Novel method for introducing alkyl group on nitrogen-containing heterocyclic ring molecule through photocatalysis C-Cl bond activation

Abstract

The invention discloses a novel method for introducing an alkyl group on a nitrogen-containing heterocyclic ring molecule by photocatalytic C-Cl bond activation, which comprises the following steps: in an organic solvent, taking a chlorinated heterocyclic ring and aryl ethylene as reactants, and reacting at room temperature in the presence of a photosensitive catalyst, alkali and amine and under blue light irradiation to obtain an alkyl-substituted nitrogen-containing heterocyclic ring compound. A series of nitrogen-containing heterocyclic compounds with different substitutions are synthesized by taking chlorinated heterocyclic rings and aryl ethylene as reactants, activating through inert C-Cl bonds under room-temperature blue light irradiation, taking olefin as an alkylating reagent and introducing different alkyl chains into nitrogen-containing heterocyclic ring molecules. The raw materials used in the method are simple and easy to obtain, the reaction conditions are mild, the compatibility of functional groups is good, and the compounds are efficiently and highly selectively synthesized under the promotion of simple and easy-to-obtain alkali and amine. Target molecules of the method have important application value in the fields of medicines and pesticides.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for synthesizing and preparing a nitrogen-containing heterocyclic compound. Background Art

[0002] As an important skeleton, nitrogen-containing heterocyclic rings are widely present in natural products and drug molecules. Therefore, the synthesis of nitrogen-containing heterocyclic compounds is of great significance. It is worth mentioning that nitrogen-containing heterocyclic compounds can also serve as important ligands (such as pyridine) to complex different transition metal atoms, improve the catalytic activity of transition metal catalysts, and realize the vigorous development of metal catalysis. However, at present, the synthesis of pyridine compounds, such as the reaction of 3-chloropyridine compounds with styrene, is mainly achieved by electrochemical methods, but the reaction still has certain shortcomings, such as the yield can only reach a moderate yield, and a strong reduction voltage is required, which makes the compatibility of the functional groups of the reaction substrates not high.

[0003]

[0004] In addition, the synthesis of such pyridine products by metal catalysis can currently only be achieved for aromatic bromides and alkyl pyridinium salts under the conditions of transition metal nickel catalysis. There are still certain challenges in activating the more inert C-Cl bond to achieve the synthesis of such compounds.

[0005]

[0006] Therefore, there is an urgent need for a green synthesis method for nitrogen-containing heterocyclic compounds with a wide substrate expansion range and simple operation. Summary of the invention

[0007] Purpose of the invention: In view of the problems existing in the prior art, the present invention provides a method for synthesizing and preparing nitrogen-containing heterocyclic compounds. The synthetic method has the advantages of a wide range of substrate expansion, simple operation and one-step synthesis. Technical solution: To achieve the above-mentioned purpose of the invention, the present invention adopts the following technical solution: a new method for introducing alkyl groups into nitrogen-containing heterocyclic molecules by photocatalytic C-Cl bond activation. In an organic solvent, chlorinated heterocyclics and aromatic vinyls are used as reactants. The reaction is carried out at room temperature in the presence of a photosensitive catalyst, a base and an amine and under blue light irradiation to obtain an alkyl-substituted nitrogen-containing heterocyclic compound. The nitrogen-containing heterocyclic compound has the following chemical formula,

[0008]

[0009] In the chemical formula, R represents an aryl group; R′ represents one of hydrogen, alkyl, aryl, and naphthyl; R 1 It represents one of aryl and heteroaryl groups.

[0010] Preferably, the molar ratio of 3-chloropyridine to 1,1-disubstituted ethylene is 3:1.

[0011] Preferably, the photosensitive catalyst is a 4CzIPN catalyst, and the added amount is 0.02 times the molar amount of 1,1-disubstituted ethylene.

[0012] Preferably, the base is potassium phosphate, and the added amount is twice the molar amount of 1,1-disubstituted ethylene.

[0013] Preferably, the amine is i-Pr2NEt (diisopropylethylamine), and the added amount is 1 times the molar amount of 1,1-disubstituted ethylene.

[0014] Preferably, the organic solvent is acetonitrile.

[0015] Preferably, the reaction product after the reaction is completed is extracted with a mixed solvent of ethyl acetate and petroleum ether, and the obtained extract is concentrated under reduced pressure and then chromatographed on a silica gel column to obtain the target pyridine compound.

[0016] Beneficial effects: Compared with the prior art, the present invention has the following advantages: using chlorinated heterocycles and aromatic vinyl as reactants, nitrogen-containing heterocyclic compounds are obtained by one-step reaction under room temperature blue light irradiation. The raw materials used in the method are simple and easy to obtain, the reaction conditions are mild, the functional group compatibility is good, and the compounds are synthesized efficiently and selectively under the promotion of simple and easy-to-obtain bases and amines. The target molecules of the method have important application value in the fields of medicine and pesticides. DETAILED DESCRIPTION

[0017] Figure 1 This is the H NMR spectrum of 2-(2,2-diphenylethyl)thiazole obtained in Example 12.

[0018] Figure 2 This is the C NMR spectrum of 2-(2,2-diphenylethyl)thiazole obtained in Example 12.

[0019] Figure 3 This is the H NMR spectrum of 4-(2,2-diphenylethyl)pyridine obtained in Example 1.

[0020] Figure 4 This is the C NMR spectrum of 4-(2,2-diphenylethyl)pyridine obtained in Example 1.

[0021] Figure 5 The present invention provides a technical route for the synthesis of nitrogen-containing heterocyclic compounds.

[0022] Specific implementation methods The present invention is further explained below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention. After reading the present invention, various equivalent forms of modifications to the present invention by those skilled in the art all fall within the scope defined by the claims attached to this application.

[0023] like Figure 5 As shown, the synthesis of the nitrogen-containing heterocyclic compound of the present invention realizes the single-electron reduction of the nitrogen-containing heterocyclic ring through visible light catalysis, and the generation of heterocyclic free radicals is formed in situ, which is captured by olefins to generate relatively stable benzyl free radicals, and then further reduced to generate benzyl carbon anion intermediates, which are captured by protons during post-treatment to generate alkylation products of nitrogen-containing heterocyclic rings. The reaction of the present invention uses simpler tertiary amines as reducing agents under the conditions of visible light catalysis, and does not require organic metal reagents (such as ZnEt2, etc.) and reducing metal elements (such as Mn, Zn) that are sensitive to water and oxygen. In addition, the reaction conditions of the present invention are mild, and the target product can be obtained with good and excellent yields under room temperature illumination. Finally, the reaction has good functional group compatibility and substrate universality, has extremely high application potential, and provides a simpler and greener synthesis method for the synthesis of nitrogen-containing heterocyclic compounds. Specific route: Add chlorinated heterocycle, 1,1-disubstituted ethylene, photosensitizer, base and amine into an organic solvent, and react at room temperature under blue light irradiation. The reaction formula is shown below to obtain a nitrogen-containing heterocyclic compound.

