Preparation method of 2, 3-diaryl indole compound

Abstract

The invention discloses a preparation method of a 2, 3-diaryl indole compound, which comprises the following steps: taking an aniline compound, an aryl ketoaldehyde compound and an aryl boric acid compound as raw materials, copper trifluoroacetate as a catalyst and cobalt disalicylaldehyde ethylenediamine as an oxidant in a reaction solvent, and reacting to generate the 2, 3-diaryl indole compound. Compared with the traditional reaction, only one reaction step is needed, the substrate is simple and easy to obtain, and the condition is mild and controllable. Meanwhile, the method is good in compatibility and can be suitable for substrates containing various functional groups. The method provided by the invention conforms to the concept of green chemistry in reagent and operation, shows obvious economic advantages, and is a brand new and efficient method for preparing the 2, 3-diaryl indole compound.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing 2,3-diarylindole compounds. Background Art

[0002] 2,3-Diarylindole compounds are a class of heterocyclic structures with biological activity, and the indole heterocyclic skeleton exists in many natural products, drug molecules and functional materials with important biological activities.

[0003] In the existing synthesis methods of 2,3-diaryl-substituted indole compounds, the most common method for constructing such skeletons is the Fisher and Cacchi indole synthesis methods. In addition, there is also a synthetic route through the transition metal-catalyzed cyclization of aniline-alkynes. For example, under palladium catalysis, the Larock indole synthesis reaction of 2,3-disubstituted indole by the heterocyclization of o-iodoaniline and disubstituted alkynes; however, there are still difficulties in the above methods, such as high reaction costs, the need to use precious metal catalysis, cumbersome pre-preparation processes of reactants, and poor regioselectivity control effects. Although there are also methods such as rhodium-catalyzed nitrone cyclization to solve the problem of controlling regioselectivity. However, the regioselective synthesis of 2,3-diaryl-substituted indole using non-precious metal conditions and easily available raw materials is still valuable. Summary of the Invention

[0004] Object of the Invention: Aiming at the problems existing in the prior art, the present invention provides a method for preparing 2,3-diaryl-substituted indole compounds with green, cheap, efficient and simple operation. The preparation method of the present invention not only solves the problem of high reaction costs of 2,3-diaryl-substituted indole compounds, but also has a simple pre-preparation process of reactants, cheap and easily available raw materials, no precious metal catalysis, and solves the problem of poor regioselectivity control. The reaction of this method has unique regioselectivity.

[0005] Technical Solution: To achieve the above object, the present invention provides a method for preparing 2,3-diarylindole compounds, which method comprises the following steps: using aniline compounds (1), aryl ketone aldehyde compounds (2) and aryl boronic acid compounds (3) as raw materials in a reaction solvent, and reacting under the action of a copper catalyst and an oxidant to generate 2,3-diarylindole compounds (4);

[0006] The reaction formula is as follows:

[0007]

[0008] Wherein R1 and R2 are electron-donating substituents; R3 is an aryl group with a para-nitro group; R4 is a halogen, an electron-donating group, a polycyclic aromatic hydrocarbon, a heteroaryl or a vinyl group.

[0009] Among them, the aniline compound (1) is selected from any one of the following compounds:

[0010]

[0011] Among them, the aryl ketone aldehyde compound (2) is selected from any one of the following compounds:

[0012]

[0013] Among them, the aryl boronic acid compound (3) is selected from any one of the following compounds:

[0014]

[0015] Among them, the copper catalyst is preferably any one or more of CuBr, CuCl, Cu(TFA)2·xH2O, and Cu(CF3SO3)2.

[0016] Preferably, the catalyst is Cu(TFA)2·xH2O.

[0017] Among them, the oxidant is preferably any one or more of CoPyCl (cobalt pyridine chloroxime), Co(salen) (cobalt bis(salicylaldehyde)ethylenediamine), DDQ (2,3-dichloro-5,6-dicyanobenzoquinone), and Na2S2O8.

[0018] Preferably, the oxidant is Co(salen).

[0019] Among them, the reaction solvent is any one or more of 1,2-dichloroethane, dichloromethane, or toluene.

[0020] Preferably, the solvent is 1,2-dichloroethane.

[0021] Among them, the molar ratio of the aniline compound (1), aryl ketone aldehyde compound (2), and aryl boronic acid compound (3) is 1:2:2 - 5, and the concentration of the aniline compound is 0.05 - 0.15 mol / L.

