A method of visible light-induced intermolecular dearomatization arylation of polycyclic arenes with cyanoarenes

Abstract

The application discloses a visible light-induced intermolecular de-arylation arylation reaction method of polycyclic aromatic hydrocarbons and cyano aromatic hydrocarbons. The method is based on the fact that visible light-induced aromatic hydrocarbons can form double radical and radical anion intermediates in turn, cyano aromatic hydrocarbons are used as aryl sources, hydrogen atoms and aryl functional groups are introduced through radical-radical coupling, and thus de-arylation functionalization products are obtained. The reaction combines energy transfer and electron transfer processes to synthesize 9,10-dihydroanthracene derivatives, and has the remarkable characteristics of mild conditions, easily available substrates, simple operation and high yield. The 9,10-dihydroanthracene derivatives can be easily oxidized into 4-(anthracene-9-yl)pyridine derivatives in the presence of an oxidant.

Description

Technical Field

[0001] This application belongs to the field of fine organic synthesis technology, specifically relating to a visible light-induced intermolecular dearomatization and arylation reaction method for polycyclic aromatic hydrocarbons and cyanoaromatic hydrocarbons. Background Technology

[0002] Polycyclic aromatic hydrocarbons (PAHs), as one of the most basic and abundant bulk industrial raw materials, have demonstrated immense value in drug development and organic functional materials due to their crucial role in improving the metabolic stability and fluorescence properties of π-conjugated systems. Therefore, the derivatization and transformation of PAHs have attracted widespread attention. Among these, the classic Birch reduction functionalization strategy using alkali metals provides an important pathway for PAH functionalization through dearomatization. However, these representative methods are often limited by harsh reaction conditions (such as stoichiometric amounts of sodium and lithium metals) and electrophilic reagents such as alkyl halides, thus restricting their application. In recent years, significant progress has also been made in constructing stereochemically dense frameworks through intramolecular radical addition to aromatic rings for dearomatization. However, these dearomatization strategies typically require complex synthetic operations, use pre-functionalized radical precursors, and have low procedural economy. Furthermore, these radical precursors are mostly limited to organohalides. Therefore, developing a novel and mild dearomatization functionalization method for PAHs is of great significance.

[0003] With the development of photochemical synthesis, visible light-induced dearomatization and functionalization of aromatics, especially through triplet energy transfer processes, has become a powerful synthetic tool for providing structurally diverse three-dimensional molecules in a mild, green, and sustainable manner. In particular, photocycloaddition reactions that generate diradical intermediates via energy transfer processes can rapidly yield dearomatized compounds from readily available aromatics, and the formation of these diradical intermediates cleverly avoids direct single-electron reduction of polycyclic aromatic hydrocarbons with low reduction potentials.

[0004] This invention proposes a method based on visible light-induced aromatic hydrocarbons that sequentially form diradical and radical anion intermediates, and introduce hydrogen atoms and aryl functional groups through radical-radical coupling to obtain dearomatized functionalized products. Cyanoaryl hydrocarbons are used as aryl sources to achieve arylation and dearomatization reactions via radical-radical coupling. This reaction combines energy transfer and electron transfer processes to synthesize 9,10-dihydroanthracene derivatives. This photochemical dearomatization method has significant advantages such as mild conditions, readily available substrates, simple operation, and high yield. Furthermore, introducing nitrogen-containing heterocycles (especially pyridine rings) into polycyclic compounds is expected to enhance their antibacterial activity and modulate their fluorescence properties. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of existing technologies and provide a visible light-induced intermolecular dearomatization and arylization reaction method for polycyclic aromatic hydrocarbons and cyanoaromatic hydrocarbons. This method is based on the fact that visible light-induced aromatic hydrocarbons can sequentially form diradical and radical anion intermediates. Using cyanoaromatic hydrocarbons as the aryl source, hydrogen atoms and aryl functional groups are introduced through radical-radical coupling, thereby obtaining the dearomatized functionalized product. This reaction combines energy transfer and electron transfer processes to synthesize 9,10-dihydroanthracene derivatives, exhibiting significant advantages such as mild conditions, readily available substrates, simple operation, and high yield. The 9,10-dihydroanthracene derivatives can be readily oxidized to 4-(anthracene-9-yl)pyridine derivatives in the presence of an oxidant.

