CN113512038A

CN113512038A - Benzo [4,5] imidazo [1,2-a ] pyridine derivative and preparation method and application thereof

Info

Publication number: CN113512038A
Application number: CN202110819255.0A
Authority: CN
Inventors: 杨凯; 罗时荷; 汪朝阳
Original assignee: South China Normal University
Current assignee: South China Normal University
Priority date: 2021-07-20
Filing date: 2021-07-20
Publication date: 2021-10-19
Anticipated expiration: 2041-07-20
Also published as: CN113512038B

Abstract

The invention discloses benzo [4,5]]Imidazo [1,2-a ]]Pyridine derivatives, and a preparation method and application thereof. The invention discloses benzo [4,5]]Imidazo [1,2-a ]]Pyridine derivatives having the structure

R¹Selected from hydrogen, alkyl, halogen, alkoxy; r²Selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; ar is selected from substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl. The benzo [4,5] provided by the invention]Imidazo [1,2-a ]]The pyridine derivatives have excellent fluorescence property and aggregation-induced emission property, and the preparation method has the advantages of simple and easy operation and raw materialsEasy obtaining, wide application range of the substrate, high yield and the like. Such benzo [4,5] s]Imidazo [1,2-a ]]The pyridine derivatives have good application prospects in the fields of chemical and biological fluorescent probes.

Description

Benzo [4,5] imidazo [1,2-a ] pyridine derivative and preparation method and application thereof

Technical Field

The invention belongs to the field of organic chemistry, and particularly relates to a benzo [4,5] imidazo [1,2-a ] pyridine derivative, and a preparation method and application thereof.

Background

Benzo [4,5] imidazo [1,2-a ] pyridine is an important nitrogen-containing fused heterocyclic compound, and has pharmaceutical activities of treating diabetes, resisting cancer, malaria, fungi, schistosome and the like. Meanwhile, the benzo [4,5] imidazo [1,2-a ] pyridine compound is also an excellent chemical/biological sensor due to its excellent fluorescent properties. In view of the potential application value of benzo [4,5] imidazo [1,2-a ] pyridine derivatives, molecules with structures containing benzo [4,5] imidazo [1,2-a ] pyridine are more and more paid attention recently.

The existing synthesis method of benzo [4,5] imidazo [1,2-a ] pyridine derivatives has some disadvantages, and the synthesis of the compounds usually needs to be catalyzed by metal salts such as Pd/Cu, or catalyzed by expensive oxidants such as high-valence iodine, or expensive alkyne compounds as raw materials. Therefore, there is a need to develop a method for synthesizing benzo [4,5] imidazo [1,2-a ] pyridine derivatives more conveniently, safely and at low cost. The benzo [4,5] imidazo [1,2-a ] pyridine derivative has excellent fluorescence property and has potential application prospect in the field of chemical sensing or biological sensing. The synthesis and research of currently reported benzo [4,5] imidazo [1,2-a ] pyridine derivative fluorescent materials which are generally 2,3, 4-substituted (compound A), 3, 4-substituted (compound B) and 7, 8-substituted (compound C);

the synthesis of benzo [4,5] imidazo [1,2-a ] pyridine compounds with 1-position substituted by aromatic ring, especially the synthesis research under the condition of not using expensive raw materials, Pd/Cu and other metals or strong oxidants, and the research on the fluorescence performance thereof is not reported. Therefore, the synthesis method and the fluorescence property research of the 1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine derivatives have important research significance.

Disclosure of Invention

In order to overcome the problems of the prior art, the invention provides a benzo [4,5] imidazo [1,2-a ] pyridine derivative; the second object of the present invention is to provide a process for producing the benzo [4,5] imidazo [1,2-a ] pyridine derivative; it is a further object of the present invention to provide an AIE type fluorescent material; the invention also aims to provide the application of the benzo [4,5] imidazo [1,2-a ] pyridine derivative provided by the first aspect of the invention in detecting nitro aromatic explosives.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the invention provides a benzo [4,5] imidazo [1,2-a ] pyridine derivative, which has a structure shown in a general formula (I):

in the formula (I), R¹Selected from hydrogen, alkyl, halogen, alkoxy; r²Selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; ar is selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl.

Preferably, in said compound of formula (I), R¹Selected from hydrogen, methyl, chlorine or fluorine.

Preferably, in said compound of formula (I), R²Selected from hydrogen, methyl, ethyl, n-butyl, phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-bromophenyl, 4-chlorophenyl, 2-nitrophenyl, 3-methoxyphenyl, 2-bromophenyl, 2-fluorophenyl or 2-naphthyl.

Preferably, in the compound represented by the formula (I), Ar is selected from phenyl.

The second aspect of the present invention provides a method for preparing benzo [4,5] imidazo [1,2-a ] pyridine derivatives provided by the first aspect of the present invention, which comprises the following steps:

mixing the 2-substituted benzimidazole derivative and the 2-halogenated cinnamaldehyde derivative, and reacting to obtain the benzo [4,5] imidazo [1,2-a ] pyridine derivative shown in the formula (I).

Preferably, the molar ratio of the 2-substituted benzimidazole derivative to the 2-halogenated cinnamaldehyde derivative is 1 (0.5-2); further preferably, the molar ratio is 1 (0.8-1.3); still more preferably, the molar ratio is 1 (0.9-1.1).

Preferably, the structure of the 2-substituted benzimidazole derivative is shown as the formula (II):

in the formula (II), R³Selected from hydrogen, alkyl, halogen, alkoxy; r⁴Selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl.

Preferably, the 2-halogenated cinnamaldehyde derivative has a structure shown in formula (III):

in the formula (III), R⁵Selected from hydrogen, substituted or unsubstituted alkyl; x represents a halogen atom.

Preferably, the reaction also comprises adding a catalyst to participate in the reaction; further preferably, the catalyst comprises a base catalyst.

Preferably, the solvent for the reaction includes at least one of N, N-dimethylformamide, N-dimethylacetamide, chlorobenzene, dimethylsulfoxide, acetone, and diethyl ether; further preferably, the solvent comprises at least one of N, N-dimethylformamide and N, N-dimethylacetamide; most preferably, the solvent is N, N-dimethylformamide.

Preferably, the temperature of the reaction is 110 ℃ to 160 ℃; further preferably, the temperature of the reaction is 115 ℃ to 150 ℃; still further preferably, the temperature of the reaction is from 120 ℃ to 140 ℃.

Preferably, the reaction time is 10h-16 h; further preferably, the reaction time is 11h-14 h; still more preferably, the reaction time is from 11.5h to 13 h.

In a third aspect, the invention provides an AIE (aggregation-induced emission) type fluorescent material, wherein the AIE type fluorescent material comprises benzo [4,5] imidazo [1,2-a ] pyridine derivatives provided by the first aspect of the invention.

Preferably, the AIE-type fluorescent material is a fluorescent probe.

The fourth aspect of the invention provides the application of the benzo [4,5] imidazo [1,2-a ] pyridine derivative provided by the first aspect of the invention in detecting nitroaromatic explosives.

Preferably, the nitroaromatic explosives comprise nitrophenol explosives; further preferably, the nitroaromatic explosives comprise at least one of 2,4, 6-trinitrophenol and 2, 4-dinitrophenol.

Preferably, the application in detecting the nitro-aromatic explosives comprises the following steps:

1) preparing a benzo [4,5] imidazo [1,2-a ] pyridine compound solution, and measuring the fluorescence intensity of the solution;

2) adding the nitro-aromatic explosive to be detected into a benzo [4,5] imidazo [1,2-a ] pyridine compound solution, and measuring the fluorescence intensity of the solution.

Preferably, in the benzo [4,5] imidazo [1,2-a ] pyridine compound solution, the solvent is a mixed solution of water and tetrahydrofuran; more preferably, the solvent is a mixed solution of water and tetrahydrofuran in a mass ratio of 1 (0.1-2); still more preferably, the solvent is a mixed solution of water and tetrahydrofuran in a mass ratio of 1 (0.2-1).

Preferably, the scanning wavelength range of the measuring conditions is 350nm to 700nm, and the photomultiplier voltage is 700V.

The invention has the beneficial effects that:

the benzo [4,5] imidazo [1,2-a ] pyridine derivative provided by the invention has excellent fluorescence property and aggregation-induced emission property, and the preparation method has the advantages of simplicity, easiness in operation, readily available raw materials, wide substrate application range, high yield and the like. The benzo [4,5] imidazo [1,2-a ] pyridine derivative has good application prospect in the fields of chemical and biological fluorescent probes.

Specifically, the invention has the following advantages:

1. the invention synthesizes 1, 4-substituted benzo [4,5] for the first time]Imidazo [1,2-a ]]Derivatives of pyridine, and the preparation of the compounds¹H NMR、¹³The structural representation of the synthesized compound is carried out by C NMR, HRMS and X-ray single crystal diffraction analysis and test methods, and the results show that all the compounds prepared by the invention are new compounds, and the invention enriches benzo [4,5]]Imidazo [1,2-a ]]Pyridine small molecule library.

2. The invention provides a simple and practical synthesis method, which takes 2-bromocinnamaldehyde and 2-substituted benzimidazole compounds as raw materials to synthesize 1, 4-substituted benzo [4,5] imidazo [1,2-a ] pyridine derivatives in one step. The synthesis method has the advantages of simplicity, easiness in operation, easiness in obtaining raw materials, wide application range of substrates, high yield and the like. The method provided by the invention can be used for synthesizing dozens of benzo [4,5] imidazo [1,2-a ] pyridine fluorescent small molecules with different substituents at 1 and 4 positions, namely a series of novel benzo [4,5] imidazo [1,2-a ] pyridine derivatives.

