Process for the preparation of heteroatom-modified 9-phenylacridines

Abstract

The application provides a preparation method of heteroatom-modified 9-phenylacridine, which comprises the following steps: under the action of a Cu(I) or Cu(II) catalyst and a base, a reaction substrate halogenated 9-phenylacridine is reacted with alcohol or thiophenol in N,N-dimethylformamide (DMF) and / or dimethyl sulfoxide (DMSO) to generate heteroatom-modified 9-phenylacridine. The synthesis method of the heteroatom-modified 9-phenylacridine reported in the prior art needs to introduce a heteroatom in the raw material in advance, which increases the cost and additional synthesis steps, and the preparation process is complicated. The method of the application greatly reduces the production cost by selecting a specific solvent and catalyst system to prepare the heteroatom-modified 9-phenylacridine by taking brominated 9-phenylacridine as the reaction substrate, and the method is simple to operate, suitable for the introduction of various heteroatoms, and has great implementation value and social and economic benefits.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic synthesis, and particularly relates to a preparation method of a heteroatom-modified photoresist initiator 9-phenylacridine. BACKGROUND

[0002] LEDs as new light sources are attracting more and more attention in the field of photocuring, and show great application potential in light output, working efficiency, cost, environmental protection, etc. Developing products matching LED light sources has become the focus of research by those skilled in the art. One main wavelength range of existing LED light sources is 365-405 nm.

[0003] 9-phenylacridine compounds can be widely used as photoinitiators in photocurable materials (such as photocurable coatings, inks and photoresists) composed of unsaturated resins and monomers. Under the irradiation of ultraviolet light or laser, these photoinitiators produce active free radicals, thereby initiating the polymerization and curing reaction of unsaturated photocurable materials. For example, patent applications CN 112835261A and CN 112433445A disclose the application of different acridine compounds in photosensitive resins.

[0004] The existing 9-phenylacridine initiator has an absorption wavelength of about 365 nm, and is rarely used as a 405 nm initiator due to the inability to match the wavelength of the 405 nm light source. How to extend the absorption wavelength of the photoinitiating system has become a problem to be solved.

[0005] Studies have shown that heteroatom-substituted 9-phenylacridine, due to the electron-donating effect of the heteroatom, has a red shift in ultraviolet absorption wavelength to about 400 nm, and has the characteristics of fast curing speed and high conversion rate under the excitation of 405 nm wavelength. The previously disclosed methods for synthesizing such compounds require the introduction of a heteroatom group in the raw material in advance, resulting in complicated steps and high production cost, for example: Journal of Organic Chemistry, 2020, 85, 15, 10167-10174; and Journal of Organic Chemistry, 2020, 85, 20, 13004-13014.

[0006] Therefore, it is of great significance to develop a simple and economical method for synthesizing heteroatom-modified 9-phenylacridine. SUMMARY

[0007] To solve the above technical problems, the purpose of the present application is to provide a preparation method of heteroatom-modified 9-phenylacridine compounds, which can simply and economically synthesize heteroatom-modified 9-phenylacridine.

[0008] The inventors of the present application have unexpectedly found that, when Cu(I) or Cu(II) is selected as a catalyst, and N,N-dimethylformamide (DMF) and / or dimethyl sulfoxide (DMSO) is selected as a solvent, a nucleophilic substitution reaction of bromo-9-phenylacridine with an alcohol or a thiol is carried out, a heteroatom-modified 9-phenylacridine with high photosensitivity at a wavelength of 405 nm is obtained, and the content of the finished product obtained after post-treatment can reach more than 95%. The process is not only simple to operate, but also low in raw material cost, and can meet the needs of industrial production, so the present application is completed.

[0009] Therefore, the present application provides a preparation method of a heteroatom-modified 9-phenylacridine, which comprises: reacting a reaction substrate, halogenated 9-phenylacridine, with an alcohol or a thiol under the action of a Cu(I) or Cu(II) catalyst and a base, in a solvent of N,N-dimethylformamide (DMF) and / or dimethyl sulfoxide (DMSO), to generate a heteroatom-modified 9-phenylacridine.

[0010] The reaction formula of the preparation method provided by the present application is as follows:

[0011]

[0012] In the formula, X represents O or S, and R represents a C1-C12 alkyl group or a mono-substituted or multi-substituted aryl group, and the substituents thereof are selected from one or more of C1-C6 alkyl groups, C1-C6 alkoxy groups, C1-C6 alkylamine groups, halogens, nitro groups, cyano groups or amine groups.