[0006] The present invention provides a method for a visible light-induced intermolecular dearomatization-arylation reaction between polycyclic aromatic hydrocarbons and cyanoaromatic hydrocarbons, comprising the following steps: The compound shown in Formula 1, the compound shown in Formula 2, a photocatalyst, a base, water, and an organic solvent were added sequentially to a reactor. The reaction was then stirred under specific temperature and light conditions. After complete reaction, post-treatment yielded the 9,10-dihydroanthracene derivative shown in Formula 3. The reaction formula is as follows: ; R1 is selected from hydrogen, halogen, and C. 1-12 Alkyl, C 6-20 Aryl, C 1-12 Alkoxy; X is selected from CR' or N; R' is selected from hydrogen or C. 1-12 Alkyl; X' is selected from CHR' or NH, R' as defined above; R2 is selected from hydrogen, halogens, and C. 1-12 Alkyl, C 6-20 Aryl, C 1-12 Alkyl groups; selected from halogens, C 1-6 Alkyl, C 1-6 Alkoxy, C 6-20 aryl-substituted C 6-20 Aryl; Furthermore, the photocatalyst is selected from one or a mixture of several of [Ir(dtbpy)(ppy)2]PF6, [Ir(dF(CF3)ppy)2(dtbbpy)]PF6, Ru(bpy)3Cl2, 4CzIPN, and 4DPAIPN; preferably, the photocatalyst is selected from [Ir(dtbpy)(ppy)2]PF6; the base is selected from one or a mixture of several of DIPEA, Et3N, and Cy2NMe, preferably, the base is selected from DIPEA.

[0007] Preferably, R1 is selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, phenyl, and methoxy. X is selected from CR' or N; R' is selected from hydrogen or methyl; R2 is selected from hydrogen, fluorine, chlorine, bromine, methyl, methoxy, phenyl, 2,6-dimethylphenyl, p-fluorophenyl, p-chlorophenyl, p-methylphenyl, p-methoxyphenyl, p-phenylphenyl, m-fluorophenyl, and m-methylphenyl.

[0008] According to the preparation method described above, the compound shown in Formula 2 is replaced with... or Consequently, the preparation and acquisition of... and .

[0009] According to the aforementioned method of the present invention, the organic solvent is selected from any one or a mixture of several of tetrahydrofuran, dichloromethane, acetone, DMSO, and DMF.

[0010] According to the method described above, the certain temperature is room temperature.

[0011] According to the aforementioned method of the present invention, the illumination is provided by an 18W blue LED.

[0012] According to the method described above, the reaction is preferably carried out in an inert atmosphere provided by nitrogen or argon; preferably argon.

[0013] According to the aforementioned method of the present invention, the molar ratio of the compound shown in Formula 1, the compound shown in Formula 2, the photocatalyst, the alkali and water is 1: (1.5~3): (0.005~0.02): (1.5~3): (5~20); preferably 1:2:0.01:2:10.

[0014] According to the aforementioned method of the present invention, the reaction time of the stirring reaction is 12 to 48 hours, preferably 24 hours.

[0015] As another aspect of the present invention, the present invention also provides a method for preparing 4-(anthracite-9-yl)pyridine derivatives, comprising the following steps: Using the 9,10-dihydroanthracene derivative shown in Formula 3 as a starting material, a reaction was carried out in the presence of an oxidant to obtain the 4-(anthracene-9-yl)pyridine derivative shown in Formula 4; the reaction formula is as follows: , where R1, X, X' have the definitions described above.

[0016] According to the aforementioned preparation method of the present invention, the reaction is carried out in the presence of a solvent, wherein the solvent is dichloromethane; the reaction temperature is room temperature to 60°C, preferably room temperature; the reaction time is 1 to 24 hours, preferably 24 hours; and more preferably, the oxidant is selected from DDQ.

[0017] Compared with existing technologies, the present invention has the following advantages: 1) This invention reports for the first time a visible light-induced intermolecular dearomatization-arylation reaction method for polycyclic aromatic hydrocarbons (PAHs) and cyanoaromatic hydrocarbons. This method is based on the fact that PAHs can sequentially form diradical and radical anion intermediates under visible light. Using cyanoaromatic hydrocarbons as the aryl source, hydrogen atoms and aryl functional groups are introduced through radical-radical coupling, thereby obtaining the dearomatized functionalized product. This reaction combines energy transfer and electron transfer processes to synthesize 9,10-dihydroanthracene derivatives, exhibiting significant advantages such as mild conditions, readily available substrates, simple operation, and high yield.