[0024]

[0025] In the formula, R represents one of an aryl group and an alkyl group; R′ represents one of hydrogen, an alkyl group, an aryl group and a naphthyl group; and the reaction product is a nitrogen-containing compound.

[0026] Example 1

[0027] Taking the preparation of 3-(2,2-diphenylethyl)pyridine having the following structure as an example, the preparation method is as follows:

[0028]

[0029] 2,4,5,6-Tetrakis(9-carbazolyl)-isophthalonitrile (4.7 mg, 0.006 mmol) and potassium phosphate (0.127 g, 0.6 mmol) were added to a dry Schlenk tube (10 mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1 mL), 3-chloropyridine hydrochloride (0.27 g, 0.9 mmol) and 1,1-diphenylethylene (60 μL, 0.3 mmol) were then added via a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2 cm away from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 24 hours. The mixture was then quenched with 1 mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:5), and then concentrated under reduced pressure. Pure 3-(2,2-diphenylethyl)pyridine was obtained by purification by column chromatography with an isolation yield of 90%. The structural characterization data are as follows and Figure 3 and 4Shown: 1 H NMR (400MHz, CDCl3) δ8.37 (dd, J=4.8, 1.7Hz, 1H), 8.28 (d, J=2.3Hz, 1H), 7.31–7.12 (m,11H),7.06(dd,J=7.8,4.8Hz,1H),4.18(t,J=7.9Hz,1H),3.35(d,J=7.9Hz,2H).

[0030] 13 C NMR (101MHz, CDCl3) δ150.44,147.45,143.62,136.39,135.55,128.50,127.92,126.48,122.98,52.88,39.16.

[0031] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 19 H 18 N 260.1434; found 260.1436.

[0032] Example 2

[0033] Taking the preparation of 5-(2,2-diphenylethyl)-2-phenylpyridine having the following structure as an example, the preparation method is as follows:

[0034]

[0035] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7mg, 0.006mmol) and potassium phosphate (0.127g, 0.6mmol) were added to a dry Schlenk tube (10mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1mL), 5-chloro-2-phenylpyridine (0.171g, 0.9mmol) and 1,1-diphenylethylene (60μL, 0.3mmol) were then added through a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2cm away from a 30W blue LED (wavelength: 460nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:10), and then concentrated under reduced pressure. Pure 5-(2,2-diphenylethyl)-2-phenylpyridine was obtained by column chromatography purification, and the separation yield was 70%. The structural characterization data are as follows: 1H NMR (400MHz, CDCl3) δ8.41–8.32(m,1H),7.98–7.87(m,2H),7.52(dd,J=8.1,0.8Hz,1H),7.48–7.40(m,2H) ),7.40–7.33(m,1H),7.31–7.21(m,9H),7.21–7.07(m,2H),4.22(t,J=7.9Hz,1H),3.39(d,J=7.9Hz,2H).

[0036] 13 C NMR (101MHz, CDCl3) δ155.07,150.22,143.72,139.15,137.21,134.06,128.68,128.66,128.53,127.95,126.65,126.49,119.77,52.87,38.88.

[0037] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 25 H 22 N 336.1747; found 336.1746.

[0038] Example 3

[0039] Taking the preparation of 5-(2,2-diphenylethyl)pyridine nonanenitrile having the following structure as an example, the preparation method thereof is as follows:

[0040]

[0041] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7mg, 0.006mmol) and potassium phosphate (0.127g, 0.6mmol) were added to a dry Schlenk tube (10mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1mL), 2-cyano-5-chloropyridine (0.125g, 0.9mmol) and 1,1-diphenylethylene (60μL, 0.3mmol) were then added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2cm away from a 30W blue LED (wavelength: 460nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:10), and then concentrated under reduced pressure. Pure 5-(2,2-diphenylethyl)pyridinenononitrile was obtained by column chromatography purification, with an isolation yield of 70%. The structural characterization data are as follows:

[0042] 1H NMR (400MHz, CDCl3) δ8.34(d,J=2.2Hz,1H),7.46(dd,J=7.9,0.8Hz,1H),7.33(dd,J=8.0,2. 2Hz,1H),7.29–7.23(m,4H),7.22–7.09(m,6H),4.16(t,J=8.0Hz,1H),3.42(d,J=8.0Hz,2H).

[0043] 13 C NMR (101MHz, CDCl3) δ151.81,142.79,140.05,137.18,131.45,128.70,127.82,127.76,126.85,117.31,52.54,39.25.

[0044] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 20 H 17 N2285.1386; found 285.1590.

[0045] Example 4

[0046] Taking the preparation of 3-(2,2-diphenylethyl)-5-fluoropyridine having the following structure as an example, the preparation method is as follows:

[0047]

[0048] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7mg, 0.006mmol) and potassium phosphate (0.127g, 0.6mmol) were added to a dry Schlenk tube (10mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1mL), 3-fluoro-5-chloropyridine (93μL, 0.9mmol) and 1,1-diphenylethylene (60μL, 0.3mmol) were then added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2cm away from a 30W blue LED (wavelength: 460nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:10), and then concentrated under reduced pressure. Pure 3-(2,2-diphenylethyl)-5-fluoropyridine was obtained by purification by column chromatography, and the separation yield was 87%. The structural characterization data are as follows: 1H NMR(400MHz, CDCl3)δ8.23(d,J=2.6Hz,1H),8.10(s,1H),7.31–7.22(m,4H),7.2 4–7.11(m,6H),6.99–6.92(m,1H),4.18(t,J=7.9Hz,1H),3.38(d,J=7.9Hz,2H).

[0049] 13 C NMR (101MHz, CDCl3) δ160.44, 146.26 (d, J = 3.7Hz), 143.24, 137.45 (d, J = 3.5Hz), 1 35.73(d,J=23.1Hz),128.61,127.83,126.67,123.12(d,J=17.7Hz),52.65,38.67.

[0050] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 19 H 17 FN 278.1340; found 278.1331.

[0051] Example 5

[0052] Taking the preparation of 3-chloro-5-(2,2-diphenylethyl)pyridine having the following structure as an example, the preparation method is as follows:

[0053]

[0054] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7mg, 0.006mmol) and potassium phosphate (0.127g, 0.6mmol) were added to a dry Schlenk tube (10mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1mL), 3,5-dichloropyridine (0.133g, 0.9mmol) and 1,1-diphenylethylene (60μL, 0.3mmol) were then added through a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2cm away from a 30W blue LED (wavelength: 460nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:10), and then concentrated under reduced pressure. Pure 3-chloro-5-(2,2-diphenylethyl)pyridine was obtained by purification by column chromatography, with an isolated yield of 67%. The structural characterization data are as follows: 1H NMR (400MHz, CDCl3) δ8.33(d,J=2.3Hz,1H),8.11(s,1H),7.30–7.22(m,5H),7.22–7.03(m,6H),4.15(t,J=7.9Hz,1H),3.33(d,J=7.9Hz,2H).

[0055] 13 C NMR (101MHz, CDCl3) δ148.22,146.42,143.22,137.02,136.19,131.49,128.65,127.89,126.72,52.69,38.78.

[0056] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 19 H 17 ClN 294.1044; found 294.1042.