3. The 1-phenyl substituted benzo [4,5] imidazo [1,2-a ] pyridine derivative prepared by the invention has excellent fluorescence property, and the molecules have aggregation-induced emission property, so that the benzo [4,5] imidazo [1,2-a ] pyridine has very good application prospect in the aspects of fluorescent materials and biological probes. The benzo [4,5] imidazo [1,2-a ] pyridine compound prepared by the invention can realize the detection of nitroaromatic explosives in aqueous solution, in particular the detection of 2,4, 6-trinitrophenol (PA) and 2, 4-Dinitrophenol (DNP).

Drawings

FIG. 1 is a chemical reaction formula diagram of benzo [4,5] imidazo [1,2-a ] pyridine derivatives prepared by the invention.

FIG. 2 is an X-ray single crystal diffractogram of Compound 2.

FIG. 3 is an X-ray single crystal diffractogram of Compound 6.

FIG. 4 is an X-ray single crystal diffractogram of Compound 9.

FIG. 5 is an X-ray single crystal diffractogram of Compound 10.

FIG. 6 is an X-ray single crystal diffractogram of Compound 24.

FIG. 7 is a graph showing the relationship between the fluorescence intensity and the scanning wavelength for Compound 2 at different water contents.

FIG. 8 is a graph showing the relationship between the water content of the aqueous solution of Compound 2 and the maximum fluorescence intensity at different scanning wavelengths.

FIG. 9 is a graph showing the relationship between the fluorescence intensity and the scanning wavelength for different water contents of Compound 5.

FIG. 10 is a graph showing the relationship between the water content of the aqueous solution of Compound 5 and the maximum fluorescence intensity at different scanning wavelengths.

FIG. 11 is a graph showing the relationship between the fluorescence intensity and the scanning wavelength for Compound 6 at different water contents.

FIG. 12 is a graph showing the relationship between the water content of the aqueous solution of Compound 6 and the maximum fluorescence intensity at different scanning wavelengths.

FIG. 13 is a graph showing the relationship between the fluorescence intensity and the scanning wavelength for Compound 7 at different water contents.

FIG. 14 is a graph showing the relationship between the water content of the aqueous solution of Compound 7 and the maximum fluorescence intensity at different scanning wavelengths.

FIG. 15 is a graph showing the relationship between the fluorescence intensity and the scanning wavelength for compound 14 at different water contents.

FIG. 16 is a graph showing the relationship between the water content of the aqueous solution of Compound 14 and the maximum fluorescence intensity at different scanning wavelengths.

FIG. 17 is a graph showing the relationship between the fluorescence intensity and the scanning wavelength for compound 18 with different water content.

FIG. 18 is a graph showing the relationship between the water content of an aqueous solution of Compound 18 and the maximum fluorescence intensity at different scanning wavelengths.

FIG. 19 is a graph of the fluorescence titration of compound 5 versus PA.

FIG. 20 is a graph of the fluorescence titration of compound 5 versus DNP.

FIG. 21 is a graph of the fluorescence titration of compound 6 versus PA.

FIG. 22 is a graph of the fluorescence titration of compound 7 versus PA.

Detailed Description

The following description of the embodiments of the present invention is provided in connection with the accompanying drawings and examples, but the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available through commercial purchase.

FIG. 1 is a chemical reaction formula diagram of benzo [4,5] imidazo [1,2-a ] pyridine derivatives prepared by the invention. The invention will be further described with reference to specific embodiments in the following, with reference to fig. 1.

Example 1

This example prepares 1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter referred to as "Compound 1") by the following procedure: 0.040g (0.30mmol) of 2-methylbenzimidazole and 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate, 2mL of a solvent N, N-dimethylformamide were mixed uniformly, and reacted under continuous stirring and heating under reflux at 140 ℃ for 12 hours, after the reaction was completed, diluted with 15mL of water, extracted with dichloromethane (15 mL. times.3), separated, the organic layer was dried over anhydrous sodium sulfate, spun under reduced pressure, and the crude product was purified and separated by silica gel column chromatography to give 63mg of yellow waxy compound 1.

Performing characterization on the obtained compound 1 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:6.59(d,J＝8.4Hz,1H,ArH-2),6.67(d,J＝6.6Hz,1H,ArH-4),6.96-7.00(m,1H,ArH-3),7.42(t,J＝7.2Hz,1H,ArH-15),7.45-7.49(m,1H,ArH-9),7.55(d,J＝7.2Hz,2H,ArH-13,17),7.59-7.62(m,2H,ArH-14,16),7.64-7.67(m,1H,ArH-8),7.73(d,J＝9.6Hz,1H,ArH-7),7.93(d,J＝8.4Hz,1H,ArH-10)；¹³C NMR(150MHz,CDCl₃),δ,ppm:112.1(C-10),114.7(C-4),116.9(C-7),119.7(C-8),120.4(C-9),125.2(C-2),129.0(C-13,17),129.1(C-14,16),129.2(C-15),129.3(C-11),130.1(C-3),134.5(C-5),141.3(C-12),145.0(C-6),149.6(C-1)；ESI-HRMS,m/z:Calcd for C₁₇H₁₃N₂[M+H]⁺,245.1073,found:245.1096。

the results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry show that the structure of the compound 1 is consistent with the expectation, and the compound 1 is proved to be 1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 83%.

Example 2

This example prepares 4-methyl-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter referred to as "Compound 2") by the following steps: 0.044g (0.30mmol) of 2-ethylbenzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of N, N-dimethylformamide as a solvent are uniformly mixed, the mixture is continuously stirred at 140 ℃, heated and refluxed for 12 hours, after the reaction is finished, the mixture is diluted by 15mL of water, then dichloromethane (15mL multiplied by 3) is used for extraction and liquid separation, an organic layer is dried by anhydrous sodium sulfate and is dried under reduced pressure, and a crude product is purified and separated by silica gel column chromatography to obtain 59mg of yellow solid compound 2 with a melting point of 150-.

Performing characterization on the obtained compound 2 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:2.78(s,3H,CH₃-18),6.59-6.63(m,2H,ArH-2,3),6.96-6.99(m,1H,ArH-9),7.30(d,J＝7.2Hz,1H,ArH-7),7.42(t,J＝7.2Hz,1H,ArH-15),7.55(d,J＝8.4Hz,2H,ArH-13,17),7.59-7.66(m,3H,ArH-8,14,16),7.98(d,J＝9.0Hz,1H,ArH-10)；¹³C NMR(150MHz,CDCl₃),δ,ppm:17.7(C-18),112.1(C-10),114.7(C-7),119.8(C-8),120.3(C-9),124.9(C-2),126.4(C-15),127.6(C-4),129.0(C-13,17),129.2(C-14,16),129.7(C-11),129.8(C-3),134.7(C-5),139.0(C-12),144.7(C-6),150.0(C-1)；ESI-HRMS,m/z:Calcd for C₁₈H₁₅N₂[M+H]⁺,259.1230,found:259.1240。

compound 2 was subjected to an X-ray single crystal diffraction test, and fig. 2 is an X-ray single crystal diffraction pattern of compound 2.

The results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy, high-resolution mass spectrometry and X-ray single crystal diffraction show that the structure of the compound 2 is consistent with the expectation, and the compound 2 is proved to be 4-methyl-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 76%.

Example 3

This example prepares 4-ethyl-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter referred to as "Compound 3") by the following steps: 0.048g (0.30mmol) of 2-propylbenzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of N, N-dimethylformamide as a solvent are uniformly mixed, the mixture is stirred and reacted at 140 ℃ for 12 hours, after the reaction is finished, the mixture is diluted by 15mL of water, and then dichloromethane (15mL multiplied by 3) is used for extraction and liquid separation, an organic layer is dried by anhydrous sodium sulfate, decompression spin-dried, and a crude product is subjected to silica gel column chromatography purification and separation to obtain 60mg of a yellow waxy compound 3.

Performing characterization on the obtained compound 3 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:1.51(t,J＝7.2Hz,3H,CH₃-19),3.23(q,J＝7.2Hz,2H,CH₂-18),6.60(d,J＝8.4Hz,1H,ArH-7),6.65(d,J＝7.2Hz,1H,ArH-2),6.95-6.99(m,1H,ArH-9),7.31(d,J＝7.2Hz,1H,ArH-3),7.42(t,J＝7.8Hz,1H,ArH-15),7.56(d,J＝7.8Hz,2H,ArH-13,17),7.59-7.62(m,2H,ArH-14,16),7.63-7.66(m,1H,ArH-8),7.98(d,J＝7.8Hz,1H,ArH-10)；¹³C NMR(150MHz,CDCl₃),δ,ppm:13.1(C-19),24.3(C-18),112.1(C-10),114.7(C-7),119.7(C-8),120.2(C-9),124.9(C-2),125.5(C-15),129.0(C-13,17),129.2(C-14,16),129.7(C-11),129.8(C-3),132.1(C-4),134.8(C-5),138.8(C-12),144.7(C-6),149.6(C-1)；ESI-HRMS,m/z:Calcd for C₁₉H₁₇N₂[M+H]⁺,273.1386,found:273.1388。

the hydrogen nuclear magnetic resonance spectrum, the carbon nuclear magnetic resonance spectrum and the high-resolution mass spectrum show that the structure of the compound 3 is consistent with the expectation, and the compound 3 is proved to be 4-ethyl-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 74%.

