A photocatalytic method for preparing tertiary benzylamine

Abstract

This invention discloses a photocatalytic method for preparing tertiary benzylamines, belonging to the field of organic synthesis. The process uses amines as raw materials and diarylamine pyran salts as catalysts. Under irradiation with 456 nm visible light, the arylation products of amine derivatives can be obtained in high yields. This invention does not require acids or high temperatures, avoids the residue of transition metals, and employs novel, inexpensive organic photocatalysts to catalyze the synthesis of various tertiary benzylamines under mild reaction conditions.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis, specifically relating to a photocatalytic method for preparing tertiary benzylamine. Background Technology

[0002] Tertiary benzylamine structures are commonly found in drug molecules, such as Imatinib and Alogliptin, which are among the top 200 best-selling small molecule drugs (see: Vitaku, E.; Smith, DT; Njardarson, JTJ Med. Chem. 2014, 57, 10257.). Currently, the most direct and economical synthetic method is the radical arylation of inexpensive and readily available tertiary amines. In 2011, the MacMillan group used Ir(ppy)3 as a photocatalyst to achieve the arylation of tertiary amines through oxidative quenching (see: McNally, Andrew; Prier, Christopher K.; MacMillan, David WC). Science 2011, 334 (1114-1117). Subsequent studies also used Ir(ppy)3 as a photocatalyst to synthesize tertiary benzylamines. Despite the aforementioned research progress, the methods have certain limitations. The reaction requires the addition of a noble metal photocatalyst, which can easily lead to metal residues and is not conducive to large-scale production. Therefore, developing a method for achieving α-position functionalization of amines using a wide range of substrates under conditions free of transition metals and high temperatures is of great research value. Summary of the Invention

[0003] The purpose of this invention is to provide a photocatalytic method for preparing tertiary benzylamine, specifically achieved through the following technical solution:

[0004] A photocatalytic method for preparing tertiary benzylamine, using amine As raw material, triarylpyran salt It acts as a photocatalyst, enabling the α-arylation and heteroarylation of amines under visible light irradiation.

[0005] Furthermore, raw materials The R1, R2, and R3 groups are various substituted aryl, heteroaryl, or alkyl groups.

[0006] Furthermore, the triarylpyran salt is a diarylamine pyran salt (DPA-TPT). .

[0007] Furthermore, the amount of photocatalyst added is 2%-5% of the molar amount of the raw material.

[0008] Furthermore, the reaction was carried out in an inert gas atmosphere using N,N-dimethylformamide as a solvent.

[0009] Furthermore, the visible light is blue light.

[0010] The synthetic route of this invention is as follows:

[0011]

[0012] Typical reactions are as follows:

[0013]

[0014] The beneficial effects of this invention are:

[0015] The present invention uses mild conditions and avoids the residue of transition metals. It employs a low-cost organic photocatalyst, a diarylamine-substituted pyran salt, and undergoes reduction quenching to achieve the α-position CH bond aryl and heteroarylization of tertiary amines, thereby preparing various tertiary benzylamines. Detailed Implementation

[0016] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below in conjunction with embodiments. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0017] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to limit the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0018] The photocatalyst diarylamine pyran salt used in this invention is synthesized by the following method:

[0019]

[0020] Based on the literature a) Qianqian Qiu, Pengfei Xu, Yanjun Zhu, Junru Yu, MengruWei, Wenbin Xi, Dr. Hui Feng, Prof. Jianrong Chen, Prof. Zhaosheng Qian. Chem. Eur. J. 2019, 25, 15983-15987. b) A. Franconetti, L. Contreras-Bernal, S. Jatunov, M. Gómez-Guillén, M. Angulo, R. Prado-Gotor, F. Phys. Chem. Chem. Phys. 2014, 16, 18442-18453. and through repeated experiments, the synthesis was carried out, and the specific steps are as follows:

[0021] Step 1: In a dry 100 mL round-bottom flask, triphenylamine (1.0 equivalent, 10 mmol) and zinc chloride (2.0 equivalent, 20 mmol) were dissolved in dichloromethane (20 mL). Then, a dichloromethane solution of acetyl chloride (1.0 equivalent, 10 mmol) (2 mL) was slowly added dropwise. The mixture was stirred vigorously at room temperature for at least 5 minutes, and then refluxed for 20 hours. After the reaction solution cooled to room temperature, it was added to an aqueous HCl solution (2 M, 100 mL), and the organic phase was extracted with dichloroethane. The collected organic phase was dried over anhydrous sodium sulfate. The desiccant was removed by filtration, and the resulting organic supernatant was concentrated using a rotary evaporator to remove the organic solvent. Finally, the solution was purified by column chromatography, eluting with a petroleum ether (60-90 °C)-ethyl acetate solution (V petroleum ether:V ethyl acetate = 20:1). The collected pure solution was concentrated using a rotary evaporator to remove the organic solvent, yielding the crude product 1-(4-(N,N-diphenylamino)phenyl)ethyl ketone.

