A class of compounds containing quinoline and indole groups, their preparation methods and applications

Abstract

The present invention discloses a class of compounds containing quinoline and indole groups, and their preparation methods and applications. The structural formula of the compounds containing quinoline and indole groups in the present invention is one of the formulas (1) to (3): wherein, R<supgt;1< / supgt> is selected from one of -H, -Me, -Cl, -<supgt;t< / supgt;Bu, and R<supgt;2< / supgt> is selected from one of -H, -Me, -OMe, -Cl, -F. The present invention synthesizes a series of compounds containing quinoline and indole groups, and its synthesis method has the advantages of easily available raw materials, simple operation, mild reaction conditions, wide substrate adaptability, etc., and has good application prospects in aspects such as organic light-emitting materials, fluorescence detection, synthesis research of other analogues, etc.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and particularly relates to a class of compounds containing quinoline and indole groups, and a preparation method and application thereof. Background Art

[0002] Quinoline and its derivatives, as well as indole and its derivatives, both have rich biological and pharmacological activities and are widely used nitrogen-containing heterocyclic compounds. At present, there are many studies on single quinoline compounds and indole compounds, while there are few studies on compounds containing both quinoline groups and indole groups. Research shows that constructing compounds containing both quinoline groups and indole groups can not only provide new design ideas for the research and development of related similar drugs, but also may apply the asymmetric quinoline ring and indole ring as large conjugated planar molecules to new organic light-emitting materials or optical devices, showing good application prospects.

[0003] Therefore, it is of great significance to develop a class of compounds containing both quinoline groups and indole groups. Summary of the Invention

[0004] The purpose of the present invention is to provide a class of compounds containing quinoline and indole groups, and a preparation method and application thereof.

[0005] The technical solution adopted by the present invention is as follows:

[0006] A class of compounds containing quinoline and indole groups, and the structural formula thereof is one of formula (1) to formula (3):

[0007] In the formula, R 1 is selected from one of -H, -Me, -Cl, - t Bu, and R 2 is selected from one of -H, -Me, -OMe, -Cl, -F.

[0008] A preparation method of a compound containing quinoline and indole groups as described above includes the following steps:

[0009] Disperse disulfide, iridium salt and alkali metal salt in a solvent. The disulfide is one of them, and carry out the reaction under the irradiation of visible light to obtain the compound containing quinoline and indole groups.

[0010] Preferably, the molar ratio of the disulfide, iridium salt and alkali metal salt is 1:1 to 3:0.01 to 0.10:1 to 3.

[0011] Preferably, the iridium salt is at least one of bis[2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine][2-2'-bi(4-tert-butylpyridine)]iridium bis(hexafluorophosphate), 4,4-bis(trifluoromethyl)-2,2'-bipyridine bis[3,5-difluoro-2-(5-trifluoromethyl-2-pyridyl)phenyl]iridium(III) hexafluorophosphate, (2-2'-bi(4-tert-butylpyridine) bis[2-(4-tert-butylphenyl)pyridine]iridium(III) hexafluorophosphate, [4,4'-bis(1,1-dimethylethyl)-2,2'-bipyridine] bis[3,5-difluoro-2-(5-fluoro-2-pyridyl)phenyl]iridium hexafluorophosphate, 4,4'-di(tert-butyl-2,2'-bipyridine] di[5-methyl-2-(4-methyl-2-pyridyl-kN)phenyl-kC] iridium hexafluorophosphate, and tris(2-phenylpyridine)iridium.

[0012] Preferably, the alkali metal salt is at least one of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, and cesium carbonate.

[0013] Preferably, the solvent is at least one of tetrahydrofuran, acetonitrile, toluene, dichloroethane, methanol, dimethyl sulfoxide, and 1,4-dioxane.

[0014] Preferably, the visible light band includes at least one of 380 nm - 390 nm, 440 nm - 445 nm, 450 nm - 455 nm, and 515 nm - 525 nm.

[0015] Preferably, the reaction is carried out at a temperature of 10°C - 80°C for a reaction time of 8 h - 18 h.

[0016] Preferably, the reaction is carried out under the condition that the stirring speed is 300 rpm - 700 rpm.

[0017] Preferably, after the reaction, the reaction product is separated and purified.

[0018] Preferably, the specific operations of the separation and purification are as follows: the reaction solution is extracted with ethyl acetate multiple times, the combined organic phase is dried with anhydrous sodium sulfate, filtered, the filtrate is taken for vacuum distillation, and the crude product obtained by vacuum distillation is purified by column chromatography.

[0019] Preferably, the eluent used in the column chromatography is composed of petroleum ether and ethyl acetate in a volume ratio of 3 - 10:1.

[0020] An organic light-emitting material, which contains the compound containing quinoline and indole groups described above.

[0021] A fluorescent probe, which contains the compound containing quinoline and indole groups described above.

[0022] Principle of the present invention: The present invention uses symmetric o-isocyanoalkynes and disulfides as raw materials, places them under visible light irradiation, and reacts under the action of iridium salts and bases. Through the interaction between disulfides and symmetric o-isocyanoalkynes, two intramolecular cyclizations are achieved, and finally a compound containing quinoline and indole groups is obtained.

[0023] The beneficial effects of the present invention are as follows: The present invention synthesizes a series of compounds containing quinoline and indole groups, and its synthesis method has the advantages of easily available raw materials, simple operation, mild reaction conditions, wide substrate adaptability, etc., and has good application prospects in the fields of organic light-emitting materials, fluorescence detection, synthesis research of other analogs, etc. Description of the drawings

[0024] Figure 1 1H NMR spectrum of the compound containing quinoline and indole groups in Example 1.

[0025] Figure 2 13C NMR spectrum of the compound containing quinoline and indole groups in Example 1.