Example 4

This example prepares 4-n-butyl-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter referred to as "Compound 4") by the following steps: 0.056g (0.30mmol) of 2-N-pentylbenzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate, and 2mL of N, N-dimethylformamide as a solvent are mixed uniformly, stirred at 140 ℃ for 12 hours, diluted with 15mL of water after the reaction is finished, extracted with dichloromethane (15 mL. times.3), separated, dried with anhydrous sodium sulfate in the organic layer, dried under reduced pressure, and the crude product is purified and separated by silica gel column chromatography to obtain 69mg of yellow waxy compound 4.

Performing characterization on the obtained compound 4 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:1.03(t,J＝7.2Hz,3H,CH₃-21),1.53-1.58(m,2H,CH₂-20),1.89-1.95(m,2H,CH₂-19),3.20(t,J＝7.2Hz,2H,CH₃-18),6.60(d,J＝8.4Hz,1H,ArH-7),6.64(d,J＝7.2Hz,1H,ArH-2),6.95-6.98(m,1H,ArH-9),7.29(d,J＝7.2Hz,1H,ArH-3),7.41(t,J＝7.2Hz,1H,ArH-15),7.55(d,J＝7.2Hz,2H,ArH-13,17),7.59-7.62(m,2H,ArH-14,16),7.63-7.66(m,1H,ArH-8),7.98(d,J＝8.4Hz,1H,ArH-10)；¹³C NMR(150MHz,CDCl₃),δ,ppm:14.1(C-21),22.7(C-20),30.7(C-18),30.9(C-19),112.1(C-10),114.7(C-7),119.7(C-8),120.1(C-9),124.9(C-2),126.2(C-15),129.0(C-13,17),129.2(C-14,16),129.7(C-11),129.8(C-3),130.8(C-4),134.8(C-5),138.8(C-12),144.7(C-6),149.7(C-1)；ESI-HRMS,m/z:Calcd for C₂₁H₂₁N₂[M+H]⁺,301.1699,found:301.1696。

the hydrogen nuclear magnetic resonance spectrum, the carbon nuclear magnetic resonance spectrum and the high-resolution mass spectrum show that the structure of the compound 4 is consistent with the expectation, and the compound 4 is proved to be 4-n-butyl-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 77 percent.

Example 5

This example prepares 4-phenyl-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter referred to as "Compound 5") by the following steps: 0.062g (0.30mmol) 2-benzyl benzimidazole and 0.063g (0.30mmol) 2-bromocinnamaldehyde, 0.103g potassium carbonate, 2mL solvent N, N-dimethylformamide are mixed uniformly, stirring reaction is carried out at 120 ℃ for 12 hours, after the reaction is finished, 15mL water is used for dilution, dichloromethane (15mL multiplied by 3) is used for extraction and liquid separation, an organic layer is dried by anhydrous sodium sulfate, decompression spin-drying is carried out, and a crude product is purified and separated by silica gel column chromatography to obtain 87mg yellow solid compound 5 with a melting point of 144-146 ℃.

Performing characterization on the obtained compound 5 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:6.65(d,J＝8.4Hz,1H,ArH-7),6.79(d,J＝7.2Hz,1H,ArH-2),6.99-7.03(m,1H,ArH-9),7.44(t,J＝7.2Hz,1H,ArH-21),7.47(t,J＝7.2Hz,1H,ArH-15),7.56-7.90(m,8H,ArH-3,8,14,16,19,20,22,23),8.02(d,J＝8.4Hz,1H,ArH-10),8.11(d,J＝7.8Hz,2H,ArH-13,17)；¹³C NMR(150MHz,CDCl₃),δ,ppm:112.4(C-10),114.7(C-7),120.2(C-8),120.5(C-9),125.0(C-2),127.6(C-15),128.4(C-21),128.7(C-19,23),129.1(C-13,17),129.2(C-14,16,20,22),129.5(C-3),129.6(C-11),130.0(C-18),134.6(C-4),136.9(C-12),140.2(C-6),145.1(C-5),148.5(C-1)；ESI-HRMS,m/z:Calcd for C₂₃H₁₇N₂[M+H]⁺,321.1386,found:321.1393。

the hydrogen nuclear magnetic resonance spectrum, the carbon nuclear magnetic resonance spectrum and the high-resolution mass spectrum show that the structure of the compound 5 is consistent with the expectation, and the compound 5 is proved to be 4-phenyl-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 90 percent.

Example 6

This example provides 4- (p-methylphenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter referred to as "Compound 6") as follows: 0.066g (0.30mmol) of 2- (4-methylbenzyl) benzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of N, N-dimethylformamide as a solvent are uniformly mixed, the mixture is stirred and reacted for 12 hours at 120 ℃, after the reaction is finished, the mixture is diluted by 15mL of water, then dichloromethane (15mL multiplied by 3) is used for extraction and liquid separation, an organic layer is dried by anhydrous sodium sulfate and is dried under reduced pressure, and a crude product is purified and separated by silica gel column chromatography to obtain 87mg of yellow solid compound 6 with a melting point of 203-.

Performing characterization on the obtained compound 6 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:2.49(s,3H,CH₃-22),6.65(d,J＝8.4Hz,1H,ArH-7),6.77(d,J＝7.2Hz,1H,ArH-2),6.99-7.02(m,1H,ArH-9),7.40(d,J＝7.8Hz,2H,ArH-20,22),7.42-7.45(m,1H,ArH-8),7.55(d,J＝7.2Hz,1H,ArH-3),7.60-7.67(m,5H,ArH-14,15,16,19,23),8.00-8.03(m,3H,ArH-10,13,17)；¹³C NMR(150MHz,CDCl₃),δ,ppm:21.4(C-24),112.4(C-10),114.7(C-7),120.2(C-8),120.4(C-9),125.0(C-2),127.2(C-15),129.0(C-19,23),129.1(C-13,14,16,17),129.4(C-20,22),129.5(C-21),129.6(C-18),130.0(C-4),134.0(C-11),134.7(C-4),138.2(C-12),139.9(C-6),145.1(C-5),148.7(C-1)；ESI-HRMS,m/z:Calcd for C₂₄H₁₉N₂[M+H]⁺,335.1543,found:335.1557。

compound 6 was subjected to X-ray single crystal diffraction testing, and fig. 3 is an X-ray single crystal diffraction pattern of compound 6.

The results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy, high-resolution mass spectrometry and single-crystal diffraction show that the structure of the compound 6 is consistent with the expectation, and the compound 6 is proved to be 4- (p-methylphenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 87%.

Example 7

This example provides 4- (p-methoxyphenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter referred to as "Compound 7") as follows: 0.071g (0.30mmol) of 2- (4-p-methoxybenzyl) benzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of solvent N, N-dimethylformamide are uniformly mixed, stirred and reacted at 120 ℃ for 12 hours, after the reaction is finished, diluted by 15mL of water, extracted and separated by dichloromethane (15mL multiplied by 3), an organic layer is dried by anhydrous sodium sulfate, and dried under reduced pressure, and a crude product is purified and separated by silica gel column chromatography to obtain 96mg of yellow solid compound 7 with a melting point of 186-.

Performing characterization on the obtained compound 7 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:3.92(s,3H,OCH₃-24),6.64(d,J＝8.4Hz,1H,ArH-7),6.77(d,J＝6.6Hz,1H,ArH-2),6.97-7.01(m,1H,ArH-9),7.12(d,J＝8.4Hz,2H,ArH-20,22),7.41-7.44(m,1H,ArH-8),7.53(d,J＝6.6Hz,1H,ArH-3),7.60-7.67(m,5H,ArH-14,15,16,19,23),8.00(d,J＝7.8Hz,1H,ArH-10),8.08(d,J＝8.4Hz,2H,ArH-13,17)；¹³C NMR(150MHz,CDCl₃),δ,ppm:55.4(C-24),112.4(C-10),114.1(C-20,22),114.7(C-7),120.2(C-8),120.4(C-9),124.9(C-2),126.7(C-18),129.1(C-13,17),129.1(C-15),129.2(C-14,16),129.3(C-3),129.6(C-11),129.9(C-4),130.3(C-19,23),134.7(C-12),137.7(C-6),145.1(C-5),148.7(C-1),159.8(C-21)；ESI-HRMS,m/z:Calcd for C₂₄H₁₉N₂O[M+H]⁺,351.1492,found:351.1535。

the results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry show that the structure of the compound 7 is consistent with the expectation, and the compound 7 is proved to be 4- (p-methoxyphenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 91%.

Example 8

This example provides 4- (p-bromophenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter referred to as "Compound 8") as follows: 0.086g (0.30mmol) of 2- (4-bromobenzyl) benzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of N, N-dimethylformamide as a solvent are uniformly mixed, the mixture is stirred and reacted for 12 hours at the temperature of 120 ℃, after the reaction is finished, the mixture is diluted by 15mL of water, then dichloromethane (15mL multiplied by 3) is used for extraction and liquid separation, an organic layer is dried by anhydrous sodium sulfate and is dried in a rotary manner under reduced pressure, and a crude product is purified and separated by silica gel column chromatography to obtain 106mg of yellow solid compound 8 with the melting point of 236-.

Performing characterization on the obtained compound 8 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:6.63(d,J＝8.4Hz,1H,ArH-7),6.79(d,J＝6.6Hz,1H,ArH-2),6.99-7.02(m,1H,ArH-9),7.43(t,J＝7.2Hz,1H,ArH-15),7.56(d,J＝6.6Hz,1H,ArH-3),7.61(d,J＝7.8Hz,2H,ArH-19,23),7.63-7.65(m,2H,ArH-14,16),7.67-7.71(m,3H,ArH-8,20,22),7.98-8.01(m,3H,ArH-10,13,17)；¹³C NMR(150MHz,CDCl₃),δ,ppm:112.3(C-10),114.7(C-7),120.1(C-8),120.6(C-9),122.6(C-21),125.2(C-2),127.5(C-15),128.2(C-3),129.0(C-20,22),129.2(C-13,17),129.5(C-11),130.1(C-18),130.7(C-14,16),131.8(C-19,23),134.5(C-4),135.7(C-12),140.6(C-6),145.0(C-5),148.2(C-1)；ESI-HRMS,m/z:Calcd for C₂₃H₁₆BrN₂[M+H]⁺,399.0491,found:399.0502。

the results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry show that the structure of the compound 8 is consistent with the expectation, and the compound 8 is proved to be 4- (p-bromophenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 89%.

