to wash the filter cake, and after drying, a dark purple powder catalyst a3 was obtained.
[0133] IR: C=0 stretching vibration: 1644 cm -1 ; Si-O stretching vibration: 1082 cm -1 Elemental analysis showed that the loading rate of catalyst a3 was 6%.
[0134] Example 1
[0135] 1,5-dihydroxynaphthalene (16 mg, 0.1 mmol), catalyst a1 (102 mg, 5% e.q. photo sensitizer equivalent), and methanol 20 mL were irradiated under a 25 W white light lamp for 50 minutes. According to the ultraviolet absorption spectrum and nuclear magnetic hydrogen spectrum data, the yield of juglone was 85%. After the system was washed and filtered, 97 mg of catalyst a1 was recovered.
[0136] Example 2
[0137] 1,5-dihydroxynaphthalene (80 mg, 0.5 mmol), catalyst a1 (510 mg, 5% e.q. photo sensitizer equivalent), and methanol 100 mL were irradiated under a 25 W white light lamp for 50 minutes. According to the ultraviolet absorption spectrum and nuclear magnetic hydrogen spectrum data, the yield of juglone was 88%.
[0138] Example 3
[0139] 1,5-dihydroxynaphthalene (16 mg, 0.1 mmol), catalyst a1 (97 mg) separated after reaction in Example 1, and methanol 20 mL were irradiated under a 25 W white light lamp for 50 minutes. According to the ultraviolet absorption spectrum and nuclear magnetic hydrogen spectrum data, the yield of juglone was 83%.
[0140] Example 4
[0141] 1,5-dihydroxynaphthalene (16 mg, 0.1 mmol), catalyst a2 (104 mg, 5% e.q. photo sensitizer equivalent), and methanol 20 mL were irradiated under a 25 W white light lamp for 50 minutes. According to the ultraviolet absorption spectrum and nuclear magnetic hydrogen spectrum data, the yield of juglone was 88%. After the system was washed and filtered, 90 mg of catalyst a2 was recovered.
[0142] Example 5
[0143] Example 1
[0144] Example 2
[0145] Example 3
[0146] Example 4
[0147] Example 5
[0148] Example 6
[0149] Example 7
[0150] Comparative Example 1
[0151] Comparative Example 2
[0152] Comparative Example 3
[0153]
[0154] Comparative Example 4
[0155] Comparative Example 5
[0156] 1,5-dihydroxynaphthalene (80 mg, 0.5 mmol), catalyst squarine compound (10.6 mg, 5% e.q. sensitizer equivalent), methanol 100 mL, irradiated under 25 W white light lamp for 50 minutes, the yield of juglone was 55% according to the UV absorption spectrum and nuclear magnetic hydrogen spectrum data.
[0157] Comparative Example 5
[0158]
[0159] 1,5-dihydroxynaphthalene (80 mg, 0.5 mmol), catalyst squarine compound (10.6 mg, 5% e.q. sensitizer equivalent), methanol 100 mL, irradiated under 25 W white light lamp for 50 minutes, the yield of juglone was 55% according to the UV absorption spectrum and nuclear magnetic hydrogen spectrum data.
[0160] The above detailed the preferred embodiments of the present application, however, the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including various technical features being combined in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application, and all fall within the protection scope of the present application.
Claims
1. A compound of formula I, wherein: R1is selected from a chromophore A having an absorption in the 400-500 nm wavelength range or a C1-C6alkyl group having a chromophore A having an absorption in the 400-500 nm wavelength range, and the chromophore A is selected from C6-C 30 fused ring heteroaryl; R2is selected from deuterium, halogen, C1-C6alkyl, C1-C6alkoxy, C1-C6haloalkyl, nitro, cyano, phenyl, pyridyl, benzyl, m is 0, 1, 2 or 3; R3is selected from C1-C6alkyl; R4is selected from H, halogen, C1-C6alkyl, C1-C6alkoxy, C1-C6haloalkyl, nitro, cyano, phenyl, pyridyl, benzyl.
2. A compound of formula II: wherein: R1is selected from a chromophore A having an absorption in the 400-500 nm wavelength range or a C1-C6alkyl group having a chromophore A having an absorption in the 400-500 nm wavelength range, and the chromophore A is selected from C6-C 30 fused ring heteroaryl; R5is selected from a chromophore B having absorption in the wavelength range of 300-400 nm; each R2is the same or different and is independently selected from deuterium, halogen, C1-C6alkyl, C1-C6alkoxy, C1-C6haloalkyl, nitro, cyano, phenyl, pyridyl, benzyl; m is 0, 1, 2 or 3; each R3is the same or different and is independently selected from C1-C6alkyl; each R4is the same or different and is independently selected from H, halogen, C1-C6alkyl, C1-C6alkoxy, C1-C6haloalkyl, nitro, cyano, phenyl, pyridyl, benzyl.
3. The compound of claim 1 or 2, wherein R5is selected from an anthracene group with or without substituents, the substituents being one or more of methyl, ethyl, propyl, isopropyl, butyl, nitro, cyano, hydroxyl, thiol, carbonyl, phenyl, and / or, the chromophore A is selected from one or more of perylenemonoimide group, perylenetetracarboxylic diimide group, rhodamine group, boron difluoride pyrrole group with or without substituents, the substituents being one or more of butyl, isobutyl, phenyl, C1-C6alkyl substituted phenyl, naphthyl, phenothiazine group, phenoxazine group, diphenylamine group, phenylethylene group, diethylaminophenylethylene group.