[0018] 2) The 9,10-dihydroanthracene derivative prepared by the method of the present invention can be readily oxidized to 4-(anthracene-9-yl)pyridine derivatives in the presence of an oxidizing agent, such as the commonly used synthetic intermediate 4-(anthracene-9-yl)pyridine (CAS:20308-98-9). Detailed Implementation

[0019] The present invention will be further described in detail below with reference to specific embodiments. Unless otherwise specified, the methods used are conventional methods in the art, and the reagents or raw materials used are commercially available from sources in the art and / or prepared by typical synthetic methods in the art.

[0020] Examples 1-19: Optimization Experiments of Reaction Conditions Using anthracene (formula 1a) and 4-cyanopyridine (formula 2a) as starting materials, the effects of different synthetic conditions on the yield of the target product (formula 3aa) were investigated. The results are shown in Table 1. The reaction formula is as follows: ; Table 1: ; a Standard reaction conditions: 1a (0.2 mmol), 2a (0.4 mmol, 2.0 equiv), Ir(dtbpy)(ppy)2PF6 (0.002 mmol, 1 mol %), DIPEA (0.4 mmol, 2.0 equiv), H2O (10 equiv), THF (1 mL), room temperature, 18 W Blue LEDs, argon, for 24 h. b Separation yield.

[0021] Taking Example 1 as an example, the typical experimental procedure is as follows: 1a (0.2 mmol), 2a (0.4 mmol, 2.0 equivalent), [Ir(dtbbpy)(ppy)2]PF6 (1.8 mg, 1 mol%), DIPEA (77.4 mg, 3 equivalent), H2O (36 mg, 10 equivalent), and THF (2 mL, 0.2 M) were added to a Shrek tube. The reaction tube was then purged three times with argon and the reaction was stirred under 18 W blue LED light (approximately 2.0 cm away) at room temperature while being cooled with a fan for 24 hours, until complete consumption of the starting materials was detected by TLC and / or GC-MS analysis. After the reaction, the combined organic phase extracts were dried over Na2SO4 and concentrated under vacuum. The residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 7:1) to give 3aa with a separation yield of 95%. (Yellow solid) 1 H NMR (400 MHz, Chloroform- d ) d (ppm) 8.43 (d, J = 5.6 Hz, 2H), 7.38 – 7.32(m, 4H), 7.30 – 7.26 (m, 4H), 6.98 (d, J = 6.0 Hz, 2H), 5.25 (s, 1H), 3.93 (s, 2H); 13 C NMR (100 MHz, Chloroform- d ) d (ppm) 152.13, 149.78, 137.68, 136.46, 128.36, 128.01, 126.97, 126.60, 123.01, 50.82, 35.44.

[0022] Based on obtaining the optimal reaction conditions (Example 1), the universality of different cyanoaromatic substrates was further explored, and the results are as follows: ; ; ; ; .

[0023] Structural characterization of the product: Compound 3ab: 1 H NMR (400 MHz, Chloroform- d) d (ppm) 8.45 (t, J J = 6.4 Hz, 2H), 7.65 – 7.56 (m, 3H), 7.54 – 7.34 (m, 8H), 7.34 – 7.24 (m, 3H), 7.11 – 6.97 (m, 2H), 5.30 (d, J J = 13.2 Hz, 1H), 3.99 (d, J J = 13.6 Hz, 2H); 13 C NMR (100 MHz, Chloroform- d ) d (ppm) 157.64, 153.07, 149.73, 139.44, 137.78, 136.45, 128.84, 128.64, 128.39, 128.05, 127.01, 126.94, 126.66, 121.61, 120.03, 51.06, 35.56。

[0024] Compound 3ac: 1 H NMR (400 MHz, Chloroform- d ) d (ppm) 8.48 (d, J J = 6.0 Hz, 1H), 7.86 – 7.80 (m, 2H), 7.41 – 7.33 (m, 5H), 7.30 – 7.26 (m, 4H), 7.16 – 7.06 (m, 2H), 6.92 – 6.89 (m, 1H), 5.29 (s, 1H), 4.06 – 3.87 (m, 2H); 13 C NMR(100 MHz, Chloroform- d ) d (ppm) 156.61, 153.22, 149.73, 137.71, 136.44, 128.76, 128.68, 128.38, 128.08, 127.05, 126.69, 121.57, 119.66, 115.65, 115.44, 51.05, 35.56. 19 F NMR (376 MHz, Chloroform- d ) d (ppm) -113.07。