[0022] Step 2: The 1-(4-(N,N-diphenylamino)phenyl)ethyl ketone (1.0 equivalent, 5 mmol) and trans-chalcone (2.0 equivalent, 10 mmol) synthesized in the previous step were added to a 100 mL dry round-bottom flask, followed by 20 mL of DCE (1,2-dichloroethane). The reaction was carried out at 80 °C, and a tetrafluoroborate-diethyl ether complex (2.0 equivalent, 10 mmol) was slowly added dropwise. The reaction solution changed from yellow to blue-purple. The mixture was then heated and refluxed for 1.5 hours. After the reaction was completed, the mixture was cooled to room temperature, washed with ice-cold diethyl ether, filtered, and dried to obtain a crude product, a dark purple solid. The crude product was purified by column chromatography using a gradient elution of dichloromethane to dichloromethane-acetone solution (V petroleum ether:V acetone = 20:1) to obtain the desired purple solid product.

[0023] 2-(4-(diphenylamino)phenyl)-4,6-diphenylpyrylium tetrafluoroborate(DPA-TPT) 1 H NMR (400 MHz, DMSO- d 6) δ 8.85 (s, 2H), 8.48 (t, J = 7.4 Hz, 4H), 8.44 (d, J = 9.1 Hz, 2H), 7.81 (d, J = 7.9 Hz, 2H), 7.77 – 7.69 (m, 5H), 7.52 (t, J = 7.8 Hz, 4H), 7.37 – 7.31 (m, 6H), 6.95 (d, J = 9.1 Hz, 2H). 13 C NMR (101 MHz, DMSO- d 6) δ 170.2, 167.7, 162.8, 154.2, 145.0, 135.5, 133.3, 131.7, 130.8,130.5, 130.4, 130.2, 129.9, 129.8, 129.6, 129.3, 128.6, 127.5, 127.2, 118.1.HRMS (ESI), m / z: [M + ] calculated for C 35 H 26 NO + 476.2009; found 476.2019.

[0024] The tertiary amine used in this invention is synthesized by the following method:

[0025]

[0026] According to the references a) R. Wang, J. Wang, Y. Zhang, B. Wang, Y. Xia, F. Xue, W. Jin and C. Liu, Adv. Synth. Catal., 2023, 365, 900. b) Saeko Nishimoto, Hiromichi Nakahashi, Masahiro Toyota, Tetrahedron Letters 61 (2020) 152599. c) Z. Li and C.-J. Li, J. Am. Chem. Soc., 2005, 127, 6968. The specific steps are as follows:

[0027] (1) Synthesis steps of secondary amine: First, prepare a dry round-bottom flask equipped with a magnetic stirrer. Add the reactants, aniline derivative (1.0 equivalent), haloformamide (1.2 equivalent), and sodium bicarbonate (1.5 equivalent), to the round-bottom flask. Finally, add DMSO solvent (1 mL / mmol) and allow it to react at room temperature for about 12 hours. Monitor the reaction with TLC. After the reaction is complete, extract the liquid with water and ethyl acetate to extract the organic matter. Finally, dry the organic phase with anhydrous MgSO4 and filter. Concentrate the solution under reduced pressure, and perform column chromatography on the residue to finally collect our product.

[0028] (2) Synthesis steps of tertiary amine: First, prepare a dry round-bottom flask equipped with a magnetic stirrer. Add the reactants, aniline derivative (1.25 equivalents), dibromobutane (1.0 equivalent), and potassium carbonate (2.0 equivalent), to the round-bottom flask. Finally, add acetonitrile (1 mL / mmol) and reflux at 90 °C for 12 hours. Monitor the reaction with TLC. After the reaction is complete, extract the organic matter by adding water and ethyl acetate. Finally, dry the organic phase with anhydrous MgSO4 and filter. Concentrate the solution under reduced pressure. The residue is then purified by silica gel column chromatography to obtain the desired product.