Example 9

This example provides 4- (p-chlorophenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter referred to as "Compound 9") as follows: 0.073g (0.30mmol) of 2- (4-chlorobenzyl) benzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of N, N-dimethylformamide as a solvent are uniformly mixed, stirred and reacted for 12 hours at the temperature of 120 ℃, after the reaction is finished, diluted by 15mL of water, extracted and separated by dichloromethane (15mL multiplied by 3), an organic layer is dried by anhydrous sodium sulfate and dried under reduced pressure, and a crude product is purified and separated by silica gel column chromatography to obtain 99mg of yellow solid compound 9 with the melting point of 212 DEG and 214 ℃.

Performing characterization on the obtained compound 9 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:6.63(d,J＝9.0Hz,1H,ArH-7),6.79(d,J＝6.6Hz,1H,ArH-2),6.99-7.02(m,1H,ArH-9),7.43(t,J＝7.2Hz,1H,ArH-15),7.53-7.57(m,3H,ArH-8,14,16),7.60-7.69(m,5H,ArH-3,19,20,22,23),7.98(d,J＝7.8Hz,1H,ArH-10),8.06(d,J＝9.0Hz,2H,ArH-13,17)；¹³C NMR(150MHz,CDCl₃),δ,ppm:112.3(C-10),114.7(C-7),120.1(C-8),120.6(C-9),125.2(C-2),127.5(C-15),128.2(C-3),128.8(C-13,17),129.1(C-19,23),129.2(C-14,16),129.5(C-21),130.1(C-18),130.4(C-20,22),134.3(C-11),134.5(C-4),135.2(C-12),140.6(C-6),145.0(C-5),148.2(C-1)；ESI-HRMS,m/z:Calcd for C₂₃H₁₆ClN₂[M+H]⁺,355.0997,found:355.0987。

compound 9 was subjected to an X-ray single crystal diffraction test, and fig. 4 is an X-ray single crystal diffraction pattern of compound 9.

The results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy, high-resolution mass spectrometry and single-crystal diffraction show that the structure of the compound 9 is consistent with the expectation, and the compound 9 is proved to be 4- (p-chlorophenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 93 percent.

Example 10

This example provides 4- (p-nitrophenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter "Compound 10") as follows: 0.076g (0.30mmol) of 2- (4-nitrobenzyl) benzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of solvent N, N-dimethylformamide are uniformly mixed, stirred and reacted for 12 hours at the temperature of 120 ℃, after the reaction is finished, diluted by 15mL of water, extracted and separated by dichloromethane (15mL multiplied by 3), an organic layer is dried by anhydrous sodium sulfate and dried by decompression and spin-dried, and a crude product is purified and separated by silica gel column chromatography to obtain 50mg of yellow solid compound 10 with the melting point of 268 minus 270 ℃.

Performing characterization on the obtained compound 10 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:6.65(d,J＝9.0Hz,1H,ArH-7),6.85(d,J＝7.2Hz,1H,ArH-2),7.02-7.05(m,1H,ArH-9),7.46(t,J＝7.2Hz,1H,ArH-15),7.62(d,J＝6.6Hz,2H,ArH-13,17),7.65-7.71(m,4H,ArH-3,8,14,16),7.99(d,J＝8.4Hz,1H,ArH-10),8.34(d,J＝9.0Hz,2H,ArH-19,23),8.43(d,J＝9.0Hz,2H,ArH-20,22)；¹³C NMR(150MHz,CDCl₃),δ,ppm:112.1(C-10),114.8(C-7),120.2(C-8),121.0(C-9),123.9(C-20,22),125.5(C-2),126.8(C-15),128.5(C-3),128.9(C-13,17),129.3(C-14,16),129.4(C-11),129.9(C-19,23),130.3(C-4),134.2(C-12),141.9(C-18),143.3(C-6),145.0(C-21),147.5(C-5),147.7(C-1)；ESI-HRMS,m/z:Calcd for C₂₃H₁₆N₃O₂[M+H]⁺,366.1237,found:366.1284。

compound 10 was subjected to an X-ray single crystal diffraction test, and fig. 5 is an X-ray single crystal diffraction pattern of compound 10.

The results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy, high-resolution mass spectrometry and single-crystal diffraction show that the structure of the compound 10 is consistent with the expectation, and the compound 10 is proved to be 4- (p-nitrophenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 45%.

Example 11

This example provides 4- (3-methoxyphenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter referred to as "Compound 11") as follows: 0.071g (0.30mmol) of 2- (3-methoxybenzyl) benzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of N, N-dimethylformamide as a solvent are uniformly mixed, the mixture is stirred and reacted for 12 hours at the temperature of 120 ℃, after the reaction is finished, the mixture is diluted by 15mL of water, then dichloromethane (15mL multiplied by 3) is used for extraction and liquid separation, an organic layer is dried by anhydrous sodium sulfate and is dried by decompression and spinning, and a crude product is purified and separated by silica gel column chromatography to obtain 99mg of yellow solid compound 11 with the melting point of 186-.

Performing characterization on the obtained compound 11 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:3.94(s,3H,OCH₃-24),6.64(d,J＝8.4Hz,1H,ArH-7),6.78(d,J＝6.6Hz,1H,ArH-2),6.98-7.04(m,2H,ArH-9,21),7.43(t,J＝7.2Hz,1H,ArH-15),7.47-7.50(m,1H,ArH-22),7.58(d,J＝6.6Hz,1H,ArH-3),7.61-7.65(m,4H,ArH-8,14,16,23),7.67(d,J＝6.6Hz,2H,ArH-13,17),7.71(s,1H,ArH-19),8.00(d,J＝8.4Hz,1H,ArH-10)；¹³C NMR(150MHz,CDCl₃),δ,ppm:55.4(C-24),112.3(C-10),114.0(C-19),114.7(C-7),114.9(C-21),120.4(C-8),120.6(C-9),121.6(C-23),125.0(C-2),127.7(C-15),129.1(C-13,17),129.2(C-14,16),129.3(C-22),129.5(C-11),129.6(C-3),130.0(C-18),134.6(C-4),138.2(C-12),140.3(C-6),145.1(C-5),148.5(C-1),159.7(C-20)；ESI-HRMS,m/z:Calcd for C₂₄H₁₉N₂O[M+H]⁺,351.1492,found:351.1496。

the results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry show that the structure of the compound 11 is consistent with the expectation, and the compound 11 is proved to be 4- (3-methoxyphenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 94%.

Example 12

This example provides 4- (2-fluorophenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter referred to as "compound 12") as follows: 0.068g (0.30mmol) of 2- (2-fluorobenzyl) benzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of N, N-dimethylformamide as a solvent are uniformly mixed, the mixture is stirred and reacted for 12 hours at the temperature of 120 ℃, after the reaction is finished, the mixture is diluted by 15mL of water, then dichloromethane (15mL multiplied by 3) is used for extraction and liquid separation, an organic layer is dried by anhydrous sodium sulfate and is dried in a rotary manner under reduced pressure, and a crude product is purified and separated by silica gel column chromatography to obtain 87mg of yellow solid compound 12 with the melting point of 65-67 ℃.

Performing characterization on the obtained compound 12 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum, a nuclear magnetic resonance fluorine spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:6.65(d,J＝9.0Hz,1H,ArH-7),6.79(d,J＝7.2Hz,1H,ArH-2),6.99-7.02(m,1H,ArH-9),7.28-7.31(m,1H,ArH-22),7.35-7.38(m,1H,ArH-21),7.43(t,J＝7.2Hz,1H,ArH-15),7.45-7.48(m,1H,ArH-8),7.59(d,J＝7.2Hz,1H,ArH-3),7.61-7.70(m,5H,ArH-13,14,16,17,20),7.98-8.01(m,2H,ArH-10,23)；¹³C NMR(150MHz,CDCl₃),δ,ppm:111.95(C-10),114.72(C-7),116.21(d,J＝22.5Hz,C-20),120.21(C-8),120.51(C-9),123.79(C-15),124.29(d,J＝3.0Hz,C-22),124.45(d,J＝13.5Hz,C-21,23),125.12(C-2),129.07(C-13,17),129.18(C-14,16),129.74(d,J＝37.5Hz,C-18),129.97(d,J＝25.5Hz,C-4),130.11(C-11),132.12(d,J＝3.0Hz,C-3),134.51(C-12),140.91(C-6),145.09(C-5),148.41(C-1),160.18(d,J＝246Hz,C-19)；¹⁹F NMR(564MHz,CDCl₃),δ:-107.8；ESI-HRMS,m/z:Calcd for C₂₃H₁₆FN₂[M+H]⁺,339.1292,found:339.1287。

the results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy, fluorine nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry show that the structure of the compound 12 is consistent with the expectation, and the compound 12 is proved to be 4- (2-fluorophenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 86%.

