Preparation method of 9-aryl xanthene compound
By using nitrogen-doped carbon catalysts for oxygen-mediated oxidation reactions, the problem of noble metal catalysts in the synthesis of xanthracene compounds has been solved, achieving green and efficient preparation of 9-arylxanthracene compounds, which are applicable to pharmaceutical and materials science.
Patent Information
- Application Number
- CN202511256650.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-04
- Publication Date
- 2025-11-18
AI Technical Summary
Existing technologies for preparing xanthracene compounds suffer from problems such as the use of precious metal catalysts, harsh reaction conditions, and trace metal residues, making it difficult to achieve efficient and green binding of aromatic amines with xanthracene derivatives.
Using nitrogen-doped carbon materials as catalysts, 9-aryloxanthracene compounds are prepared by reacting with xanthracene compounds and aromatic amine compounds in organic solvents via oxygen-mediated single-electron oxidation. The reaction conditions are mild, and the catalyst can be recycled and reused.
The green synthesis of 9-aryloxanthracene compounds has been achieved. The catalyst is readily available, recyclable, and widely applicable, conforming to the concept of green chemistry. It is suitable for large-scale applications and can be used in the fields of pharmaceuticals and materials science.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of organic synthesis, and particularly relates to a preparation method of 9-aryloxyxanthene compounds. BACKGROUND
[0002] Xanthene compounds are a kind of heterocyclic aromatic compounds with unique conjugated structure, and their core skeletons are widely distributed in natural products, drug molecules and functional materials. Research shows that the xanthene skeleton is not only an important component of many bioactive molecules (such as anti-inflammatory, antibacterial and antitumor drugs), but also plays a key role in the fields of fluorescent probes, organic optoelectronic materials and asymmetric catalytic ligands. Aromatic amines are an important class of compounds, which are widely used in the fields of medicine, ligand and material. However, there are still few reports on the method of combining xanthene compounds and aromatic amine compounds to construct new substances. Although significant progress has been made in the functionalization of xanthene compounds by using transition metal catalysts (such as palladium and rhodium), there are still some limitations, such as the use of noble metal catalysts, harsh reaction conditions, the use of strong oxidants, etc. In addition, the residual trace amount of metal may affect the quality of drugs, which is particularly important for pharmaceutical companies, and does not meet the development concept of green chemistry. Therefore, it is of great scientific significance and application prospect to develop an efficient and green method to combine aromatic amines and xanthene derivatives. SUMMARY
[0003] The present application aims to provide a preparation method of 9-aryloxyxanthene compounds to solve the problems in the background art.
[0004] To solve the above technical problems, the present application provides the following technical scheme: a 9-aryloxyxanthene compound, which has the following structural formula:
[0005]
[0006] wherein R is any one of hydrogen, methyl, cyclohexyl, trifluoromethyl or halogen; R 1 and R 2 are any one of hydrogen, methyl, ethyl, ester group or hydroxyethyl; and R 3 is any one of hydrogen or ester group.
[0007] A preparation method of 9-aryloxyxanthene compounds, which comprises the following steps:
[0008] The xanthene compound, the aromatic amine compound and the nitrogen-doped carbon material are added to an organic solvent, and then the reaction is carried out under a protective atmosphere. After filtration, concentration and purification, the 9-aryloxyxanthene compound is obtained.
[0009] Further, the aromatic amine compound is any one of N-methylaniline, N,N-diethylaniline, N-phenylglycine ethyl ester, methyl anthranilate, N-hydroxyethyl aniline.
[0010] Further, the xanthene compound is any one of 4-cyclohexylxanthene, 4-methylxanthene, 4-chloroxanthene, 4-trifluoromethylxanthene.
[0011] Further, the molar ratio of the xanthene compound and the aromatic amine compound is 2:1.
[0012] Further, the amount of the nitrogen-doped carbon material is 100 g based on 1 mol of the xanthene compound as a reactant.
[0013] Further, the organic solvent is at least one of hexafluoroisopropanol, trifluoroethanol, tert-butanol, toluene, tetrahydrofuran, acetonitrile, dimethyl sulfoxide.
[0014] Further, the organic solvent is preferably hexafluoroisopropanol.
[0015] Further, the protective atmosphere is oxygen.
[0016] Further, the reaction temperature is 30-90℃.
[0017] Further, the reaction temperature is preferably 50℃.
[0018] Further, the reaction time is 12-30 hours.
[0019] Further, the reaction time is preferably 24 hours.
[0020] Further, the concentration method is vacuum concentration.
[0021] Further, the purification method is column chromatography.
[0022] Further, the eluent used in the column chromatography is prepared by mixing petroleum ether and ethyl acetate at a volume ratio of 20:1.