[0022] Among them, the molar ratio of the aniline compound (1) to the copper catalyst is 4:1 - 10:1, and the molar ratio of the aniline compound (1) to the oxidant is 4:1 - 10:1.

[0023] Preferably, the molar ratio of the aniline compound (1) to the aryl ketone aldehyde compound (2) is 1:2, and the concentration of the aniline compound should be 0.1 mol / L; the molar ratio of the aniline compound (1) to the aryl boronic acid compound (3) is 1:3; the molar ratio of the aniline compound (1) to the copper catalyst is 5:1, and the molar ratio of the aniline compound (1) to the oxidant is 5:1.

[0024] Among them, the reaction temperature in the reaction system is 60 - 80 °C, the time is 4 - 8 h, and the reaction system needs to be carried out under air.

[0025] Preferably, the reaction temperature in the reaction system is 80 °C and the reaction time is 4 hours.

[0026] The present invention provides a method for preparing 2,3-diarylindole compounds. In the present invention, an aryl ketone aldehyde compound (2) is used as a raw material, an aniline compound (1) and an aryl boronic acid compound (3) are added to the reaction system, and they are mixed with a catalytic amount of copper ions and an oxidant. The reaction temperature is controlled at 80 °C and the reaction time is 4 h. Compared with the traditional reaction, this reaction only requires one reaction step, the substrates are simple and easily available, the conditions are mild and controllable, and the conversion efficiency is high. At the same time, this method has good compatibility and can be applied to substrates containing various functional groups. This method conforms to the concept of green chemistry in terms of reagents and operations and shows obvious economic advantages. It is a new and efficient method for preparing 2,3-diarylindole compounds. The solutions of the compounds are all yellow and can present a more vivid color than traditional indigo dyes. The obtained compounds have stable properties and can be adjusted in color depth through different substituents. Therefore, they can be used as organic colorants and applied in the fields of textiles, printing, etc.

[0027] In the prior art, the general synthetic methods for 2,3-diarylindole compounds, namely the Fisher synthesis method and the Cacchi synthesis method, require the reactants to be pre-synthesized in advance and the preparation process is relatively cumbersome. In the transition metal-catalyzed cyclization synthesis method, there are difficulties in controlling regioselectivity, and precious metals such as rhodium are used in the transition metal-catalyzed cyclization synthesis method. The present invention uses an aniline compound (1) and an aryl ketone aldehyde compound (2) to condense into an intermediate, and the aryl boronic acid compound (3) adds to and then eliminates the intermediate, and is directionally converted into 2,3-diaryl-substituted indole. The method of the present invention not only solves the problem of high reaction cost, but also has a simple pre-preparation process of the reactants, cheap and easily available raw materials, no precious metal catalysis, and relatively low reaction cost. The preparation method of the present invention solves the problem of poor control of regioselectivity and has unique regioselectivity.

[0028] It can be seen from the conditions of the present invention and the raw materials used that the reaction cost is low. The metals copper and cobalt involved in the catalyst and oxidant are both non-precious metals. At the same time, there are two possible selective products 4 and 4ab in the reaction of the present invention, but only product 4 was observed during the screening conditions of the present invention, and there was no regioisomer 4ab. Therefore, it has a unique regioselectivity.

[0029]

[0030] In addition, in the preparation process of the present invention, not only the raw materials of the reaction system are very important, but also the catalyst, oxidant and solvent in the system are very important for the progress of the whole reaction. Among them, the solvent DCE determines the formation of the product, and the catalyst and oxidant are used to increase the yield.

[0031] Advantages: Compared with the prior art, the present invention has the following advantages:

[0032] 1. The present invention provides a new synthetic route for preparing 2,3-diarylindole compounds. This reaction is applicable to the formation of various functional groups and has a wide range of substrate applicability.

[0033] 2. The reaction conditions of the present invention are mild, the reaction time is short, the reaction temperature is low, the pre-preparation process of the reactants is simple, the raw materials are cheap and easily available, there is no precious metal catalysis, and the reaction cost is low.

[0034] 3. The reaction of the present invention has a unique regioselectivity.