Example 13

This example provides 4- (2-bromophenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter "Compound 13") as follows: 0.086g (0.30mmol) of 2- (2-bromobenzyl) benzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of N, N-dimethylformamide as a solvent are mixed uniformly, the mixture is stirred and reacted at 120 ℃ for 12 hours, after the reaction is finished, the mixture is diluted by 15mL of water, then dichloromethane (15mL multiplied by 3) is used for extraction and liquid separation, an organic layer is dried by anhydrous sodium sulfate and is dried by decompression and rotation, and a crude product is purified and separated by silica gel column chromatography to obtain 99mg of yellow solid compound 13 with a melting point of 79-81 ℃.

Performing characterization on the obtained compound 13 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:6.66(d,J＝9.0Hz,1H,ArH-7),6.79(d,J＝6.6Hz,1H,ArH-2),6.98-7.02(m,1H,ArH-9),7.33-7.36(m,1H,ArH-22),7.42(t,J＝7.8Hz,1H,ArH-15),7.47-7.52(m,2H,ArH-3,8),7.64-7.70(m,6H,ArH-13,14,16,17,21,23),7.79(d,J＝7.8Hz,1H,ArH-20),7.97(d,J＝8.4Hz,1H,ArH-10)；¹³C NMR(150MHz,CDCl₃),δ,ppm:111.7(C-10),114.7(C-7),120.2(C-8),120.5(C-9),123.7(C-19),125.1(C-2),127.5(C-15),129.0(C-22),129.1(C-13,17),129.2(C-14,16),129.6(C-21),129.8(C-23),130.0(C-20),130.1(C-3),132.0(C-11),133.4(C-18),134.5(C-4),137.7(C-12),141.0(C-6),145.1(C-5),148.4(C-1)；ESI-HRMS,m/z:Calcd for C₂₃H₁₆BrN₂[M+H]⁺,399.0491,found:399.0502。

the results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry show that the structure of the compound 13 is consistent with the expectation, and the compound 13 is proved to be 4- (2-bromophenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 83%.

Example 14

This example provides 4- (1-naphthyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter referred to as "compound 14") as follows: 0.077g (0.30mmol) of 2- (2- (1-naphthyl) methyl) benzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of solvent N, N-dimethylformamide are mixed uniformly, the mixture is stirred and reacted for 12 hours at the temperature of 120 ℃, after the reaction is finished, the mixture is diluted by 15mL of water, then dichloromethane (15mL multiplied by 3) is used for extraction and liquid separation, an organic layer is dried by anhydrous sodium sulfate and is dried by decompression, a crude product is purified and separated by silica gel column chromatography, 89mg of yellow solid compound 14 is obtained, and the melting point is 177-179 ℃.

Performing characterization on the obtained compound 14 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:6.71(d,J＝9.0Hz,1H,ArH-7),6.85(d,J＝7.2Hz,1H,ArH-2),7.00-7.04(m,1H,ArH-9),7.40-7.45(m,2H,ArH-20,21),7.52-7.56(m,2H,ArH-3,8),7.66-7.73(m,6H,ArH-13,14,15,16,17,25),6.81(d,J＝7.2Hz,1H,ArH-22),7.85(d,J＝8.4Hz,1H,ArH-24),6.93(d,J＝8.4Hz,1H,ArH-26),7.98(d,J＝8.4Hz,1H,ArH-19),8.01(d,J＝8.4Hz,1H,ArH-10)；¹³C NMR(150MHz,CDCl₃),δ,ppm:112.0(C-10),114.7(C-7),120.3(C-8),120.5(C-9),125.1(C-2),125.6(C-26),125.9(C-25),126.0(C-20),126.1(C-21),128.0(C-19),128.5(C-15),128.9(C-22,24),129.1(C-13,17),129.2(C-14,16),129.6(C-3),130.1(C-27),130.3(C-23),132.1(C-11),134.1(C-18),134.6(C-4),134.8(C-12),140.8(C-6),145.1(C-5),149.4(C-1)；ESI-HRMS,m/z:Calcd for C₂₇H₁₉N₂[M+H]⁺,371.1543,found:371.1554。

the results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry show that the structure of the compound 14 is consistent with the expectation, and the compound 14 is proved to be 4- (1-naphthyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 80%.

Example 15

This example prepares 7-methyl-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine and 8-methyl-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (although as a mixture, hereinafter referred to as "compound 15") by the following steps: 0.044g (0.30mmol) of 2, 5-dimethylbenzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of N, N-dimethylformamide as a solvent are uniformly mixed, the mixture is stirred and reacted for 12 hours at the temperature of 120 ℃, after the reaction is finished, the mixture is diluted by 15mL of water, then dichloromethane (15mL multiplied by 3) is used for extraction and liquid separation, an organic layer is dried by anhydrous sodium sulfate and is dried by decompression, and a crude product is purified and separated by silica gel column chromatography to obtain 54mg of yellow solid compound 15.

Performing characterization on the obtained compound 15 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:2.25(s,3H,CH₃-18),2.47(s,3H,CH₃-18’),6.32(s,1H,ArH-7),6.44(d,J＝8.4Hz,1H,ArH-10’),6.62-6.64(m,2H,ArH-2/ArH-2’),6.78(d,J＝8.4Hz,1H,ArH-4’),7.23(d,J＝7.8Hz,1H,ArH-4),7.39-7.44(m,2H,ArH-3/ArH-3’),7.52-7.53(m,4H,ArH-14,16/ArH-14’,16’),7.56-7.64(m,6H,ArH-13,15,17/ArH-8’,13’,17’),7.68-7.69(m,3H,ArH-9,10/ArH-7’),7.78(d,J＝8.4Hz,1H,ArH-10)；¹³C NMR(150MHz,CDCl₃),δ,ppm:21.72(C-18’),21.93(C-18),111.85(C-7’),114.18(C-10’),114.54(C-10),116.66(C-4’),116.85(C-4’),119.14(C-7),122.12(C-8’),126.88(C-9),127.33(C-2),128.61(C-2’),128.88(C-11’),129.00(C-13,13’,17,17’),129.04(C-14,16),129.08(C-14’,16’),129.33(C-11),129.96(C-3),129.99(C-3’),130.09(C-9),134.56(C-12’),134.61(C-12),135.18(C-8),141.13(C-6’),141.16(C-6),143.10(C-5),145.38(C-5’),149.33(C-1),149.65(C-1’)；ESI-HRMS,m/z:Calcd for C₁₈H₁₅N₂[M+H]⁺,259.1230,found:259.1273。

the results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry show that the structure of the compound 15 is consistent with the expectation, and the compound 15 is proved to be 7-methyl-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine and 8-methyl-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine, and the yield is 70%.

Example 16

This example provides the following procedure for the preparation of 7-chloro-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter referred to as "Compound 16"): 0.050g (0.30mmol) of 2-methyl-5-chlorobenzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of N, N-dimethylformamide as a solvent are uniformly mixed, the mixture is stirred and reacted for 12 hours at the temperature of 120 ℃, after the reaction is finished, the mixture is diluted by 15mL of water, then dichloromethane (15mL multiplied by 3) is used for extraction and liquid separation, an organic layer is dried by anhydrous sodium sulfate and is dried by decompression, a crude product is purified and separated by silica gel column chromatography to obtain 35mg of yellow solid compound 16, and the melting point is 159-.

Performing characterization on the obtained compound 16 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:6.47(d,J＝9.0Hz,1H,ArH-10),6.71(d,J＝6.6Hz,1H,ArH-2),6.92-6.94(dd,J₁＝9.0Hz,J₂＝1.8Hz,1H,ArH-9),7.50-7.52(m,1H,ArH-3),7.54(d,J＝7.2Hz,2H,ArH-13,17),6.07-6.63(m,2H,ArH-14,16),7.655-7.68(m,1H,ArH-15),7.72(d,J＝9.0Hz,1H,ArH-4),7.87(d,J＝1.8Hz,1H,ArH-7)；¹³C NMR(150MHz,CDCl₃),δ,ppm:112.5(C-7),115.4(C-10),116.8(C-4),119.0(C-9),120.9(C-2),127.8(C-15),128.9(C-13,17),129.3(C-14,16),129.8(C-8),130.3(C-3),130.9(C-11),134.1(C-6),141.3(C-5),145.8(C-12),150.3(C-1)；ESI-HRMS,m/z:Calcd for C₁₇H₁₂ClN₂[M+H]⁺,279.0684,found:279.0710。

the results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry show that the structure of the compound 16 is consistent with the expectation, and the compound 16 is proved to be 7-chloro-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 42%.

Example 17

This example provides the following procedure for the preparation of 8-chloro-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter referred to as "Compound 17"): 0.050g (0.30mmol) of 2-methyl-5-chlorobenzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of N, N-dimethylformamide as a solvent are uniformly mixed, the mixture is stirred and reacted for 12 hours at the temperature of 120 ℃, after the reaction is finished, the mixture is diluted by 15mL of water, then dichloromethane (15mL multiplied by 3) is used for extraction and liquid separation, an organic layer is dried by anhydrous sodium sulfate and is dried by decompression, and a crude product is purified and separated by silica gel column chromatography to obtain 36mg of yellow solid compound 17 with the melting point of 184-.

Performing characterization on the obtained compound 17 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:6.52(d,J＝1.8Hz,1H,ArH-10),6.71(d,J＝6.6Hz,1H,ArH-2),7.38-7.40(dd,J₁＝9.0Hz,J₂＝1.8Hz,1H,ArH-8),7.48-7.51(m,1H,ArH-3),7.55(d,J＝7.2Hz,2H,ArH-13,17),7.63-7.66(m,2H,ArH-14,16),7.68-7.73(m,2H,ArH-4,15),7.83(d,J＝9.0Hz,2H,ArH-7)；¹³C NMR(150MHz,CDCl₃),δ,ppm:112.4(C-7),114.7(C-10),117.0(C-4),120.4(C-8),125.7(C-2),125.9(C-15),128.9(C-13,17),129.3(C-14,16),129.5(C-9),129.6(C-11),130.4(C-3),133.9(C-5),141.2(C-6),143.5(C-12),150.1(C-1)；ESI-HRMS,m/z:Calcd for C₂₁H₂₀BrN₂O₅S[M+H]⁺,491.0276,found:491.0263。

the results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry show that the structure of the compound 17 is consistent with the expectation, and the compound 17 is proved to be 8-chloro-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 43 percent.