[0013] According to the preparation method provided by the present application, the reaction process can be carried out in a closed or non-closed system.

[0014] In a preferred embodiment of the present application, the halogenated 9-phenylacridine is 2-bromo-9-phenylacridine, 2-chloro-9-phenylacridine, 2-iodo-9-phenylacridine, 2,3-dibromo-9-phenylacridine, 2,4-dibromo-9-phenylacridine, 2,7-dibromo-9-phenylacridine, or 9-phenylacridine with halogen substituents on the acridine ring.

[0015] In a preferred embodiment of the present application, the reaction temperature is controlled at 50-150°C, and the reaction time is 1-24 h. Preferably, the reaction temperature is 90-110°C, and the reaction time is 8-16 h.

[0016] In a preferred embodiment of the present application, the Cu(I) catalyst is CuI or CuBr, and the Cu(II) catalyst is Cu(OAc)2.

[0017] In a preferred embodiment of the present application, the base can be an alkoxide or a thiophenoxide corresponding to the alcohol or thiophenol used in the reaction. Preferably, the base is used in an amount of 2.5 to 3.5 equivalents of the halogenated 9-phenylacridine substrate. In the most preferred embodiment of the present application, the base is sodium methoxide, sodium ethoxide or sodium tert-butoxide.

[0018] Preferably, the catalyst is used in an amount of 5% to 20% of the molar equivalent of the halogenated 9-phenylacridine substrate.

[0019] According to the preparation method provided by the present application, the alcohol or thiophenol can be used in an amount of 1 to 10 molar equivalents of the halogenated 9-phenylacridine substrate, preferably 1.5 to 5 molar equivalents.

[0020] In some embodiments of the present application, the alcohol is one or more of C1 to C6 alcohols, such as one or more of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol and tert-butanol.

[0021] In some embodiments of the present application, the thiophenol is one or more of 4-methoxythiophenol, 4-methylthiophenol, 3-methylthiophenol, 2-methylthiophenol, 4-tert-butylthiophenol, 4-chlorothiophenol and C1 to C6 alkyl-substituted thiophenols.

[0022] According to the preparation method provided by the present application, the solvent is used in an amount such that the concentration of the halogenated 9-phenylacridine in the reaction system is 0.1 to 5 mol / L, preferably 0.5 to 2 mol / L.

[0023] In a preferred embodiment of the present application, the preparation method can comprise the following steps:

[0024] S1. The halogenated 9-phenylacridine is added to the solvent and stirred until uniform, then the catalyst and the alcohol or thiophenol are added, and the reaction temperature and time are controlled, and the reaction is carried out under stirring;

[0025] S2. After the reaction is completed, water is added to quench the reaction, the aqueous phase is extracted with an organic solvent for several times, the organic phases are combined, washed with saturated brine, and the organic phase is dried with anhydrous sodium sulfate, and the solvent is removed under reduced pressure to obtain the crude product;

[0026] S3. The crude product is rinsed with methanol, recrystallized with toluene, and vacuum dried to obtain the product.

[0027] The synthesis method of heteroatom-modified 9-phenylacridine reported in the prior art needs to introduce heteroatoms in the raw material in advance, which increases the cost and additional synthesis steps, and the preparation process is complicated. The method of the present application uses halogenated 9-phenylacridine as the reaction substrate to prepare heteroatom-modified 9-phenylacridine by selecting a specific solvent and catalyst system, greatly reducing the production cost, and the method is simple to operate, suitable for the introduction of various heteroatoms, and has great implementation value and social and economic benefits. BRIEF DESCRIPTION OF DRAWINGS

[0028] Hereinafter, embodiments of the present application will be described in detail with reference to the accompanying drawings, in which:

[0029] Figure 1 and Figure 2 NMR spectrum of 2-methoxy-9-phenylacridine prepared in Example 1;

[0030] Figure 3 and Figure 4 NMR spectrum of 2-ethoxy-9-phenylacridine prepared in Example 2;

[0031] Figure 5 and Figure 6 NMR spectrum of 2-isopropoxy-9-phenylacridine prepared in Example 3;

