A polysubstituted benzo[a]carbazole compound, a preparation method and application thereof

Abstract

The application discloses a polysubstituted benzo[a]carbazole compound and a preparation method and application thereof. 1 is selected from one or more of hydrogen, halogen, an organic group; R 2 is selected from one or more of hydrogen, halogen, an organic group. t The BuNC is subjected to reaction under the action of a palladium catalyst and an alkali to obtain the polysubstituted benzo[a]carbazole compound. The polysubstituted benzo[a]carbazole compound has fluorescence performance, the preparation method has the advantages of simple operation, mild conditions, good regioselectivity and wide substrate applicability, and has a good application prospect in the fields of organic luminescent materials, fluorescence detection and synthesis research of other similar compounds.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of organic synthesis, and particularly relates to a polysubstituted benzo[a]carbazole compound and a preparation method and application thereof. BACKGROUND

[0002] Benzo[a]carbazole and its derivatives have rich biological and pharmacological activities, such as antifungal, antitumor, anti-inflammatory, anti-estrogen and kinase inhibition properties. In addition, due to their unique luminescent properties, they are also widely used in the field of material science, for example, dye-sensitized solar cells and organic light-emitting diodes. However, there are few reports on the synthesis of polysubstituted benzo[a]carbazole compounds with different functional groups. Therefore, it is very important to explore novel and efficient methods for synthesizing polysubstituted benzo[a]carbazole compounds from simple and readily available starting materials, while improving the adaptability and functional group tolerance of the reaction.

[0003] Isocyanides have been widely used in the synthesis of various valuable heterocyclic compounds in transition metal-catalyzed transformations in recent years (M. Li, R. Zhang, Q. Gao, H. Jiang, M. Lei, W. Wu, Angew. Chem. Int. Ed. 2022, 61, e202208203; Z.-L. Ren, J.-Y. Qiu, L.-L. Yuan, Y.-F. Yuan, S. Cai, J. Li, C. Kong, P. He, L. Wang, Org. Lett. 2022, 24, 859; S. Zheng, H.-J. Fan, S.-S. Liu, Y. Xu, Z.-W. Zhao, H.-H. Kong, P. He, L. Wang, Z.-L. Ren, Org. Chem. Front. 2024, 11, 1775; S. Plunkett, J. B. Diccianni, R. Panish, J. Balsells, Org. Lett. 2024, 26, 6933.). Functionalized diarylalkynes are often used to construct fused aromatic heterocyclic compounds due to their rich reaction sites, but there is no report on the synthesis of polysubstituted benzo[a]carbazole compounds using isocyanides and functionalized diarylalkynes. SUMMARY

[0004] In view of the deficiencies of the prior art, the purpose of the present application is to provide a polysubstituted benzo[a]carbazole compound and a preparation method and application thereof.The present application realizes the synthesis of polysubstituted benzo[a]carbazole compounds through a tandem cyclization process of isonitrile and functionalized diaryl alkyne compounds catalyzed by a palladium catalyst, which is atom and step economical and efficient, and has wide substrate applicability.In addition to the innovativeness in the synthesis methodology, the present application also has certain application prospects in the fields of organic light-emitting materials and fluorescent detection.

[0005] The technical scheme adopted by the present application is as follows:

[0006] A polysubstituted benzo[a]carbazole compound has the structural formula:

[0007]

[0008] wherein, R 1 is selected from one or more of hydrogen, halogen, an organic group; R 2 is selected from one or more of hydrogen, halogen, an organic group.

[0009] The number of substituents R 1 , R 2 is 4 respectively, and each is independently selected from one of hydrogen, halogen, an organic group.

[0010] Preferably, the halogen is one or more of fluorine, chlorine, and bromine; the organic group is one or more of a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C1-C6 alkoxy group, and a substituted or unsubstituted C1-C6 ester group; and the substituent is halogen (fluorine, chlorine, and bromine).

[0011] Preferably, the R 1 is selected from one or more of hydrogen, 3-chloro, 4-tert-butyl, 4-methoxycarbonyl, 5-methyl, 5-methoxy, 5-fluoro, 5-chloro, 5-bromo, 5-trifluoromethyl, and 4,5-dimethyl; and the R 2 is selected from one or more of hydrogen, 4-fluoro, 5-fluoro, and 5-methoxy.

[0012] The above-mentioned preparation method of the polysubstituted benzo[a]carbazole compound comprises the following steps:

[0013] and t BuNC is reacted under the action of a palladium catalyst and a base to obtain the polysubstituted benzo[a]carbazole compound.

[0014] Preferably, the R t The molar ratio of BuNC, the palladium catalyst, the base, and the base is 1:1.0-3.0:0.05-0.1:1.0-3.0.

[0015] Preferably, the palladium catalyst is at least one of tetrakis(triphenylphosphine)palladium, palladium iodide, bis(triphenylphosphine)palladium dichloride, and palladium acetate.

[0016] Preferably, the base is at least one of DBU, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, and cesium carbonate.