[0035] 4. The compounds prepared by the present invention have good dyeing effects and uniform dyeing, and can be used as organic colorants and applied in the textile field. Description of the Drawings

[0036] Figure 1 They are isatin, compound 3, compound 1, compound 23, and compound 14 respectively. Weigh 0.01 mmol of the product and dissolve it in 2 ml of DCM to prepare a solution with a concentration of 0.005 M. As shown in the figure, the obtained compounds are stable, and the compound solutions are all yellow. The color depth can be adjusted by different substituents. For example, from compound 3 to compound 14, the color gradually deepens. Among them, Figure a is the front view of isatin, compound 3, compound 1, compound 23, and compound 14 respectively; Figure b is the comprehensive top view of isatin, compound 3, compound 1, compound 23, and compound 14 respectively; Figures c, d, e, and f are the top views of compound 3, compound 1, compound 23, and compound 14 respectively.

[0037] Figure 2Dyeing experiment of Compound 14. Weigh 0.04 mmol of the product and dissolve it in 4 ml of DCM to prepare a solution with a concentration of 0.01 M as the dyeing solution. As shown in the figure, Figure g shows the dyeing solution and the cotton fabric to be dyed; Figure h shows the process of soaking the cotton fabric; Figures i, j, and k show the dyeing states at different time points after dyeing. It can be seen that Compound 14 has a good dyeing effect and uniform dyeing, and can be used as an organic colorant and applied in the textile field. Detailed implementation mode

[0038] According to the following embodiments, the present invention can be better understood. However, those skilled in the art can easily understand that the content described in the embodiments is only used to illustrate the present invention and should not and will not limit the present invention described in detail in the claims.

[0039] The experimental methods described in the embodiments are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, can be obtained from commercial channels or simply prepared by existing technologies.

[0040] Cu(TFA)2·xH2O was purchased from Titan Technology brand: Adamas, product number: 011484413, CAS number: 123333-88-0.

[0041] Co(salen) was purchased from Bide Pharmatech, CAS number: 14167-18-1.

[0042] Example 1

[0043] Reaction condition screening

[0044]

[0045] As can be seen from Table 1, the reaction conditions were screened according to the above reaction formula. Using 4,4'-dimethoxydiphenylamine (1a), 2-(4-nitrophenyl)-2-oxoacetaldehyde (2a) and phenylboronic acid (3a) as starting materials, with CoPyCl as the oxidant and DCE as the reaction solvent, the reaction catalysts in Table 1 were screened (entries 1-6). Among them, 1a (0.2 mmol), 2a (0.4 mmol), 3a (0.6 mmol), catalyst (0.04 mmol), oxidant (0.04 mmol) and solvent (2.0 mL, c 0.1 M) were added to a pressure-resistant tube, and stirred at 80 °C for 4 hours under air conditions. After the reaction, it was cooled to room temperature, extracted with ethyl acetate, and the organic layer was washed successively with saturated NaHCO3 solution and saturated NaCl solution, dried over Na2SO4 and filtered. The obtained organic layer was concentrated under reduced pressure to obtain the crude product. The crude product was separated by silica gel column chromatography with an eluent of PE:DCM = 3:1 to obtain the target product, and the reaction had a higher yield under the catalysis of Cu(TFA)2·xH2O (entry 6). Then the solvents in Table 1 were investigated (entries 6-9). Among them, the raw materials remained unchanged, the catalyst was Cu(TFA)2·xH2O, and the oxidant was CoPyCl. 1a (0.2 mmol), 2a (0.4 mmol), 3a (0.6 mmol), catalyst (0.04 mmol), oxidant (0.04 mmol) and solvent (2.0 mL, c 0.1 M) were added to a pressure-resistant tube and stirred and heated at 80 °C for 4 hours. The reaction had a narrow solvent applicability, and the highest yield was obtained in DCE (entry 6). Then the reaction oxidants were screened (entries 10-12). Among them, the raw materials remained unchanged, the catalyst was Cu(TFA)2·xH2O, and the reaction solvent was DCE. 1a (0.2 mmol), 2a (0.4 mmol), 3a (0.6 mmol), catalyst (0.04 mmol), oxidant (0.04 mmol) and solvent (2.0 mL, c 0.1 M) were added to a pressure-resistant tube and stirred at 80 °C for 4 hours. The reaction had a higher yield under the oxidation of Co(salen) (entry 10). Therefore, considering comprehensively, entry 10 was selected as the standard reaction conditions, that is, 45.9 mg (0.2 mmol) of 4,4'-dimethoxydiphenylamine, 71.7 mg (0.4 mmol) of 2-(4-nitrophenyl)-2-oxoacetaldehyde, 73.2 mg (0.6 mmol) of phenylboronic acid, 12.3 mg (0.04 mmol) of Cu(TFA)2·xH2O, 13.1 mg (0.04 mmol) of Co(salen) and 2 ml of DCE were added to a pressure-resistant tube, the reaction temperature was set at 80 °C, and stirred for 4 hours.