[0032] Figure 7 and Figure 8 NMR spectrum of 2-((4-methoxyphenyl)thio)-9-phenylacridine prepared in Example 4;

[0033] Figure 9 and Figure 10 NMR spectrum of 2-butoxy-9-phenylacridine prepared in Example 5;

[0034] Figure 11 and Figure 12 NMR spectrum of 2,3-dimethoxy-9-phenylacridine prepared in Example 6;

[0035] Figure 13 and Figure 14 NMR spectrum of 2-((4-chlorophenyl)thio)-9-phenylacridine prepared in Example 7. DETAILED DESCRIPTION

[0036] The present application will be further described in detail below in conjunction with the specific embodiments, and the examples given are only for the purpose of illustrating the present application, but not for limiting the scope of the present application.

[0037] Example 1

[0038] Preparation of 2-methoxy-9-phenylacridine

[0039]

[0040] In a three-necked flask was added 33.4 g of 2-bromo-9-phenylacridine (100 mmol) and 100 ml of DMF, stirred uniformly, 16.2 g of sodium methoxide (300 mmol, 3 equivalents), 1.9 g of cuprous iodide (10 mmol, 0.1 equivalent), 16 g of methanol (500 mmol, 5 equivalents) were added in sequence; the reaction mixture was stirred at 100°C for 12 h; after the reaction was substantially complete as detected by thin layer chromatography, it was allowed to cool to room temperature, and 200 mL of water was added. The aqueous phase was extracted with 200 mL of DCM three times, the organic phase was washed with saturated brine, and dried over anhydrous sodium sulfate, filtered, and the organic solvent was evaporated to obtain 27 g of crude product, which was recrystallized from methanol and toluene, and dried in a vacuum oven to obtain 25.6 g of product, with a yield of 90% and a purity greater than 95%.

[0041] 1 H NMR (400 MHz, CDC13, 300 K): δ (ppm) = 8.19 (d, J = 8.7 Hz, 1H), 8.13 (d, J = 9.4 Hz, 1H), 7.65-7.61 (m, 1H), 7.57-7.49 (m, 4H), 7.41-7.31 (m, 4H), 6.75 (d, J = 2.7 Hz, 1H), 3.65 (s, 3H).

[0042] 13 C NMR (101 MHz, CDC13, 300 K): δ (ppm) = 156.9, 146.8, 145.6, 145.1, 136.2, 130.8, 130.2, 129.2, 129.0, 128.6, 128.3, 126.3, 125.9, 125.8, 125.4, 125.2, 102.0, 55.3.

[0043] The nuclear magnetic resonance spectrum of 2-methoxy-9-phenylacridine prepared in this example is shown in Figure 1 and 2 .

[0044] Example 2

[0045] Preparation of 2-ethoxy-9-phenylacridine

[0046]

[0047] In a three-necked flask was added 33.4 g of 2-bromo-9-phenylacridine (100 mmol) and 100 ml of DMSO, stirred uniformly, 20.4 g of sodium ethoxide (300 mmol, 3 eq), 1.4 g of cuprous bromide (10 mmol, 0.1 eq) were added in sequence, 23 g of ethanol (500 mmol, 5 eq); the reaction mixture was stirred at 100°C overnight; after TLC detection of the reaction was substantially complete, it was brought to room temperature. 200 mL of water was added, the aqueous phase was extracted with 200 mL of DCM three times, the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered and the organic solvent was evaporated to obtain 27 g of crude product, which was recrystallized from methanol and toluene, dried under vacuum to obtain 25.4 g of product, with a yield of 85% and a purity greater than 95%.

[0048] 1 H NMR (400 MHz, CDC13, 300 K): δ (ppm) = 8.25 (d, J = 8.7 Hz, 1H), 8.19 (d, J = 9.4 Hz, 1H), 7.71-7.67 (m, 1H), 7.64-7.54 (m, 4H), 7.48-7.37 (m, 4H), 6.81 (d, J = 2.7 Hz, 1H), 3.91 (q, J = 7.0 Hz, 2H), 1.38 (t, J = 7.0 Hz, 3H).

[0049] 13 C NMR (101 MHz, CDC13, 300 K): δ (ppm) = 156.2, 146.9, 145.7, 144.7, 136.3, 130.9, 130.2, 129.3, 128.8, 128.5, 128.2, 126.3, 126.0, 125.7, 125.3, 125.3, 102.7, 63.5, 14.5.