[0025] Compound 3ad: 1 H NMR (400 MHz, Chloroform- d ) d (ppm) 8.48 (d, J J = 5.2 Hz,1H), 7.86 – 7.80 (m, 2H), 7.41 – 7.33 (m, 5H), 7.31 – 7.24 (m, 4H), 7.10 (t, J J = 8.4 Hz, 2H), 6.90 (d, J J = 5.2 Hz, 1H), 5.29 (s, 1H), 4.01 (d, J J = 18.0 Hz,1H), 3.95 (d, J J = 18.4 Hz, 1H); 13 C NMR (100 MHz, Chloroform- d ) d (ppm) 156.61,153.22, 149.73, 137.71, 136.44, 128.76, 128.68, 128.38, 128.08, 127.05,126.69, 121.57, 119.66, 115.44, 51.05, 35.56。

[0026] Compound 3ae: 1 H NMR (400 MHz, Chloroform- d ) d (ppm) 8.54 (d, J J = 5.2 Hz,1H), 7.44 – 7.36 (m, 4H), 7.33 – 7.23 (m, 8H), 7.10 (s, 1H), 6.99 (d, J J = 5.2Hz, 1H), 5.33 (s, 1H), 4.01 (d, J J = 18.4 Hz, 1H), 3.95 (d, J J = 18.4 Hz, 1H),2.25 (s, 3H);[[ID=​​​​(ppm) 157.66, 152.97, 149.65,138.85, 137.83, 136.65, 136.45, 129.37, 128.39, 128.03, 126.98, 126.82,126.65, 121.35, 119.78, 51.06, 35.56, 21.21.

[0027] Compound 3af: 1 H NMR (400 MHz, Chloroform- d ) d (ppm) 8.48 (d, J = 5.2 Hz, 1H), 7.45 (dd, J = 1.2, 1.2 Hz, 1H), 7.42 (s, 1H), 7.40 – 7.31 (m, 6H), 7.31 –7.26 (m, 3H), 6.96 – 6.88 (m, 2H), 5.30 (s, 1H), 3.94 (dd, J = 10.4, 10.4 Hz,2H), 3.86 (s, 3H); 13 C NMR (100 MHz, Chloroform-d) d (ppm) 159.93, 157.41,153.12, 149.61, 140.90, 137.73, 136.43, 129.60, 128.38, 128.05, 127.01,126.67, 121.75, 120.22, 119.33, 114.88, 112.15, 55.31, 51.04, 35.54.

[0028] Compound 3ag: 1 H NMR (400 MHz, Chloroform- d ) d (ppm) 8.52 (d, J = 5.2 Hz, 1H), 7.92 (d, J = 8.8 Hz, 2H), 7.68 – 7.61 (m, 5H), 7.48 – 7.43 (m, 3H), 7.39 – 7.36 (m, 4H), 7.30 – 7.26 (m, 4H), 6.92 (d, J= 4.8 Hz, 1H), 5.31 (s, 1H), 4.03 (d, J = 18.4 Hz, 1H), 3.95 (d, J = 18.4 Hz, 1H); 13 C NMR (100 MHz, Chloroform- d ) d (ppm) 153.13, 149.78, 138.30, 137.79, 136.47, 128.80, 128.41, 128.08, 127.37, 127.34, 127.06, 127.04, 126.70, 121.67, 119.95, 51.08, 35.58。

[0029] Compound 3ah: 1 H NMR (400 MHz, Chloroform- d ) d (ppm) 8.48 (d, J = 6.0 Hz, 1H), 7.86 – 7.80 (m, 2H), 7.41 – 7.33 (m, 5H), 7.31 – 7.24 (m, 4H), 7.10 (t, J = 8.8 Hz, 2H), 6.90 (d, J = 5.2 Hz, 1H), 5.29 (s, 1H), 4.01 (d, J = 18.0 Hz, 1H), 3.95 (d, J = 18.4 Hz, 1H); 13C NMR (100 MHz, Chloroform- d ) d (ppm) 156.61, 153.22, 149.73, 137.71, 136.44, 128.76, 128.68, 128.38, 128.08, 127.05, 126.69, 121.57, 119.66, 115.65, 115.44, 51.05, 35.56. 19F NMR (376 MHz, Chloroform-d) δ (ppm) -112.86。

[0030] Compound 3ai: 1 H NMR (400 MHz, Chloroform- d ) d (ppm) 8.54 (d, J J = 5.2 Hz, 1H), 7.46 – 7.35 (m, 5H), 7.32 – 7.22 (m, 7H), 7.11 (s, 1H), 6.99 (d, J J = 5.6 Hz, 1H), 5.33 (s, 1H), 4.01 (d, J J = 18.4 Hz, 1H), 3.95 (d, J J = 18.4 Hz, 1H), 2.25 (s, 3H); 13 C NMR (100 MHz, Chloroform- d ) d (ppm) 159.73, 152.23, 149.24, 140.34, 137.74, 136.46, 135.59, 130.66, 129.61, 128.35, 128.13, 128.00, 126.96, 126.62, 125.80, 123.34, 121.04, 50.95, 35.48, 20.20。