[0046] Table 1 Screening of reaction conditions using compound 4a as an example.

[0047]

[0048] As can be seen from Table 1 of the present invention, during the reaction process of the present invention, the solvent, catalyst, and oxidant all have a great influence on the yield of the entire reaction system. Among them, the solvent DCE determines the formation of the product.

[0049] Experimental results of the present invention show that under the reaction conditions of Entry 10, no product is formed when the reaction solvent 1,2-dichloroethane is replaced with dichloromethane, DMSO, or toluene.

[0050] Example 2

[0051]

[0052] Weigh 45.9 mg (0.2 mmol) of 4,4'-dimethoxydiphenylamine (1a), 71.7 mg (0.4 mmol) of 2-(4-nitrophenyl)-2-oxoacetaldehyde (2a), 73.2 mg (0.6 mmol) of phenylboronic acid (3a), 12.3 mg (0.04 mmol) of Cu(TFA)2·xH2O, and 13.1 mg (0.04 mmol) of Co(salen) in sequence using an analytical balance and load them into a pressure-resistant tube. Use a pipette to measure 2 ml (0.1 M) of DCE and load it into the pressure-resistant tube and seal it. Set the reaction temperature to 80 °C and stir the reaction for 4 hours under air conditions. After the reaction is completed, cool it to room temperature and extract with ethyl acetate. The organic layer is washed successively with saturated NaHCO3 solution and saturated NaCl solution, dried with Na2SO4, filtered, and the obtained organic layer is concentrated under reduced pressure to obtain a crude product. The crude product is separated by silica gel column chromatography with an eluent of PE:DCM = 3:1 to obtain the target product with a yield of 56%.

[0053] Using the above synthesis method, different reaction raw materials are replaced while other conditions remain the same, and a total of 24 2,3-diarylindole compounds are synthesized. The structures of the compounds and the reaction raw materials are shown in Table 2:

[0054] Table 2 Structures of 2,3-diarylindole compounds

[0055]

[0056]

[0057]

[0058]

[0059] The characterization of the products in Table 2 above is as follows:

[0060] 5-Methoxy-1-(4-methoxyphenyl)-3-(4-nitrophenyl)-2-phenyl-1H-indole (1)

[0061]

[0062] 1 H NMR (600 MHz, CDCl3): δ 8.17 (d, J = 8.8 Hz, 2H), 7.48 (d, J = 8.8 Hz, 2H), 7.26 - 7.23 (m, 2H), 7.19 (t, J = 8.5 Hz, 3H), 7.13 (d, J = 8.8 Hz, 2H), 7.08 (d, J = 7.0 Hz, 2H), 6.93 (dd, J = 8.9 Hz, 2.4 Hz, 1H), 6.89 (d, J = 8.8 Hz, 2H), 3.88 (s, 3H), 3.82 (s, 3H).

[0063] 13C NMR (151 MHz, CDCl3): δ 158.9, 155.8, 145.6, 143.1, 139.5, 133.9, 131.2, 131.1, 130.4, 130.2, 129.4, 128.4, 128.2, 127.0, 123.9, 114.5, 114.0, 113.3, 112.1, 100.8, 56.2, 55.6.

[0064] HRMS (ESI): m / z calcd for C 28 H 23 N2O4 + (M + H) + 451.16523, found 451.16583.

[0065] 2-(4-Fluorophenyl)-5-methoxy-1-(4-methoxyphenyl)-3-(4-nitrophenyl)-1H-indole (2)

[0066]

[0067] 1 H NMR (600 MHz, CDCl3): δ 8.19 (d, J = 8.8 Hz, 2H), 7.47 (d, J = 8.8 Hz, 2H), 7.23 (d, J = 2.4 Hz, 1H), 7.17 (d, J = 8.9 Hz, 1H), 7.11 (d, J = 8.8 Hz, 2H), 7.06 (d, J = 5.5 Hz, 1H), 7.04 (d, J = 5.5 Hz, 1H), 6.94 - 6.89 (m, 5H), 3.88 (s, 3H), 3.84 (s, 3H). ​