[0017] Preferably, the reaction temperature is 80-100°C, and the reaction time is 8-16 hours.

[0018] Preferably, the method for preparing the polysubstituted benzo[a]carbazole compound comprises the following steps:

[0019] Preferably, the method for preparing the polysubstituted benzo[a]carbazole compound comprises the following steps: t The BuNC, palladium catalyst, and base are dispersed in a solvent, and the reaction is stirred at 80-100°C. After the reaction is completed, the product is cooled to room temperature, separated, and purified to obtain the polysubstituted benzo[a]carbazole compound.

[0020] Further preferably, the base is at least one of DBU, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, and cesium carbonate. t The molar ratio of the BuNC, palladium catalyst, and base is 1:1.0-3.0:0.05-0.1:1.0-3.0.

[0021] Further preferably, the palladium catalyst is at least one of tetrakis(triphenylphosphine)palladium, palladium iodide, bis(triphenylphosphine)palladium dichloride, and palladium acetate.

[0022] Further preferably, the base is at least one of DBU, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, and cesium carbonate.

[0023] Further preferably, the solvent is at least one of acetonitrile, toluene, tetrahydrofuran, dichloroethane, methanol, dimethyl sulfoxide, and 1,4-dioxane.

[0024] Further preferably, the reaction time is 8-16 hours.

[0025] Further preferably, the specific operation of the separation and purification is as follows: the reaction liquid is extracted with ethyl acetate for 3-5 times, the organic phases are combined, dried with anhydrous sodium sulfate, filtered, and the filtrate is distilled under reduced pressure to remove the organic solvent to obtain a crude product, which is purified by column chromatography to obtain the polysubstituted benzo[a]carbazole compound.

[0026] More preferably, the eluent of the column chromatography is composed of petroleum ether and ethyl acetate in a volume ratio of 5-3:1.

[0027] The polysubstituted benzo[a]carbazole compound is used as an organic light-emitting material or for preparing an organic light-emitting material.

[0028] The application of the above multi-substituted benzo[a]carbazole compounds as fluorescent probes.

[0029] Preferably, the multi-substituted benzo[a]carbazole compounds can distinguish different solvents.

[0030] The principle of the application is that a functionalized diaryl alkyne compound and a tert-butyl isonitrile are used as raw materials, reacted under the action of a palladium catalyst and a base, sequentially inserted by alkyne and isonitrile, then intramolecular cyclization, reductive elimination and 1,5-acyl migration are carried out to obtain the multi-substituted benzo[a]carbazole compound.

[0031] The application has the following beneficial effects:

[0032] The application synthesizes a series of novel multi-substituted benzo[a]carbazole compounds, which have fluorescent properties, and the preparation method has the advantages of simple and easily available raw materials, simple operation, mild conditions, good regioselectivity and wide substrate adaptability, and has good application prospects in the fields of organic light-emitting materials, fluorescent detection and synthesis of other similar compounds. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 and Figure 2 The hydrogen spectrum and the carbon spectrum of the target product obtained in Example 1 are shown in Figures 1 and 2, respectively.

[0034] Figure 3 and Figure 4 The hydrogen spectrum and the carbon spectrum of the target product obtained in Example 2 are shown in Figures 3 and 4, respectively.

[0035] Figure 5 and Figure 6 The hydrogen spectrum and the carbon spectrum of the target product obtained in Example 3 are shown in Figures 5 and 6, respectively.

[0036] Figure 7 and Figure 8 The hydrogen spectrum and the carbon spectrum of the target product obtained in Example 4 are shown in Figures 7 and 8, respectively.

[0037] Figure 9 and Figure 10 The hydrogen spectrum and the carbon spectrum of the target product obtained in Example 5 are shown in Figures 9 and 10, respectively.

[0038] Figure 11 and Figure 12 The hydrogen spectrum and the carbon spectrum of the target product obtained in Example 6 are shown in Figures 11 and 12, respectively.

[0039] Figure 13 and Figure 14 The hydrogen spectrum and the carbon spectrum of the target product obtained in Example 7 are shown in Figures 13 and 14, respectively.

[0040] Figure 15 and Figure 16These are the hydrogen spectrum and carbon spectrum of the target product obtained in Example 8, respectively.

[0041] Figure 17 and Figure 18 These are the hydrogen spectrum and carbon spectrum of the target product obtained in Example 10, respectively.

[0042] Figure 19 and Figure 20 These are the hydrogen spectrum and carbon spectrum of the target product obtained in Example 12, respectively.

[0043] Figure 21 and Figure 22 These are the hydrogen spectrum and carbon spectrum of the target product obtained in Example 13, respectively.

[0044] Figure 23 and Figure 24 These are the hydrogen spectrum and carbon spectrum of the target product obtained in Example 14, respectively.

[0045] Figure 25 The images show the fluorescence emission spectra of the target products in Examples 1, 5, 6, 7, and 10.