[0026] Figure 3 1H NMR spectrum of the compound containing quinoline and indole groups in Example 2.

[0027] Figure 4 13C NMR spectrum of the compound containing quinoline and indole groups in Example 2.

[0028] Figure 5 1H NMR spectrum of the compound containing quinoline and indole groups in Example 3.

[0029] Figure 6 13C NMR spectrum of the compound containing quinoline and indole groups in Example 3.

[0030] Figure 7 1H NMR spectrum of the compound containing quinoline and indole groups in Example 4.

[0031] Figure 8 13C NMR spectrum of the compound containing quinoline and indole groups in Example 4.

[0032] Figure 9 1H NMR spectrum of the compound containing quinoline and indole groups in Example 5.

[0033] Figure 10 13C NMR spectrum of the compound containing quinoline and indole groups in Example 5.

[0034] Figure 11 1H NMR spectrum of the compound containing quinoline and indole groups in Example 6.

[0035] Figure 12 13C NMR spectrum of the compound containing quinoline and indole groups in Example 6.

[0036] Figure 13 1H NMR spectrum of the compound containing quinoline and indole groups in Example 7.

[0037] Figure 14 13C NMR spectrum of the compound containing quinoline and indole groups in Example 7.

[0038] Figure 15 1H NMR spectrum of the compound containing quinoline and indole groups in Example 8.

[0039] Figure 16 13C NMR spectrum of the compound containing quinoline and indole groups in Example 8.

[0040] Figure 17 1H NMR spectrum of the compound containing quinoline and indole groups in Example 9.

[0041] Figure 18 13C NMR spectrum of the compound containing quinoline and indole groups in Example 9.

[0042] Figure 19 1H NMR spectrum of the compound containing quinoline and indole groups in Example 10.

[0043] Figure 20 13C NMR spectrum of the compound containing quinoline and indole groups in Example 10.

[0044] Figure 21 1H NMR spectrum of the compound containing quinoline and indole groups in Example 11.

[0045] Figure 22 13C NMR spectrum of the compound containing quinoline and indole groups in Example 11.

[0046] Figure 23 1H NMR spectrum of the compound containing quinoline and indole groups in Example 12.

[0047] Figure 24 13C NMR spectrum of the compound containing quinoline and indole groups in Example 12.

[0048] Figure 25 1H NMR spectrum of the compound containing quinoline and indole groups in Example 13.

[0049] Figure 26 13C NMR spectrum of the compound containing quinoline and indole groups in Example 13.

[0050] Figure 27 Fluorescence emission spectra of the compound containing quinoline and indole groups in Example 1 after mixing with different ions.

[0051] Figure 28 Fluorescence emission spectra of the compound containing quinoline and indole groups in Example 1 after mixing with Au at different concentrations 3+ at different concentrations. Detailed implementation manners

[0052] The present invention will be further explained and described below in conjunction with specific embodiments.

[0053] Example 1:

[0054] A compound containing quinoline and indole groups, and its preparation method includes the following steps:

[0055] Disperse 0.1 mmol of 0.25 mmol of 0.002 mmol of bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridium bis(hexafluorophosphate) (abbreviated in English as Ir[dF(CF3)ppy]2(dtbbpy)PF6) and 0.2 mmol of cesium carbonate into 2 mL of methanol, place it under visible light with a wavelength of 450 nm - 455 nm, and react at room temperature for 12 h under the condition of a stirring speed of 500 rpm. Extract the reaction solution with ethyl acetate three times, combine the organic phases, dry them with anhydrous sodium sulfate, filter, take the filtrate for vacuum distillation, and subject the crude product obtained by vacuum distillation to column chromatography purification. The eluent used in column chromatography is composed of petroleum ether and ethyl acetate according to a volume ratio of 5:1, and the compound containing quinoline and indole groups is obtained (yield: 77%).

[0056] The 1H nuclear magnetic resonance spectrum of the compound containing quinoline and indole groups in this example is as Figure 1 shown, and the 13C nuclear magnetic resonance spectrum is as Figure 2 shown. The spectral data are as follows:

[0057] 11H NMR (400 MHz, CDCl3): δ 8.81 (s, 1H), 8.68 (d, J = 8.8 Hz, 1H), 8.37 (d, J = 8.4 Hz, 1H), 7.99 - 7.93 (m, 1H), 7.89 (d, J = 8.0 Hz, 1H), 7.79 - 7.74 (m, 1H), 7.67 (d, J = 7.9 Hz, 1H), 7.61 - 7.56 (m, 1H), 7.47 - 7.40 (m, 2H), 7.37 - 7.32 (m, 1H), 6.89 (t, J = 7.6 Hz, 1H), 6.78 (t, J = 7.2 Hz, 1H), 6.73 - 6.69 (m, 2H), 6.67 - 6.62 (m, 2H), 6.36 (d, J = 8.0 Hz, 1H).

[0058] 13 13C NMR (101 MHz, CDCl3): δ 161.1, 154.8, 150.4, 148.6, 143.4, 141.3, 133.1, 132.1, 131.9, 131.4, 130.8, 130.5, 130.2, 130.0, 129.6, 129.4, 128.5, 128.4, 128.2, 127.7, 127.1, 126.9, 126.2, 126.0, 125.6, 123.1, 122.4, 118.4.

[0059] The infrared test data of the compound containing quinoline and indole groups in this example are as follows:

[0060] IR (KBr) Vmax : 3486, 2921, 1730, 1598, 1472, 1367, 1201, 823, 751, 690 cm -1 .

[0061] The mass spectrometry data of the compound containing quinoline and indole groups in this example are as follows:

[0062] HRMS (ESI) calcd for C 30 H 19 N2S2 [M + H] + : 471.0984, Found: 471.0978.