[0023] Further, the synthesis reaction formula of the 9-aryloxanthene compound of the present application is as follows:
[0024]
[0025] Further, the preparation method of the nitrogen-doped carbon material is as follows:
[0026] The nitrogen source and the carbon black are added to deionized water, and stirring is continuously carried out at 80 DEG C for 4 hours, then the solvent is removed by using a rotary evaporator, and the mixture is dried by using a vacuum drying box at 80 DEG C. After the dried mixture is fully ground, it is placed in a tube furnace, and is calcined at 500-900 DEG C for 1-4 hours at a temperature rising rate of 10 DEG C / min under a nitrogen atmosphere, and is naturally cooled.
[0027] Further, the nitrogen source is at least one of dicyandiamide, melamine and urea.
[0028] Further, the nitrogen source is preferably dicyandiamide.
[0029] Further, the mass ratio of the nitrogen source to the carbon black is 2:1.
[0030] Further, the calcination temperature is preferably 800 DEG C, and the calcination time is preferably 2 hours.
[0031] Compared with the prior art, the present application has the beneficial effects that: the present application provides a 9-aryloxac xanthene compound, which is novel in structure and can be applied to the fields of medicine, agricultural chemicals and material science. The preparation method of the 9-aryloxac xanthene compound has the advantages of simple synthesis steps, cheap and easily available raw materials, high atomic economy, wide applicability, safe operation, recyclable and reusable catalyst, etc., and is suitable for large-scale popularization and application.
[0032] Specifically:
[0033] 1) The catalyst nitrogen-doped carbon material used in the method for preparing the 9-aryloxac xanthene compound has the advantages of easy preparation, controllable catalytic activity and recyclable and reusable, thereby avoiding the problem of metal catalyst residues in the product and being more in line with the modern green chemical concept. The catalyst can effectively adsorb oxygen, and based on the single-electron oxidation mediation strategy, the target product is obtained through the free radical and free radical coupling mechanism, which is a key factor for the method to be realized.
[0034] 2) The method for preparing the 9-aryloxac xanthene compound has the advantages of simple operation, easily available raw materials, green oxygen as the oxidant, wide substrate applicability, good functional group compatibility, good atomic and step economy, recyclable and reusable catalyst, etc., and is in line with the green and clean production concept.
[0035] 3) The 9-aryloxyxanthene compound prepared by the present application can be further modified for drug molecules, such as: nonsteroidal anti-inflammatory drug (NSAIDs) ibuprofen and gout drug febuxostat, which provides a new idea for the application of 9-aryloxyxanthene compound in the field of drug synthesis, and is expected to provide a new green preparation method for the chemical medicine field. BRIEF DESCRIPTION OF DRAWINGS
[0036] The accompanying drawings are included to provide a further understanding of the present application, and are incorporated in and constitute a part of the specification, illustrate embodiments of the present application and explain the present application, and do not constitute a limitation of the present application. In the drawings:
[0037] Figure 1 is the yield of the full cycle experiment of the nitrogen-doped carbon material of the present application.
[0038] Figure 2 is the H NMR spectrum of the compound 3a prepared in Example 1. 1 HNMR spectrum.
[0039] Figure 3 is the C NMR spectrum of the compound 3a prepared in Example 1. 13 C NMR spectrum.
[0040] Figure 4 is the H NMR spectrum of the compound 3b prepared in Example 2. 1 H NMR spectrum.
[0041] Figure 5 is the C NMR spectrum of the compound 3b prepared in Example 2. 13 C NMR spectrum.
[0042] Figure 6 is the H NMR spectrum of the compound 3c prepared in Example 3. 1 HNMR spectrum.
[0043] Figure 7 is the C NMR spectrum of the compound 3c prepared in Example 3. 13 C NMR spectrum.
[0044] Figure 8 is the H NMR spectrum of the compound 3d prepared in Example 4. 1 H NMR spectrum.
[0045] Figure 9 is the C NMR spectrum of the compound 3d prepared in Example 4. 13 C NMR spectrum.
[0046] Figure 10 is the H NMR spectrum of the compound 3e prepared in Example 5. 1 HNMR spectrum.