[0031] Compound 3ai: 1 H NMR (400 MHz, Chloroform- d ) d (ppm) 8.55 (d, J J = 5.2 Hz, 1H), 7.40 – 7.33 (m, 4H), 7.29 – 7.25 (m, 4H), 7.19 – 7.14 (m, 1H), 7.07 (d, J J = 8.0 Hz, 2H), 6.99 (d, J J = 5.2 Hz, 1H), 6.91 (s, 1H), 5.30 (s, 1H), 3.93 (s, 2H), 1.96 (s, 6H); 13 C NMR (100 MHz, Chloroform- d ) d(ppm) 159.67, 152.41, 149.57, 140.39, 137.84, 136.50, 135.77, 128.30, 127.99, 127.71, 127.46, 126.95, 126.60, 123.77, 121.22, 50.87, 35.49, 20.18。

[0032] Compound 3ak: 1 H NMR (400 MHz, Chloroform- d ) d (ppm) 8.01 (d, J J = 5.2 Hz, 1H), 7.37 – 7.33 (m, 4H), 7.30 – 7.27 (m, 4H), 6.89 (d, J J = 5.6 Hz, 1H), 6.54 (s, 1H), 5.26 (s, 1H), 3.92 (s, 2H).) 13 C NMR (100 MHz, Chloroform- d ) d (ppm) 147.49, 147.32, 137.08, 136.42, 128.37, 128.15, 127.22, 126.74, 120.79, 108.62, 108.24, 76.67, 50.76, 35.36. 19 F NMR (376 MHz, Chloroform- d ) d (ppm) -68.07。

[0033] Compound 3al: 1 H NMR (400 MHz, Chloroform- d ) d (ppm) 8.18 (d, J J = 5.2 Hz, 1H), 7.37 – 7.32 (m, 4H), 7.30 – 7.26 (m, 4H), 6.98 (s, 1H), 6.89 (d, J J = 5.2 Hz, 1H), 5.22 (s, 1H), 3.93 (s, 2H); 13 C NMR (100 MHz, Chloroform- d ) d(ppm) 151.79, 149.58, 136.96, 136.43, 128.41, 128.23, 127.30, 126.82, 123.36, 121.87, 50.67, 35.39。

[0034] Compound 3am: 1 H NMR (400 MHz, Chloroform- d ) d (ppm) 8.42 (s, 1H), 8.19 (d, J = 4.8 Hz, 1H), 7.40 – 7.32 (m, 4H), 7.30 – 7.26 (m, 1H), 7.26 – 7.21 (m, 3H), 6.72 (dd, J = 4.8, 6.4 Hz, 1H), 5.68 (s, 1H), 4.23 (d, J = 18.8 Hz, 1H), 4.04 (d, J = 19.2 Hz, 1H); 13 C NMR (100 MHz, Chloroform- d ) d (ppm) 145.71, 145.66, 140.07, 139.95, 138.36, 138.11, 136.38, 136.02, 128.50, 128.47, 128.10, 127.19, 126.84, 123.66, 43.91, 43.89, 35.23; 19 F NMR (376 MHz, Chloroform- d ) d (ppm) -130.60。

[0035] Compound 3ao: 1 H NMR (400 MHz, Chloroform- d ) d (ppm) 8.61 (s, 1H), 8.24 (d, J = 5.2 Hz, 1H), 7.36 (d, J = 8.4 Hz, 2H), 7.29 – 7.15 (m, 5H), 6.82 (d, J = 5.2 Hz, 1H), 5.90 (s, 1H), 4.36 (d,J = 18.8 Hz, 1H), 4.13 (d, J = 22.4 Hz,1H); 13 C NMR (100 MHz, Chloroform- d ) d (ppm) 151.65, 149.89, 149.17, 147.97,136.69, 134.84, 131.00, 128.39, 128.26, 127.10, 126.73, 124.98, 122.83,45.89, 34.94。