[0068] 13 13C NMR (151 MHz, CDCl3): δ 162.5 (d, J = 248.9 Hz), 159.0, 155.8, 145.7, 142.8, 138.3, 133.9, 132.9 (d, J = 8.2 Hz), 130.2, 130.2, 129.4, 127.2 (d, J = 3.4 Hz), 126.9, 124.0, 115.7 (d, J = 21.6 Hz), 114.6, 114.2, 113.4, 112.1, 100.8, 56.2, 55.6. 19 19F NMR (565 MHz, CDCl3): δ -112.57 (ddd, J = 14.0 Hz, 8.8 Hz, 5.3 Hz).

[0069] HRMS (ESI): m / z calcd for C 28 H 22 FN2O4 + (M + H) + 469.15581, found 469.15598.

[0070] 2-(4-Chlorophenyl)-5-methoxy-1-(4-methoxyphenyl)-3-(4-nitrophenyl)-1H-indole (3)

[0071]

[0072] 1 1H NMR (600 MHz, CDCl3): δ 8.19 (d, J = 8.3 Hz, 2H), 7.49 (d, J = 8.3 Hz, 2H), 7.23 (d, J = 2.4 Hz, 1H), 7.18 (d, J = 8.5 Hz, 3H), 7.12 (d, J = 8.4 Hz, 2H), 7.02 (d, J = 8.1 Hz, 2H), 6.94 - 6.92 (m, 3H), 3.87 (s, 3H), 3.85 (s, 3H).

[0073] 13 13C NMR (151 MHz, CDCl3): δ 159.0, 155.8, 145.7, 142.6, 137.8, 134.2, 133.9, 132.3, 130.2, 130.1, 129.5, 129.3, 128.7, 126.8, 123.9, 114.6, 114.3, 113.5, 112.1, 100.7, 56.0, 55.5.

[0074] HRMS (ESI): m / z calcd for C28 H 21 ClN2O4Na + (M + Na) + 507.10821, found 507.10846.

[0075] 5-Methoxy-1,2-bis(4-methoxyphenyl)-3-(4-nitrophenyl)-1H-indole (4)

[0076]

[0077] 1 H NMR (600 MHz, CDCl3): δ 8.18 (d, J = 8.4 Hz, 2H), 7.49 (d, J = 8.4 Hz, 2H), 7.25 (d, J = 2.4 Hz, 1H), 7.17 (d, J = 8.9 Hz, 1H), 7.13 (d, J = 8.7 Hz, 2H), 6.99 (d, J = 8.4 Hz, 2H), 6.90 (d, J = 8.9 Hz, 3H), 6.73 (d, J = 8.5 Hz, 2H), 3.88 (s, 3H), 3.83 (s, 3H), 3.77 (s, 3H).

[0078] 13 C NMR (151 MHz, CDCl3): δ 159.4, 158.8, 155.7, 145.5, 143.3, 139.5, 133.9, 132.4, 130.5, 130.1, 129.4, 127.0, 123.9, 123.2, 114.5, 113.9, 113.6, 112.9, 112.0, 100.7, 56.1, 55.6, 55.2.

[0079] HRMS (ESI): m / z calcd for C 29 H 24 N2O4Na + (M + Na) + 503.15774, found 503.15784.

[0080] 2-(3-Chlorophenyl)-5-methoxy-1-(4-methoxyphenyl)-3-(4-nitrophenyl)-1H-indole (5)

[0081]

[0082] 11H NMR (600 MHz, CDCl3): δ 8.20 (d, J = 8.7 Hz, 2H), 7.48 (d, J = 8.8 Hz, 2H), 7.22 (d, J = 2.6 Hz, 2H), 7.17 (d, J = 8.9 Hz, 1H), 7.14 - 7.12 (m, 3H), 7.07 (t, J = 1.8 Hz, 1H), 6.96 (dt, J = 7.8 Hz, 1.4 Hz, 1H), 6.94 - 6.91 (m, 3H), 3.87 (s, 3H), 3.84 (s, 3H).

[0083] 13 13C NMR (151 MHz, CDCl3): δ 159.1, 155.9, 145.8, 142.5, 137.6, 134.2, 134.0, 133.0, 131.0, 130.3, 130.0, 129.7, 129.4, 129.4, 128.3, 126.8, 124.0, 114.7, 114.6, 113.8, 112.2, 100.8, 56.1, 55.6.