[0063] In summary, the structural formula of the compound containing quinoline and indole groups in this example is as follows:

[0064] Example 2:

[0065] A compound containing quinoline and indole groups, and its preparation method includes the following steps:

[0066] 0.1 mmol of 0.25 mmol of 0.002 mmol of Ir[dF(CF3)ppy]2(dtbbpy)PF6 and 0.2 mmol of cesium carbonate were dispersed in 2 mL of methanol, placed under visible light with a wavelength of 450 nm - 455 nm, and reacted at room temperature for 12 h under the condition of a stirring speed of 500 rpm. The reaction solution was extracted 3 times with ethyl acetate, the combined organic phases were dried over anhydrous sodium sulfate, filtered, the filtrate was taken for distillation under reduced pressure, and the crude product obtained by distillation under reduced pressure was purified by column chromatography. The eluent used for column chromatography was composed of petroleum ether and ethyl acetate in a volume ratio of 5:1, and a compound containing quinoline and indole groups was obtained (yield: 68%).

[0067] The 1H NMR spectrum of the compound containing quinoline and indole groups in this example is as Figure 3 shown, and the 13C NMR spectrum is as Figure 4 shown. The spectral data are as follows:

[0068] 1 H NMR (400 MHz, CDCl3): δ 8.73 (s, 1H), 8.46 (s, 1H), 8.25 (d, J = 8.5 Hz, 1H), 7.84 (d, J = 7.9 Hz, 1H), 7.78 (d, J = 8.4 Hz, 1H), 7.53 (d, J = 7.6 Hz, 4H), 7.38 (d, J = 8.0 Hz, 2H), 7.32 - 7.27 (m, 1H), 7.22 (d, J = 7.6 Hz, 2H), 6.78 - 6.70 (m, 3H), 6.67 - 6.62 (m, 2H), 6.10 (s, 1H), 2.64 (s, 3H), 2.09 (s, 3H).

[0069] 13 C NMR (101 MHz, CDCl3): δ 160.3, 153.0, 149.4, 147.1, 142.3, 141.0, 138.4, 133.0, 132.9, 132.2, 132.1, 131.6, 131.3, 130.4, 130.0, 129.9, 129.2, 128.5, 128.3, 127.50, 127.1, 126.8, 125.8, 125.8, 124.9, 123.6, 117.9, 22.0, 21.5.

[0070] The infrared test data of the compound containing quinoline and indole groups in this example are as follows:

[0071] IR (KBr) Vmax: 3476, 2920, 1734, 1602, 1472, 1361, 1200, 822, 740, 690 cm -1 。

[0072] The mass spectrometry data of the compound containing quinoline and indole groups in this example are as follows:

[0073] HRMS(ESI) calcd for C 32 H 23 N2S2 [M + H] + : 499.1297, Found: 499.1295.

[0074] In summary, the structural formula of the compound containing quinoline and indole groups in this example is as follows: Example 3:

[0075] A compound containing quinoline and indole groups, and its preparation method includes the following steps:

[0076] Disperse 0.1 mmol of 0.25 mmol of 0.002 mmol of Ir[dF(CF3)ppy]2(dtbbpy)PF6 and 0.2 mmol of cesium carbonate into 2 mL of methanol, place it under visible light with a wavelength of 450 nm - 455 nm, react at room temperature for 12 h under the condition of a stirring speed of 500 rpm, extract the reaction solution with ethyl acetate 3 times, combine the organic phases, dry them with anhydrous sodium sulfate, filter, take the filtrate for vacuum distillation, and take the crude product obtained by vacuum distillation for column chromatography purification. The eluent used in column chromatography is composed of petroleum ether and ethyl acetate according to a volume ratio of 5:1, thus obtaining the compound containing quinoline and indole groups (yield: 62%).

[0077] The 1H NMR spectrum of the compound containing quinoline and indole groups in this example is as Figure 5 shown, and the 13C NMR spectrum is as Figure 6 shown. The spectral data are as follows:

[0078] 1 1H NMR(400 MHz, CDCl3): δ 8.75 (d, J = 8.0 Hz, 2H), 8.31 (d, J = 8.0 Hz, 1H), 7.91 (d, J = 8.0 Hz, 2H), 7.66 - 7.61 (m, 1H), 7.55 (d, J = 8.0 Hz, 1H), 7.40 - 7.36 (m, 3H), 6.77 - 6.72 (m, 1H), 6.68 - 6.62 (m, 4H), 6.17 (s, 1H).

[0079] 1313C NMR (101 MHz, CDCl3): δ 161.2, 152.9, 150.2, 147.0, 142.8, 142.2, 134.8, 133.4, 132.3, 132.1, 132.0, 131.8, 131.2, 130.3, 123.0, 129.5, 129.3, 129.0, 128.6, 128.1, 127.8, 127.1, 126.6, 126.4, 125.0, 122.8, 119.1.

[0080] The infrared test data of the compound containing quinoline and indole groups in this example are as follows:

[0081] IR (KBr) Vmax : 3476, 2921, 1640, 1591, 1470, 1321, 1269, 823, 754, 693 cm -1 .

[0082] The mass spectrometry data of the compound containing quinoline and indole groups in this example are as follows:

[0083] HRMS (ESI) calcd for C 30 H 17 Cl2N2S2 [M + H] + : 539.0205, Found: 539.0201.