[0036] Compound 3ap: 1 H NMR (400 MHz, Chloroform- d ) d (ppm) 7.97 (d, J = 5.6 Hz,1H), 7.35 – 7.31 (m, 4H), 7.26 – 7.22 (m, 6H), 6.62 (d, J = 5.6 Hz, 1H), 6.38(s, 1H), 5.18 (s, 1H), 3.99 (d, J = 18.4 Hz, 1H), 3.90 (d, J = 18 Hz, 1H), 3.85(s, 3H); 13 C NMR (100 MHz, Chloroform- d ) d (ppm) 164.50, 155.16,​​​​​​​​​​​​= 1.6 Hz, 1H), 7.42 – 7.35 (m, 4H), 7.29 –7.22 (m, 4H), 5.52 (s, 1H), 4.27 (d, J = 18.8 Hz, 1H), 4.00 (d, J = 18.8 Hz, 1H); 13 C NMR (100 MHz, Chloroform- d ) d (ppm) 159.16, 144.17, 143.40, 142.36,136.73, 136.17, 128.58, 128.09, 127.10, 126.61, 52.12, 35.47.

[0038] Compound 3ar: 1 H NMR (400 MHz, Chloroform- d ) d (ppm) 8.49 (d, J = 5.6 Hz, 1H), 7.98 (d, J = 8.4 Hz, 1H), 7.82 (d, J = 8.4 Hz, 1H), 7.62 – 7.54 (m, 2H), 7.46 – 7.34 (m, 4H), 7.24 – 7.18 (m, 3H), 7.02 (t, J = 7.6 Hz, 2H), 6.93 (d, J = 7.6 Hz, 2H), 6.17 (s, 1H), 4.59 (d, J = 18.8 Hz, 1H), 4.17 (d, J = 18.8 Hz, 1H); 13 C NMR (100 MHz, Chloroform- d ) d (ppm) 163.47, 142.21, 138.24, 137.25,135.41, 129.55, 127.97, 127.84, 127.54, 126.89, 126.47, 126.45, 126.06,119.89, 50.71, 35.75.

[0039] Based on the optimal reaction conditions (Example 1), the universality of anthracene substrates was further explored, and the results are as follows: ; ; .

[0040] Structural characterization: Compound 3ba: 1 H NMR (400 MHz, Chloroform- d ) d (ppm)8.40 – 8.34 (m, 2H),7.36 – 7.30 (m, 2H), 7.25 – 7.21 (m, 2H), 7.16 (d, J = 6.0 Hz, 1H), 7.10 –7.05 (m, 1H), 7.00 – 6.95 (m, 2H), 5.19 (d, J = 5.2 Hz, 1H), 3.90 (d, J = 18.4Hz, 1H), 3.86 (d, J = 18.4 Hz, 1H), 2.36 (d, J = 3.2 Hz, 3H); 13 C NMR (100 MHz, Chloroform- d ) d (ppm) 152.60, 152.50, 149.61, 137.82, 137.74, 137.44, 136.62,136.59, 136.48, 136.22, 136.14, 134.66, 133.29, 128.98, 128.65, 128.34,128.19, 128.00, 127.85, 127.72, 127.33, 126.88, 126.51, 122.99, 50.86, 50.43,35.37, 34.99, 21.07, 21.04.

[0041] Compound 3ca: 1 H NMR (400 MHz, Chloroform- d ) d (ppm) 8.42 (d, J = 4.8 Hz,2H), 7.38 – 7.32 (m, 2H), 7.30 – 7.27 (m, 2H), 7.20 (s, 1H), 7.12 (t,J = 7.6Hz, 1H), 7.01 (d, J = 6.0 Hz, 2H), 5.23 (s, 1H), 3.95 – 3.90 (m, 2H), 2.70(dd, J = 10.0, 2.4 Hz, 1H), 2.66 (dd, J = 10.4, 2.4 Hz, 1H), 1.27 (dt, J = 8.0,2.0 Hz, 3H); 13 C NMR (100 MHz, Chloroform- d ) d [[ID=ID=15]](ppm) 152.70, 152.59, 149.58,149.56, 143.03, 142.68, 137.85, 137. VII9, 137.49, 136.70, 136.57, 136.28,134.89, 133.63, 128.35, 128.27, 128.01, 127.94, 127.82, 127.46, 126.90,126.55, 126.53, 126.17, 123.11, 123.05, 56.30, 50.98, 50.50, 35.49, 35.06,28.48, 28.45, VII92, 15.70, 15.56。

[0042] Compound 3da: 1 H NMR (400 MHz, Chloroform- d ) d (ppm) 8.45 (t, J = 6.4 Hz,2H), 7.65 – 7.56 (m, 3H), 7.54 – 7.34 (m, 8H), 7.34 – 7.27 (m, 2H), 7.02 (t, J = 6.0,3.6 Hz, 2H), 5.30 (d, J = 13.2 Hz, 1H), 3.99 (d, J = 13.6 Hz, 2H); 13 C NMR(100 MHz, Chloroform- d ) d(ppm) 152.10, 152.01, 149.82, 140.71, 140.68,139.97, 139.70, 138.14, 137.59, 136.86, 136.77, 136.36, 136.32, 135.54,128.75, 128.72, 128.44, 128.39, 128.36, 128.03, 127.26, 127.23, 127.03,127.00, 126.70, 126.65, 125.78, 125.41, 123.03, 122.96, 51.01, 50.52, 35.60, 35.13.