[0057] Example 6

[0058] Taking the preparation of 3-(2,2-diphenylethyl)-4-methylpyridine having the following structure as an example, the preparation method is as follows:

[0059]

[0060] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7mg, 0.006mmol) and potassium phosphate (0.127g, 0.6mmol) were added to a dry Schlenk tube (10mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1mL), 3-chloro-4-methylpyridine (0.1mL, 0.9mmol) and 1,1-diphenylethylene (60μL, 0.3mmol) were then added through a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2cm away from a 30W blue LED (wavelength: 460nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:10), and then concentrated under reduced pressure. Pure 3-(2,2-diphenylethyl)-4-methylpyridine was obtained by column chromatography purification, and the separation yield was 86%. The structural characterization data are as follows: 1H NMR(400MHz, CDCl3)δ8.22(d,J=5.0Hz,1H),8.02(s,1H),7.36–7.02(m,10H),6 .96(d,J=4.9Hz,1H),4.16(t,J=7.7Hz,1H),3.33(d,J=7.7Hz,2H),2.09(s,3H).

[0061] 13 C NMR (101MHz, CDCl3) δ150.69,147.23,145.52,143.76,134.12,128.44,127.95,126.49,124.97,51.77,36.47,18.71.

[0062] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 20 H 20 N 274.1590; found 274.1590.

[0063] Example 7

[0064] Taking the preparation of 2-(2,2-diphenylethyl)-4-methylpyridine having the following structure as an example, the preparation method is as follows:

[0065]

[0066] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7mg, 0.006mmol) and potassium phosphate (0.127g, 0.6mmol) were added to a dry Schlenk tube (10mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1mL), 2-chloro-4-methylpyridine (0.1mL, 0.9mmol) and 1,1-diphenylethylene (60μL, 0.3mmol) were then added through a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2cm away from a 30W blue LED (wavelength: 460nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:10), and then concentrated under reduced pressure. Pure 2-(2,2-diphenylethyl)-4-methylpyridine was obtained by purification by column chromatography with an isolation yield of 88%. The structural characterization data are as follows:

[0067] 1H NMR(400MHz, CDCl3)δ8.34(dd,J=5.1,0.7Hz,1H),7.31–7.18(m,8H),7.18–7.02(m,2H),6.83(dd ,J=4.9,1.4Hz,1H),6.73–6.65(m,1H),4.60(t,J=8.0Hz,1H),3.45(d,J=7.9Hz,2H),2.16(s,3H).

[0068] 13 C NMR (101MHz, CDCl3) δ159.52,148.86,146.92,144.30,128.27,128.01,126.08,124.68,122.11,50.89,44.14,20.87.

[0069] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 20 H 20 N 274.1590; found 274.1587.

[0070] Example 8

[0071] Taking the preparation of 2-chloro-6-(2,2-diphenylethyl)pyridine having the following structure as an example, the preparation method is as follows:

[0072]

[0073] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7mg, 0.006mmol) and potassium phosphate (0.127g, 0.6mmol) were added to a dry Schlenk tube (10mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1mL), 2,6-dichloropyridine (0.133g, 0.9mmol) and 1,1-diphenylethylene (60μL, 0.3mmol) were then added through a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2cm away from a 30W blue LED (wavelength: 460nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:10), and then concentrated under reduced pressure. Pure 2-chloro-6-(2,2-diphenylethyl)pyridine was obtained by purification by column chromatography, and the separation yield was 78%. The structural characterization data are as follows: 1H NMR(400MHz, CDCl3)δ7.34(t,J=7.7Hz,1H),7.29–7.18(m,8H),7.18–7.08(m,2H),7.06(dd, J=7.9,0.8Hz,1H),6.73(dd,J=7.6,0.8Hz,1H),4.58(t,J=8.0Hz,1H),3.49(d,J=8.0Hz,2H).

[0074] 13 C NMR (101MHz, CDCl3) δ160.97,150.62,143.81,138.50,128.37,127.95,126.27,122.21,121.63,50.68,43.77.

[0075] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 19 H 17 ClN 294.1044; found 294.1046.

[0076] Example 9

[0077] Taking the preparation of 5-chloro-2-(2,2-diphenylethyl)pyridine having the following structure as an example, the preparation method is as follows:

[0078]

[0079] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7mg, 0.006mmol) and potassium phosphate (0.127g, 0.6mmol) were added to a dry Schlenk tube (10mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1mL), 2,5-dichloropyridine (0.133g, 0.9mmol) and 1,1-diphenylethylene (60μL, 0.3mmol) were then added through a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2cm away from a 30W blue LED (wavelength: 460nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:10), and then concentrated under reduced pressure. Pure 5-chloro-2-(2,2-diphenylethyl)pyridine was obtained by purification by column chromatography, with an isolated yield of 52%. The structural characterization data are as follows:

[0080] 1H NMR (400MHz, CDCl3) δ8.46 (d, J=2.5Hz, 1H), 7.37 (dd, J=8.3, 2.6Hz, 1H), 7.26–7.19 (m, 8H ),7.19–7.04(m,2H),6.80(d,J=8.3Hz,1H),4.56(t,J=8.0Hz,1H),3.49(d,J=7.9Hz,2H).

[0081] 13 C NMR (101MHz, CDCl3) δ158.18,148.09,143.92,135.68,129.45,128.45,127.98,126.34,124.44,51.02,43.65.

[0082] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 19 H 17 ClN 294.1044; found 294.1039.

[0083] Example 10

[0084] Taking the preparation of 2-(2,2-diphenylethyl)quinoline having the following structure as an example, the preparation method is as follows:

[0085]

[0086] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7mg, 0.006mmol) and potassium phosphate (0.127g, 0.6mmol) were added to a dry Schlenk tube (10mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1mL), 2-chloroquinoline (0.147g, 0.9mmol) and 1,1-diphenylethylene (60μL, 0.3mmol) were then added through a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2cm away from a 30W blue LED (wavelength: 460nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:10), and then concentrated under reduced pressure. Pure 2-(2,2-diphenylethyl)quinoline was obtained by purification by column chromatography with an isolation yield of 57%. The structural characterization data are as follows:

[0087] 1H NMR (400MHz, CDCl3) δ8.04(d,J=8.5Hz,1H),7.86(d,J=8.4Hz,1H),7.72–7.62(m,2H),7.44(t,J=7.5Hz, 1H),7.35–7.16(m,8H),7.10(t,2H),6.98(d,J=8.4Hz,1H),4.72(t,J=8.0Hz,1H),3.72(d,J=8.0Hz,2H).

[0088] 13 C NMR (101MHz, CDCl3) δ160.60,147.93,144.27,135.76,129.25,128.84,128.35,128.06,127.47,126.69,126.20,125.74,122.03,51.07,44.99.

[0089] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 23 H 20 N 310.1590; found 310.1575.