[0046] Figure 26 The image shows the fluorescence emission spectra of the target product mixed with different solvents in Example 1. Detailed Implementation

[0047] The technical solution of the present invention will be further described in detail below with reference to specific embodiments and accompanying drawings, but the scope of protection and implementation of the present invention are not limited thereto.

[0048] In the following examples, 1.0 equivalent is 0.1 mmol / L.

[0049] Example 1

[0050] Add to the reaction tube (1.0 equivalent) t BuNC (2.0 equivalents), Pd(PPh3)4 (0.1 equivalents), DBU (2.0 equivalents), and acetonitrile (2 mL) were reacted at 90 °C and stirred at 500 rpm for 12 hours. After the reaction was completed, the mixture was extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and then purified by column chromatography. The eluent was a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 to obtain the target product in a yield of 76%.

[0051] The proton and carbon spectra of the obtained target product are as follows: Figure 1 and Figure 2 As shown, the structural characterization data is as follows:

[0052] 1H NMR (400MHz, DMSO-d6) δ13.21(s,1H),8.76(dd,J=7.4,2.2Hz,1H),8.28(dd,J=6.9,1.7Hz,1H),8.03(d,J=8. 1Hz,1H),7.95–7.87(m,2H),7.79(d,J=8.1Hz,1H),7.56(t,J=7.7Hz,1H),7.38(t,J=7.6Hz,1H),1.52(s,9H).

[0053] 13 C NMR(101MHz,DMSO-d6)δ155.6(q,J=34.7Hz),139.5,139.1,136.4,129.7,129.0,128.3,126.5,1 25.9,123.0,121.1,121.0,120.3,117.3,115.6(q,J=289.1Hz),116.8,112.5,102.7,65.8,28.0.

[0054] 19 F NMR (376MHz, DMSO-d6) δ -68.6.

[0055] HRMS (APCI) calcd for C 23 H 19 F3N3O[M+H] + :410.1475,Found:410.1474.

[0056] Based on the above data, the structure of the target product is inferred as follows:

[0057]

[0058] Example 2

[0059] Add to the reaction tube (1.0 equivalent) t BuNC (2.0 equivalents), Pd(PPh3)4 (0.1 equivalents), DBU (2.0 equivalents), and acetonitrile (2 mL) were reacted at 90 °C and stirred at 500 rpm for 12 hours. After the reaction was completed, the mixture was extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and then purified by column chromatography. The eluent was a mixture of petroleum ether and ethyl acetate in a volume ratio of 3:1 to obtain the target product in a yield of 43%.

[0060] The proton and carbon spectra of the obtained target product are as follows: Figure 3 and Figure 4 As shown, the structural characterization data is as follows:

[0061] 1 H NMR(400MHz,DMSO-d6)δ13.56(s,1H),8.80–8.74(m,1H),8.30–8.25(m,1H),8.00–7.91( m,2H),7.80(d,J=7.1Hz,1H),7.57(t,J=7.9Hz,1H),7.44(d,J=7.6Hz,1H),1.34(s,9H).

[0062] 13 C NMR (101MHz, DMSO-d6) δ155.8 (q, J=33.8Hz), 141.6, 139.9, 137.1, 129.7, 129.6, 128.7, 127.4, 125. 7,125.5,123.4,123.0,120.2,119.4,117.2,116.0(q,J=289.2Hz),115.2,111.6,104.2,66.1,27.9.

[0063] 19 F NMR (376MHz, DMSO-d6) δ -67.0.

[0064] HRMS (APCI) calcd for C 23 H 18 ClF3N3O[M+H] + :444.1085,Found:444.1084.

[0065] Based on the above data, the structure of the target product is inferred as follows:

[0066]

[0067] Example 3

[0068] Add to the reaction tube 1.0 equivalent) t BuNC (2.0 equivalents), Pd(PPh3)4 (0.1 equivalents), DBU (2.0 equivalents), and acetonitrile (2 mL) were reacted at 90 °C and stirred at 500 rpm for 12 hours. After the reaction was completed, the mixture was extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and then purified by column chromatography. The eluent was a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 to obtain the target product in a yield of 70%.

[0069] The proton and carbon spectra of the obtained target product are as follows: Figure 5 and Figure 6As shown, the structural characterization data is as follows:

[0070] 1 H NMR (400MHz, DMSO-d6) δ13.09(s,1H),8.73(dd,J=7.6,1.8Hz,1H),8.27(dd,J=7.5,1.8Hz,1H),8.01(s ,1H),7.92–7.84(m,2H),7.71(d,J=8.6Hz,1H),7.64(dd,J=8.6,1.8Hz,1H),1.53(s,9H),1.33(s,9H).

[0071] 13 C NMR (101MHz, DMSO-d6) δ155.8 (q, J = 34.5Hz), 143.3, 139.3, 137.6, 136.5, 129.6, 128.8, 128.1, 125.8, 124 .4,122.9,120.8,120.3,117.4,117.1,116.9,115.6(q,J=289.0Hz),112.0,102.2,65.7,34.5,31.5,28.0.