[0029] Example 1

[0030] Weigh out 1,4-dicyanobenzene (25.6 mg, 0.2 mmol), sodium carbonate (4.2 mg, 0.04 mmol), (48.6 mg, 0.3 mmol) and the photocatalyst diarylamine pyran salt (5.6 mg, 0.01 mmol) were carefully added to the reaction tube. The tube was then evacuated three times using a double-row tube, and 2 mL of N,N-dimethylformamide was added under a nitrogen atmosphere. The reaction was then placed under two 456 nm, 45 W blue light lamps and reacted at room temperature for 12 h. The product was obtained by dry loading and column chromatography (300-400 mesh silica gel). 37.1 mg (petroleum ether: ethyl acetate = 20:1), yield 71%. 1 H NMR (400 MHz, Chloroform-d)δ7.58 (d, J = 7.1 Hz, 2H), 7.34 (d, J = 7.9 Hz, 2H), 6.96 (d, J= 7.9 Hz, 2H), 6.35 (d, J = 8.1 Hz, 2H), 4.69 (d, J = 8.7 Hz, 1H), 3.72 (t, J= 5.4 Hz, 1H), 3.39 (q, J = 8.2 Hz, 1H), 2.42 (q, J = 8.9 Hz, 1H), 2.21 (s,3H), 1.99 (dq, J = 9.8, 6.4, 5.3 Hz, 2H), 1.93 – 1.85 (m, 1H).

[0031] Weigh out 1,4-dicyanobenzene (25.6 mg, 0.2 mmol), sodium carbonate (4.2 mg, 0.04 mmol), (73.5 mg, 0.3 mmol) and the photocatalyst diarylamine pyran salt (5.6 mg, 0.01 mmol) were carefully added to the reaction tube. The tube was then evacuated three times using a double-row tube, and 2 mL of N,N-dimethylformamide was added under a nitrogen atmosphere. The reaction was then placed under two 456 nm, 45 W blue light lamps and reacted at room temperature for 12 h. The product was obtained by dry loading and column chromatography (300-400 mesh silica gel). 42.1 mg (petroleum ether: ethyl acetate = 20:1), yield 61%. 1H NMR (400MHz, Chloroform-d) δ 7.60 (d, J = 8.0 Hz, 2H), 7.33 (d, J = 8.0 Hz, 2H), 6.83 (d, J = 8.9 Hz, 1H), 6.69 (d, J = 2.7 Hz, 1H), 6.45 (dd, J = 9.0, 3.0 Hz, 1H), 4.67 (dd, J = 8.4, 2.2 Hz, 1H), 3.78 (s, 3H), 3.76 – 3.70 (m, 1H), 3.39 (q, J = 8.2 Hz, 1H), 2.52 – 2.40 (m, 1H), 2.03 (dt, J = 11.1, 6.8 Hz, 2H), 1.94 – 1.87 (m, 1H). 13 C NMR (101 MHz, Chloroform-d) δ 150.1, 148.7, 140.8,132.5, 126.7, 127.8 – 119.6 (m), 118.8, 116.2, 114.3, 110.8, 110.6 (q, J =5.5 Hz), 63.2, 56.8, 49.8, 36.0, 23.3. HRMS (ESI) cacld for C 19 H 17 F3N2NaO (M+):369.1185, found 369.1185.

[0032] Example 2

[0033] Weigh out 1,4-dicyanobenzene (25.6 mg, 0.2 mmol), sodium carbonate (4.2 mg, 0.04 mmol), (56.7 mg, 0.3 mmol) and the photocatalyst diarylamine pyran salt (5.6 mg, 0.01 mmol) were added to a reaction tube. The tube was evacuated three times using a double-row tube. 2 mL of N,N-dimethylformamide was added under a nitrogen atmosphere, and the reaction was then placed under two 456 nm, 45 W blue light lamps and reacted at room temperature for 12 h. The product was obtained by dry loading and column chromatography (300-400 mesh silica gel). 45.3 mg (petroleum ether: ethyl acetate = 20:1), yield 75%. 1H NMR (400 MHz, Chloroform-d) δ 7.59 (d, J = 8.0 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H), 6.97 (d,J = 8.3 Hz, 2H), 6.48 (d, J = 8.4 Hz, 2H), 4.61 (dd, J = 11.8, 5.9 Hz, 1H),3.84 (d, J = 13.1 Hz, 1H), 3.47 (dd, J = 14.5, 11.2 Hz, 1H), 2.21 (s, 3H),2.01 – 1.88 (m, 2H), 1.79 – 1.66 (m, 2H), 1.58 – 1.40 (m, 2H), 1.39 – 1.22 (m, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 150.4, 146.3, 132.6, 129.8, 126.7,125.1, 119.0, 63.0, 45.4, 38.2, 29.6, 28.4, 26.6. HRMS (ESI) cacld for C 20 H 23 N2(M+): 291.1856, found 291.1856.