4. The compound according to any one of claims 1 to 3, wherein R5is selected from an anthracene group with or without substituents, preferably the substituents are phenyl, and / or, R1is selected from C1-C3alkyl with perylenemonoimide or C1-C3alkyl with perylenemonoimide with substituents, preferably R1is ethyl with perylenemonoimide; Preferably, the compound of formula I has the following structure: Preferably, the compound of formula II has the following structure:
5. A supported catalyst, the catalyst comprising a support and a structure of formula a bonded to the support: wherein: R1is selected from a chromophore A having an absorption in the 400-500 nm wavelength range or a C1-C6alkyl group having a chromophore A having an absorption in the 400-500 nm wavelength range, and the chromophore A is selected from C6-C 30 fused ring heteroaryl; Preferably, the chromophore A is selected from one or more of perylenemonoimide group, perylenetetracarboxylic diimide group, rhodamine group, boron difluoride pyrrole group with or without substituents, the substituents being one or more of butyl, isobutyl, phenyl, C1-C6alkyl substituted phenyl, naphthyl, phenothiazine group, phenoxazine group, diphenylamine group, phenylethylene group, diethylaminophenylethylene group; R5is selected from a chromophore B having absorption in the wavelength range of 300-400 nm, preferably R5is selected from an anthracene group with or without substituents, the substituents being one or more of methyl, ethyl, propyl, isopropyl, butyl, nitro, cyano, hydroxyl, thiol, carbonyl, phenyl; R2, R4and m are as defined in any one of claims 1-3; L is propyl; "*" indicates the site of attachment to the support.
6. A process for the preparation of a compound of formula I according to claim 1 comprising the steps of: The first reaction of intermediate 3 with an azide compound containing a chromophore A having absorption in the 400-500 nm waveband generates a compound shown in formula I; The structure of intermediate 3 is shown as follows: R2 is selected from deuterium, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, nitro, cyano, phenyl, pyridyl, benzyl; m is 0, 1, 2 or 3; R3 is selected from C1-C6 alkyl; R4 is H; Preferably, the conditions of the first reaction include: the first solvent, intermediate 3, azide compound are subjected to the first reaction under the action of the first catalyst, the first reaction liquid is subjected to solid-liquid separation, and a compound shown in formula I is obtained; and / or, the chromophore A is selected from one or more of perylenetetracarboxylic diimide group, rhodamine group, fluorophore group; and / or, the first solvent is selected from at least one of chloroform, dichloromethane, methanol, ethanol, isopropanol, water, preferably chloroform, ethanol and water; and / or, the first catalyst is selected from at least one of triethylamine, copper sulfate or sodium ascorbate, preferably a mixture of triethylamine, copper sulfate and sodium ascorbate; and / or, the temperature of the first reaction is 20-30℃; and / or, the time of the first reaction is 12-36h; and / or, the molar ratio of intermediate 3 to azide compound is (1-3):
1.
7. A process for the preparation of a compound of formula II as claimed in claim 2, comprising the steps of: The second reaction of intermediate 4 with a compound shown in formula I generates a compound shown in formula II; The structure of intermediate 4 is shown as follows: R5 is selected from a chromophore B having absorption in the 300-400 nm waveband; preferably, R5 is selected from an anthracene group with or without a substituent, and the substituent is one or more of methyl, ethyl, propyl, isopropyl, butyl, nitro, cyano, hydroxyl, thiol, carbonyl, phenyl; R2 is selected from deuterium, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, nitro, cyano, phenyl, pyridyl, benzyl; m is 0, 1, 2 or 3; R3 is selected from C1-C6 alkyl; R4 is selected from H, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, nitro, cyano, phenyl, pyridyl, benzyl; Preferably, the conditions of the second reaction include: the second solvent, intermediate 4, a compound shown in formula I and formic acid are subjected to the second reaction, and the second reaction liquid is subjected to solid-liquid separation to obtain a compound shown in formula II; Preferably, the second solvent is selected from one or more of benzene, toluene, xylene, n-butanol, isobutanol, tert-butanol; preferably, n-butanol and toluene; and / or, the temperature of the second reaction is 80-120℃; and / or, the time of the second reaction is 0.5-6h; and / or, the molar ratio of intermediate 4 to a compound shown in formula I is (3:1)-(0.5:1), preferably 1:1, and the molar ratio of intermediate 4 to formic acid is (3:1)-(0.5:1), preferably 1:
1.
8. A process for the preparation of the catalyst of claim 4 comprising the steps of: a third reaction of a compound of formula II and a modified carrier with a modifying agent, wherein the modifying agent is NH2-L-Si(OR)3, L is selected from C1-C6 alkyl, and R is selected from C1-C6 alkyl, to form the catalyst; Preferably, the conditions of the third reaction comprise: mixing a third solvent, the compound of formula II, and the carrier to perform the third reaction, and solid-liquid separation of the third reaction solution to obtain the catalyst. Preferably, the third solvent is selected from tetrahydrofuran, dichloromethane, chloroform, toluene, dioxane, dimethylformamide, dimethylacetamide, or dimethyl sulfoxide, preferably dichloromethane. And / or, the temperature of the third reaction is 20-30°C. And / or, the time of the third reaction is 12-24 h. And / or, the mass ratio of the carrier to the compound of formula II is 1:(1-5).
9. Use of the catalyst of claim 4 or the catalyst obtained by the preparation method of claim 8 in a photocatalytic reaction. Preferably, the use is photocatalytic oxidation of naphthol compounds to synthesize naphthoquinone compounds.
10. Use according to claim 9, characterized in that, The structure of the naphthol compound is shown in general formula b1, and the structure of the naphthoquinone compound is shown in general formula b2: wherein R3 is selected from hydroxyl, amino, nitro, methoxy.