[0050] The NMR spectrum of 2-ethoxy-9-phenylacridine prepared in this example is shown in Figure 3 and 4 .

[0051] Example 3

[0052] Preparation of 2-isopropoxy-9-phenylacridine

[0053]

[0054] In a three-necked flask, 41.3 g of 2-bromo-9-phenylacridine (100 mmol) and 100 ml of DMF were added and stirred well, 28.8 g of sodium tert-butoxide (300 mmol, 3 eq), 1.9 g of copper acetate (10 mmol, 0.1 eq) were added in sequence, 30 g of isopropyl alcohol (500 mmol, 5 eq); the reaction mixture was stirred at 120 °C overnight; after TLC detection of the reaction was substantially complete, it was brought to room temperature. 200 mL of water was added, the aqueous phase was extracted with 200 mL of DCM three times, the organic phase was washed with saturated brine and dried with anhydrous sodium sulfate, filtered and the organic solvent was evaporated to obtain 29 g of crude product, which was recrystallized from methanol and toluene, dried under vacuum to obtain 26.1 g of product, with a yield of 83% and a purity greater than 95%.

[0055] 1 H NMR (400 MHz, CDC13, 300 K): δ (ppm) = 8.25 (d, J = 8.6 Hz, 1H), 8.20 (d, J = 9.5 Hz, 1H), 7.71-7.67 (m, 1H), 7.65-7.54 (m, 4H), 7.46-7.37 (m, 4H), 6.84 (d, J = 2.7 Hz, 1H), 4.44 (p, J = 6.1 Hz, 1H), 1.29 (p, J = 6.0 Hz, 6H).

[0056] 13 C NMR (101 MHz, CDC13, 300 K): δ (ppm) = 154.9, 146.8, 145.4, 144.7, 136.3, 130.8, 130.3, 129.2, 128.9, 128.5, 128.2, 126.3, 126.1, 125.9, 125.7, 125.3, 117.7, 116.2, 104.4, 69.9, 21.6.

[0057] The nuclear magnetic resonance spectrum of 2-isopropoxy-9-phenylacridine prepared in this example is shown in Figure 5 and 6 .

[0058] Example 4

[0059] Preparation of 2-((4-methoxyphenyl)thio)-9-phenylacridine

[0060]

[0061] In a three-necked flask, 33.4 g of 2-bromo-9-phenylacridine (100 mmol) and 100 ml of DMF were added and stirred uniformly, 16.2 g of sodium methoxide (300 mmol, 3 equivalents), 1.9 g of cuprous iodide (10 mmol, 0.1 equivalent), 35 g of 4-methoxythiophenol (250 mmol, 2.5 equivalents) were added in sequence; the reaction mixture was stirred at 100°C for 12 h; after the reaction was substantially complete as detected by thin layer chromatography, it was allowed to cool to room temperature. 200 mL of water was added, the aqueous phase was extracted with 200 mL of DCM three times, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, filtered and the organic solvent was evaporated to obtain 40 g of crude product, which was recrystallized from methanol and toluene, and dried in vacuum to obtain 35.8 g of product, with a yield of 91% and a purity greater than 95%.

[0062] 1 H NMR (400 MHz, CDC13, 300 K): δ (ppm) = 8.13 (d, J = 8.7 Hz, 1H), 8.02 (d, J = 9.2 Hz, 1H), 7.63-7.59 (m, 1H), 7.56 (d, J = 8.7 Hz, 1H), 7.42-7.39 (m, 4H), 7.30-7.25 (m, 3H), 7.22-7.19 (m, 2H), 7.17-7.16 (m, 1H), 6.76-6.72 (m, 2H), 3.72 (s, 3H).

[0063] 13 C NMR (101 MHz, CDC13, 300 K): δ (ppm) = 160.1, 148.2, 147.3, 145.6, 136.9, 135.8, 135.4, 130.3, 130.1, 129.8, 129.6, 129.5, 128.3, 128.1, 126.7, 125.8, 125.3, 125.2, 123.1, 122.8, 115.1, 55.3.

[0064] The nuclear magnetic resonance spectrum of 2-((4-methoxyphenyl)thio)-9-phenylacridine prepared in this example is shown in Figure 7 and 8 .

[0065] Example 5

[0066] 2-butoxy-9-phenylacridine was prepared in a similar manner to Example 1-4, with a yield of 80% and a purity greater than 95%.