[0034] Weigh out 1,4-dicyanobenzene (25.6 mg, 0.2 mmol), sodium carbonate (4.2 mg, 0.04 mmol), (48.9 mg, 0.3 mmol) and photocatalyst diarylamine pyran salt (5.6 mg, 0.01 mmol) were added to a reaction tube. The tube was evacuated three times using a double-row tube. 2 mL of N,N-dimethylformamide was added under a nitrogen atmosphere, and the reaction was then placed under two 456 nm, 45 W UV lamps at room temperature for 12 h. The product was obtained by dry loading and column chromatography (300-400 mesh silica gel). 37.4 mg (petroleum ether: ethyl acetate = 20:1), yield 71%. 1H NMR (400 MHz, Chloroform-d) δ 7.49 (d, J = 6.2 Hz, 2H), 7.42 (d, J = 7.7 Hz, 2H), 7.15 (d,J = 7.3 Hz, 2H), 6.91 – 6.88 (m, 2H), 6.87 (s, 1H), 4.45 – 4.38 (m, 1H), 3.99 – 3.92 (m, 3H), 3.62 (t, J = 9.9 Hz, 1H), 3.41 (d, J = 13.2 Hz, 1H), 3.16 –3.07 (m, 1H).

[0035] Example 3

[0036] Weigh out 1,4-dicyanobenzene (25.6 mg, 0.2 mmol), sodium carbonate (4.2 mg, 0.04 mmol), (43.8 mg, 0.3 mmol) and photocatalyst diarylamine pyran salt (5.6 mg, 0.01 mmol) were added to a reaction tube. The tube was evacuated three times using a double-row tube. 2 mL of N,N-dimethylformamide was added under a nitrogen atmosphere, and the reaction was then placed under two 456 nm, 45 W UV lamps at room temperature for 36 h. The product was obtained by dry loading and column chromatography (300-400 mesh silica gel). 23.1 mg (petroleum ether: ethyl acetate = 20:1), yield 47%. 1 H NMR (400 MHz, Chloroform-d) δ 7.6 (d, J = 8.2 Hz, 2H), 7.5 (d, J = 8.8 Hz, 2H), 7.3 (d, J =8.2 Hz, 2H), 6.7 (d, J = 9.0 Hz, 2H), 4.7 (s, 2H), 3.2 (s, 3H). 13 C NMR (101MHz, Chloroform-d) δ 151.7, 143.2, 133.8, 132.9, 127.1, 120.4, 118.8, 111.9,111.5, 98.8, 56.0, 39.2. HRMS (ESI) cacld for C 16 H 14 N3 + (M+H) + : 248.1182, found248.1173.

[0037] Example 4

[0038] Weigh out 1,4-dicyanobenzene (25.6 mg, 0.2 mmol), sodium carbonate (4.2 mg, 0.04 mmol), and the photocatalyst diarylamine pyran salt (5.6 mg, 0.01 mmol), add them to the reaction tube, evacuate the tube three times using a double-row tube, add 2 mL of N,N-dimethylformamide under a nitrogen atmosphere, and finally add... (44.1 mg, 0.3 mmol), then irradiated under two 456 nm, 45 W blue light lamps, and reacted at room temperature for 12 h. The product was obtained by dry loading and column chromatography (300-400 mesh silica gel). 35.2 mg (petroleum ether: ethyl acetate = 20:1), yield 71%. 1 H NMR (400MHz, Chloroform-d) δ 7.6 (d, J = 8.1 Hz, 2H), 7.3 (d, J = 8.0 Hz, 2H), 7.2(t, J = 7.7 Hz, 1H), 7.0 (d, J = 7.2 Hz, 1H), 6.7 – 6.6 (m, 2H), 4.5 (t, J =4.6 Hz, 1H), 2.9 (s, 3H), 2.6 (dt, J = 15.7, 4.4 Hz, 1H), 2.5 – 2.4 (m, 1H), 2.2 (dq, J = 11.9, 5.9, 5.4 Hz, 1H), 2.0 (dt, J = 13.1, 4.5 Hz, 1H). 13 C NMR(101 MHz, Chloroform-d) δ 149.9, 145.4, 132.3, 128.5, 127.5, 127.2, 122.2,118.8, 116.1, 110.7, 110.1, 63.0, 37.8, 29.6, 23.8.