[0084] HRMS (ESI): m / z calcd for C 28 H 21 ClN2O4Na + (M + Na) + 507.10821, found 507.10837.

[0085] 5-Methoxy-1-(4-methoxyphenyl)-3-(4-nitrophenyl)-2-(m-tolyl)-1H-indole (6)

[0086]

[0087] 1 1H NMR (600 MHz, CDCl3): δ 8.17 (d, J = 8.8 Hz, 2H), 7.49 (d, J = 8.7 Hz, 2H), 7.25 (d, J = 2.4 Hz, 1H), 7.18 (d, J = 8.9 Hz, 1H), 7.13 (d, J = 8.8 Hz, 2H), 7.08 (t, J = 7.5 Hz, 1H), 7.05 (d, J = 7.6 Hz, 1H), 6.92 (dd, J = 8.9 Hz, 2.4 Hz, 1H), 6.90 - 6.87 (m, 4H), 3.88 (s, 3H), 3.83 (s, 3H), 2.18 (s, 3H).

[0088] 1313C NMR(151MHz,CDCl3):δ158.9,155.7,145.5,143.2,139.7,138.0,133.9,131.8,131.0,130.5,130.2,129.4,129.0,128.3,128.3,126.9,123.8,114.4,113.9,113.1,112.1,100.8,56.1,55.6,21.5.

[0089] HRMS(ESI):m / z calcd for C 29 H 24 N2O4Na + (M+Na) + 487.16283,found 487.16296.

[0090] 2-(3,4-Dichlorophenyl)-5-methoxy-1-(4-methoxyphenyl)-3-(4-nitrophenyl)-1H-indole (7)

[0091]

[0092] 1 1H NMR(600MHz,CDCl3):δ8.21(d,J=8.6Hz,2H),7.47(d,J=8.6Hz,2H),7.25(d,J=3.1Hz,1H),7.18(d,J=2.4Hz,1H),7.15(dd,J=5.5Hz,3.5Hz,2H),7.11(d,J=8.7Hz,2H),6.93(d,J=8.6Hz,3H),6.89(dd,J=8.3Hz,2.0Hz,1H),3.86(s,3H),3.84(s,3H).

[0093] 13 13C NMR(151MHz,CDCl3):δ159.2,155.9,146.0,142.2,136.3,134.1,132.7,132.7,132.5,131.2,130.5,130.3,130.3,129.9,129.4,126.8,124.2,114.9,114.8,114.1,112.2,100.7,56.1,55.7.

[0094] HRMS(ESI):m / z calcd for C 28 H 20 Cl2N2O4Na + (M+Na) +541.0692337, found 541.06934.

[0095] 2-(2-Bromophenyl)-5-methoxy-1-(4-methoxyphenyl)-3-(4-nitrophenyl)-1H-indole (8)

[0096]

[0097] 1 H NMR (600 MHz, CDCl3): δ 8.15 (d, J = 8.6 Hz, 2H), 7.49 (t, J = 8.9 Hz, 3H), 7.31 (d, J = 2.4 Hz, 1H), 7.24 - 7.16 (m, 6H), 6.96 (dd, J = 8.9 Hz, 2.4 Hz, 1H), 6.85 (d, J = 8.5 Hz, 2H). 3.89 (s, 3H), 3.80 (s, 3H).

[0098] 13 C NMR (151 MHz, CDCl3): δ 159.0, 155.8, 145.7, 142.7, 138.2, 133.7, 133.5, 133.0, 130.6, 129.9, 129.3, 129.2, 127.3, 126.4, 125.7, 123.9, 114.9, 114.3, 113.6, 112.2, 101.0, 56.2, 55.5.

[0099] HRMS (ESI): m / z calcd for C 28 H 21 BrN2O4Na + (M + Na) + 551.05769, found 551.05780.