[0067]

[0068] 1H NMR (400 MHz, CDC13, 300 K): δ (ppm) = 8.33 (d, J = 8.8 Hz, 1 H), 8.27 (d, J = 9.4 Hz, 1 H), 7.73 (t, J = 7.8 Hz, 1 H), 7.65 - 7.57 (m, 4 H), 7.49 (d, J = 9.4 Hz, 1 H), 7.45 - 7.40 (m, 3 H), 6.82 (s, 1 H), 3.86 (t, J = 6.5 Hz, 2 H), 1.77 - 1.70 (m, 2 H), 1.51 - 1.41 (m, 2 H), 0.94 (t, J = 7.4 Hz, 3 H).

[0069] 13 C NMR (101 MHz, CDC13, 300 K): δ (ppm) = 156.6, 130.2, 129.4, 128.6, 128.4, 126.4, 126.1, 125.9, 125.4, 102.7, 67.7, 31.0, 19.2, 13.8.

[0070] The H NMR spectrum of 2-butoxy-9-phenylacridan prepared in this example is shown in Figure 9 and 10 .

[0071] Example 6

[0072] 2,3-Dimethoxy-9-phenylacridan was prepared in a similar manner to Example 1-4 in a yield of 77% and a purity of more than 95%.

[0073]

[0074] 1 H NMR (400 MHz, CDC13, 300 K): δ (ppm) = 8.25 (d, J = 8.7 Hz, 1 H), 7.74 - 7.70 (m, 1 H), 7.63 - 7.57 (m, 5 H), 7.45 - 7.36 (m, 3 H), 6.81 (s, 1 H), 4.41 (s, 3 H), 3.79 (s, 3 H).

[0075] 13 C NMR (101 MHz, CDC13, 300 K): δ (ppm) = 150.0, 136.0, 130.1, 129.4, 128.6, 128.4, 126.4, 125.0, 124.5, 121.7, 105.5, 102.6, 56.4, 55.8.

[0076] The H NMR spectrum of 2,3-dimethoxy-9-phenylacridan prepared in this example is shown in Figure 11 and12 As shown.

[0077] Example 7

[0078] 2-((4-chlorophenyl)thio)-9-phenylacridine was prepared in a manner similar to that in Example 4, with a yield of 86% and a purity greater than 95%.

[0079]

[0080] 1 H NMR (400MHz, CDCl3, 300K): δ (ppm) = 8.17 (d, J = 8.7Hz, 1H), 8.10 (d, J = 9.0Hz, 1H), 7.69-7.65 (m, 1H ),7.62-7.59(m,1H),7.50-7.45(m,4H),7.37-7.32(m,2H),7.27-7.24(m,2H),7.22-7.16(m,4H).

[0081] 13 C NMR (101MHz, CDCl3, 300K): δ (ppm) = 148.6, 147.5, 146.4, 135.2, 134.0, 133.9, 133.4, 132.5, 131.5,130.4,130.3,130.1,129.5,129.4,128.5,128.4,126.8,126.4,126.1,125.4,125.2.

[0082] The NMR spectrum of 2-((4-chlorophenyl)thio)-9-phenylacridine obtained in this embodiment is as follows. Figure 13 and 14 As shown.

[0083] Example 8

[0084] 2-Methoxy-9-phenylacridine was prepared in a manner similar to that in Example 1, except that the optimal reaction conditions were screened by changing the reaction temperature, catalyst, base, and solvent. The results are shown in Table 1. The specific procedures are as follows:

[0085] In a three-necked flask, 33.4 g of 2-bromo-9-phenylacridine (100 mmol) and 100 ml of DMF were added and stirred uniformly, 3 equivalents of base, 0.1 equivalent of catalyst, and 5 equivalents of methanol were sequentially added; the reaction mixture was stirred for 12 h at different concentrations; after the reaction was substantially complete as detected by thin layer chromatography, the mixture was cooled to room temperature, and 200 ml of water was added. The aqueous phase was extracted with 200 ml of DCM three times, the organic phase was washed with saturated brine, and dried with anhydrous sodium sulfate, filtered, and the organic solvent was evaporated to obtain a crude product, which was rinsed with methanol, recrystallized with toluene, and dried in vacuum to obtain the product.