[0043] Compound 3ea: 1 H NMR (400 MHz, Chloroform- d ) d (ppm) 8.43 (dt, J = 6.4, 1.6Hz, 2H), 7.40 – 7.24 (m, 8H), 7.03 – 6.92 (m, 2H), 5.23 (d, J = 13.2 Hz, 1H), 3.95 (d, J = 6 Hz, 1H), 3.89 (s, 1H), 1.34 (d, J = 2.8 Hz, 9H); 13 C NMR (100 MHz, Chloroform- d ) d (ppm) 152.45, 152.35, 149.90, 149.67, 149.63, 149.16, 137.90,137.87, 137.18, 136.79, 136.68, 135.85, 134.67, 133.51, 128.34, 128.31,127.98, 127.93, 127.60, 126.88, 126.85, 126.49, 125.23, 124.85, 123.96,123.62, 123.12, 122.94, 122.85, 51.25, 50.41, 45.35, 35.80, 34.99, 34.41, 31.35, 23.36, 22.39.

[0044] Compound 3fa: 11H NMR (400 MHz, Chloroform- d ) d (ppm) 8.47 – 8.37 (m, 2H), 7.52 – 7.30 (m, 4H), 7.29 – 7.24 (m, 2H), 7.20 (dd, J J = 8.0, 4.4 Hz, 1H), 6.95(dd, J J = 4.4, 2.4 Hz, 2H), 5.19 (s, 1H), 3.90 – 3.84 (m, 2H); 13 13C NMR (100 MHz, Chloroform- d ) d (ppm) 149.68, 149.62, 139.87, 138.77, 137.10, 136.89, 136.69, 135.81, 135.53, 135.48, 131.15, 130.93, 130.04, 129.94, 129.67, 128.39, 128.07, 127.24, 126.88, 122.99, 120.80, 120.19, 50.55, 50.30, 35.12, 34.92。

[0045] Compounds 3ga and 3ga': 1 1H NMR (400 MHz, Chloroform- d ) d (ppm) 8.51 (d, J J = 6.0 Hz, 2H), 8.40 (d, J J = 4.4 Hz, 2H), 7.41 (d, J J = 7.6 Hz, 2H), 7.31 – 7.28 (m, 3H), 7.24 (d, J J = 3.2 Hz, 5H), 7.22 – 7.17 (m, 2H), 7.07 – 7.01 (m, 4H), 6.93 – 6.88 (m, 2H), 5.24 (s, 1H), 3.99 – 3.84 (m, 2H), 3.66 (d, J J = 18.4 Hz, 1H), 1.96 (s, 3H), 1.59 (d, J J = 7.2 Hz, 3H); 13 It should be noted that there is a small error in the original text where "3H" should probably be "3H". This has been corrected in the translation.C NMR (100 MHz, Chloroform- d ) d (ppm)151.93, 149.88, 149.42, 142.81, 141.38, 137.70, 136.54, 128.29, 127.76,127.04, 126.59, 126.54, 126.38, 126.16, 126.01, 124.65, 123.11, 49.71, 48.35,38.23, 35.75, 27.81, 20.37.

[0046] Compound 3ka: 1 H NMR (400 MHz, Chloroform- d ) d (ppm) 8.44 (s, 2H), 7.18 –7.05 (m, 6H), 6.90 – 6.77 (m, 4H), 6.22 (s, 1H), 5.28 (s, 1H); 13 C NMR (100MHz, Chloroform- d ) d (ppm) 149.84, 139.04, 129.45, 128.02, 121.26, 114.21,47.16.