[0090] Embodiment 11

[0091] Taking the preparation of 1-(2,2-diphenylethyl)isoquinoline having the following structure as an example, the preparation method is as follows:

[0092]

[0093] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7mg, 0.006mmol) and potassium phosphate (0.127g, 0.6mmol) were added to a dry Schlenk tube (10mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1mL), 3-chloroisoquinoline (0.147g, 0.9mmol) and 1,1-diphenylethylene (60μL, 0.3mmol) were then added through a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2cm away from a 30W blue LED (wavelength: 460nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:10), and then concentrated under reduced pressure. Pure 1-(2,2-diphenylethyl)isoquinoline was obtained by purification by column chromatography, and the isolation yield was 75%. The structural characterization data are as follows:

[0094] 1H NMR(400MHz, CDCl3)δ8.36(d,J=5.7Hz,1H),8.06(dd,J=8.5,1.1Hz,1H),7.85–7.69(m,1H),7.66–7.55(m,1H),7.54 –7.46(m,1H),7.45–7.40(m,1H),7.29–7.15(m,8H),7.15–7.02(m,2H),4.91(t,J=7.7Hz,1H),4.02(d,J=7.7Hz,2H).

[0095] 13 C NMR (101MHz, CDCl3) δ159.64,144.47,141.76,136.08,129.60,128.28,128.05,127.33,126.88,126.13,124.97,119.24,50.38,40.60.

[0096] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 23 H 20 N 310.1590; found 310.1587.

[0097] Example 12

[0098] Taking the preparation of 2-(2,2-diphenylethyl)thiazole having the following structure as an example, the preparation method is as follows:

[0099]

[0100] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7 mg, 0.006 mmol) and potassium phosphate (0.127 g, 0.6 mmol) were added to a dry Schlenk tube (10 mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1 mL), 2-chlorothiazole (78 μL, 0.9 mmol) and 1,1-diphenylethylene (60 μL, 0.3 mmol) were then added via a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2 cm away from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 24 hours. The mixture was then quenched with 1 mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:10), and then concentrated under reduced pressure. Pure 2-(2,2-diphenylethyl)thiazole was obtained by purification by column chromatography with an isolated yield of 77%. The structural characterization data are as follows and Figure 1 and 2 Shown: 1H NMR (400MHz, CDCl3) δ7.63(d,J=3.3Hz,1H),7.36–7.23(m,8H),7.22–7.14(m,2H),7.07(d,J=3.3Hz,1H),4.57(t,J=8.0Hz,1H),3.77(d,J=8.0Hz,2H).

[0101] 13 C NMR (101MHz, CDCl3) δ168.76,143.27,142.02,128.54,127.88,126.56,118.35,51.48,39.33.

[0102] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 17 H 16 NS 266.0998; found 266.0994.

[0103] Example 13

[0104] Taking the preparation of 2-(2,2-diphenylethyl)benzo[d]thiazole having the following structure as an example, the preparation method is as follows:

[0105]

[0106] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7mg, 0.006mmol) and potassium phosphate (0.127g, 0.6mmol) were added to a dry Schlenk tube (10mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1mL), 2-chlorobenzothiazole (114μL, 0.9mmol) and 1,1-diphenylethylene (60μL, 0.3mmol) were then added through a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2cm away from a 30W blue LED (wavelength: 460nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:10), and then concentrated under reduced pressure. Pure 2-(2,2-diphenylethyl)benzo[d]thiazole was obtained by purification by column chromatography with an isolated yield of 65%. The structural characterization data are as follows: 1H NMR (400MHz, CDCl3) δ7.94(d,J=8.1Hz,1H),7.73(d,J=8.0Hz,1H),7.41(t,J=7.7Hz,1H),7. 37–7.20(m,9H),7.16(t,J=17.5,10.6Hz,2H),4.67(t,J=8.0Hz,1H),3.87(d,J=8.0Hz,2H).

[0107] 13 C NMR (101MHz, CDCl3) δ169.82,143.14,128.62,127.87,126.66,125.80,124.67,122.55,121.43,51.06,40.41.

[0108] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 21 H 18 NS 316.1154; found 316.1148.

[0109] Embodiment 14

[0110] Taking the preparation of 2-chloro-3-(2,2-diphenylethyl)quinoxaline having the following structure as an example, the preparation method is as follows:

[0111]

[0112] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7mg, 0.006mmol) and potassium phosphate (0.127g, 0.6mmol) were added to a dry Schlenk tube (10mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1mL), 2,3-dichloroquinoxaline (0.18g, 0.9mmol) and 1,1-diphenylethylene (60μL, 0.3mmol) were then added through a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2cm away from a 30W blue LED (wavelength: 460nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:10), and then concentrated under reduced pressure. Pure 2-chloro-3-(2,2-diphenylethyl)quinoxaline was obtained by column chromatography purification, and the isolated yield was 46%. The structural characterization data are as follows:

[0113] 1H NMR (400MHz, CDCl3) δ8.12–7.81(m,2H),7.80–7.57(m,2H),7.42–7.06(m,10H),5.01(t,J=7.8Hz,1H),3.91(d,J=7.8Hz,2H).

[0114] 13 C NMR (101MHz, CDCl3) δ153.47,147.60,143.72,140.80,140.60,130.15,129.98,128.64,128.44,128.04,128.01,126.39,48.72,40.86.

[0115] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 22 H 18 ClN2345.1153; found 345.1148.

[0116] Embodiment 15

[0117] Taking the preparation of 3-(2-(4-methoxyphenyl)-2-phenylethyl)pyridine having the following structure as an example, the preparation method thereof is as follows:

[0118] 2,4,5,6-Tetra(9-carbazolyl)-isophthalonitrile (4.7 mg, 0.006 mmol) and potassium phosphate (0.127 g, 0.6 mmol) were added to a dry Schlenk tube (10 mL). The Schlenk tube was then connected to a vacuum tube and pumped with nitrogen three times. Dry acetonitrile (1 mL), 3-chloropyridine (86 μL, 0.9 mmol) and 1-methoxy-4-(1-phenylvinyl)benzene (63 μL, 0.3 mmol) were then added via a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2 cm away from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1 mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:5), and then concentrated under reduced pressure. Pure 3-(2-(4-methoxyphenyl)-2-phenylethyl)pyridine was obtained by purification by column chromatography. The isolated yield was 82%. The structural characterization data are as follows:

[0119] 1H NMR (400MHz, CDCl3) δ8.39–8.31(m,1H),8.27(s,1H),7.27–7.13(m,6H),7.13–6.93( m,3H),6.86–6.69(m,2H),4.12(t,J=7.9Hz,1H),3.74(s,3H),3.31(d,J=7.9Hz,2H).

[0120] 13 C NMR (101MHz, CDCl3) δ158.14,150.45,147.39,144.11,136.49,135.78,135.75,128.91, 128.52,127.85,126.43,123.02,113.90,55.22,52.08,39.41.HRMS(ESI-TOF)m / z:[M+H] + Calcd for C 20 H 20 NO 290.1539; found 290.1537.