[0039] Weigh out 1,4-dicyanobenzene (25.6 mg, 0.2 mmol), sodium carbonate (4.2 mg, 0.04 mmol), and the photocatalyst diarylamine pyran salt (5.6 mg, 0.01 mmol), add them to a reaction tube, evacuate the tube three times using a double-row tube, add 2 mL of N,N-dimethylformamide under a nitrogen atmosphere, and then add... (47.3 mg, 0.3 mmol), then irradiated under two 456 nm, 45 W UV lamps, and reacted at room temperature for 12 h. The product was obtained by dry loading and column chromatography (300-400 mesh silica gel). 51.4 mg (petroleum ether: ethyl acetate = 20:1), yield 83%. 1 H NMR (400MHz, Chloroform-d) δ 7.5 (d, J = 8.4 Hz, 2H), 7.4 (d, J = 8.2 Hz, 2H), 7.2(s, 2H), 7.2 (d, J = 1.7 Hz, 2H), 7.2 (d, J = 2.7 Hz, 1H), 7.2 (q, J = 4.5, 4.0 Hz, 1H), 6.8 – 6.8 (m, 1H), 6.8 (d, J = 7.4 Hz, 2H), 5.8 (s, 1H), 3.7 (dt, J = 10.8, 5.2 Hz, 1H), 3.5 – 3.4 (m, 1H), 3.0 (dt, J = 15.6, 4.9 Hz, 1H), 2.9 – 2.8 (m, 1H).

[0040] Example 5

[0041] Weigh out 1,4-dicyanobenzene (25.6 mg, 0.2 mmol), sodium carbonate (4.2 mg, 0.04 mmol), and the photocatalyst diarylamine pyran salt (5.6 mg, 0.01 mmol), add them to the reaction tube, evacuate the tube three times using a double-row tube, add 2 mL of N,N-dimethylformamide under a nitrogen atmosphere, and finally add... (38.1 mg, 0.3 mmol), then irradiated under two 456 nm, 45 W blue light lamps, and reacted at room temperature for 12 h. The product was obtained by dry loading and column chromatography (300-400 mesh silica gel). 23 mg (petroleum ether: ethyl acetate = 10:1), yield 50%. 1 H NMR (400 MHz, Chloroform-d) δ 7.6 (d, J = 8.1 Hz, 2H), 7.4 (d, J = 8.0 Hz, 2H), 3.6 (s,2H), 2.4 (td, J = 9.3, 8.3, 3.0 Hz, 1H), 2.2 (s, 3H), 1.9 – 1.8 (m, 4H), 1.6 (d, J = 12.5 Hz, 1H), 1.3 (h, J = 12.4 Hz, 5H). 13C NMR (101 MHz, Chloroform-d)δ 146.6, 132.0, 129.1, 119.1, 110.3, 62.8, 57.5, 37.8, 28.7, 26.3, 25.9.

[0042] Example 6

[0043] Weigh out 1,4-dicyanobenzene (25.6 mg, 0.2 mmol), sodium carbonate (4.2 mg, 0.04 mmol), and the photocatalyst diarylamine pyran salt (5.6 mg, 0.01 mmol), add them to the reaction tube, evacuate the tube three times using a double-row tube, add 2 mL of N,N-dimethylformamide under a nitrogen atmosphere, and finally add... (63.3 mg, 0.3 mmol), then irradiated under two 456 nm, 45 W blue light lamps, and reacted at room temperature for 24 h. The product was obtained by dry loading and column chromatography (300-400 mesh silica gel). 39.1 mg (petroleum ether: ethyl acetate = 20:1), yield 61%. 1 H NMR (400 MHz, Chloroform-d) δ 7.6 (d, J = 8.4 Hz, 2H), 7.4 (d, J = 8.1 Hz, 2H), 7.3 – 7.3 (m, 2H), 7.2 – 7.2 (m, 3H), 7.2 (dd, J = 8.8, 7.3 Hz, 2H), 6.8 –6.7 (m, 3H), 5.2 (q, J = 7.0 Hz, 1H), 4.6 – 4.4 (m, 2H), 1.6 (d, J = 7.0 Hz, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 148.8, 148.6, 139.4, 132.4, 129.1,128.4, 127.6, 126.7, 126.3, 118.8, 117.9, 114.5, 110.7, 57.2, 50.6, 18.7.HRMS (ESI) cacld for C 22 H 21 N2 + (M+H) + : 313.1699, found 313.1697.