[0047] Figure 11H NMR spectrum of the compound 3e prepared for Example 5 13 H NMR spectrum of the compound 3e prepared for Example 5
[0048] Figure 12 H NMR spectrum of the compound 3e prepared for Example 5 1 H NMR spectrum of the compound 3e prepared for Example 5
[0049] Figure 13 H NMR spectrum of the compound 3e prepared for Example 5 13 H NMR spectrum of the compound 3e prepared for Example 5
[0050] Figure 14 H NMR spectrum of the compound 3e prepared for Example 5 1 H NMR spectrum of the compound 3e prepared for Example 5
[0051] Figure 15 H NMR spectrum of the compound 3e prepared for Example 5 13 H NMR spectrum of the compound 3e prepared for Example 5
[0052] Figure 16 H NMR spectrum of the compound 3e prepared for Example 5 1 H NMR spectrum of the compound 3e prepared for Example 5
[0053] Figure 17 H NMR spectrum of the compound 3e prepared for Example 5 13 H NMR spectrum of the compound 3e prepared for Example 5
[0054] Figure 18 H NMR spectrum of the compound 3e prepared for Example 5 1 H NMR spectrum of the compound 3e prepared for Example 5
[0055] Figure 19 H NMR spectrum of the compound 3e prepared for Example 5 13 H NMR spectrum of the compound 3e prepared for Example 5
[0056] Figure 20 H NMR spectrum of the compound 3e prepared for Example 5 19 H NMR spectrum of the compound 3e prepared for Example 5
[0057] Figure 21 H NMR spectrum of the compound 3e prepared for Example 5 1 H NMR spectrum of the compound 3e prepared for Example 5
[0058] Figure 22 H NMR spectrum of the compound 3e prepared for Example 5 13 H NMR spectrum of the compound 3e prepared for Example 5
[0059] Figure 23 H NMR spectrum of the compound 3e prepared for Example 5 1 H NMR spectrum of the compound 3e prepared for Example 5
[0060] Figure 24 H NMR spectrum of the compound 3e prepared for Example 5 13 H NMR spectrum of the compound 3e prepared for Example 5 DETAILED DESCRIPTION
[0061] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative effort belong to the scope of protection of the present application.
[0062] Materials and sources used in the present application: carbon black is Cabot XC72R, and the rest of the reagents are not particularly specified and can be obtained through commercial channels.
[0063] The nitrogen-doped carbon material is prepared by the following method:
[0064] 2 g of dicyandiamide and 1 g of XC72R are dissolved in 50 mL of ethanol, stirred at 80°C for 4 hours, vacuum dried for 12 hours after spinning off the solvent, and then the solid powder is ground uniformly and placed in a tube furnace, ventilated for 30 minutes under nitrogen atmosphere, calcined at 800°C with a temperature rising rate of 10°C / min for 2 hours, and cooled to room temperature to obtain the nitrogen-doped carbon material.
[0065] Example 1:
[0066] The preparation method of N-methyl-4-(9H-xanthen-9-yl)aniline is as follows:
[0067] 0.2 mmol of xanthene, 0.1 mmol of N-methylaniline, 20 mg of nitrogen-doped carbon material and 2 mL of hexafluoroisopropanol are added to a reaction tube, reacted at 50°C under oxygen atmosphere for 24 hours, filtered, and the filtrate is vacuum concentrated, and then the obtained crude product is column chromatographed (the eluent used in column chromatography is prepared by mixing petroleum ether and ethyl acetate in a volume ratio of 20:1) to obtain the product, which is recorded as compound 3a (brown solid; yield is 95%).
[0068] Example 2:
[0069] The preparation method of N,N-diethyl-4-(9H-xanthen-9-yl)aniline is as follows:
[0070] To a reaction tube was added 0.2 mmol of xanthene, 0.1 mmol of N,N-diethyl aniline, 20 mg of nitrogen-doped carbon material, and 2 mL of hexafluoroisopropanol, and the reaction was allowed to proceed at 50 °C under an oxygen atmosphere for 24 hours. The reaction mixture was filtered, and the filtrate was concentrated under vacuum. The resulting crude product was purified by column chromatography using a mixture of petroleum ether and ethyl acetate (20:1 by volume) as the eluent to obtain the product, which was designated as compound 3b (white solid; yield: 80%).
[0071] Example 3:
[0072] The preparation of ethyl (4-(9H-xanthen-9-yl)phenyl)glycinate was as follows:
[0073] To a reaction tube was added 0.2 mmol of xanthene, 0.1 mmol of N-phenyl glycine ethyl ester, 20 mg of nitrogen-doped carbon material, and 2 mL of hexafluoroisopropanol, and the reaction was allowed to proceed at 50 °C under an oxygen atmosphere for 24 hours. The reaction mixture was filtered, and the filtrate was concentrated under vacuum. The resulting crude product was purified by column chromatography using a mixture of petroleum ether and ethyl acetate (20:1 by volume) as the eluent to obtain the product, which was designated as compound 3c (black solid; yield: 55%).
[0074] Example 4:
[0075] The preparation of methyl 2-amino-5-(9H-xanthen-9-yl)benzoate was as follows:
[0076] To a reaction tube was added 0.2 mmol of xanthene, 0.1 mmol of methyl anthranilate, 20 mg of nitrogen-doped carbon material, and 2 mL of hexafluoroisopropanol, and the reaction was allowed to proceed at 50 °C under an oxygen atmosphere for 24 hours. The reaction mixture was filtered, and the filtrate was concentrated under vacuum. The resulting crude product was purified by column chromatography using a mixture of petroleum ether and ethyl acetate (20:1 by volume) as the eluent to obtain the product, which was designated as compound 3d (brown solid; yield: 45%).