Example 18

This example provides the following procedure for the preparation of 7, 8-dichloro-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter "compound 18"): 0.060g (0.30mmol) of 2-methyl-5, 6-dichlorobenzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of solvent N, N-dimethylformamide are mixed uniformly, stirred and reacted for 12 hours at the temperature of 120 ℃, after the reaction is finished, diluted by 15mL of water, extracted by dichloromethane (15mL multiplied by 3), separated, dried by anhydrous sodium sulfate on an organic layer, dried by decompression and spun, and a crude product is purified and separated by silica gel column chromatography to obtain 70mg of yellow solid compound 18 with the melting point of 231-.

Performing characterization on the obtained compound 18 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:6.60(s,1H,ArH-7),6.72(dd,J₁＝7.8Hz,J₁＝1.2Hz,1H,ArH-4),7.51-7.53(m,3H,ArH-14,15,16),7.63-7.66(m,2H,ArH-2,3),7.69-7.70(m,2H,ArH-13,17),7.95(s,1H,ArH-10)；¹³C NMR(150MHz,CDCl₃),δ,ppm:112.7(C-10),115.9(C-4),116.9(C-7),120.3(C-8),123.9(C-9),128.1(C-2),128.7(C-13,17),129.4(C-15),129.5(C-14,16),130.3(C-11),130.6(C-3),133.5(C-6),141.3(C-5),144.2(C-12),150.8(C-1)；ESI-HRMS,m/z:Calcd for C₁₇H₁₁Cl₂N₂[M+H]⁺,313.0294,found:313.0289。

the results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry show that the structure of the compound 18 is consistent with the expectation, and the compound 18 is proved to be 7, 8-dichloro-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 75%.

Example 19

This example prepares 7, 8-dichloro-4-methyl-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter referred to as "Compound 19") by the following procedure: 0.064g (0.30mmol) of 2-ethyl-5, 6-dichlorobenzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of solvent N, N-dimethylformamide are uniformly mixed, stirred and reacted for 12 hours at the temperature of 120 ℃, after the reaction is finished, diluted by 15mL of water, extracted by dichloromethane (15mL multiplied by 3), separated, dried by anhydrous sodium sulfate on an organic layer, dried by decompression and spun, and a crude product is purified and separated by silica gel column chromatography to obtain 70mg of light yellow solid compound 19, and the melting point is 253 ℃ and 255 ℃.

Performing characterization on the obtained compound 19 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:2.74(s,3H,CH₃-18),6.67(d,J＝7.2Hz,1H,ArH-2),7.34(d,J＝7.2Hz,1H,ArH-3),7.52(d,J＝7.2Hz,2H,ArH-13,17),7.63-7.65(m,2H,ArH-14,16),7.68-7.70(t,J＝7.2Hz,1H,ArH-15),8.03(s,1H,ArH-10)；¹³C NMR(150MHz,CDCl₃),δ,ppm:17.6(C-18),112.7(C-10),115.9(C-7),120.5(C-8),123.8(C-9),128.6(C-4),128.7(C-13,17),129.0(C-2),129.1(C-14,16),129.4(C-15),130.4(C-11),130.4(C-3),133.7(C-5),138.9(C-12),143.9(C-6),151.3(C-1)；ESI-HRMS,m/z:Calcd for C₁₈H₁₃Cl₂N₂[M+H]⁺,327.0450,found:327.0449。

the results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry show that the structure of the compound 19 is consistent with the expectation, and the compound 19 is proved to be 7, 8-dichloro-4-methyl-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 72%.

Example 20

This example provides the following procedure for the preparation of 7, 8-difluoro-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter referred to as "compound 20"): 0.050g (0.30mmol) of 2-methyl-5, 6-difluorobenzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of solvent N, N-dimethylformamide are uniformly mixed, stirred and reacted for 12 hours at the temperature of 120 ℃, after the reaction is finished, diluted by 15mL of water, extracted by dichloromethane (15mL multiplied by 3) and separated, an organic layer is dried by anhydrous sodium sulfate and dried under reduced pressure, and a crude product is purified and separated by silica gel column chromatography to obtain 56mg of light yellow solid compound 20 with the melting point of 177-.

Performing characterization on the obtained compound 20 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:6.31-6.33(m,1H,ArH-7),6.70(d,J＝6.6Hz,1H,ArH-4),7.47-7.49(m,1H,ArH-10),7.53(d,J＝7.2Hz,2H,ArH-14,16),7.71-7.65(m,3H,ArH-2,3,15),7.67-7.70(m,2H,ArH-13,17)；¹³C NMR(150MHz,CDCl₃),δ,ppm:102.7(d,J＝24Hz,C-7),106.1(d,J＝24Hz,C-10),112.4(C-4),116.8(C-2),124.0(d,J＝10.5Hz,C-11),128.9(C-13,17),129.3(C-15),129.4(C-14,16),130.5(C-3),133.6(C-5),140.7(d,J＝9Hz,C-6),140.8(C-12),144.9-146.6(dd,J₁＝240Hz,J₂＝15Hz,C-8),148.7-150.4(dd,J₁＝244.5Hz,J₂＝15Hz,C-9),150.7(d,J＝3Hz,C-1)；¹⁹F NMR(564MHz,CDCl₃),δ:-142.3,-138.2；ESI-HRMS,m/z:Calcd for C₁₇H₁₁F₂N₂[M+H]⁺,281.0885,found:281.0885。

the results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry show that the structure of the compound 20 is consistent with the expectation, and the compound 20 is proved to be 7, 8-difluoro-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 67%.

Example 21

This example provides 7, 8-dimethyl-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter referred to as "Compound 21") as follows: 0.048g (0.30mmol) of 2,5, 6-trimethylfluorobenzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of solvent N, N-dimethylformamide are mixed uniformly, stirred and reacted at 120 ℃ for 12 hours, after the reaction is finished, diluted by 15mL of water, extracted by dichloromethane (15mL multiplied by 3), separated, dried by anhydrous sodium sulfate for an organic layer, dried under reduced pressure, and purified and separated by silica gel column chromatography to obtain 64mg of colorless waxy compound 21.

Performing characterization on the obtained compound 21 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:2.15(s,3H,ArH-18),2.39(s,3H,ArH-19),6.31(s,1H,ArH-7),6.65(d,J＝7.2Hz,1H,ArH-4),7.41-7.44(m,1H,ArH-2),7.56(d,J＝7.2Hz,2H,ArH-13,17),7.60-7.63(m,2H,ArH-2,15),7.65-7.70(m,3H,ArH-10,14,16)；¹³C NMR(150MHz,CDCl₃),δ,ppm:20.5(C-18),20.7(C-19),111.6(C-7),114.7(C-10),116.7(C-4),119.4(C-2),127.7(C-8),128.4(C-9),129.0(C-13,17),129.1(C-14,16),129.5(C-15),129.9(C-11),134.6(C-6),134.7(C-3),141.0(C-12),143.7(C-5),149.2(C-1)；ESI-HRMS,m/z:Calcd for C₁₉H₁₇N₂[M+H]⁺,273.1386,found:273.1422。

the results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry show that the structure of the compound 21 is consistent with the expectation, and the compound 21 is proved to be 7, 8-dimethyl-1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 78%.

Example 22

This example prepares 7-methyl-4- (p-chlorophenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine and 8-methyl-4- (p-chlorophenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (although in a mixture, hereinafter referred to as "compound 22") as follows: 0.077g (0.30mmol) of 5-methyl-2- (4-chlorobenzyl) benzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of N, N-dimethylformamide as a solvent were mixed uniformly, and the mixture was stirred at 120 ℃ for 12 hours to react, after the reaction was completed, the mixture was diluted with 15mL of water, extracted with dichloromethane (15 mL. times.3), separated, dried over anhydrous sodium sulfate for the organic layer, and then spun under reduced pressure, and the crude product was purified and separated by silica gel column chromatography to obtain 88mg of yellow solid compound 22.

Performing characterization on the obtained compound 22 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:2.29(s,3H,CH₃-22),2.50(s,3H,CH₃-22^’),6.39(s,1H,ArH-10^’),6.51(d,J＝8.4Hz,1H,ArH-7’),6.73-6.75(m,2H,ArH-2,2’),6.84(d,J＝8.4Hz,1H,ArH-8’),7.27(d,J＝8.4Hz,1H,ArH-9),4.84-4.52(m,2H,ArH-3,3’),7.52-7.54(m,4H,ArH-20,22/20’,22’),7.58-7.70(m,10H,ArH-14,15,16,19,23/14’,15’,16’,19’,23’),7.77(s,1H,ArH-7),7.87(d,J＝8.4Hz,1H,ArH-10),8.05-8.06(m,4H,ArH-13,17/ArH-13’,17’)；¹³C NMR(150MHz,CDCl₃),δ,ppm:21.7(C-22),22.0(C-22’),112.0(C-7,10’),114.2(C-10),114.6(C-7’),119.6(C-9),119.6(C-8’),122.3(C-8),126.9(C-2),126.9(C-2’),127.2(C-9’),127.6(C-11),127.9(C-21),128.1(C-21’),128.8(C-13,17/13’,17’),129.0(C-19,23),129.0(C-19’,23’),129.1(C-14,16),129.1(C-14’,16’),129.6(C-11’),130.0(C-15),130.0(C-15’),130.4(C-3),130.4(C-20,22),130.4(C-20’,22’),134.2(C-3’),134.5(C-4),134.6(C-4’),135.2(C-6),135.3(C-6’),140.4(C-12),140.4(C-12’),143.2(C-5),145.5(C-5’),148.0(C-1),148.3(C-1’)；ESI-HRMS,m/z:Calcd for C₂₄H₁₈ClN₂[M+H]⁺,369.1153,found:369.1192。

the results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry show that the structure of the compound 22 is consistent with the expectation, and the compound 22 is proved to be 7-methyl-4- (p-chlorophenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 80%.