[0044] Example 7

[0045] Weigh out 1,4-dicyanobenzene (25.6 mg, 0.2 mmol), sodium carbonate (4.2 mg, 0.04 mmol), (54.9 mg, 0.3 mmol) and photocatalyst diarylamine pyran salt (5.6 mg, 0.01 mmol) were added to a reaction tube. The tube was evacuated three times using a double-row tube. 2 mL of N,N-dimethylformamide was added under a nitrogen atmosphere, and the reaction was then placed under two 456 nm, 45 W blue light lamps at room temperature for 36 h. The product was obtained by dry loading and column chromatography (300-400 mesh silica gel). 34.1 mg (petroleum ether: ethyl acetate = 5:1), yield 60%. 1 H NMR (400 MHz, Chloroform-d) δ 7.6 (d, J = 8.3 Hz, 2H), 7.5 (d, J = 8.2 Hz, 2H), 7.3 (ddd, J= 9.2, 4.5, 2.8 Hz, 2H), 7.3 (dd, J = 8.0, 1.6 Hz, 2H), 7.3 (d, J = 1.6 Hz,1H), 7.2 – 7.1 (m, 2H), 6.8 – 6.7 (m, 1H), 6.5 (d, J = 7.7 Hz, 2H), 5.5 (s,1H), 4.2 (s, 1H).

[0046] Example 8

[0047] Weigh out 20.8 mg (0.2 mmol) of 4-cyanopyridine and 4.2 mg (0.04 mmol) of sodium carbonate. (32.4 mg, 0.3 mmol) and photocatalyst diarylamine pyran salt (5.6 mg, 0.01 mmol) were added to a reaction tube. The tube was evacuated three times using a double-row tube. 2 mL of N,N-dimethylformamide was added under a nitrogen atmosphere, and the reaction was then placed under two 456 nm, 90 W blue light lamps at room temperature for 24 h. The product was obtained by dry loading and column chromatography (300-400 mesh silica gel). 33.2 mg (petroleum ether: ethyl acetate = 5:1), yield 61%. 1H NMR(400 MHz, Chloroform-d) δ 8.6 (d, J = 4.5 Hz, 2H), 7.4 (d, J = 4.8 Hz, 2H), 6.9 (d, J = 7.9 Hz, 2H), 6.5 (d, J = 8.0 Hz, 2H), 5.3 (s, 1H), 3.1 (s, 3H), 3.0 (s, 3H), 2.2 (s, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 169.7, 150.2,147.4, 143.4, 129.8, 127.5, 122.7, 113.7, 57.4, 37.1, 36.3, 20.3. HRMS (ESI)cacld for C 16 H 20 N3O + (M+H) + : 270.1601, found 270.1591.

[0048] Example 9

[0049] Weigh Add 26.8 mg (0.2 mmol), sodium carbonate (4.2 mg, 0.04 mmol), and the photocatalyst diarylamine pyran salt (5.6 mg, 0.01 mmol) to the reaction tube. Perform three evacuations using a double-row tube. Add 2 mL of N,N-dimethylformamide under a nitrogen atmosphere. Finally, add... (48.6 mg, 0.3 mmol), then irradiated under two 456 nm, 45 W blue light lamps, and reacted at room temperature for 12 h. The product was obtained by dry loading and column chromatography (300-400 mesh silica gel). 30.1 mg (petroleum ether: ethyl acetate = 5:1), yield 56%. 1H NMR (400 MHz, Chloroform-d) δ 8.2 (s, 1H), 8.0 (d, J = 4.1 Hz, 1H), 7.1 (d, J = 4.8 Hz, 1H), 7.1 (td,J = 7.3, 2.0 Hz, 2H), 6.9 – 6.8 (m, 2H), 6.8 (t, J = 7.3 Hz, 1H), 4.7 (dd, J= 8.3, 4.0 Hz, 1H), 4.0 (s, 3H), 3.5 (dt, J = 11.9, 4.6 Hz, 1H), 3.1 – 3.0(m, 1H), 2.0 – 1.9 (m, 1H), 1.9 (dt, J = 14.1, 4.1 Hz, 1H), 1.8 (td, J = 8.8,8.3, 4.6 Hz, 1H), 1.8 – 1.7 (m, 1H), 1.7 – 1.6 (m, 1H), 1.6 – 1.5 (m, 1H). 13 CNMR (101 MHz, Chloroform-d) δ 152.6, 151.8, 142.7, 141.5, 132.7, 128.8,122.4, 121.0, 120.1, 56.0, 54.4, 54.1, 32.8, 26.0, 22.7. HRMS (ESI) cacld forC 17 H 21 N2O + (M+H) + : 269.1649, found 269.1641.