[0121] Example 16

[0122] Taking the preparation of 3-(2-(4-(methylthio)phenyl)-2-phenylethyl)pyridine having the following structure as an example, the preparation method thereof is as follows:

[0123]

[0124] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7 mg, 0.006 mmol) and potassium phosphate (0.127 g, 0.6 mmol) were added to a dry Schlenk tube (10 mL). The Schlenk tube was then connected to a vacuum tube and pumped with nitrogen three times. Dry acetonitrile (1 mL), 3-chloropyridine (86 μL, 0.9 mmol) and 1-(methylthio)-4-(1-phenylvinyl)benzene (68 mg, 0.3 mmol) were then added via a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2 cm away from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1 mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:5), and then concentrated under reduced pressure. Pure 3-(2-(4-(methylthio)phenyl)-2-phenylethyl)pyridine was obtained by purification by column chromatography. The isolated yield was 80%. The structural characterization data are as follows:

[0125] 1H NMR(400MHz, CDCl3)δ8.36(d,J=4.6Hz,1H),8.30–8.21(m,1H),7.26–7.21(m,3H ),7.21–6.92(m,8H),4.13(t,J=7.9Hz,1H),3.31(d,J=7.9Hz,2H),2.42(s,3H).

[0126] 13 C NMR (101MHz, CDCl3) δ150.36,147.44,143.55,140.54,136.42,136.29,135.47,128.53, 128.41,127.82,126.79,126.54,123.03,52.32,39.09,15.89.HRMS(ESI-TOF)m / z:[M+H] + Calcd for C 20 H 20 NS 306.1311; found 306.1307.

[0127] Embodiment 17

[0128] Taking the preparation of 3-(2-(4-phenoxyphenyl)-2-phenethyl)pyridine having the following structure as an example, the preparation method is as follows:

[0129]

[0130] 2,4,5,6-Tetra(9-carbazolyl)-isophthalonitrile (4.7 mg, 0.006 mmol) and potassium phosphate (0.127 g, 0.6 mmol) were added to a dry Schlenk tube (10 mL). The Schlenk tube was then connected to a vacuum tube and pumped with nitrogen three times. Dry acetonitrile (1 mL), 3-chloropyridine (86 μL, 0.9 mmol) and 1-phenoxy-4-(1-phenyl)benzene (82 mg, 0.3 mmol) were then added via a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2 cm away from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1 mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:5), and then concentrated under reduced pressure. Pure 3-(2-(4-phenoxyphenyl)-2-phenethyl)pyridine was obtained by purification by column chromatography. The isolated yield was 83%. The structural characterization data are as follows:

[0131] 1H NMR(400MHz, CDCl3)δ8.37(d,J=4.8Hz,1H),8.32–8.04(m,1H),7.32–7.11(m,10H),7.10–7.0 2(m,2H),7.03–6.92(m,2H),6.91–6.82(m,2H),4.16(t,J=7.9Hz,1H),3.32(d,J=7.9Hz,2H).

[0132] 13 C NMR (101MHz, CDCl3) δ157.26,155.75,150.49,147.54,143.75,138.61,136.48,135.59, 129.76,129.22,128.62,127.95,126.61,123.24,123.07,118.91,118.85,52.30,39.41.

[0133] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 25 H 22 NO 352.1696; found 352.1697.

[0134] Embodiment 18

[0135] Taking the preparation of 3-(2-phenyl-2-(p-tolyl)ethyl)pyridine having the following structure as an example, the preparation method thereof is as follows:

[0136] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7mg, 0.006mmol) and potassium phosphate (0.127g, 0.6mmol) were added to a dry Schlenk tube (10mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1mL), 3-chloropyridine (86μL, 0.9mmol) and 1-methyl-4-(1-phenylvinyl)benzene (58mg, 0.3mmol) were then added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2cm away from a 30W blue LED (wavelength: 460nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:5), and then concentrated under reduced pressure. Pure 3-(2-phenyl-2-(p-tolyl)ethyl)pyridine was obtained by purification by column chromatography, and the separation yield was 90%. The structural characterization data are as follows:

[0137] 1H NMR (400MHz, CDCl3) δ8.35(dd,J=4.8,1.6Hz,1H),8.27(d,J=2.3Hz,1H),7.27–7.03(m,11H),4.14(t,J=7.9Hz,1H),3.32(d,J=7.9Hz,2H),2.27(s,3H).

[0138] 13 C NMR (101MHz, CDCl3) δ150.48,147.41,143.97,140.68,136.44,136.02,135.74,129.23, 128.52,127.91,127.82,126.43,123.01,52.53,39.27,21.02.HRMS(ESI-TOF)m / z:[M+H] + Calcd for C 20 H 20 N 274.1590; found 274.1585.

[0139] Embodiment 19

[0140] Taking the preparation of 3-(2-([1,1'-biphenyl]-4-yl)-2-phenylethyl)pyridine having the following structure as an example, the preparation method thereof is as follows:

[0141]

[0142] 2,4,5,6-Tetrakis(9-carbazolyl)-isophthalonitrile (4.7 mg, 0.006 mmol) and potassium phosphate (0.127 g, 0.6 mmol) were added to a dry Schlenk tube (10 mL). The Schlenk tube was then connected to a vacuum tube and pumped with nitrogen three times. Dry acetonitrile (1 mL), 3-chloropyridine (86 μL, 0.9 mmol) and 4-(1-phenyl)-1,1'-biphenyl (77 mg, 0.3 mmol) were then added via a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2 cm away from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1 mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:5), and then concentrated under reduced pressure. Pure 3-(2-([1,1'-biphenyl]-4-yl)-2-phenylethyl)pyridine was obtained by purification by column chromatography. The isolated yield was 83%. The structural characterization data are as follows:

[0143] 1H NMR(400MHz, CDCl3)δ8.37(dd,J=4.9,1.6Hz,1H),8.31(d,J=2.6Hz,1H),7.66–7.51(m,2H),7.51–7.43(m,2H), 7.44–7.34(m,2H),7.33–7.16(m,9H),7.07(dd,J=7.8,4.8Hz,1H),4.22(t,J=7.9Hz,1H),3.38(d,J=7.9Hz,2H).

[0144] 13 C NMR (101MHz, CDCl3) δ150.41,147.46,143.54,142.73,140.68,139.32,136.43,135.53, 128.70,128.56,128.29,127.93,127.20,127.15,126.96,126.56,123.02,52.56,39.17.

[0145] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 25 H 22 N 336.1747; found 336.1743.

[0146] Embodiment 20

[0147] Taking the preparation of 3-(2-(4-fluorophenyl)-2-phenylethyl)pyridine having the following structure as an example, the preparation method thereof is as follows:

[0148]

[0149] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7mg, 0.006mmol) and potassium phosphate (0.127g, 0.6mmol) were added to a dry Schlenk tube (10mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1mL), 3-chloropyridine (86μL, 0.9mmol) and 1-fluoro-4-(1-phenyl)benzene (60mg, 0.3mmol) were then added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2cm away from a 30W blue LED (wavelength: 460nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:5), and then concentrated under reduced pressure. Pure 3-(2-(4-fluorophenyl)-2-phenylethyl)pyridine was obtained by purification by column chromatography, and the isolated yield was 85%. The structural characterization data are as follows:

[0150] 1 H NMR(400MHz, CDCl3)δ8.37(dd,J=4.8,1.7Hz,1H),8.27(d,J=2.2Hz,1H),7.28–7.15(m,6H),7.1 5–7.09(m,2H),7.09–7.04(m,1H),7.00–6.85(m,2H),4.16(t,J=7.9Hz,1H),3.38–3.26(m,2H).