[0077] Example 5:
[0078] The preparation of 2-((4-(9H-xanthen-9-yl)phenyl)amino)ethan-1-ol was as follows:
[0079] To a reaction tube was added 0.2 mmol of xanthene, 0.1 mmol of N- hydroxyethyl aniline, 20 mg of nitrogen-doped carbon material, and 2 mL of hexafluoroisopropanol, and reacted at 50°C for 24 hours under an oxygen atmosphere, filtered, and the filtrate was vacuum concentrated. The crude product obtained by the concentration was subjected to column chromatography (eluent was prepared by mixing petroleum ether and ethyl acetate at a volume ratio of 20:1) to obtain the product, which was designated as compound 3a (yellow solid; yield: 85%).
[0080] Example 6:
[0081] A method for preparing 4-(2-cyclohexyl-9H-xanthen-9-yl)-N-methyl aniline is as follows:
[0082] To a reaction tube was added 0.2 mmol of xanthene, 0.1 mmol of N- hydroxyethyl aniline, 20 mg of nitrogen-doped carbon material, and 2 mL of hexafluoroisopropanol, and reacted at 50°C for 24 hours under an oxygen atmosphere, filtered, and the filtrate was vacuum concentrated. The crude product obtained by the concentration was subjected to column chromatography (eluent was prepared by mixing petroleum ether and ethyl acetate at a volume ratio of 20:1) to obtain the product, which was designated as compound 3a (yellow solid; yield: 85%).
[0083] Example 7:
[0084] A method for preparing N-methyl-4-(2-methyl-9H-xanthen-9-yl) aniline is as follows:
[0085] To a reaction tube was added 0.2 mmol of xanthene, 0.1 mmol of N- hydroxyethyl aniline, 20 mg of nitrogen-doped carbon material, and 2 mL of hexafluoroisopropanol, and reacted at 50°C for 24 hours under an oxygen atmosphere, filtered, and the filtrate was vacuum concentrated. The crude product obtained by the concentration was subjected to column chromatography (eluent was prepared by mixing petroleum ether and ethyl acetate at a volume ratio of 20:1) to obtain the product, which was designated as compound 3a (yellow solid; yield: 85%).
[0086] Example 8:
[0087] A method for preparing 4-(2-chloro-9H-xanthen-9-yl)-N-methyl aniline is as follows:
[0088] Into a reaction tube was added 0.2 mmol of 4-chloroxanthene, 0.1 mmol of N-methylaniline, 20 mg of nitrogen-doped carbon material, and 2 mL of hexafluoroisopropanol, and the mixture was reacted at 50°C under an oxygen atmosphere for 24 h, filtered, and the filtrate was concentrated under vacuum. The obtained crude product was subjected to column chromatography (using a mixture of petroleum ether and ethyl acetate in a volume ratio of 20:1 as the eluent) to obtain the product, which was designated as compound 3h (white solid; yield: 58%).
[0089] Example 9:
[0090] The preparation method of N-methyl-4-(2-(trifluoromethyl)-9H-xanthen-9-yl)aniline was as follows:
[0091] Into a reaction tube was added 0.2 mmol of 4-chloroxanthene, 0.1 mmol of N-methylaniline, 20 mg of nitrogen-doped carbon material, and 2 mL of hexafluoroisopropanol, and the mixture was reacted at 50°C under an oxygen atmosphere for 24 h, filtered, and the filtrate was concentrated under vacuum. The obtained crude product was subjected to column chromatography (using a mixture of petroleum ether and ethyl acetate in a volume ratio of 20:1 as the eluent) to obtain the product, which was designated as compound 3h (white solid; yield: 58%).
[0092] Application Example 1:
[0093] The present example provides an application of a 9-aryloxanthene compound, specifically, the product 3e in Example 5 of the present application is used to modify febuxostat to obtain a drug derivative product suitable for treating hyperuricemia of gout symptoms, and the preparation method is as follows:
[0094] Into a reaction tube was added 0.2 mmol of 4-chloroxanthene, 0.1 mmol of N-methylaniline, 20 mg of nitrogen-doped carbon material, and 2 mL of hexafluoroisopropanol, and the mixture was reacted at 50°C under an oxygen atmosphere for 24 h, filtered, and the filtrate was concentrated under vacuum. The obtained crude product was subjected to column chromatography (using a mixture of petroleum ether and ethyl acetate in a volume ratio of 20:1 as the eluent) to obtain the product, which was designated as compound 3h (white solid; yield: 58%).
[0095] Application Example 2:
[0096] The embodiment provides application of a 9-aryloxyxanthene compound, in particular, the product 3e in the embodiment 5 of the application is used for modifying ibuprofen to obtain a drug derivative product suitable for treating fever and inflammation, and a preparation method thereof is as follows:
[0097] The reaction tube is added with ibuprofen 0.24 mmol, 4-dimethylaminopyridine 0.03 mmol, N,N'-dicyclohexyl carbodiimide 0.4 mmol, 2 mL of dichloromethane, and stirred for 10 min under air at room temperature, then 1 mL of dichloromethane solution containing 0.2 mmol of 3e is added dropwise, and reacted for 12 h, filtered, and the filtrate is vacuum concentrated, and the obtained crude product is subjected to column chromatography (the eluent used in column chromatography is prepared by mixing petroleum ether and ethyl acetate at a volume ratio of 10:1), to obtain the product, which is denoted as compound 3k (white solid; yield is 82%).