[0050] Example 10

[0051] Pick Add 42.4 mg (0.2 mmol), sodium carbonate (4.2 mg, 0.04 mmol), and the photocatalyst diarylamine pyran salt (5.6 mg, 0.01 mmol) to the reaction tube. Perform three evacuations using a double-row tube. Add 2 mL of N,N-dimethylformamide under a nitrogen atmosphere. Finally, add... (48.6 mg, 0.3 mmol), then irradiated under two 456 nm, 45 W blue light lamps, and reacted at room temperature for 24 h. The product was obtained by dry loading and column chromatography (300-400 mesh silica gel). 34.3 mg (petroleum ether: ethyl acetate = 10:1), yield 50%. 1H NMR (400MHz, Chloroform-d) δ 8.5 (d, J = 5.1 Hz, 1H), 7.6 – 7.6 (m, 2H), 7.6 (dd, J =3.3, 1.7 Hz, 1H), 7.2 (d, J = 9.0 Hz, 1H), 7.2 – 7.1 (m, 3H), 6.9 (d, J = 8.5Hz, 2H), 6.8 (t, J = 7.3 Hz, 1H), 4.5 (dd, J = 7.3, 4.2 Hz, 1H), 3.5 – 3.4(m, 1H), 3.2 – 3.2 (m, 1H), 2.3 (d, J = 1.5 Hz, 3H), 2.0 (dq, J = 11.3, 3.7Hz, 1H), 1.9 (ddd, J = 9.9, 7.4, 3.0 Hz, 1H), 1.8 (dt, J = 10.7, 4.4 Hz, 2H), 1.7 – 1.6 (m, 1H), 1.6 (dq, J = 8.9, 4.3 Hz, 1H). 13 C NMR (101 MHz, Chloroform-d) δ 162.9, 160.5, 156.3, 154.1, 151.5, 149.7, 139.2 (d, J = 7.7 Hz), 131.6(d, J = 5.3 Hz), 129.1, 125.5 (d, J = HRMS (ESI) cacld for C 23 H 24 FN2 + (M+H) + : 347.1918, found 347.1927.

[0052] Example 11

[0053] Take sodium carbonate (4.2 mg, 0.04 mmol), (48.6 mg, 0.3 mmol) and photocatalyst diarylamine pyran salt (5.6 mg, 0.01 mmol) were added to the reaction tube. The tube was evacuated three times using a double-row tube. 2 mL of N,N-dimethylformamide was added under a nitrogen atmosphere, and finally, [the following was added]... (42.4 mg, 0.2 mmol), then irradiated under two 456 nm, 45 W blue light lamps, and reacted at room temperature for 36 h. The product was obtained by dry loading and column chromatography (300-400 mesh silica gel). 31.1 mg (petroleum ether: ethyl acetate = 20:1), yield 56%. 1 H NMR (400 MHz, Chloroform-d) δ 7.7 (d, J = 4.7 Hz, 1H), 7.5 (d, J = 3.8 Hz, 1H), 7.3 – 7.3(m, 2H), 7.0 (d, J = 8.2 Hz, 2H), 6.6 (d, J = 8.2 Hz, 2H), 5.0 (d, J = 7.3Hz, 1H), 3.8 (t, J = 7.8 Hz, 1H), 3.4 (q, J = 7.9 Hz, 1H), 2.4 (dq, J = 18.3,8.8 Hz, 2H), 2.4 – 2.3 (m, 1H), 2.2 (s, 3H), 2.2 – 2.1 (m, 1H). 13 C NMR (101MHz, Chloroform-d) δ 168.2, 150.8, 144.7, 141.0, 129.7, 126.0, 124.7, 124.2,120.0, 112.3, 110.7, 57.2, 48.8, 32.3, 24.1, 20.2. HRMS (ESI) cacld forC 18 H 19 N2O + (M+H) + :279.1492, found 279.1499.

[0054] Example 12

[0055] Pick (50.4 mg, 0.2 mmol), sodium carbonate (4.2 mg, 0.04 mmol), (48.6 mg, 0.3 mmol) and photocatalyst diarylamine pyran salt (5.6 mg, 0.01 mmol) were added to a reaction tube. The tube was evacuated three times using a double-row tube. 2 mL of N,N-dimethylformamide was added under a nitrogen atmosphere, and the reaction was then placed under two 456 nm, 45 W blue light lamps at room temperature for 36 h. The product was obtained by dry loading and column chromatography (300-400 mesh silica gel). 35.6 mg (petroleum ether: ethyl acetate = 20:1), yield 47%. 1 H NMR (400 MHz, Chloroform-d) δ 8.0 (d, J = 7.9 Hz, 1H), 7.7 (d, J = 7.4 Hz, 1H), 7.3 (d, J =8.2 Hz, 1H), 7.3 (d, J = 6.7 Hz, 1H), 6.9 (d, J = 8.0 Hz, 2H), 6.4 (d, J =8.1 Hz, 2H), 5.5 (d, J = 8.5 Hz, 1H), 3.8 (t, J = 8.1 Hz, 1H), 3.4 (q, J =8.5 Hz, 1H), 2.5 – 2.4 (m, 1H), 2.2 (s, 3H), 2.1 – 2.1 (m, 1H), 2.0 (dd, J =7.9, 4.0 Hz, 1H), 1.7 (s, 9H). 13 C NMR (101 MHz, Chloroform-d) δ 157.6, 149.0,144.9, 142.3, 133.5, 129.5, 125.1, 124.3, 124.0, 120.4, 114.8, 112.2, 85.7,58.8, 48.8, 33.2, 28.2, 23.2, 20.2. HRMS (ESI) cacld for C 23 H 28 N3O2 + (M+H) + :378.2176, found 378.2171.