[0072] 19 F NMR (376MHz, DMSO-d6) δ -68.8.

[0073] HRMS (APCI) calcd for C 27 H 27 N3F3O[M+H] + :466.2101,Found:466.2103.

[0074] Based on the above data, the structure of the target product is inferred as follows:

[0075]

[0076] Example 4

[0077] Add to the reaction tube (1.0 equivalent) t BuNC (2.0 equivalents), Pd(PPh3)4 (0.1 equivalents), DBU (2.0 equivalents), and acetonitrile (2 mL) were reacted at 90 °C and stirred at 500 rpm for 12 hours. After the reaction was completed, the mixture was extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and then purified by column chromatography. The eluent was a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 to obtain the target product in a yield of 49%.

[0078] The proton and carbon spectra of the obtained target product are as follows: Figure 7 and Figure 8 As shown, the structural characterization data is as follows:

[0079] 1 H NMR (400MHz, DMSO-d6) δ13.55(s,1H),8.79(s,1H),8.75(dd,J=7.4,2.3Hz,1H),8.31–8.27(m,1H) ,8.14(dd,J=8.6,1.6Hz,1H),7.97–7.89(m,2H),7.85(d,J=8.6Hz,1H),3.89(s,3H),1.53(s,9H).

[0080] 13 C NMR(101MHz,DMSO-d6)δ166.4,155.6(q,J=34.7Hz),142.2,140.1,136.2,130.0,129.5,128.7,127.1,1 26.0,123.2,123.0,122.2,120.9,120.5,117.0,115.6(q,J=289.0Hz),112.6,104.0,65.9,52.2,27.9.

[0081] 19 F NMR (376MHz, DMSO-d6) δ -68.7.

[0082] HRMS (APCI) calcd for C 25 H 21 N3F3O3[M+H] + :468.1530,Found:468.1532.

[0083] Based on the above data, the structure of the target product is inferred as follows:

[0084]

[0085] Example 5

[0086] Add to the reaction tube (1.0 equivalent) tBuNC (2.0 eq), Pd(PPh3)4(0.1 eq), DBU (2.0 eq) and acetonitrile (2 mL), the reaction was stirred at 90 °C with 500 rpm for 12 h, after the reaction was completed, extracted with ethyl acetate three times, combined organic phase and dried with anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and then separated and purified by column chromatography, eluent was petroleum ether: ethyl acetate mixed solvent with volume ratio of 3: 1, the target product was obtained, the yield was 70%.

[0087] The hydrogen spectrum and carbon spectrum of the obtained target product are shown in Figure 9 and Figure 10 The structure characterization data are as follows:

[0088] 1 H NMR (400 MHz, DMSO-d6) δ 13.04 (s, 1H), 8.73 (dd, J = 7.7, 2.0 Hz, 1H), 8.25 (dd, J = 7.7, 2.0 Hz, 1H), 7.91-7.86 (m, 2H), 7.86-7.82 (m, 1H), 7.55 (s, 1H), 7.18 (dd, J = 8.3, 1.5 Hz, 1H), 2.50 (s, 3H), 1.49 (s, 9H).

[0089] 13 C NMR (101 MHz, DMSO-d6) δ 155.6 (q, J = 34.6 Hz), 140.0, 138.9, 136.5, 136.1, 129.6, 128.7, 128.1, 125.8, 122.7, 122.6, 120.8, 120.3, 118.8, 117.4, 117.0, 115.7 (q, J = 289.0 Hz), 112.2, 102.4, 65.6, 28.0, 21.5.

[0090] 19 F NMR (376 MHz, DMSO-d6) δ -68.7.

[0091] HRMS (APCI) calcd for C 24 H 21 N3F3O [M+H] + : 424.1631, Found: 424.1630.

[0092] The structure of the target product is inferred from the above data as follows:

[0093]

[0094] Example 6

[0095] Into a reaction tube was added (1.0 eq), t BuNC (2.0 eq), Pd(PPh3)4(0.1 eq), DBU (2.0 eq) and acetonitrile (2 mL), stirred at 90 °C with 500 rpm for 12 h, after the reaction was completed, extracted with ethyl acetate three times, combined the organic phase and dried with anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and then separated and purified by column chromatography, eluent was petroleum ether: ethyl acetate mixed solvent with a volume ratio of 5:1, to obtain the target product, the yield was 67%.

[0096] The hydrogen spectrum and carbon spectrum of the obtained target product were as shown in Figure 11 and Figure 12 The structure characterization data were as follows:

[0097] 1 H NMR (400 MHz, DMSO-d6) δ 13.07 (s, 1H), 8.69 (dd, J = 8.4, 1.3 Hz, 1H), 8.25 (dd, J = 8.5, 1.2 Hz, 1H), 7.91-7.87 (m, 2H), 7.86-7.82 (m, 1H), 7.21 (d, J = 2.3 Hz, 1H), 7.03 (dd, J = 8.8, 2.4 Hz, 1H), 3.90 (s, 3H), 1.51 (s, 9H).