[0098] Experiment 1: The nitrogen-doped carbon material is subjected to full cycle experiment, and the reaction condition is as follows:
[0099] The reaction tube is added with 0.2 mmol of xanthene, 0.1 mmol of N-methylaniline, 20 mg of nitrogen-doped carbon material and 2 mL of hexafluoroisopropanol, and reacted for 24 h under oxygen atmosphere at 50 DEG C, filtered, and the filtrate is vacuum concentrated, and the obtained crude product is subjected to column chromatography, the eluent used in column chromatography is prepared by mixing petroleum ether and ethyl acetate at a volume ratio of 20:1, to obtain the target compound. Under the same condition, the catalyst is repeatedly used for 10 times.
[0100] The yield is shown in Table 1. Figure 1
[0101] Experiment 2: The products in the embodiments 1-9 and application examples 1-2 are characterized.
[0102] In the embodiment 1, the nuclear magnetic resonance hydrogen spectrum of compound 3a is shown in Table 1, and the nuclear magnetic resonance carbon spectrum is shown in Table 2. Figure 2 Figure 3 The nuclear magnetic resonance hydrogen spectrum, the nuclear magnetic resonance carbon spectrum and the nuclear magnetic resonance fluorine spectrum are as follows:
[0103] The nuclear magnetic resonance hydrogen spectrum, the nuclear magnetic resonance carbon spectrum and the nuclear magnetic resonance fluorine spectrum are as follows:
[0104] 1 H NMR (500 MHz, CDCI3): δ 7.08 (t, J1= 10.0 Hz, J2= 5.0 Hz, 2H), 7.01 (d, J = 10.0 Hz, 2H), 6.97 (d, J = 10.0 Hz, 2H), 6.91 (d, J = 10.0 Hz, 2H), 6.87 (t, J1= 10.0 Hz, J2= 5.0 Hz, 2H), 6.41 (d, J = 10.0 Hz, 2H), 5.04 (s, 1H), 3.47 (s, 1H), 2.67 (s, 3H).
[0105] 13 C NMR (126 MHz, CDCI3): δ 151.1, 148.0, 135.5, 129.8, 129.3, 127.6, 125.2, 123.2, 116.4, 112.6, 43.5, 30.8.
[0106] According to the comprehensive analysis of the hydrogen spectrum and carbon spectrum, the structure of the compound 3a obtained in the embodiment is as follows:
[0107]
[0108] In Example 2, the hydrogen spectrum of the compound 3b is as shown in Figure 4 , and the carbon spectrum is as shown in Figure 5 .
[0109] The spectrum data of the hydrogen spectrum and the carbon spectrum are as follows:
[0110] 1 H NMR (500 MHz, CDCI3): δ 7.08 (t, J1= 10.0 Hz, J2= 5.0 Hz, 2H), 7.01 (d, J = 10.0 Hz, 2H), 6.97 (d, J = 10.0 Hz, 2H), 6.91 (d, J = 10.0 Hz, 2H), 6.87 (t, J1= 10.0 Hz, J2= 5.0 Hz, 2H), 6.41 (d, J = 10.0 Hz, 2H), 5.04 (s, 1H), 3.47 (s, 1H), 2.67 (s, 3H).
[0111] 13 C NMR (126 MHz, CDCI3): δ 151.1, 148.0, 135.5, 129.8, 129.3, 127.6, 125.2, 123.2, 116.4, 112.6, 43.5, 30.8.
[0112] According to the comprehensive analysis of the hydrogen spectrum and carbon spectrum, the structure of the compound 3a obtained in the embodiment is as follows:
[0113] In Example 3, the hydrogen spectrum of the compound 3c is as shown inFigure 6 The structure of compound 3a is shown in the following: Figure 7
[0114] The structure of compound 3a is shown in the following:
[0115] 1 H NMR (500 MHz, CDC13): δ 7.18 (t, J1= 10.0 Hz, J2= 5.0 Hz, 2H), 7.10 (d, J = 5.0 Hz, 2H), 6.94-7.05 (m, 6H), 6.50 (d, J = 10.0 Hz, 2H), 5.13 (s, 1H), 4.19-4.24 (m, 3H), 3.83 (s, 2H), 1.27 (t, J1= 10.0 Hz, J2= 5.0 Hz, 3H).
[0116] 13 C NMR (126 MHz, CDC13): δ 171.2, 151.1, 145.7, 136.4, 129.8, 129.4, 127.7, 125.0, 123.2, 116.4, 113.2, 61.4, 45.9, 43.5, 14.2.