[0047] Application Examples ; 3aa (51.4 mg, 0.2 mmol) and DDQ (90.8 mg, 2 equivalents) were added to DCM (15 mL) and reacted at room temperature for 24 hours, monitored by TLC until the starting material was completely consumed. The reaction mixture was concentrated under vacuum, diluted with dichloromethane, and washed with saturated brine. The combined organic phase extracts were dried over Na₂SO₄ and concentrated under vacuum. The resulting residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 3:1) to give 4a in 80% separation. 1 H NMR (400 MHz, Chloroform- d ) d (ppm) 8.86 (s, 2H), 8.55 (s, 1H), 8.07 (d, J = 8.4 Hz, 2H), 7.56 (d, J = 8.4 Hz, 2H), 7.48 (t,J = 6.8 Hz, 2H), 7.45 – 7.41(m, 3H), 7.37 (s, 1H); 13 C NMR (100 MHz, Chloroform- d ) d (ppm) 149.73, 147.72, 133.42, 131.15, 129.34, 128.54, 127.65, 126.08, 125.81, 125.32.

[0048] The above description is only a preferred embodiment of the present invention. Any technical solution that achieves the purpose of the present invention by essentially the same means is within the protection scope of the present invention.

Claims

1. A method for a visible light-induced intermolecular dearomatization-arylation reaction between polycyclic aromatic hydrocarbons and cyanoaromatic hydrocarbons, characterized in that, Includes the following steps: The compound shown in Formula 1, the compound shown in Formula 2, a photocatalyst, a base, water, and an organic solvent were added sequentially to a reactor. The reaction was then stirred under specific temperature and light conditions. After complete reaction, post-treatment yielded the 9,10-dihydroanthracene derivative shown in Formula 3. The reaction formula is as follows: ； R1 is selected from hydrogen, halogen, and C. 1-12 Alkyl, C 6-20 Aryl, C 1-12 Alkoxy; X is selected from CR' or N; R' is selected from hydrogen or C. 1-12 Alkyl; X' is selected from CHR' or NH, R' is selected from hydrogen or C 1-12 alkyl; R2 is selected from hydrogen, halogens, and C. 1-12 Alkyl, C 6-20 Aryl, C 1-12 Alkyl groups; selected from halogens, C 1-6 Alkyl, C 1-6 Alkoxy, C 6-20 aryl-substituted C 6-20 Aryl; Furthermore, the photocatalyst is selected from one or a mixture of several of [Ir(dtbpy)(ppy)2]PF6, [Ir(dF(CF3)ppy)2(dtbbpy)]PF6, Ru(bpy)3Cl2, 4CzIPN, and 4DPAIPN; the alkali is selected from one or a mixture of several of DIPEA, Et3N, and Cy2NMe.

2. The method according to claim 1, characterized in that, R1 is selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, phenyl, and methoxy. X is selected from CR' or N; R' is selected from hydrogen or methyl; X' is selected from CHR' or NH, and R' is selected from hydrogen or methyl; R2 is selected from hydrogen, fluorine, chlorine, bromine, methyl, methoxy, phenyl, 2,6-dimethylphenyl, p-fluorophenyl, p-chlorophenyl, p-methylphenyl, p-methoxyphenyl, p-phenylphenyl, m-fluorophenyl, and m-methylphenyl.

3. The method according to claim 1, characterized in that, The photocatalyst is selected from [Ir(dtbpy)(ppy)2]PF6; the base is selected from DIPEA.

4. The method according to claim 1, characterized in that, The compound shown in Formula 2 is replaced with or Consequently, the preparation and acquisition of... and , where R1,X' is as defined in claim 1.

5. The method according to any one of claims 1-4, characterized in that, The organic solvent is selected from any one or a mixture of several of tetrahydrofuran, dichloromethane, acetone, DMSO, and DMF.

6. The method according to any one of claims 1-4, characterized in that, The specified temperature is room temperature; the illumination is provided by an 18W blue LED; the reaction is carried out under an inert atmosphere, which is selected from nitrogen or argon.

7. The method according to any one of claims 1-4, characterized in that, The molar ratio of the compound shown in Formula 1, the compound shown in Formula 2, the photocatalyst, the alkali, and the water is 1: (1.5~3): (0.005~0.02): (1.5~3): (5~20).

8. The method according to any one of claims 1-4, characterized in that, The reaction time for the stirring reaction is 12 to 48 hours.

9. A method for preparing a 4-(anthracite-9-yl)pyridine derivative, comprising the following steps: Using the 9,10-dihydroanthracene derivative shown in Formula 3 as a starting material, a reaction was carried out in the presence of an oxidant to obtain the 4-(anthracene-9-yl)pyridine derivative shown in Formula 4; the reaction formula is as follows: Where R1, X, X' have the characteristics defined in claim 1.

10. The preparation method according to claim 9, characterized in that, The oxidant is selected from DDQ; the reaction is carried out in the presence of a solvent, namely dichloromethane; the reaction temperature is from room temperature to 60°C; and the reaction time is 1 to 24 hours.

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