[0098] 13 C NMR (101 MHz, DMSO-d6) δ 158.9, 155.7 (q, J = 34.6 Hz), 141.1, 138.9, 135.6, 129.2, 128.5, 128.1, 125.8, 122.7, 122.0, 120.1, 117.4, 117.3, 115.7 (q, J = 289.0 Hz), 114.8, 110.6, 102.4, 95.5, 65.6, 55.5, 28.0.

[0099] 19 F NMR (376 MHz, DMSO-d6) δ -68.7.

[0100] HRMS (APCI) calcd for C 24 H 21 N3F3O2[M+H] + : 440.1580, Found: 440.1581.

[0101] The structure of the target product was inferred from the above data as follows:

[0102]

[0103] Example 7

[0104] Into the reaction tube was added (1.0 equivalent), t BuNC (2.0 equivalents), Pd(PPh3)4(0.1 equivalent), DBU (2.0 equivalents) and acetonitrile (2 mL), and the reaction was stirred at 90 °C with a rotation speed of 500 rpm for 12 hours. After the reaction was completed, the reaction was extracted with ethyl acetate three times, the organic phase was combined and dried with anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and then separated and purified by column chromatography with a mixture of petroleum ether: ethyl acetate (5:1 by volume) as the eluent to obtain the target product with a yield of 41%.

[0105] The hydrogen spectrum and carbon spectrum of the obtained target product are shown in Figure 13 and Figure 14 The structural characterization data are as follows:

[0106] 1 H NMR (400 MHz, DMSO-d6) δ 13.33 (s, 1H), 8.73 (dd, J = 7.0, 1.6 Hz, 1H), 8.27 (dd, J = 8.2, 1.4 Hz, 1H), 8.02 (dd, J = 8.9, 5.2 Hz, 1H), 7.95 - 7.87 (m, 2H), 7.55 (dd, J = 9.4, 2.4 Hz, 1H), 7.26 (td, J = 9.2, 2.4 Hz, 1H), 1.51 (s, 9H).

[0107] 13 C NMR (101 MHz, DMSO-d6) δ 161.6 (d, J = 240.6 Hz), 156.1 (q, J = 34.7 Hz), 140.7 (d, J = 12.7 Hz), 140.2 (d, J = 1.7 Hz), 136.4, 130.0, 129.5, 128.9, 126.4, 123.3, 123.1 (d, J = 10.5 Hz), 120.7, 118.3, 117.6, 117.1, 116.0 (q, J = 289.0 Hz), 110.0 (d, J = 24.4 Hz), 103.7, 99.4 (d, J = 25.8 Hz), 66.3, 28.5.

[0108] 19 F NMR (376 MHz, DMSO-d6) δ -68.7, -113.79 (td, J = 9.4, 5.2 Hz).

[0109] HRMS (APCI) calcd for C 23 H 18 N3F4O [M+H]+ :428.1381,Found:428.1384.

[0110] Based on the above data, the structure of the target product is inferred as follows:

[0111]

[0112] Example 8

[0113] Add to the reaction tube (1.0 equivalent) t BuNC (2.0 equivalents), Pd(PPh3)4 (0.1 equivalents), DBU (2.0 equivalents), and acetonitrile (2 mL) were reacted at 90 °C and stirred at 500 rpm for 12 hours. After the reaction was completed, the mixture was extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and then purified by column chromatography. The eluent was a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 to obtain the target product in a yield of 40%.

[0114] The proton and carbon spectra of the obtained target product are as follows: Figure 15 and Figure 16 As shown, the structural characterization data is as follows:

[0115] 1 H NMR (400MHz, DMSO-d6) δ13.34(s,1H),8.73(dd,J=7.4,1.9Hz,1H),8.28(dd,J=7.5,1.9Hz,1H),8.00 (d,J=8.6Hz,1H),7.95–7.88(m,2H),7.79(d,J=1.9Hz,1H),7.42(dd,J=8.6,2.0Hz,1H),1.50(s,9H).

[0116] 13 C NMR (101MHz, DMSO-d6) δ156.0 (q, J=34.7Hz), 140.6, 140.1, 136.6, 131.5, 130.3, 129.7, 129.0, 126. 5,123.5,122.9,121.9,120.8,120.4,117.5,116.9,116.1(q,J=289.2Hz),112.6,104.0,66.3,28.5.

[0117] 19 F NMR (376MHz, DMSO-d6) δ -68.7.

[0118] HRMS (APCI) calcd for C23 H 18 ClN3F3O[M+H] + :444.1085,Found:444.1086.