[0117] The structure of compound 3a is shown in the following:
[0118] The structure of compound 3a is shown in the following: Figure 8 Figure 9
[0119] The structure of compound 3a is shown in the following:
[0120] 1 H NMR (500 MHz, CDC13): δ 7.18 (t, J1= 10.0 Hz, J2= 5.0 Hz, 2H), 7.10 (d, J = 5.0 Hz, 2H), 6.94-7.05 (m, 6H), 6.50 (d, J = 10.0 Hz, 2H), 5.13 (s, 1H), 4.19-4.24 (m, 3H), 3.83 (s, 2H), 1.27 (t, J1= 10.0 Hz, J2= 5.0 Hz, 3H).
[0121] 13 C NMR (126 MHz, CDC13): δ 171.2, 151.1, 145.7, 136.4, 129.8, 129.4, 127.7, 125.0, 123.2, 116.4, 113.2, 61.4, 45.9, 43.5, 14.2.
[0122] Based on the comprehensive analysis of the hydrogen spectrum and carbon spectrum data, the structure of the compound 3d obtained in the example is as follows:
[0123]
[0124] In Example 5, the hydrogen spectrum of compound 3e is as shown in Figure 10 , and the carbon spectrum is as shown in Figure 11 .
[0125] The spectrum data of the hydrogen spectrum and the carbon spectrum are as follows:
[0126] 1 H NMR (500 MHz, CDC13): δ 7.12-7.18 (m, 2H), 7.05-7.09 (m, 2H), 7.01 (t, Ji = 10.0 Hz, J2 = 5 Hz, 2H), 6.89-6.96 (m, 4H), 6.48 (d, J = 5.0 Hz, 2H), 5.09 (d, J = 5.0 Hz, 1H), 3.64-3.68 (m, 2H), 2.96-3.15 (m, 4H).
[0127] 13 C NMR (126 MHz, CDC13): δ 151.1, 146.8, 136.3, 129.8, 129.4, 127.7, 125.1, 123.2, 116.5, 113.5, 61.2, 46.2, 43.5.
[0128] Based on the comprehensive analysis of the hydrogen spectrum and carbon spectrum data, the structure of the compound 3e obtained in the example is as follows:
[0129]
[0130] In Example 6, the hydrogen spectrum of compound 3f is as shown in Figure 12 , and the carbon spectrum is as shown in Figure 13 .
[0131] The spectrum data of the hydrogen spectrum and the carbon spectrum are as follows:
[0132] 1H NMR (500 MHz, CDCI3): δ 7.14 (t, J1= 10.0 Hz, J2= 5.0 Hz, 1 H), 6.99-7.08 (m, 6 H), 6.93 (t, J1= 10.0 Hz, J2= 5.0 Hz, 1 H), 6.88 (s, 1 H), 6.50 (d, J = 10.0 Hz, 2 H), 5.10 (s, 1 H), 2.77 (s, 3 H), 2.34-2.38 (m, 1 H), 1.77 (d, J = 10.0 Hz, 4 H), 1.69 (d, J = 10.0 Hz, 1 H), 1.29-1.34 (m, 1 H).
[0133] 13 C NMR (126 MHz, CDCI3): δ 151.3, 149.4, 147.9, 142.9, 135.6, 129.7, 129.2, 127.9, 127.5, 125.8, 125.4, 124.7, 122.9, 116.4, 116.1, 112.6, 43.9, 43.8, 34.8, 34.4, 30.8, 26.9, 26.9, 26.2.
[0134] According to the comprehensive analysis of the hydrogen spectrum and carbon spectrum data, the structure of the compound 3f synthesized in this embodiment is as follows:
[0135]
[0136] In Example 7, the hydrogen spectrum of the compound 3g is as shown in Figure 14 , and the carbon spectrum is as shown in Figure 15 .
[0137] The spectrum data of the hydrogen spectrum and the carbon spectrum are as follows:
[0138] 1 H NMR (500 MHz, CDCI3): δ 7.14 (t, J1= 10.0 Hz, J2= 5.0 Hz, 1 H), 6.99-7.08 (m, 6 H), 6.93 (t, J1= 10.0 Hz, J2= 5.0 Hz, 1 H), 6.88 (s, 1 H), 6.50 (d, J = 10.0 Hz, 2 H), 5.10 (s, 1 H), 2.77 (s, 3 H), 2.34-2.38 (m, 1 H), 1.77 (d, J = 10.0 Hz, 4 H), 1.69 (d, J = 10.0 Hz, 1 H), 1.29-1.34 (m, 1 H).
[0139] 13 C NMR (126 MHz, CDCI3): δ 151.2, 149.1, 148.0, 135.8, 132.5, 130.0, 129.8, 129.3, 128.4, 127.6, 125.3, 124.8, 123.0, 116.4, 116.2, 112.6, 43.6, 30.8, 20.8.
[0140] Based on the comprehensive analysis of the nuclear magnetic resonance hydrogen spectrum and carbon spectrum data, the structure of the compound 3g synthesized in this embodiment is as follows:
[0141]
[0142] In Example 8, the nuclear magnetic resonance hydrogen spectrum of compound 3h is as shown in Figure 16 , the nuclear magnetic resonance carbon spectrum is as shown in Figure 17 , and the nuclear magnetic resonance fluorine spectrum is as shown in .