[0151] 13 C NMR (101MHz, CDCl3) δ161.46 (d, J = 245.0Hz), 150.40, 147.54, 143.49, 139.38 (d, J = 3.3Hz), 136.43, 135.36, 129.39 (d, J = 7.8Hz), 128.62, 127.83, 126.66, 123.05, 115.32 (d, J = 21.2Hz), 52.13, 39.33.

[0152] 19 F NMR (376MHz,CDCl3)δ-116.45.

[0153] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 19 H 17 FN 278.1340; found 278.1340.

[0154] Embodiment 21

[0155] Taking the preparation of 3-(2-(3-fluorophenyl)-2-phenylethyl)pyridine having the following structure as an example, the preparation method is as follows:

[0156]

[0157] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7mg, 0.006mmol) and potassium phosphate (0.127g, 0.6mmol) were added to a dry Schlenk tube (10mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1mL), 3-chloropyridine (86μL, 0.9mmol) and 1-fluoro-3-(1-phenyl)benzene (60mg, 0.3mmol) were then added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2cm away from a 30W blue LED (wavelength: 460nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:5), and then concentrated under reduced pressure. Pure 3-(2-(3-fluorophenyl)-2-phenylethyl)pyridine was obtained by purification by column chromatography, and the isolated yield was 87%. The structural characterization data are as follows:

[0158] 1 H NMR (400MHz, CDCl3) δ8.36(dd,J=4.8,1.6Hz,1H),8.28(d,J=2.3Hz,1H),7.28–7.15(m,7H),7.06(dd,J= 7.8, 4.8Hz, 1H), 6.96 (d, J = 7.7Hz, 1H), 6.94–6.74 (m, 2H), 4.17 (t, J = 7.9Hz, 1H), 3.32 (d, J = 7.9Hz, 2H).

[0159] 13 C NMR (101MHz, CDCl3) δ162.92 (d, J = 246.1Hz), 150.35, 147.58, 146.32 (d, J = 6.9Hz), 142.96, 136.42, 135.21, 129.97 (d, J = 8.3Hz) ,128.67,127.89,126.80,123.68(d,J=2.8Hz),123.09,114.84(d,J=21.6Hz),113.45(d,J=21.0Hz),52.61(d,J=1.8Hz),39.02.

[0160] 19 F NMR (376MHz,CDCl3)δ-112.80.

[0161] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 19 H 17 FN 278.1340; found 278.1337.

[0162] Embodiment 22

[0163] Taking the preparation of 3-(2-(2-methoxyphenyl)-2-phenylethyl)pyridine having the following structure as an example, the preparation method thereof is as follows:

[0164]

[0165] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7 mg, 0.006 mmol) and potassium phosphate (0.127 g, 0.6 mmol) were added to a dry Schlenk tube (10 mL). The Schlenk tube was then connected to a vacuum tube and pumped with nitrogen three times. Dry acetonitrile (1 mL), 3-chloropyridine (86 μL, 0.9 mmol) and 1-methoxy-2-(1-phenyl)benzene (63 mg, 0.3 mmol) were then added via a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2 cm away from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1 mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:5), and then concentrated under reduced pressure. Pure 3-(2-(2-methoxyphenyl)-2-phenylethyl)pyridine was obtained by purification by column chromatography. The isolated yield was 80%. The structural characterization data are as follows:

[0166] 1 H NMR (400MHz, CDCl3) δ8.34(dd,J=4.7,1.6Hz,1H),8.31(d,J=2.2Hz,1H),7.35–7.20(m,6H),7.20–7.07(m,2H),7.05(ddd,J=7.8,4 .8,0.8Hz,1H),6.90(td,J=7.5,1.2Hz,1H),6.77(dd,J=8.2,1.1Hz,1H),4.68(t,J=7.9Hz,1H),3.66(s,3H),3.29(d,J=7.9Hz,2H).

[0167] 13 C NMR (101MHz, CDCl3) δ156.73,150.43,147.17,143.27,136.35,136.01,132.33,128 .30,128.19,127.86,127.46,126.15,122.85,120.53,110.66,55.32,44.91,38.34.

[0168] HRMS (ESI-TOF) m / z: [M+H] +Calcd for C 20 H 20 NO 290.1539; found 290.1539.

[0169] Embodiment 23

[0170] Taking the preparation of 3-(2-phenyl-2-(o-tolyl)ethyl)pyridine having the following structure as an example, the preparation method is as follows:

[0171]

[0172] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7mg, 0.006mmol) and potassium phosphate (0.127g, 0.6mmol) were added to a dry Schlenk tube (10mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1mL), 3-chloropyridine (86μL, 0.9mmol) and 1-methyl-2-(1-phenyl)benzene (58mg, 0.3mmol) were then added through a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2cm away from a 30W blue LED (wavelength: 460nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:5), and then concentrated under reduced pressure. Pure 3-(2-phenyl-2-(o-tolyl)ethyl)pyridine was obtained by purification by column chromatography, with an isolated yield of 78%. The structural characterization data are as follows:

[0173] 1 H NMR (400MHz, CDCl3) δ8.38 (dd, J=4.8, 1.7Hz, 1H), 8.26 (d, J=2.3Hz, 1H), 7.41 (dd, J=7.7, 1.2Hz,1H),7.25–7.04(m,10H),4.36(t,J=7.8Hz,1H),3.32(d,J=7.8Hz,2H),2.11(s,3H).

[0174] 13 C NMR (101MHz, CDCl3) δ150.41,147.42,143.10,141.71,136.52,136.27,135.73,130 .64,128.39,128.30,126.76,126.47,126.37,126.19,123.00,48.49,39.61,19.81.

[0175] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C20 H 20 N 274.1590; found 274.1591.

[0176] Embodiment 24

[0177] Taking the preparation of 3-(2-(2-fluorophenyl)-2-phenylethyl)pyridine having the following structure as an example, the preparation method is as follows:

[0178]

[0179] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7mg, 0.006mmol) and potassium phosphate (0.127g, 0.6mmol) were added to a dry Schlenk tube (10mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1mL), 3-chloropyridine (86μL, 0.9mmol) and 1-fluoro-2-(1-phenyl)benzene (60mg, 0.3mmol) were then added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2cm away from a 30W blue LED (wavelength: 460nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:5), and then concentrated under reduced pressure. Pure 3-(2-(2-fluorophenyl)-2-phenylethyl)pyridine was obtained by column chromatography purification with an isolation yield of 88%. The structural characterization data are as follows:

[0180] 1 H NMR (400MHz, CDCl3) δ8.35 (dd, J=4.9, 1.6Hz, 1H), 8.30 (d, J=2.2Hz, 1H), 7.32–7.22 (m, 6H), 7.20 –7.08(m,2H),7.08–7.02(m,2H),6.97–6.87(m,1H),4.54(t,J=8.0Hz,1H),3.35(d,J=8.1Hz,2H).