Example 23

This example preparation of 7, 8-difluoro-4- (p-chlorophenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter referred to as "Compound 23") was carried out as follows: 0.083g (0.30mmol) of 5, 6-difluoro-2- (4-chlorobenzyl) benzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of solvent N, N-dimethylformamide are uniformly mixed, stirred and reacted for 12 hours at the temperature of 120 ℃, after the reaction is finished, diluted by 15mL of water, extracted by dichloromethane (15mL multiplied by 3), separated, dried by anhydrous sodium sulfate and dried by decompression, and a crude product is purified and separated by silica gel column chromatography to obtain 78mg of yellow solid compound 23 with the melting point of 237-.

Performing characterization on the obtained compound 23 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:6.36-6.39(m,1H,ArH-7),6.82(d,J＝7.2Hz,1H,ArH-2),7.54-7.59(m,5H,ArH-14,15,16,20,22),7.66-7.73(m,4H,ArH-3,10,19,23),8.02(d,J＝8.4Hz,2H,ArH-13,17)；¹³C NMR(150MHz,CDCl₃),δ,ppm:102.7(d,J＝19.5Hz,C-7),106.1(d,J＝19.5Hz,C-10),112.7(C-4),124.3(d,J＝10.5Hz,C-11),127.5(C-3),128.3(C-15),128.9(C-13,17),129.0(C-19,23),129.5(C-14,16),130.3(C-20,22),130.6(C-21),133.6(C-18),134.6(C-4),134.8(C-12),140.0(C-5),140.8(d,J＝10.5Hz,C-6),145.1-146.8(dd,J₁＝240Hz,J₂＝15Hz,C-8),148.7-150.4(dd,J₁＝244.5Hz,J₂＝15Hz,C-9),149.5(d,J＝3Hz,C-1)；¹⁹F NMR(564MHz,CDCl₃),δ:-141.9,-138.0；

ESI-HRMS,m/z:Calcd for C₂₃H₁₄ClF₂N₂[M+H]⁺,391.0808,found:391.0808。

the results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy, fluorine nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry show that the structure of the compound 23 is consistent with the expectation, and the compound 23 is proved to be 7, 8-difluoro-4- (p-chlorophenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 67%.

Example 24

This example preparation of 7, 8-dimethyl-4- (p-chlorophenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine (hereinafter referred to as "Compound 24") was carried out as follows: 0.081g (0.30mmol) of 5, 6-dimethyl-2- (4-chlorobenzyl) benzimidazole, 0.063g (0.30mmol) of 2-bromocinnamaldehyde, 0.103g of potassium carbonate and 2mL of solvent N, N-dimethylformamide are uniformly mixed, stirred and reacted for 12 hours at the temperature of 120 ℃, after the reaction is finished, diluted by 15mL of water, extracted by dichloromethane (15mL multiplied by 3), separated, dried by anhydrous sodium sulfate in an organic layer, dried by rotary drying under reduced pressure, and purified and separated by silica gel column chromatography to obtain 94mg of yellow solid compound 24 with the melting point of 238-.

Performing characterization on the obtained compound 24 by using a nuclear magnetic resonance hydrogen spectrum, a nuclear magnetic resonance carbon spectrum and a high-resolution mass spectrum, wherein the characterization results are as follows:

¹H NMR(600MHz,CDCl₃),δ,ppm:2.17(s,3H,ArH-22),2.39(s,3H,ArH-23),6.36(s,1H,ArH-7),6.72(d,J＝6.6Hz,1H,ArH-2),7.47(d,J＝6.6Hz,1H,ArH-3),7.52(d,J＝8.4Hz,2H,ArH-20,22),7.59(d,J＝7.2Hz,2H,ArH-13,17),7.62-7.64(m,2H,ArH-14,16),7.68(d,t＝7.2Hz,1H,ArH-15),7.75(s,1H,ArH-10),8.06(d,J＝8.4Hz,2H,ArH-19,23)；¹³C NMR(150MHz,CDCl₃),δ,ppm:20.5(C-12),20.8(C-13),111.8(C-7),114.7(C-10),119.9(C-15),126.7(C-8),127.9(C-9),128.0(C-3),128.8(C-13,17),129.0(C-19,23),129.1(C-20,22),129.8(C-11),129.9(C-21),130.4(C-14,16),134.1(C-18),134.7(C-6),135.4(C-4),140.2(C-12),143.9(C-5),147.8(C-1)；ESI-HRMS,m/z:Calcd for C₂₅H₂₀ClN₂[M+H]⁺,383.1310,found:383.1308；

compound 24 was subjected to an X-ray single crystal diffraction test, and fig. 6 is an X-ray single crystal diffraction pattern of compound 24.

The results of hydrogen nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy, high resolution mass spectrometry and single crystal diffraction show that the structure of the compound 24 is consistent with the expectation, and the compound 24 is proved to be 7, 8-dimethyl-4- (p-chlorophenyl) -1-phenylbenzo [4,5] imidazo [1,2-a ] pyridine with the yield of 82%.

The benzo [4,5] imidazo [1,2-a ] pyridine derivative prepared by the invention has excellent fluorescence property and aggregation-induced emission property, and the aggregation-induced emission property test is carried out according to the prepared compound, and the specific test examples are as follows:

test example 1

The aggregation-induced emission assay procedure for compound 2 was as follows:

dissolving compound 2 in tetrahydrofuran, adding a certain amount of water, and preparing into tetrahydrofuran/water (THF/H) of compound 2 with a total volume of 5mL and a concentration of 10 μmol/L according to different mass ratios of water content (0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%)₂O) solution, and the fluorescence intensity of the tetrahydrofuran/water solution of the series of compound 1 was measured by fluorescence spectroscopy (test conditions: excitation wavelength of 252nm, scanning wavelength range of 350-700 nm, slit of 5.0nm, photomultiplier voltage of 700V). FIG. 7 shows the water content (THF/H) of Compound 2₂O) in which the abscissa is the excitation wavelength and the ordinate is the fluorescence intensity. FIG. 8 is an aqueous solution (THF/H) of Compound 2₂O) water content-maximum fluorescence intensity curve under different scanning wavelengths, wherein the abscissa is the water content (f)_w) The ordinate is the maximum fluorescence intensity at different scanning wavelengths.

Test example 2

The aggregation-induced emission assay procedure for compound 5 was as follows:

dissolving compound 5 in tetrahydrofuran, adding a certain amount of water, and preparing into tetrahydrofuran/water (THF/H) of compound 5 with a total volume of 5mL and a concentration of 10 μmol/L according to different mass ratios of water content (0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%)₂O) solution, and the fluorescence intensity of the tetrahydrofuran/water solution of the series of compound 5 was measured by fluorescence spectroscopy (test conditions: 278nm of excitation wavelength, 350-700 nm of scanning wavelength range, 5.0nm of slit and 700V of photomultiplier voltage). FIG. 9 shows different water contents (THF/H) of Compound 5₂O) in which the abscissa is the excitation wavelength and the ordinate is the fluorescence intensity. FIG. 10 shows an aqueous solution (THF/H) of Compound 5₂O) water content-different sweepPlot of maximum fluorescence intensity at a trace wavelength with water cut (f) on the abscissa_w) The ordinate is the maximum fluorescence intensity at different scanning wavelengths. As can be seen from fig. 10, when the water content of the tetrahydrofuran aqueous solution as a solvent was about 80%, the maximum fluorescence intensity of compound 5 was the strongest.

Test example 3

The aggregation-induced emission assay procedure for compound 6 was as follows:

dissolving compound 6 in tetrahydrofuran, adding a certain amount of water, and preparing into tetrahydrofuran/water (THF/H) of compound 6 with a total volume of 5mL and a concentration of 10 μmol/L according to different mass ratios of water content (0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%)₂O) solution, and the fluorescence intensity of the tetrahydrofuran/water solution of the series of compound 6 was measured by fluorescence spectroscopy (test conditions: excitation wavelength 289nm, scanning wavelength range 350-700 nm, slit 5.0nm, photomultiplier voltage 700V). FIG. 11 shows different water contents (THF/H) of Compound 6₂O) in which the abscissa is the excitation wavelength and the ordinate is the fluorescence intensity. FIG. 12 is an aqueous solution (THF/H) of Compound 6₂O) water content-maximum fluorescence intensity curve under different scanning wavelengths, wherein the abscissa is the water content (f)_w) The ordinate is the maximum fluorescence intensity at different scanning wavelengths. As can be seen from fig. 12, the maximum fluorescence intensity of compound 6 was the strongest when the water content of the solvent tetrahydrofuran aqueous solution was 60% to 70%.