[0084] In summary, the structural formula of the compound containing quinoline and indole groups in this example is as follows: Example 4:

[0085] A compound containing quinoline and indole groups, and its preparation method includes the following steps:

[0086] Disperse 0.1 mmol of 0.25 mmol of 0.002 mmol of Ir[dF(CF3)ppy]2(dtbbpy)PF6 and 0.2 mmol of cesium carbonate in 2 mL of methanol, place it under visible light with a wavelength of 450 nm - 455 nm, react at room temperature for 12 h under the condition of a stirring speed of 500 rpm, extract the reaction solution 3 times with ethyl acetate, combine the organic phases, dry them with anhydrous sodium sulfate, filter, take the filtrate for vacuum distillation, and subject the crude product obtained by vacuum distillation to column chromatography purification. The eluent used in column chromatography is composed of petroleum ether and ethyl acetate in a volume ratio of 5:1, thus obtaining the compound containing quinoline and indole groups (yield: 73%).

[0087] The nuclear magnetic resonance hydrogen spectrum of the compound containing quinoline and indole groups in this example is as Figure 7As shown, the carbon-13 NMR spectrum is as follows Figure 8 As shown, the spectral data for interpretation is as follows:

[0088] 1 H NMR(400MHz,CDCl3)δ8.75(s,1H),8.51(d,J=8.4Hz,1H),8.13(s,1H),7.85(d,J=8.0Hz,1H),7.59-7.53(m,2H),7.48(s,1H),7.43(d,J=7.6Hz,1H),7.34-7.30(m,1H),6.80(t,J=7.2Hz,1H),6.74-6.65(m,5H),6.25(d,J=8.0Hz,1H),2.70(s,3H),2.45(s,3H).

[0089] 13 C NMR(101MHz,CDCl3)δ161.4,155.3,150.4,148.7,143.0,141.4,140.3,140.2,132.7,132.4,131.2,130.4,130.0,123.0,129.3,129.0,128.5,127.5,127.3,126.8,126.6,125.9,125.8,123.5,123.1,122.8,118.9,22.0,21.8.

[0090] The infrared test data of the compound containing quinoline and indole groups in this example is as follows:

[0091] IR(KBr) Vmax : 3465,2921,1733,1628,1461,1328,1267,813,755,697cm -1 .

[0092] The mass spectrometry data of the compound containing quinoline and indole groups in this example is as follows:

[0093] HRMS(ESI)calcd for C 32 H 23 Br2N2S2[M+H] + : 499.1297,Found:499.1293.

[0094] In summary, the structural formula of the compound containing quinoline and indole groups in this example is as follows: Example 5:

[0095] A compound containing quinoline and indole groups, and its preparation method includes the following steps:

[0096] 0.1 mmol of 0.25 mmol of 0.002 mmol of Ir[dF(CF3)ppy]2(dtbbpy)PF6 and 0.2 mmol of cesium carbonate were dispersed in 2 mL of methanol, placed under visible light with a wavelength of 450 nm - 455 nm, and reacted at room temperature for 12 h under the condition of a stirring speed of 500 rpm. The reaction solution was extracted 3 times with ethyl acetate. The combined organic phases were dried over anhydrous sodium sulfate, filtered, and the filtrate was taken for vacuum distillation. The crude product obtained by vacuum distillation was purified by column chromatography. The eluent used in column chromatography was composed of petroleum ether and ethyl acetate in a volume ratio of 5:1, and the compound containing quinoline and indole groups was obtained (yield: 68%).

[0097] The 1H NMR spectrum of the compound containing quinoline and indole groups in this example is as Figure 9 shown, and the 13C NMR spectrum is as Figure 10 shown. The spectral data are as follows:

[0098] 1 H NMR (400 MHz, CDCl3): δ 8.78 (s, 1H), 8.59 (d, J = 8.8 Hz, 1H), 8.32 (d, J = 2.0 Hz, 1H), 7.88 - 7.83 (m, 2H), 7.72 (d, J = 1.6 Hz, 1H), 7.58 - 7.54 (m, 1H), 7.42 (d, J = 8.0 Hz, 1H), 7.33 - 7.30 (m, 1H), 6.96 (dd, J = 8.4, 2.4 Hz, 1H), 6.80 - 6.73 (m, 3H), 6.67 - 6.63 (m, 2H), 6.31 (d, J = 8.0 Hz, 1H), 1.56 (s, 9H), 1.35 (s, 9H).

[0099] 13 C NMR (101 MHz, CDCl3): δ 161.2, 155.3, 154.3, 153.7, 150.4, 148.8, 142.7, 140.3, 132.8, 132.4, 131.6, 131.3, 130.1, 123.0, 129.0, 128.4, 127.5, 127.3, 127.1, 126.9, 126.6, 125.9, 125.7, 125.7, 123.0, 122.7, 119.9, 115.4, 35.3, 35.2, 31.4, 31.1.

[0100] The infrared test data of the compound containing quinoline and indole groups in this example are as follows:

[0101] IR (KBr)Vmax : 3438, 2960, 1614, 1467, 1365, 1267, 1081, 824, 754, 691 cm -1 。

[0102] The mass spectrometry data of the compound containing quinoline and indole groups in this example are as follows:

[0103] HRMS(ESI) calcd for C 38 H 35 N2S2 [M + H] + : 583.2236, Found: 583.2232.

[0104] In summary, the structural formula of the compound containing quinoline and indole groups in this example is as follows:

[0105] Example 6:

[0106] A compound containing quinoline and indole groups, and its preparation method includes the following steps:

[0107] Disperse 0.1 mmol of 0.25 mmol of 0.002 mmol of Ir[dF(CF3)ppy]2(dtbbpy)PF6 and 0.2 mmol of cesium carbonate into 2 mL of methanol, place it under visible light with a wavelength of 450 nm - 455 nm, react at room temperature for 12 h under the condition of a stirring speed of 500 rpm, extract the reaction solution with ethyl acetate 3 times, combine the organic phases, dry with anhydrous sodium sulfate, filter, take the filtrate for vacuum distillation, and take the crude product obtained by vacuum distillation for column chromatography purification. The eluent used in column chromatography is composed of petroleum ether and ethyl acetate according to a volume ratio of 5:1, thus obtaining the compound containing quinoline and indole groups (yield: 70%).