[0181] 13C NMR(101MHz, CDCl3) δ160.54(d,J=245.5Hz),150.36,147.57,142.36,136.32,135.26,130.70(d,J=14.2Hz),128.80(d,J=4.3Hz),128 .56, 128.18 (d, J = 8.4Hz), 128.03, 126.72, 124.24 (d, J = 3.5Hz), 123.10, 115.62 (d, J = 22.7Hz), 45.48 (d, J = 1.8Hz), 38.12 (d, J = 1.3Hz).

[0182] 19 FNMR (376MHz,CDCl3)δ-117.27.

[0183] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 19 H 17 FN 278.1340; found 278.1337.

[0184] Embodiment 25

[0185] Taking the preparation of 3-(2-(4-(but-2-yn-1-ethoxy)phenyl)-2-phenethylpyridine having the following structure as an example, the preparation method thereof is as follows:

[0186]

[0187] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7 mg, 0.006 mmol) and potassium phosphate (0.127 g, 0.6 mmol) were added to a dry Schlenk tube (10 mL). The Schlenk tube was then connected to a vacuum tube and filled with nitrogen three times. Dry acetonitrile (1 mL), 3-chloropyridine (86 μL, 0.9 mmol) and 1-(but-2-yn-1-oxy)-4-(1-phenylvinyl)benzene (75 mg, 0.3 mmol) were then added via a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2 cm away from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1 mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:5), and then concentrated under reduced pressure. Pure 3-(2-(4-(but-2-yn-1-ethoxy)phenyl)-2-phenethylpyridine was obtained by purification by column chromatography. The isolated yield was 73%. The structural characterization data are as follows:

[0188] 1H NMR (400MHz, CDCl3) δ8.36 (dd, J=4.8, 1.7Hz, 1H), 8.28 (d, J=2.2Hz, 1H), 7.28–7.04 (m, 9H), 6.99–6. 72(m,2H),4.59(q,J=2.3Hz,2H),4.13(t,J=7.8Hz,1H),3.32(d,J=7.9Hz,2H),1.85(t,J=2.3Hz,3H).

[0189] 13 C NMR (101MHz, CDCl3) δ156.47,150.45,147.42,143.99,136.47,136.39,135.69,128.8 6,128.52,127.89,126.46,123.00,114.81,83.69,74.10,56.45,52.12,39.40,3.74.

[0190] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 23 H 22 NO 328.1696; found 328.1691.

[0191] Embodiment 26

[0192] Taking the preparation of 3-(2-(4-(pent-4-en-1-yloxy)phenyl)-2-phenethylpyridine having the following structure as an example, the preparation method is as follows:

[0193]

[0194] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7 mg, 0.006 mmol) and potassium phosphate (0.127 g, 0.6 mmol) were added to a dry Schlenk tube (10 mL). The Schlenk tube was then connected to a vacuum tube and pumped with nitrogen three times. Dry acetonitrile (1 mL), 3-chloropyridine (86 μL, 0.9 mmol) and 1-(pent-4-en-1-yloxy)-4-(1-phenyl)benzene (79 mg, 0.3 mmol) were then added via a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2 cm away from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1 mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:5), and then concentrated under reduced pressure. Pure 3-(2-(4-(pent-4-en-1-yloxy)phenyl)-2-phenethylpyridine was obtained by purification by column chromatography. The isolated yield was 54%. The structural characterization data are as follows: 1 HNMR (400MHz, CDCl3) δ8.36 (dd, J=4.9, 1.7Hz, 1H), 8.27 (d, J=2.3Hz, 1H), 7.2 5–7.21(m,3H),7.19–7.13(m,3H),7.09–7.04(m,3H),6.79–6.76(m,2H),5.83( ddt,J=16.9,10.2,6.6Hz,1H),5.07–4.96(m,2H),4.12(t,J=7.9Hz,1H),3.90 (t,J=6.4Hz,2H),3.31(d,J=7.9Hz,2H),2.23–2.18(m,2H),1.87–1.82(m,2H).

[0195] 13 C NMR (101MHz, CDCl3) δ157.59,150.42,147.35,144.11,137.84,136.46,135.73,135.61,12 8.84,128.48,127.83,126.38,122.99,115.15,114.44,67.08,52.06,39.37,30.11,28.43.

[0196] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 24 H 26 NO 344.2009; found 344.2005.

[0197] Embodiment 27

[0198] Taking the preparation of 3-(2-(naphthalene-2-yl)-2-phenylethyl)pyridine having the following structure as an example, the preparation method is as follows:

[0199]

[0200] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7mg, 0.006mmol) and potassium phosphate (0.127g, 0.6mmol) were added to a dry Schlenk tube (10mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1mL), 3-chloropyridine (86μL, 0.9mmol) and 2-(1-phenylvinyl)naphthalene (69mg, 0.3mmol) were then added through a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2cm away from a 30W blue LED (wavelength: 460nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:5), and then concentrated under reduced pressure. Pure 3-(2-(naphthalene-2-yl)-2-phenylethyl)pyridine was obtained by purification by column chromatography, and the separation yield was 75%. The structural characterization data are as follows:

[0201] 1 H NMR (400MHz, CDCl3) δ8.66–7.91(m,2H),7.91–7.66(m,3H),7.63(d,J=1.7Hz,1H),7.47–7.34(m,2H),7.29(dd,J=8.4,1 .8Hz,1H),7.26–7.17(m,5H),7.17–7.09(m,1H),6.99(dd,J=7.8,4.8Hz,1H),4.32(t,J=7.9Hz,1H),3.56–3.29(m,2H).

[0202] 13 C NMR (101MHz, CDCl3) δ150.52,147.56,143.60,141.16,136.48,135.62,133.50,132.32,128. 63,128.32,128.16,127.83,127.67,126.70,126.66,126.17,125.71,123.09,52.96,39.04.

[0203] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 23 H 20N 310.1590; found 310.1585.

[0204] Embodiment 28

[0205] Taking the preparation of methyl 4-(1-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-2-(pyridin-3-yl)ethyl)benzoate having the following structure as an example, the preparation method thereof is as follows:

[0206]

[0207] 2,4,5,6-Tetra(9-carbazolyl)-isophthalonitrile (4.7 mg, 0.006 mmol) and potassium phosphate (0.127 g, 0.6 mmol) were added to a dry Schlenk tube (10 mL). The Schlenk tube was then connected to a vacuum tube and filled with nitrogen three times. Dry acetonitrile (1 mL), 3-chloropyridine (86 μL, 0.9 mmol) and methyl 4-(1-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene-2-yl)vinyl)benzoate (109 mg, 0.3 mmol) were then added via a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2 cm away from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1 mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:5), and then concentrated under reduced pressure. Pure 4-(1-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-2-(pyridin-3-yl)ethyl)benzoic acid methyl ester was obtained by purification by column chromatography. The isolated yield was 43%. The structural characterization data are as follows:

[0208] 1 H NMR(400MHz, CDCl3)δ8.39(dd,J=4.8,1.7Hz,1H),8.24(d,J=2.2Hz,1H),7.93–7.83(m, 2H),7.36(s,1H),7.16(dt,J=7.8,2.0Hz,1H),7.11–7.06(m,3H),6.99(s,1H),4.29(dd ,J=9.4,6.0Hz,1H),3.87(s,3H),3.38(dd,J=13.5,6.0Hz,1H),3.26(dd,J=13.5,9.5Hz ,1H),2.05(s,3H),1.68(q,J=1.4Hz,4H),1.30(d,J=8.9Hz,6H),1.24(d,J=5.6Hz,6H).