[0119] The structure of the target product is inferred from the above data as follows:

[0120]

[0121] Example 9

[0122] In the reaction tube was added (1.0 equivalent), t BuNC (2.0 equivalents), Pd(PPh3)4(0.1 equivalent), DBU (2.0 equivalents) and acetonitrile (2 mL), and the reaction was stirred at 90 °C at a rotation speed of 500 rpm for 12 hours. After the reaction was completed, the reaction mixture was extracted with ethyl acetate three times, the organic phases were combined and dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and then purified by column chromatography using a mixture of petroleum ether: ethyl acetate (5:1 by volume) as the eluent to obtain the target product in a yield of 36%.

[0123] The structure characterization data of the obtained target product are shown as follows:

[0124] 1 H NMR (400 MHz, DMSO-d6) δ 13.34 (s, 1H), 8.73 (dd, J = 8.2, 1.5 Hz, 1H), 8.28 (dd, J = 7.3, 2.0 Hz, 1H), 7.98 - 7.93 (m, 2H), 7.93 - 7.88 (m, 2H), 7.55 (dd, J = 8.6, 1.9 Hz, 1H), 1.50 (s, 9H).

[0125] 13 C NMR (101 MHz, DMSO-d6) δ 155.5 (q, J = 34.6 Hz), 140.4, 139.4, 136.1, 129.8, 129.3, 128.5, 126.0, 124.1, 123.0, 122.7, 120.3, 120.2, 119.2, 117.0, 116.4, 115.6 (q, J = 288.8 Hz), 115.1, 103.5, 65.9, 28.0.

[0126] 19 F NMR (376 MHz, DMSO-d6) δ -68.7.

[0127] HRMS (APCI) calcd for C 23 H 18BrN3F3O[M+H] + :488.0580,Found:488.0582.

[0128] Based on the above data, the structure of the target product is inferred as follows:

[0129]

[0130] Example 10

[0131] Add to the reaction tube (1.0 equivalent) t BuNC (2.0 equivalents), Pd(PPh3)4 (0.1 equivalents), DBU (2.0 equivalents), and acetonitrile (2 mL) were reacted at 90 °C and stirred at 500 rpm for 12 hours. After the reaction was completed, the mixture was extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and then purified by column chromatography. The eluent was a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 to obtain the target product in 50% yield.

[0132] The proton and carbon spectra of the obtained target product are as follows: Figure 17 and Figure 18 As shown, the structural characterization data is as follows:

[0133] 1 H NMR (400MHz, DMSO-d6) δ13.59(s,1H),8.77(dd,J=7.9,1.6Hz,1H),8.31(dd,J=7.9,1.6Hz,1H),8.23 (d,J=8.4Hz,1H),8.05(d,J=1.7Hz,1H),8.00–7.95(m,2H),7.73(dd,J=8.5,1.7Hz,1H),1.52(s,9H).

[0134] 13 C NMR(101MHz,DMSO-d6)δ155.5(q,J=34.7Hz),140.5,138.6,136.5,130.0,129.7,128.8,126.5,126.1,125.9,123.8, 123.2,122.0,120.4,117.4(q,J=3.6Hz),116.9,116.0,115.6(q,J=289.0Hz),109.6(q,J=4.1Hz),104.0,66.0,28.0.

[0135] 19 F NMR(376MHz,DMSO-d6)δ-59.8,-68.7.

[0136] HRMS (APCI) calcd for C 24 H 18 N3F6O[M+H] + :478.1349,Found:478.1348.

[0137] Based on the above data, the structure of the target product is inferred as follows:

[0138]

[0139] Example 11

[0140] Add to the reaction tube (1.0 equivalent) t BuNC (2.0 equivalents), Pd(PPh3)4 (0.1 equivalents), DBU (2.0 equivalents), and acetonitrile (2 mL) were reacted at 90 °C and stirred at 500 rpm for 12 hours. After the reaction was completed, the mixture was extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and then purified by column chromatography. The eluent was a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 to obtain the target product in a yield of 57%.

[0141] The structural characterization data of the obtained target product are shown below:

[0142] 1 H NMR (400MHz, DMSO-d6) δ12.96(s,1H),8.72(dd,J=8.3,1.3Hz,1H),8.25(dd,J=7.6,1.7Hz ,1H),7.91–7.82(m,2H),7.78(s,1H),7.55(s,1H),2.42(s,3H),2.37(s,3H),1.52(s,9H).

[0143] 13 C NMR(101MHz,DMSO-d6)δ155.6(q,J=34.6Hz),138.7,138.4,136.1,135.8,129.5,129.3,128.6,128.0,125 .8,122.8,121.1,120.3,119.2,117.4,116.9,115.7(q,J=289.1Hz),112.6,102.1,65.6,27.9,20.2,20.1.

[0144] 19 F NMR (376MHz, DMSO-d6) δ -68.6.

[0145] HRMS (APCI) calcd for C 25 H 23 N3F3O[M+H] + :438.1788,Found:438.1787.