[0108] The 1H NMR spectrum of the compound containing quinoline and indole groups in this example is as Figure 11 shown, and the 13C NMR spectrum is as Figure 12 shown. The spectral data are as follows:

[0109] 11H NMR (400 MHz, CDCl3): δ 8.77 - 8.73 (m, 2H), 8.36 (d, J = 8.4 Hz, 1H), 7.95 (t, J = 7.2 Hz, 1H), 7.80 - 7.72 (m, 2H), 7.66 (d, J = 7.2 Hz, 1H), 7.45 - 7.37 (m, 2H), 7.16 (s, 1H), 6.85 (t, J = 7.6 Hz, 1H), 6.55 (d, J = 7.6 Hz, 2H), 6.36 (d, J = 8.0 Hz, 2H), 6.26 (d, J = 7.6 Hz, 1H), 2.29 (s, 3H), 1.97 (s, 3H).

[0110] 13 13C NMR (101 MHz, CDCl3): δ 161.2, 154.8, 150.5, 148.4, 144.4, 141.3, 138.0, 136.0, 132.3, 132.2, 131.6, 130.7, 130.3, 130.1, 129.9, 129.3, 129.2, 129.1, 128.4, 128.1, 128.0, 127.0, 126.6, 126.2, 125.8, 123.1, 122.2, 118.2, 21.2, 20.7.

[0111] The infrared test data of the compound containing quinoline and indole groups in this example are as follows:

[0112] IR (KBr) Vmax : 3337, 2922, 1683, 1551, 1473, 1329, 1369, 810, 756, 693 cm -1 .

[0113] The mass spectrometry data of the compound containing quinoline and indole groups in this example are as follows:

[0114] HRMS (ESI) calcd for C 32 H 23 N2S2 [M + H] + : 499.1297, Found: 499.1295.

[0115] In summary, the structural formula of the compound containing quinoline and indole groups in this example is as follows:

[0116] Example 7:

[0117] A compound containing quinoline and indole groups, except that is replaced with otherwise, the preparation process is exactly the same as in Example 6.

[0118] The yield of the compound containing quinoline and indole groups in this example is 69%.

[0119] The 1H NMR spectrum of the compound containing quinoline and indole groups in this example is as Figure 13 shown, and the 13C NMR spectrum is as Figure 14 shown. The spectral data are as follows:

[0120] 1 H NMR (400 MHz, CDCl3): δ 8.80 (d, J = 9.2 Hz, 1H), 8.68 (s, 1H), 8.33 (d, J = 8.4 Hz, 1H), 7.99 - 7.94 (m, 1H), 7.83 - 7.77 (m, 2H), 7.65 (d, J = 7.6 Hz, 1H), 7.45 - 7.40 (m, 1H), 7.24 (dd, J = 8.8, 2.4 Hz, 1H), 6.89 - 6.84 (m, 2H), 6.60 - 6.56 (m, 2H), 6.29 (d, J = 7.6 Hz, 1H), 6.06 - 6.02 (m, 2H), 3.69 (s, 3H), 3.55 (s, 3H).

[0121] 13 C NMR (101 MHz, CDCl3): δ 161.5, 159.4, 157.8, 154.9, 150.6, 148.3, 145.3, 140.9, 134.7, 130.8, 130.4, 130.3, 123.0, 129.5, 128.3, 128.0, 127.7, 125.8, 125.7, 124.6, 123.2, 122.2, 121.1, 118.2, 117.6, 114.0, 113.8, 55.5, 55.1.

[0122] The infrared test data of the compound containing quinoline and indole groups in this example are as follows:

[0123] IR (KBr) Vmax : 3458, 2922, 1602, 1467, 1364, 1268, 1029, 819, 756, 635 cm -1 .

[0124] The mass spectrometry data of the compound containing quinoline and indole groups in this example are as follows:

[0125] HRMS (ESI) calcd for C 32 H 23 N2O2S2 [M + H] +: 531.1195, Found: 531.1192。

[0126] As can be seen from the above, the structural formula of the compound containing quinoline and indole groups in this example is as follows:

[0127] Example 8:

[0128] A compound containing quinoline and indole groups, except that is replaced with otherwise, the preparation process is exactly the same as that of Example 6.

[0129] The yield of the compound containing quinoline and indole groups in this example is 48%.

[0130] The 1H NMR spectrum of the compound containing quinoline and indole groups in this example is as shown in Figure 15 , and the 13C NMR spectrum is as shown in Figure 16 . The spectral data are as follows:

[0131] 1 H NMR (400 MHz, CDCl3): δ 8.79 (s, 1H), 8.74 (d, J = 8.0 Hz, 1H), 8.38 (d, J = 8.4 Hz, 1H), 8.02 - 7.97 (m, 1H), 7.89 - 7.80 (m, 2H), 7.68 (d, J = 7.6 Hz, 1H), 7.45 (t, J = 8.0 Hz, 1H), 7.40 - 7.35 (m, 1H), 7.03 (dd, J = 10.0, 2.4 Hz, 1H), 6.88 (t, J = 7.4 Hz, 1H), 6.70 - 6.66 (m, 2H), 6.34 (t, J = 8.8 Hz, 2H), 6.27 (d, J = 7.6 Hz, 1H).

[0132] 13 C NMR (101 MHz, CDCl3): δ 163.2, 161.9, 160.9, 160.8, 159.4, 154.9, 150.1, 148.7, 143.6, 134.0, 134.1, 134.0, 131.3, 131.2, 130.8, 130.5, 130.2, 128.8, 128.7, 128.5, 128.4, 128.4, 128.1, 127.1, 127.0, 126.0, 125.1, 123.2, 122.7, 118.6, 118.1, 117.9, 115.8, 115.8, 115.6, 115.5.