[0143] The deconvolution data of the nuclear magnetic resonance hydrogen spectrum, the nuclear magnetic resonance carbon spectrum and the nuclear magnetic resonance fluorine spectrum are as follows:
[0144] 1 H NMR (500 MHz, CDCI3): δ 7.17 (t, J1= 10.0 Hz, J2= 5.0 Hz, 1 H), 7.07-7.13 (m, 2 H), 7.01-7.03 (m, 3 H), 6.94-6.98 (m, 3 H), 6.52 (d, J = 10.0 Hz, 2 H), 5.07 (s, 1 H), 3.65 (s, 1 H), 2.78 (s, 3 H).
[0145] 13 C NMR (126 MHz, CDCI3): δ 150.8, 149.7, 148.2, 134.7, 129.8, 129.4, 129.3, 127.8, 127.8, 127.7, 126.9, 124.5, 123.4, 117.8, 116.4, 112.7, 43.4, 30.7.
[0146] Based on the comprehensive analysis of the nuclear magnetic resonance hydrogen spectrum and carbon spectrum data, the structure of the compound 3h synthesized in this embodiment is as follows:
[0147]
[0148] In Example 9, the nuclear magnetic resonance hydrogen spectrum of compound 3i is as shown in Figure 18 , the nuclear magnetic resonance carbon spectrum is as shown in Figure 19 , and the nuclear magnetic resonance fluorine spectrum is as shown in Figure 20 .
[0149] The deconvolution data of the nuclear magnetic resonance hydrogen spectrum, the nuclear magnetic resonance carbon spectrum and the nuclear magnetic resonance fluorine spectrum are as follows:
[0150] 1H NMR (500 MHz, CDCI3): δ 7.34 (d, J = 10.0 Hz, 1 H), 7.18 (s, 1 H), 7.10-7.14 (m, 2 H), 7.04 (d, J = 10.0 Hz, 1 H), 6.99 (d, J = 10.0 Hz, 1 H), 6.92 (m, 3 H), 6.46 (d, J = 5.0 Hz, 2 H), 5.07 (s, 1 H), 3.69 (s, 1 H), 2.72 (s, 3 H).
[0151] 13 C NMR (126 MHz, CDCI3): δ 153.4, 150.5, 148.2, 134.5, 129.8, 129.2, 127.9, 127.2 (q, J = 3.7 Hz), 125.7, 125.4, 125.2, 125.1, 124.8 (q, J = 3.6 Hz), 124.6, 123.8, 117.0, 116.5, 112.7, 43.3, 30.7.
[0152] 19 F NMR (471 MHz, CDCI3): δ -61.62.
[0153] According to the comprehensive analysis of the nuclear magnetic resonance hydrogen spectrum, carbon spectrum and fluorine spectrum data, the structure of the compound 3i synthesized in the embodiment is as follows:
[0154]
[0155] In the application example 1, the nuclear magnetic resonance hydrogen spectrum of the compound 3j is as shown in Figure 21 , and the nuclear magnetic resonance carbon spectrum is as shown in Figure 22 .
[0156] The spectral data of the nuclear magnetic resonance hydrogen spectrum and the nuclear magnetic resonance carbon spectrum are as follows:
[0157] 1 H NMR (500 MHz, CDCI3): δ 8.16 (d, J = 1.5 Hz, 1 H), 8.05-8.07 (m, 1 H), 7.17 (t, J1= 10.0 Hz, J2= 5.0 Hz, 2 H), 6.94-7.10 (m, 9 H), 6.57 (d, J = 10.0 Hz, 2 H), 5.14 (s, 1 H), 4.46-4.47 (m, 2 H), 3.89 (d, J = 10.0 Hz, 2 H), 3.46-3.48 (m, 2 H), 2.74 (s, 3 H), 1.62 (s, 2 H), 1.09 (d, J = 5.0 Hz, 6 H).
[0158] 13C NMR (126 MHz, CDC13): δ 167.5, 162.6, 162.0, 161.8, 151.1, 146.2, 136.3, 132.6, 132.2, 129.7, 129.4, 127.7, 125.9, 125.0, 123.1, 121.2, 116.4, 115.4, 113.2, 112.7, 103.0, 75.7, 63.9, 43.5, 43.0, 28.2, 19.1, 17.6.
[0159] Based on the comprehensive analysis of the hydrogen spectrum and carbon spectrum data, the compound 3j synthesized in this embodiment is 2-((4-(9H-xanthen-9-yl)phenyl)amino)ethyl-2-(3-cyano-4-isobutoxyphenyl)-4-methylthiazole-5-carboxylate, and its structural formula is as follows:
[0160]
[0161] In Example 2, the hydrogen spectrum of compound 3k is as shown in Figure 23 , and the carbon spectrum is as shown in Figure 24 .