[0146] Based on the above data, the structure of the target product is inferred as follows:

[0147]

[0148] Example 12

[0149] Add to the reaction tube (1.0 equivalent) t BuNC (2.0 equivalents), Pd(PPh3)4 (0.1 equivalents), DBU (2.0 equivalents), and acetonitrile (2 mL) were reacted at 90 °C and stirred at 500 rpm for 12 hours. After the reaction was completed, the mixture was extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and then purified by column chromatography. The eluent was a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 to obtain the target product in a yield of 49%.

[0150] The proton and carbon spectra of the obtained target product are as follows: Figure 19 and Figure 20 As shown, the structural characterization data is as follows:

[0151] 1 H NMR (400MHz, DMSO-d6) δ13.18(s,1H),8.53(dd,J=9.9,2.6Hz,1H),8.33(dd,J=9.2,5.3Hz,1H),8.0 4(d,J=8.0Hz,1H),7.79(td,J=8.6,2.5Hz,2H),7.60–7.56(m,1H),7.42–7.38(m,1H),1.51(s,9H).

[0152] 13C NMR (101MHz, DMSO-d6) δ161.2 (d, J = 246.3Hz), 155.6 (q, J = 34.7Hz), 139.5, 138.4 (d, J = 4.5Hz), 135.9, 129.2 (d, J = 9.5Hz), 126.8, 126.6, 121. 5,121.4,121.2(d,J=7.6Hz),120.9,118.6(d,J=25.0Hz),117.2,117.1 ,115.6(q,J=289.0Hz),112.6,107.5(d,J=23.3Hz),102.8,65.9,28.0.

[0153] 19 F NMR(376MHz, DMSO-d6)δ-68.6,-110.23(td,J=9.0,5.4Hz).

[0154] HRMS (APCI) calcd for C 23 H 18 N3F4O[M+H] + :428.1381,Found:428.1380.

[0155] Based on the above data, the structure of the target product is inferred as follows:

[0156]

[0157] Example 13

[0158] Add to the reaction tube (1.0 equivalent) t BuNC (2.0 equivalents), Pd(PPh3)4 (0.1 equivalents), DBU (2.0 equivalents), and acetonitrile (2 mL) were reacted at 90 °C and stirred at 500 rpm for 12 hours. After the reaction was completed, the mixture was extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and then purified by column chromatography. The eluent was a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 to obtain the target product in a yield of 70%.

[0159] The proton and carbon spectra of the obtained target product are as follows: Figure 21 and Figure 22 As shown, the structural characterization data is as follows:

[0160] 1H NMR (400 MHz, DMSO-d6) δ 13.26 (s, 1H), 8.83 (dd, J = 9.1, 5.4 Hz, 1H), 8.02 (d, J = 8.0 Hz, 1H), 7.90 (dd, J = 10.1, 2.6 Hz, 1H), 7.86 (td, J = 8.7, 2.5 Hz, 1H), 7.79 (d, J = 8.2 Hz, 1H), 7.59 - 7.53 (m, 1H), 7.42 - 7.36 (m, 1H), 1.51 (s, 9H).

[0161] 13 C NMR (101 MHz, DMSO-d6) δ 161.8 (d, J = 246.9 Hz), 155.5 (q, J = 34.7 Hz), 139.5, 139.2, 137.4, 131.3 (d, J = 9.6 Hz), 126.6, 126.3 (d, J = 9.5 Hz), 121.1 (d, J = 5.3 Hz), 120.9, 118.2, 118.0, 117.4, 117.0, 116.7, 115.6 (q, J = 288.9 Hz), 112.6, 110.0 (d, J = 23.3 Hz), 102.0 (d, J = 4.1 Hz), 65.9, 28.0.

[0162] 19 F NMR (376 MHz, DMSO-d6) δ -68.6, -109.6 (td, J = 9.3, 5.5 Hz).

[0163] HRMS (APCI) calcd for C 23 H 18 N3F4O [M] + : 428.1381, Found: 428.1378.

[0164] The structure of the target product is inferred from the above data as follows:

[0165]

[0166] Example 14

[0167] In a reaction tube was added (1.0 equivalent), tBuNC (2.0 eq), Pd(PPh3)4(0.1 eq), DBU (2.0 eq) and acetonitrile (2 mL), the reaction was stirred at 90 °C with 500 rpm for 12 h, after the reaction was completed, extracted with ethyl acetate three times, combined organic phase and dried with anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and then separated and purified by column chromatography, eluent was petroleum ether: ethyl acetate mixed solvent with volume ratio of 5:1, the target product was obtained with a yield of 73%.

[0168] The hydrogen spectrum and carbon spectrum of the obtained target product are shown in Figure 23 and Figure 24 The structure characterization data are as follows:

[0169] 1 H NMR (400 MHz, DMSO-d6) δ 13.03 (s, 1H), 8.66 (d, J = 8.9 Hz, 1H), 7.99 (d, J = 8.0 Hz, 1H), 7.74 (d, J = 8.1 Hz, 1H), 7.59 - 7.55 (m, 2H), 7.54 - 7.50 (m, 1H), 7.37 - 7.33 (m, 1H), 4.00 (s, 3H), 1.52 (s, 9H).