[0209] 13C NMR (101MHz, CDCl3) δ166.94,150.36,148.52,147.55,143.14,142.52,137.79,136.44,135.40,133.06,129.61,128.57,128.46,128 .13,124.44,122.99,77.20,51.99,49.07,39.62,35.10,34.05,33.80,32.05,31.95,31.85,31.65,19.41.HRMS(ESI-TOF)m / z:[M+H] + Calcd for C 30 H 36 NO2442.2741; found 442.2741.

[0210] Embodiment 29

[0211] Taking the preparation of 3-(2-([1,1'-biphenyl]-4-yl)propyl)pyridine having the following structure as an example, the preparation method thereof is as follows:

[0212]

[0213] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7 mg, 0.006 mmol) and potassium phosphate (0.127 g, 0.6 mmol) were added to a dry Schlenk tube (10 mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1 mL), 3-chloropyridine (86 μL, 0.9 mmol) and 4-(1-propene-2-yl)biphenyl (58 mg, 0.3 mmol) were then added via a syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2 cm away from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1 mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:5), and then concentrated under reduced pressure. Pure 3-(2-([1,1'-biphenyl]-4-yl)propyl)pyridine was obtained by purification by column chromatography. The isolated yield was 90%. The structural characterization data are as follows:

[0214] 1H NMR (400MHz, CDCl3) δ8.41 (dd, J=4.9, 1.6Hz, 1H), 8.36 (d, J=2.2Hz, 1H), 7.63– 7.55(m,2H),7.55–7.47(m,2H),7.46–7.38(m,2H),7.37–7.27(m,2H),7.24–7. 17(m,2H),7.13(ddd,J=7.8,4.8,0.8Hz,1H),3.05(dt,J=14.1,7.1Hz,1H),2.9 3(dd,J=13.5,7.1Hz,1H), 2.84(dd,J=13.5,7.6Hz,1H), 1.31(d,J=6.9Hz,3H).

[0215] 13 C NMR (101MHz, CDCl3) δ150.44,147.39,144.95,140.86,139.18,136.54,135.86,128.72, 127.44,127.12,127.10,126.97,123.09,41.96,41.30,21.26.HRMS(ESI-TOF)m / z:[M+H] + Calcd for C 20 H 20 N 274.1590; found 274.1590.

[0216] Embodiment 30

[0217] Taking the preparation of 3-phenethylpyridine having the following structure as an example, the preparation method is as follows:

[0218]

[0219] 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4.7mg, 0.006mmol) and potassium phosphate (0.127g, 0.6mmol) were added to a dry Schlenk tube (10mL). The Schlenk tube was then connected to a vacuum tube and nitrogen was pumped in three times. Dry acetonitrile (1mL), 3-chloropyridine (86μL, 0.9mmol) and styrene (35μL, 0.3mmol) were then added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed 1 to 2cm away from a 30W blue LED (wavelength: 460nm) and stirred at room temperature for 24 hours. Then, the mixture was quenched with 1mL of water, extracted with a mixed solvent of ethyl acetate and petroleum ether (1:5), and then concentrated under reduced pressure. Pure 3-phenylethylpyridine was obtained by column chromatography purification with an isolation yield of 42%. The structural characterization data are as follows:

[0220] 1 H NMR (400MHz, CDCl3) δ8.46–8.38(m,2H),7.41(dt,J=7.8,2.0Hz,1H),7.30–7.23(m,2H),7.22–7.06(m,4H),2.90(s,4H).

[0221] 13 C NMR (101MHz, CDCl3) δ149.92,147.40,140.77,136.80,135.96,128.44,128.43,126.17,123.21,37.44,34.90.

[0222] HRMS (ESI-TOF) m / z: [M+H] + Calcd for C 13 H 14 N 184.1121; found 184.1124. The above-mentioned embodiments show that the present invention provides a one-step synthesis of alkyl-substituted nitrogen-containing heterocyclic compounds by a two-component reaction, and the method has the advantages of readily available raw materials, mild conditions, simple operation, good yield and a wide range of substrate expansion.

[0223] The above descriptions are only some embodiments of the present invention. It should be pointed out that, for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A new method for introducing alkyl groups into nitrogen-containing heterocyclic molecules by photocatalytic C-Cl bond activation, characterized in that: In an organic solvent, a chlorinated heterocyclic ring and an aromatic vinyl are used as reactants, and react at room temperature in the presence of a photosensitive catalyst, a base and an amine under blue light irradiation to obtain an alkyl-substituted nitrogen-containing heterocyclic compound, wherein the nitrogen-containing heterocyclic compound has the following chemical formula: ， In the chemical formula, R represents an aryl group; R' represents one of hydrogen, alkyl, aryl, and naphthyl; R 1 It represents one of aryl and heteroaryl groups.

2. The novel method for introducing alkyl groups into nitrogen-containing heterocyclic molecules by photocatalytic C-Cl bond activation according to claim 1, characterized in that: The molar ratio of the 3-chloropyridine to the 1,1-disubstituted ethylene is 3:

1.

3. The novel method for introducing alkyl groups into nitrogen-containing heterocyclic molecules by photocatalytic C-Cl bond activation according to claim 1, characterized in that: The photosensitive catalyst is a 4CzIPN catalyst, and the added amount is 0.02 times the molar amount of 1,1-disubstituted ethylene.

4. The novel method for introducing alkyl groups into nitrogen-containing heterocyclic molecules by photocatalytic C-Cl bond activation according to claim 1, characterized in that: The base is potassium phosphate, and the amount added is twice the molar amount of 1,1-disubstituted ethylene.

5. The novel method for introducing alkyl groups into nitrogen-containing heterocyclic molecules by photocatalytic C-Cl bond activation according to claim 1, characterized in that: The amine is i-Pr2NEt (diisopropylethylamine), and the added amount is 1 times the molar amount of 1,1-disubstituted ethylene.

6. The novel method for introducing alkyl groups into nitrogen-containing heterocyclic molecules by photocatalytic C-Cl bond activation according to claim 1, characterized in that: The organic solvent is acetonitrile.

7. The novel method for introducing alkyl groups into nitrogen-containing heterocyclic molecules by photocatalytic C-Cl bond activation according to claim 1, characterized in that: The reaction product after the reaction is completed is extracted with a mixed solvent of ethyl acetate and petroleum ether, and the obtained extract is concentrated under reduced pressure and then subjected to silica gel column chromatography to obtain the target pyridine compound.

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