[0162] The spectrum data of the hydrogen spectrum and the carbon spectrum are as follows:
[0163] 1 H NMR (500 MHz, CDC13): δ 7.16 (t, J1= 10.0 Hz, J2= 5.0 Hz, 4H), 7.03-7.10 (m, 6H), 6.93-6.96 (m, 4H), 6.41 (d, J = 5.0 Hz, 2H), 5.11 (s, 1H), 4.16-4.23 (m, 2H), 3.59-3.68 (m, 2H), 3.24 (m, 2H), 2.42 (d, J = 10.0 Hz, 2H), 1.79-1.85 (m, 1H), 1.45 (d, J = 10.0 Hz, 3H), 0.88 (d, J = 5.0 Hz, 6H).
[0164] 13C NMR (126 MHz, CDCI3): δ 174.8, 151.1, 146.3, 140.7, 137.8, 136.1, 129.8, 129.5, 129.3, 127.7, 127.1, 125.1, 123.2, 116.4, 113.2, 63.3, 45.1, 45.1, 43.5, 42.8, 30.2, 22.5, 18.4.
[0165] According to the comprehensive analysis of the hydrogen spectrum and carbon spectrum data, the compound 3k synthesized in the embodiment is (2-((4-(9H-xanthen-9-yl)phenyl)amino-2-(4-isobutylphenyl)propanoate ethyl ester (9H-xanthen-9-yl)phenyl)amino)ethyl-2-(4-isobutylphenyl)propanoate), and the structural formula is as follows:
[0166]
[0167] It should be noted that the relational terms herein such as first and second and the like are used only to differentiate one entity or action from another, and do not necessarily require or imply that there is any such actual relationship or order between these entities or actions. In addition, the terms "comprising", "including" or any other variant thereof are intended to cover non-exclusive inclusion, so that processes, methods, articles or devices including a series of elements not only include those elements, but also include other elements not explicitly listed or inherent to such processes, methods, articles or devices.
[0168] Finally, it should be noted that the above only describes the preferred embodiments of the present application, and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent replacements to some technical features. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.
Claims
1. A 9-aryloxanthracene compound having the structure shown below: Its features are: R is any one of hydrogen, methyl, cyclohexyl, trifluoromethyl, or halogen; R 1 R 2 It is any one of hydrogen, methyl, ethyl, ester, or hydroxyethyl; R 3 It can be either hydrogen or ester group.
2. The method for preparing 9-aryloxanthracene compounds according to claim 1, characterized in that: 9-aryloxanthracene compounds are obtained by adding xanthracene compounds, aromatic amine compounds, and nitrogen-doped carbon materials to an organic solvent and reacting them under a protective atmosphere. After filtration, concentration, and purification, 9-aryloxanthracene compounds are obtained.
3. The method for preparing 9-aryloxanthracene compounds according to claim 2, characterized in that: The aromatic amine compounds are any one of N-methylaniline, N,N-diethylaniline, N-phenylglycine ethyl ester, methyl anthranilate, and N-hydroxyethylaniline; the oxanthracene compounds are any one of 4-cyclohexyloxanthracene, 4-methyloxanthracene, 4-chlorooxanthracene, and 4-trifluoromethyloxanthracene.
4. The method for preparing 9-aryloxanthracene compounds according to claim 2, characterized in that: The molar ratio of xanthracene compounds to aromatic amine compounds is 2:1; based on 1 mol of xanthracene compounds as reactants, the amount of nitrogen-doped carbon material used is 100 g.
5. The method for preparing 9-aryloxanthracene compounds according to claim 2, characterized in that: The organic solvent is at least one of hexafluoroisopropanol, trifluoroethanol, tert-butanol, toluene, tetrahydrofuran, acetonitrile, and dimethyl sulfoxide.
6. The method for preparing 9-aryloxanthracene compounds according to claim 2, characterized in that: The protective atmosphere is oxygen.
7. The method for preparing 9-aryloxanthracene compounds according to claim 2, characterized in that: The reaction temperature is 30–90℃.
8. The method for preparing 9-aryloxanthracene compounds according to claim 2, characterized in that: The reaction time is 12 to 30 hours.
9. The method for preparing 9-aryloxanthracene compounds according to claim 2, characterized in that: The preparation method of nitrogen-doped carbon material is as follows: nitrogen source and carbon black are added to deionized water and stirred continuously at a constant temperature of 80°C for 4 hours. Then, the solvent is removed by rotary evaporator and the mixture is dried in a vacuum drying oven at 80°C. After the dried mixture is thoroughly ground, it is placed in a tube furnace and purged with nitrogen for 30 minutes. Then, it is calcined at 500-900°C for 1-4 hours at a heating rate of 10°C / min and then naturally cooled.
10. The method for preparing 9-aryloxanthracene compounds according to claim 9, characterized in that: The mass ratio of nitrogen source to carbon black is 2:1, and the nitrogen source is at least one of dicyandiamide, melamine, and urea.