Test example 4

The aggregation-induced emission assay procedure for compound 7 was as follows:

dissolving compound 7 in tetrahydrofuran, adding a certain amount of water, and preparing into tetrahydrofuran/water (THF/H) of compound 7 with a total volume of 5mL and a concentration of 10 μmol/L according to different mass ratios of water content (0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%)₂O) solution, and the fluorescence intensity of the tetrahydrofuran/water solution of the series of compound 7 was measured by fluorescence spectroscopy (test conditions: excitation wavelength of 281nm, scanning wavelength range of 350-700 nm, and narrow bandSlot 5.0nm, photomultiplier voltage 700V). FIG. 13 shows different water contents (THF/H) of Compound 7₂O) in which the abscissa is the excitation wavelength and the ordinate is the fluorescence intensity. FIG. 14 is an aqueous solution (THF/H) of Compound 7₂O) water content-maximum fluorescence intensity curve under different scanning wavelengths, wherein the abscissa is the water content (f)_w) The ordinate is the maximum fluorescence intensity at different scanning wavelengths. As can be seen from fig. 14, when the water content of the tetrahydrofuran aqueous solution as a solvent was about 80%, the maximum fluorescence intensity of compound 7 was the strongest.

Test example 5

The aggregation-induced emission assay procedure for compound 14 was as follows:

dissolving compound 14 in tetrahydrofuran, adding a certain amount of water, and preparing into tetrahydrofuran/water (THF/H) of compound 14 with a series of total volume of 5mL and concentration of 10 μmol/L according to different mass ratio of water content (0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%)₂O) solution, and the series of compound 14 tetrahydrofuran/water solutions were tested for fluorescence intensity by fluorescence spectroscopy (test conditions: excitation wavelength 256nm, scanning wavelength range 350-700 nm, slit 5.0nm, photomultiplier voltage 700V). FIG. 15 shows different water contents (THF/H) of Compound 14₂O) in which the abscissa is the excitation wavelength and the ordinate is the fluorescence intensity. FIG. 16 is an aqueous solution (THF/H) of Compound 14₂O) water content-maximum fluorescence intensity curve under different scanning wavelengths, wherein the abscissa is the water content (f)_w) The ordinate is the maximum fluorescence intensity at different scanning wavelengths. As can be seen from fig. 16, the maximum fluorescence intensity of the compound was the strongest when the water content of the solvent tetrahydrofuran aqueous solution was 40% to 60%.

Test example 6

The aggregation-induced emission assay procedure for compound 18 was as follows:

dissolving compound 18 in tetrahydrofuran, adding a certain amount of water, and adding water according to different mass ratios, wherein the water content is (0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%)95%) was prepared as a series of tetrahydrofuran/water (THF/H) of Compound 18 in a total volume of 5mL at a concentration of 10. mu. mol/L₂O) solution, and the series of tetrahydrofuran/water solutions of compound 18 were tested for fluorescence intensity by fluorescence spectroscopy (test conditions: excitation wavelength 256nm, scanning wavelength range 350-700 nm, slit 5.0nm, photomultiplier voltage 700V). FIG. 17 shows different water contents (THF/H) of Compound 18₂O) in which the abscissa is the excitation wavelength and the ordinate is the fluorescence intensity. FIG. 18 is an aqueous solution (THF/H) of Compound 18₂O) water content-maximum fluorescence intensity curve under different scanning wavelengths, wherein the abscissa is the water content (f)_w) The ordinate is the maximum fluorescence intensity at different scanning wavelengths. As can be seen from fig. 18, when the water content of the tetrahydrofuran aqueous solution as a solvent was about 70%, the maximum fluorescence intensity of compound 18 was the strongest.

The experimental results of the test examples show that the benzo [4,5] imidazo [1,2-a ] pyridine derivative prepared by the invention has excellent fluorescence property and aggregation-induced emission property, and the following specific test examples are as follows: test example 7

The test procedure for detecting the nitro-aromatic explosive 2,4, 6-trinitrophenol by the compound 5 is as follows:

a solution of Compound 5 at a concentration of 10. mu. mol/L (solvent THF/H) was prepared₂O, water content of 80% by mass), to which 0 to 10 equivalents (based on the compound 5) of a 2,4, 6-trinitrophenol (PA) solution was gradually added. The fluorescence titration curve of compound 5 against PA was plotted with the scanning wavelength range as abscissa and the fluorescence intensity as ordinate, and the result is shown in fig. 19. FIG. 19 is a fluorescence titration curve diagram of compound 5 against PA, and it can be seen from FIG. 19 that as PA is gradually added into the probe solution, the fluorescence intensity of the solution is gradually reduced, and thus the detection of the typical nitroaromatic explosive PA in the aqueous solution by the probe can be realized by the principle.

Test example 8

The test procedure for detecting nitroaromatic explosive 2, 4-dinitrophenol by using compound 5 is as follows:

preparation ofCompound 5 at a concentration of 10. mu. mol/L (solvent THF/H)₂O, water content of 80% by mass), to which 0 to 10 equivalents (based on the compound 5) of a 2, 4-Dinitrophenol (DNP) solution is gradually added. The scanning wavelength range is plotted as abscissa and the fluorescence intensity is plotted as ordinate, and the fluorescence titration curve of compound 5 against DNP is plotted, and the result is shown in fig. 20. FIG. 20 is a fluorescence titration curve diagram of compound 5 against DNP, and it can be seen from FIG. 20 that as DNP is gradually added into the probe solution, the fluorescence intensity of the solution gradually decreases, and the detection of DNP, which is a typical nitroaromatic explosive, in an aqueous solution by the probe can be realized by the principle.

Test example 9

The test procedure for detecting the nitro-aromatic explosive 2,4, 6-trinitrophenol by the compound 6 is as follows:

a solution of Compound 6 (solvent THF/H) was prepared at a concentration of 10. mu. mol/L₂O, water content of 80% by mass), to which 0 to 10 equivalents (based on the compound 6) of a 2,4, 6-trinitrophenol (PA) solution was gradually added. The scanning wavelength range is plotted as abscissa and the fluorescence intensity is plotted as ordinate, and the result is shown in FIG. 21. FIG. 21 is a fluorescence titration curve diagram of compound 6 on PA, and it can be seen from FIG. 21 that as PA is gradually added into the probe solution, the fluorescence intensity is gradually reduced, and thus the detection of typical nitro aromatic explosives PA in aqueous solution by the probe can be realized by the principle.

Test example 10

The test procedure for detecting the nitro-aromatic explosive 2,4, 6-trinitrophenol by the compound 7 is as follows:

a solution of Compound 7 at a concentration of 10. mu. mol/L (solvent THF/H) was prepared₂O, water content of 80% by mass), to which 0 to 15 equivalents (based on the compound 7) of a 2,4, 6-trinitrophenol (PA) solution was gradually added. The fluorescence titration curve for PA was plotted with the scanning wavelength range as abscissa and the fluorescence intensity as ordinate, and the result is shown in FIG. 22. FIG. 22 is a fluorescence titration curve diagram of compound 7 against PA, and it can be seen from FIG. 22 that as PA is gradually added into the probe solution, the fluorescence intensity is gradually reduced, and thus the detection of the typical nitroaromatic explosive PA in the aqueous solution by the probe can be realized by the principle.

As can be seen from the test examples, the benzo [4,5] imidazo [1,2-a ] pyridine derivative disclosed by the invention has excellent AIE fluorescence property and aggregation-induced emission property, can be used for detecting nitro aromatic explosives in an aqueous solution, has high test sensitivity and low requirement on the concentration of an object to be detected, and has good application prospect in the fields of chemical and biological fluorescent probes.

Claims

1. A benzo [4,5] imidazo [1,2-a ] pyridine derivative has a structure shown as a general formula (I):

2. A benzo [4,5] amine according to claim 1]Imidazo [1,2-a ]]Pyridine derivatives characterized by: in the compound of the formula (I), R¹Selected from hydrogen, methyl, chlorine or fluorine; r²Selected from hydrogen, methyl, ethyl, n-butyl, phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-bromophenyl, 4-chlorophenyl, 2-nitrophenyl, 3-methoxyphenyl, 2-bromophenyl, 2-fluorophenyl or 2-naphthyl; ar is selected from phenyl.

3. A process for the preparation of benzo [4,5] imidazo [1,2-a ] pyridine derivatives according to claim 1 or 2, characterized in that: the method comprises the following steps:

4. The process for preparing a benzo [4,5] imidazo [1,2-a ] pyridine derivative according to claim 3, which comprises: the molar ratio of the 2-substituted benzimidazole derivative to the 2-halogenated cinnamaldehyde derivative is 1 (0.5-2).

5. The process for preparing benzo [4,5] imidazo [1,2-a ] pyridine derivatives according to claim 4, wherein: the structure of the 2-substituted benzimidazole derivative is shown as a formula (II):

6. The process for preparing benzo [4,5] imidazo [1,2-a ] pyridine derivatives according to claim 4, wherein: the 2-halogenated cinnamaldehyde derivative has a structure shown in a formula (III):

7. The process for preparing a benzo [4,5] imidazo [1,2-a ] pyridine derivative according to claim 3, which comprises: the reaction also comprises adding a catalyst to participate in the reaction; the catalyst comprises a base catalyst.

8. The process for preparing a benzo [4,5] imidazo [1,2-a ] pyridine derivative according to claim 3, which comprises: the reaction temperature is 110-160 ℃, and the reaction time is 10-16 h.

9. An AIE-type fluorescent material, characterized in that: the AIE type fluorescent material comprises benzo [4,5] imidazo [1,2-a ] pyridine derivatives as claimed in any one of claims 1 or 2.

10. Use of a benzo [4,5] imidazo [1,2-a ] pyridine derivative according to any of claims 1 or 2 for the detection of nitroaromatic explosives.