[0086] Table 1

[0087]

[0088] From the data in the table, it can be seen that:

[0089] 1. Comparing tests 5, 9, and 10, it can be seen that when the commonly used nucleophilic substitution catalyst FeCl2and Ag2O are used, the yield is only 5% and 15%, while the Cu catalyst of the present application is used, the yield is unexpectedly as high as 90% under the same conditions;

[0090] 2. Comparing test 5 with test 11, it can be seen that the inexpensive CuI is used as the catalyst in the present application, and under the same addition amount, the yield is comparable to that of the Pd catalyst, greatly reducing the production cost;

[0091] 3. Comparing tests 5 and 13 with tests 14-16, it can be seen that under the same conditions, the use of DMF or DMSO as the solvent in the present application significantly improves the reaction yield compared with the commonly used toluene, dioxane, and acetonitrile (MeCN) as the solvent;

[0092] 4. Test 4 shows that the use of lithium hexamethyldisilazide (LiHDMS) instead of the base of the present application has a yield of only 28%, which is not of practical value for production.

[0093] The above examples are only preferred embodiments of the present application and do not limit the present application in any way. Any equivalent replacement or modification of the technical solutions and technical content disclosed in the present application by any person skilled in the art without departing from the scope of the technical solutions of the present application still falls within the protection scope of the present application.

Claims

1. A method for preparing heteroatom-modified 9-phenylacridine, the method comprising: Using N,N-dimethylformamide (DMF) and / or dimethyl sulfoxide (DMSO) as solvents, and in the presence of a Cu(II) catalyst and a base, the substrate 2-bromo-9-phenylacridine is reacted with R-XH to generate heteroatom-modified 9-phenylacridine. The reaction formula for the preparation method is as follows: Wherein, X in R-XH is oxygen or sulfur, and R represents a monosubstituted or polysubstituted aryl group, the substituent being selected from one or more of C1~C6 alkyl, C1~C6 alkoxy, C1~C6 alkylamine, nitro, and cyano; or R-XH is propanol, isopropanol, n-butanol, or isobutanol. The alkali is sodium methoxide, sodium ethoxide, or sodium tert-butoxide.

2. The preparation method according to claim 1, wherein, The reaction temperature is 50℃~150℃, and the reaction time is 1~24h.

3. The preparation method according to claim 2, wherein, The reaction temperature is 90℃~110℃, and the reaction time is 8~16h.

4. The preparation method according to claim 1, wherein, The Cu(II) catalyst is Cu(OAc)2.

5. The preparation method according to claim 1, wherein, The amount of base used is 2.5 to 3.5 equivalents of the reaction substrate 2-bromo-9-phenylacridine.

6. The preparation method according to claim 1, wherein, The amount of catalyst used is 5% to 20% molar equivalent of the reaction substrate 2-bromo-9-phenylacridine.

7. The preparation method according to claim 1, wherein, The amount of R-XH used is 1 to 10 molar equivalents of the reaction substrate 2-bromo-9-phenylacridine.

8. The preparation method according to claim 7, wherein, The amount of R-XH used is 1.5 to 5 molar equivalents of the reaction substrate 2-bromo-9-phenylacridine.

9. The preparation method according to claim 1, wherein, The R-XH is one or more of 4-methoxythiophenol, 4-methylthiophenol, 3-methylthiophenol, 2-methylthiophenol, and 4-tert-butylthiophenol.

10. The preparation method according to claim 1, wherein, The amount of solvent used is such that the concentration of 2-bromo-9-phenylacridine in the reaction system is 0.1~5 mol / L.

11. The preparation method according to claim 10, wherein, The amount of solvent used is such that the concentration of 2-bromo-9-phenylacridine in the reaction system is 0.5~2 mol / L.

12. The preparation method according to any one of claims 1 to 11, wherein, The preparation method includes the following steps: S1. Add 2-bromo-9-phenylacridine to the solvent and stir until homogeneous. Then add the catalyst and R-XH, and control the reaction temperature and time while stirring. S2. After the reaction is complete, water is added to quench the reaction. The aqueous phase is extracted several times with an organic solvent. The organic phases are combined, washed with saturated brine, and then dried with anhydrous sodium sulfate. The crude product is obtained after removing the solvent under reduced pressure. S3. The crude product is washed with methanol, recrystallized from toluene, and dried under vacuum to obtain the final product.

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