[0133] The infrared test data of the compound containing quinoline and indole groups in this example are as follows:

[0134] IR (KBr) Vmax : 3459, 2921, 1729, 1598, 1475, 1362, 1230, 821, 756, 637 cm -1 .

[0135] The mass spectrometry data of the compound containing quinoline and indole groups in this example are as follows:

[0136] HRMS (ESI) calcd for C 30 H 17 F2N2S2 [M + H] + : 507.0796, Found: 507.0792.

[0137] In summary, the structural formula of the compound containing quinoline and indole groups in this example is as follows:

[0138] Example 9:

[0139] A compound containing quinoline and indole groups, except that is replaced with otherwise, the preparation process is exactly the same as that in Example 6.

[0140] The yield of the compound containing quinoline and indole groups in this example is 50%.

[0141] The 1H NMR spectrum of the compound containing quinoline and indole groups in this example is as shown in Figure 17 and the 13C NMR spectrum is as shown in Figure 18 . The spectral data are as follows:

[0142] 1 1H NMR (400 MHz, CDCl3): δ 8.94 (s, 1H), 8.57 (d, J = 8.4 Hz, 1H), 8.34 (d, J = 8.4 Hz, 1H), 7.88 (t, J = 7.2 Hz, 1H), 7.72 - 7.67 (m, 1H), 7.63 (d, J = 7.6 Hz, 1H), 7.51 - 7.46 (m, 1H), 7.36 (t, J = 7.6 Hz, 1H), 6.78 (t, J = 7.6 Hz, 1H), 6.73 - 6.68 (m, 1H), 6.66 (d, J = 8.0 Hz, 1H), 6.37 - 6.31 (m, 2H), 6.29 - 6.27 (m, 1H), 6.00 (d, J = 7.6 Hz, 1H), 3.40 (s, 3H), 3.27 (s, 3H).

[0143] 1313C NMR(101MHz,CDCl3): δ 160.4, 159.7, 159.1, 154.7, 149.6, 147.6, 140.8, 138.4, 138.3, 135.1, 134.5, 130.4, 130.3, 130.1, 129.8, 129.1, 128.8, 127.8, 126.2, 126.2, 123.2, 122.9, 122.3, 119.7, 118.3, 117.4, 116.2, 112.6, 108.2, 55.7, 54.8.

[0144] The infrared test data of the compound containing quinoline and indole groups in this example are as follows:

[0145] IR(KBr) Vmax : 3426, 2933, 1745, 1506, 1462, 1379, 1263, 856, 756, 609 cm -1 .

[0146] The mass spectrometry data of the compound containing quinoline and indole groups in this example are as follows:

[0147] HRMS(ESI) calcd for C 32 H 23 N2O2S2 [M + H] + : 531.1196, Found: 531.1193.

[0148] In summary, the structural formula of the compound containing quinoline and indole groups in this example is as follows:

[0149] Example 10:

[0150] A compound containing quinoline and indole groups, except that is replaced with , the preparation process is exactly the same as that in Example 6.

[0151] The yield of the compound containing quinoline and indole groups in this example is 31%.

[0152] The 1H NMR spectrum of the compound containing quinoline and indole groups in this example is as shown in Figure 19 , and the 13C NMR spectrum is as shown in Figure 20 . The spectral data are as follows:

[0153] 11H NMR (400 MHz, CDCl3): δ 8.83 (s, 1H), 8.68 (d, J = 8.4 Hz, 1H), 8.39 (d, J = 8.4 Hz, 1H), 8.00 (t, J = 7.6 Hz, 1H), 7.89 (s, 1H), 7.82 (t, J = 7.6 Hz, 1H), 7.67 (d, J = 7.6 Hz, 1H), 7.43 (d, J = 7.2 Hz, 1H), 7.30 (s, 2H), 6.91 (d, J = 7.4 Hz, 1H), 6.76 (d, J = 7.0 Hz, 1H), 6.69 (s, 1H), 6.62 - 6.55 (m, 2H), 6.29 (d, J = 7.6 Hz, 1H).

[0154] 13 13C NMR (101 MHz, CDCl3): δ 160.2, 154.8, 150.2, 148.7, 142.6, 140.0, 136.0, 134.5, 134.4, 133.7, 131.8, 131.3, 131.2, 130.9, 130.6, 130.1, 130.0, 129.6, 129.5, 128.6, 128.4, 128.1, 126.6, 126.4, 125.9, 125.4, 125.2, 122.9, 118.8.

[0155] The infrared test data of the compound containing quinoline and indole groups in this example are as follows:

[0156] IR (KBr) Vmax : 3464, 2920, 1644, 1471, 1426, 1268, 1107, 821, 758, 626 cm -1 .

[0157] The mass spectrometry data of the compound containing quinoline and indole groups in this example are as follows:

[0158] HRMS (ESI) calcd for C 30 H 17 Cl2N2S2 [M + H] + : 539.0205, Found: 539.0201.

[0159] In summary, the structural formula of the compound containing quinoline and indole groups in this example is as follows: Example 11:

[0160] A compound containing quinoline and indole groups, except that is replaced with , the preparation process is exactly the same as that in Example 6.

[0161] The yield of the compound containing quinoline and indole groups in this example is 31%.