[0056] Example 13

[0057] Weigh out 1,4-dicyanobenzene (25.6 mg, 0.2 mmol), sodium carbonate (4.2 mg, 0.04 mmol), (79.2 mg, 0.3 mmol) and photocatalyst diarylamine pyran salt (5.6 mg, 0.01 mmol) were added to a reaction tube. The tube was evacuated three times using a double-row tube. 2 mL of N,N-dimethylformamide was added under a nitrogen atmosphere, and the reaction was then placed under two 456 nm, 45 W blue light lamps at room temperature for 24 h. The product was obtained by dry loading and column chromatography (300-400 mesh silica gel). 38.2 mg (petroleum ether: ethyl acetate = 5:1), yield 52%. 1 H NMR (400 MHz, Chloroform-d) δ 7.8 (d, J = 8.8 Hz,2H), 7.6 (d, J = 8.2 Hz, 2H), 7.4 (d, J = 8.2 Hz, 2H), 6.6 (d, J = 8.8 Hz,2H), 4.4 (t, J = 5.6 Hz, 2H), 4.2 (s, 1H), 3.6 (s, 2H), 3.2 (q, J = 6.9 Hz,2H), 2.8 (t, J = 5.6 Hz, 2H), 2.3 (s, 3H), 1.6 (p, J = 7.2 Hz, 2H), 1.5 (dt,J = 14.9, 7.3 Hz, 2H), 1.0 (t, J = 7.3 Hz, 3H). 13 C NMR (101 MHz, Chloroform-d)δ 166.8, 152.3, 145.1, 132.1, 131.6, 129.3, 119.1, 117.8, 111.3, 110.7, 61.9,61.8, 55.7, 43.0, 42.7, 31.3, 20.2, 13.8. HRMS (ESI) cacld for C 22 H 28 N3O2 + (M+H) + 366.2176, found 366.2168.

[0058] The embodiments described above are merely preferred embodiments of the present invention, and while the descriptions are specific and detailed, they are not intended to limit the present invention. It should be noted that various changes and modifications can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the concept and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A photocatalytic method for preparing tertiary benzylamine, characterized in that, amine Using Ar-LG as the substrate and diarylamine pyran salt as the raw material, Ar-LG as the substrate, and diarylamine pyran salt as the raw material. As a photocatalyst, it enables the α-position arylation or heteroarylation of amines under visible light irradiation to prepare various substituted tertiary benzylamines. The reaction system also requires the addition of 20 mol% sodium carbonate as a raw material, with N,N-dimethylformamide as a solvent, and is carried out in an inert gas atmosphere; Among them, when the raw material amine is The substrate is 1,4-dicyanophenyl, and the product is... When the raw material amine is The substrate is 1,4-dicyanophenyl, and the product is... When the raw material amine is The substrate is 1,4-dicyanophenyl, and the product is... When the raw material amine is The substrate is 1,4-dicyanophenyl, and the product is... When the raw material amine is The substrate is 1,4-dicyanophenyl, and the product is... When the raw material amine is The substrate is 1,4-dicyanophenyl, and the product is... When the raw material amine is The substrate is 1,4-dicyanophenyl, and the product is... When the raw material amine is The substrate is 1,4-dicyanophenyl, and the product is... When the raw material amine is The substrate is 1,4-dicyanophenyl, and the product is... When the raw material amine is The substrate is 1,4-dicyanophenyl, and the product is... When the raw material amine is The substrate is 4-cyanopyridine, and the product is... When the raw material amine is Substrate is The product is When the raw material amine is The substrate is The product is When the raw material amine is The substrate is The product is When the raw material amine is Substrate is The product is When the raw material amine is The substrate is 1,4-dicyanophenyl, and the product is... .

2. The photocatalytic method for preparing tertiary benzylamine according to claim 1, characterized in that, The amount of photocatalyst added is 2%-5% of the raw material molar amount.

3. The photocatalytic method for preparing tertiary benzylamine according to claim 1, characterized in that, The visible light mentioned is blue light.

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