[0170] 13 C NMR (101 MHz, DMSO-d6) δ 159.7, 155.6 (q, J = 34.6 Hz), 139.5, 139.5, 136.6, 131.9, 126.2, 124.8, 121.1, 120.9, 120.8, 112.0, 117.6, 115.8, 115.7 (q, J = 289.0 Hz), 115.0, 112.3, 104.9, 101.6, 65.7, 55.5, 28.0.

[0171] 19 F NMR (376 MHz, DMSO-d6) δ -68.6.

[0172] HRMS (APCI) calcd for C 24 H 21 N3F3O2[M] + : 440.1580, Found: 440.1579.

[0173] The structure of the target product is inferred from the above data as follows:

[0174]

[0175] Application test:

[0176] 1) Respectively, the target product benz[a]carbazole compound in example 1, 5, 6, 7 and 10 is configured 10 mL concentration 10 -3 M acetonitrile solution, then 20 μL solution of the target product is mixed with 2 mL acetonitrile uniformly, and then fluorescence test is carried out, and the corresponding fluorescence emission spectrum of the target product is shown in Figure 25 .

[0177] From Figure 25 It can be seen that the benz[a]carbazole compounds in example 1, 5, 6, 7 and 10 have excellent fluorescence performance, and the product with electron donating methoxy substitution will have obvious fluorescence intensity reduction, and other substituents do not have obvious intensity reduction, which shows that the electronic effect may affect the fluorescence absorption and fluorescence emission of the product.

[0178] Through test, the products in other examples also have excellent fluorescence performance, and can be applied to the synthesis of fluorescent materials.

[0179] 2) Respectively, the target product benz[a]carbazole compound in example 1 is configured 10 mL concentration 10 -3 M 1,4-dioxane, methanol, 1,2-dichloroethane, N,N-dimethylformamide, tetrahydrofuran and toluene solution, then 20 μL solution of the target product is mixed with 2 mL different solvents uniformly, and then fluorescence test is carried out, and the corresponding fluorescence emission spectrum of the target product is shown in Figure 26 .

[0180] From Figure 26 It can be seen that N,N-dimethylformamide is a solvent that can cause the fluorescence intensity of the target product to be significantly reduced, and other solvents have little effect on the fluorescence intensity.

[0181] The above examples are the preferred embodiments of the present application, but the embodiments of the present application are not limited to the above examples, and any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present application are equivalent replacement methods, and are all included in the protection scope of the present application.

Claims

1. A method for preparing polysubstituted benzo[a]carbazole compounds, characterized in that, Includes the following steps: and t BuNC reacts with a palladium catalyst and a base to yield polysubstituted benzo[a]carbazole compounds; the structural formula of the polysubstituted benzo[a]carbazole compounds is as follows: Among them, R 1 Selected from one or more of hydrogen, halogens, and organic groups; R 2 It is selected from one or more of hydrogen, halogen, and organic groups; the organic group is one or more of substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, and substituted or unsubstituted C1-C6 ester groups, and the substituent is halogen.

2. The method for preparing polysubstituted benzo[a]carbazole compounds according to claim 1, characterized in that, The R 1 It is selected from one or more of hydrogen, 3-chloro, 4-tert-butyl, 4-methoxycarboxyl, 5-methyl, 5-methoxy, 5-fluorine, 5-chloro, 5-bromo, 5-trifluoromethyl, and 4,5-dimethyl; The R 2 It is selected from one or more of hydrogen, 4-fluoro, 5-fluoro, and 5-methoxy.

3. The method for preparing polysubstituted benzo[a]carbazole compounds according to claim 1, characterized in that, Includes the following steps: Will t BuNC, palladium catalyst and base were dispersed in solvent and reacted by stirring at 80-100℃. After the reaction was completed, the mixture was cooled to room temperature and the product was separated and purified to obtain polysubstituted benzo[a]carbazole compounds.

4. The method for preparing polysubstituted benzo[a]carbazole compounds according to claim 1 or 3, characterized in that: The t The molar ratio of BuNC, palladium catalyst and base is 1:1.0~3.0:0.05~0.1:1.0~3.

0.

5. The method for preparing polysubstituted benzo[a]carbazole compounds according to claim 1 or 3, characterized in that: The palladium catalyst is at least one of tetra(triphenylphosphine)palladium, palladium iodide, bis(triphenylphosphine)palladium dichloride, and palladium acetate; The alkali is at least one of DBU, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, and cesium carbonate.

6. The method for preparing polysubstituted benzo[a]carbazole compounds according to claim 3, characterized in that: The solvent is at least one selected from acetonitrile, toluene, tetrahydrofuran, dichloroethane, methanol, dimethyl sulfoxide, and 1,4-dioxane.

7. The method for preparing polysubstituted benzo[a]carbazole compounds according to claim 1 or 3, characterized in that: The reaction time is 8 to 16 hours.

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