[0162] The 1H NMR spectrum of the compound containing quinoline and indole groups in this example is as Figure 21 shown, and the 13C NMR spectrum is as Figure 22 shown. The spectral data are as follows:

[0163] 1 H NMR(400MHz,CDCl3): δ8.79(s,1H),8.68(d,J = 9.6Hz,1H),8.37(d,J = 8.4Hz,1H),7.99 - 7.94(m,1H),7.80 - 7.75(m,1H),7.69(d,J = 8.0Hz,1H),7.48 - 7.42(m,2H),7.35(d,J = 7.2Hz,1H),7.25(d,J = 8.0Hz,1H),6.93 - 6.89(m,1H),6.67 - 6.59(m,2H),6.55(d,J = 7.6Hz,1H),6.42 - 6.35(m,2H),2.70(s,3H),1.81(s,3H).

[0164] 13 C NMR(101MHz,CDCl3): δ161.2,154.8,150.5,148.4,144.0,141.9,138.9,134.7,132.5,132.3,132.1,131.4,131.0,130.8,130.4,129.8,129.5,129.2,128.5,128.4,128.1,127.7,127.0,125.9,125.4,125.3,123.0,122.3,118.4,20.3,20.1.

[0165] The infrared test data of the compound containing quinoline and indole groups in this example are as follows:

[0166] IR(KBr) Vmax : 3463,2925,2120,1595,1463,1266,1205,1047,805,753cm -1 .

[0167] The mass spectrometry data of the compound containing quinoline and indole groups in this example are as follows:

[0168] HRMS(ESI)calcd for C 32 H 23 N2S2[M + H] +: 498.1224, Found: 498.1227.

[0169] In summary, the structural formula of the compound containing quinoline and indole groups in this example is as follows: Example 12:

[0170] A compound containing quinoline and indole groups, except that is replaced with otherwise, the preparation process is exactly the same as that of Example 6.

[0171] The yield of the compound containing quinoline and indole groups in this example is 61%.

[0172] The 1H NMR spectrum of the compound containing quinoline and indole groups in this example is as shown in Figure 23 and the 13C NMR spectrum is as shown in Figure 24 The spectral data are as follows:

[0173] 1 H NMR (400 MHz, CDCl3): δ 8.91 (s, 1H), 8.75 (d, J = 8.4 Hz, 1H), 8.35 (d, J = 8.0 Hz, 1H), 7.95 (t, J = 7.2 Hz, 1H), 7.78 (t, J = 7.6 Hz, 1H), 7.63 - 7.57 (m, 2H), 7.34 (t, J = 7.2 Hz, 1H), 7.07 (s, 1H), 6.81 (t, J = 7.6 Hz, 1H), 6.39 (s, 1H), 6.20 (s, 2H), 6.00 (d, J = 7.6 Hz, 1H), 2.50 (s, 3H), 1.88 (s, 3H), 1.69 (s, 6H).

[0174] 13 C NMR (101 MHz, CDCl3): δ 160.3, 154.6, 150.7, 148.1, 142.4, 139.9, 139.6, 138.1, 135.7, 134.9, 133.1, 130.6, 130.5, 130.3, 130.0, 129.9, 128.9, 128.5, 128.0, 126.4, 126.0, 125.9, 124.0, 123.2, 122.0, 118.2, 26.0, 21.1, 20.4.

[0175] The infrared test data of the compound containing quinoline and indole groups in this example are as follows:

[0176] IR (KBr) Vmax: 3486, 2924, 1575, 1473, 1408, 1328, 1193, 848, 755, 686 cm -1 。

[0177] The mass spectrometry data of the compound containing quinoline and indole groups in this example are as follows:

[0178] HRMS(ESI) calcd for C 34 H 27 N2S2 [M + H] + : 527.1610, Found: 527.1606.

[0179] In summary, the structural formula of the compound containing quinoline and indole groups in this example is as follows: Example 13:

[0180] A compound containing quinoline and indole groups, except that is replaced with otherwise, the preparation process is exactly the same as that of Example 6.

[0181] The yield of the compound containing quinoline and indole groups in this example is 36%.

[0182] The 1H NMR spectrum of the compound containing quinoline and indole groups in this example is as shown in Figure 25 and the 13C NMR spectrum is as shown in Figure 26 The spectral data are as follows:

[0183] 1 1H NMR(400 MHz, CDCl3): δ 9.21(s, 1H), 8.59(d, J = 8.4 Hz, 1H), 8.46(d, J = 8.4 Hz, 1H), 7.99(t, J = 8.0 Hz, 1H), 7.89(d, J = 8.8 Hz, 1H), 7.82(d, J = 7.6 Hz, 1H), 7.71 - 7.75(m, 2H), 7.60(d, J = 8.0 Hz, 1H), 7.47 - 7.38(m, 4H), 7.33(t, J = 7.2 Hz, 1H), 7.23(t, J = 8.0 Hz, 1H), 7.06 - 7.01(m, 1H), 6.99 - 6.96(m, 2H), 6.93(s, 1H), 6.88(t, J = 7.6 Hz, 1H), 6.51(d, J = 8.8 Hz, 1H), 6.17(d, J = 8.0 Hz, 1H).

[0184] 1313C NMR (101 MHz, CDCl3): δ 159.0, 154.5, 150.9, 148.3, 142.5, 141.4, 136.5, 135.7, 132.8, 132.6, 132.4, 131.9, 131.3, 130.8, 130.8, 130.6, 129.5, 129.4, 129.2, 129.0, 128.4, 127.9, 127.9, 127.2, 127.0, 126.9, 126.4, 126.3, 126.3, 126.0, 125.8, 125.2, 124.7, 123.5, 123.3, 122.0, 118.4.

[0185] The infrared test data of the compound containing quinoline and indole groups in this example are as follows:

[0186] IR (KBr) Vmax : 3048, 2921, 1704, 1468, 1313, 1265, 956, 812, 753, 633 cm -1 .

[0187] The mass spectrometry data of the compound containing quinoline and indole groups in this example are as follows:

[0188] HRMS (ESI) calcd for C 38 H 22 N2S2 [M] + : 570.1224, Found: 570.1229.

[0189] In summary, the structural formula of the compound containing quinoline and indole groups in this example is as follows: Application test:

[0190] 1) Prepare 10 mL of 21 metal ion aqueous solutions with a concentration of 0.01 mol / L respectively (the metal ions include Ag + , Al 3 + , Au 3+ , Ca 2+ , Cd 2+ , Ce 3+ , Co 2+ , Cs + , Cu 2+ , Eu 2+ , Fe 2+ , Hg 2+ , Ir 3+ , K + , La 3+ , Li + , Mg 2+ , Na+ , Ni 2+ , Pd 2+ and Zn 2+ (the corresponding anions are OAc- and Cl-), and a 10 mL tetrahydrofuran solution of the compound containing quinoline and indole groups with a concentration of 0.0001 mol / L was prepared using the compound containing quinoline and indole groups in Example 1. Then, 2 mL of the tetrahydrofuran solution of the compound containing quinoline and indole groups was mixed evenly with 20 μL of the aqueous metal ion solution, and then the fluorescence test was carried out on the mixed solution (the blank control was the tetrahydrofuran solution of the compound containing quinoline and indole groups). The fluorescence emission (PL) spectra of the compound containing quinoline and indole groups in Example 1 after mixing with different ions are shown as Figure 27 shown.

[0191] It can be seen from Figure 27 that there are three ions (Fe 2+ , Pd 2+ and Au 3+ ) that will cause a significant decrease in fluorescence intensity. Among them, Au 3+ is the only metal ion that causes a significant decrease in fluorescence intensity, while other metal ions have a relatively small effect on the change in fluorescence intensity, indicating that Au 3+ is the best ion to inhibit the fluorescence intensity of the compound containing quinoline and indole groups.

[0192] 2) Prepare a 10 mL aqueous solution of Au 3+ with a concentration of 0.01 mol / L (the corresponding anion is Cl-), and prepare a 10 mL tetrahydrofuran solution of the compound containing quinoline and indole groups with a concentration of 0.0001 mol / L using the compound containing quinoline and indole groups in Example 1. Then, 2 mL of the tetrahydrofuran solution of the compound containing quinoline and indole groups was mixed evenly with different volumes (20 μL, 50 μL, and 100 μL) of the aqueous solution of Au 3+ . Then, the fluorescence test was carried out on the mixed solutions (recorded as sample 1, sample 2, and sample 3 in sequence) (the blank control was the tetrahydrofuran solution of the compound containing quinoline and indole groups). The fluorescence emission spectra of the compound containing quinoline and indole groups in Example 1 after mixing with different concentrations of Au 3+ are shown as Figure 28 shown.

[0193] It can be seen from Figure 28 that as the concentration of Au 3+ increases, the fluorescence intensity near 460 nm gradually decreases, indicating that the compound containing quinoline and indole groups in Example 1 can be used as a fluorescence probe for Au 3+ .

[0194] After testing, the compounds containing quinoline and indole groups in Examples 2 to 13 also have excellent fluorescence properties and can also be used as fluorescent probes.

[0195] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. A class of compounds containing quinoline and indole groups, characterized in that, The structural formula is one of the formulas (1) to (3): , wherein, R 1 is selected from one of -H, -Me, -Cl, - t Bu, and R 2 is selected from one of -H, -Me, -OMe, -Cl, -F.

2. A method for preparing a compound containing quinoline and indole groups as described in claim 1, characterized in that, It includes the following steps: Disperse a disulfide, an iridium salt and an alkali metal salt in a solvent, wherein the disulfide is one of , and carry out a reaction under the irradiation of visible light to obtain a compound containing quinoline and indole groups.

3. The preparation method according to claim 2, characterized in that: The molar ratio of the disulfide, iridium salt, and alkali metal salt is 1:1 to 3:0.01 to 0.10:1 to 3.

4. The preparation method according to claim 2 or 3, characterized in that: The iridium salt is at least one of bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bipyridyl(4-tert-butylpyridine)]iridium bis(hexafluorophosphate), 4,4-bis(trifluoromethyl)-2,2-bipyridine bis[3,5-difluoro-2-(5-trifluoromethyl-2-pyridyl)phenyl]iridium(III) hexafluorophosphate, (2-2'-bipyridyl(4-tert-butylpyridine) bis[2-(4-tert-butylphenyl)pyridine]iridium(III) hexafluorophosphate, [4,4'-bis(1,1-dimethylethyl)-2,2'-bipyridine] bis[3,5-difluoro-2-(5-fluoro-2-pyridyl)phenyl]iridium hexafluorophosphate, 4,4'-di(tert-butyl-2,2'-bipyridine]di[5-methyl-2-(4-methyl-2-pyridyl-kN)phenyl-kC]iridium hexafluorophosphate, tris(2-phenylpyridine)iridium.

5. The preparation method according to claim 2 or 3, characterized in that: The alkali metal salt is at least one of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, cesium carbonate.

6. The preparation method according to claim 2 or 3, characterized in that: The solvent is at least one of tetrahydrofuran, acetonitrile, toluene, dichloroethane, methanol, dimethyl sulfoxide, 1,4-dioxane.

7. The preparation method according to claim 2 or 3, characterized in that: The visible light band includes at least one of 380 nm to 390 nm, 440 nm to 445 nm, 450 nm to 455 nm, 515 nm to 525 nm.

8. The preparation method according to claim 2 or 3, characterized in that: The reaction is carried out at a temperature of 10 °C to 80 °C, and the reaction time is 8 h to 18 h.

9. An organic light-emitting material, characterized in that, It contains the compound containing quinoline and indole groups described in claim 1.

10. A fluorescent probe, characterized in that, It contains the compound containing quinoline and indole groups described in claim 1.

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