[0100] 2-(Benzo[d][1,3]dioxol-5-yl)-5-methoxy-1-(4-methoxyphenyl)-3-(4-nitrophenyl)-1H-indole (9)

[0101]

[0102] 11H NMR (600 MHz, CDCl3): δ 8.19 (d, J = 8.8 Hz, 2H), 7.50 (d, J = 8.4 Hz, 2H), 7.23 (d, J = 2.4 Hz, 1H), 7.14 (t, J = 9.3 Hz, 3H), 6.92 - 6.90 (m, 3H), 6.64 (d, J = 8.0 Hz, 1H), 6.57 (d, J = 8.0 Hz, 1H), 6.53 (s, 1H), 5.94 (s, 2H), 3.87 (s, 3H), 3.84 (s, 3H). 13 13C NMR (151 MHz, CDCl3): δ 158.9, 155.8, 147.64, 147.62, 145.6, 143.0, 139.2, 133.8, 130.4, 130.1, 129.4, 126.8, 125.4, 124.7, 123.9, 114.6, 113.9, 113.2, 112.1, 111.2, 108.5, 101.4, 100.8, 56.1, 55.6.

[0103] HRMS (ESI): m / z calcd for C 29 H 22 N2O6Na + (M + Na) + 517.13701, found 517.13727.

[0104] 2-(Benzo[b]thiophen-3-yl)-5-methoxy-1-(4-methoxyphenyl)-3-(4-nitrophenyl)-1H-indole (10)

[0105]

[0106] 1 1H NMR (600 MHz, CDCl3): δ 8.05 (d, J = 8.9 Hz, 2H), 7.77 (d, J = 8.1 Hz, 1H), 7.47 (d, J = 8.9 Hz, 2H), 7.34 - 7.32 (m, 2H), 7.25 - 7.22 (m, 3H), 7.20 (s, 1H), 7.14 - 7.11 (m, 2H), 6.96 (dd, J = 8.9 Hz, 2.4 Hz, 1H), 6.78 (d, J = 8.5 Hz, 2H), 3.90 (s, 3H), 3.74 (s, 3H).

[0107] 1313C NMR (151 MHz, CDCl3): δ 158.9, 155.8, 145.5, 142.8, 139.6, 138.1, 134.0, 133.3, 130.2, 129.2, 129.1, 128.7, 127.0, 126.7, 124.8, 124.6, 123.9, 123.1, 122.7, 115.4, 114.4, 113.5, 112.2, 100.9, 56.2, 55.5.

[0108] HRMS (ESI): m / z calcd for C 30 H 22 N2O4SNa + (M + Na) + 529.11925, found 529.11938.

[0109] 5-Methoxy-1-(4-methoxyphenyl)-2-(naphthalen-2-yl)-3-(4-nitrophenyl)-1H-indole (11)

[0110]

[0111] 1 1H NMR (600 MHz, CDCl3): δ 8.14 (d, J = 8.7 Hz, 2H), 7.78 (d, J = 8.1 Hz, 1H), 7.67 (d, J = 8.5 Hz, 1H), 7.61 (d, J = 8.1 Hz, 1H), 7.59 (s, 1H), 7.51 (d, J = 8.7 Hz, 2H), 7.48 (t, J = 7.1 Hz, 1H), 7.44 (t, J = 7.8 Hz, 1H), 7.29 (d, J = 2.4 Hz, 1H), 7.22 (d, J = 8.9 Hz, 1H), 7.19 - 7.17 (m, 3H), 6.96 (dd, J = 8.9 Hz, 2.4 Hz, 1H), 6.86 (d, J = 8.8 Hz, 2H), 3.90 (s, 3H), 3.79 (s, 3H).

[0112] 13 13C NMR (151 MHz, CDCl3): δ 158.9, 155.8, 145.6, 143.0, 139.3, 134.1, 133.0, 132.7, 130.9, 130.4, 130.3, 129.4, 128.5, 128.3, 128.3, 128.1, 127.8, 127.0, 126.8, 126.5, 123.9, 114.6, 114.4, 113.4, 112.1, 100.8, 56.1, 55.5.

[0113] HRMS (ESI): m / z calculated for C 34 H 24 N2O4Na + (M + Na) + 523.16283, found 523.16309.

[0114] 5-Methoxy-1-(4-methoxyphenyl)-3-(4-nitrophenyl)-2-(4-phenylnaphthalen-1-yl)-1H-indole (12)

[0115]

[0116] 1 H NMR (600 MHz, CDCl3): δ 8.04 (d, J = 8.9 Hz, 2H), 7.87 (d, J = 9.8 Hz, 1H), 7.73 (d, J = 9.0 Hz, 1H), 7.50 - 7.39 (m, 7H), 7.41 (d, J = 7.2 Hz, 1H), 7.39 (d, J = 2.4 Hz, 1H), 7.32 (q, J = 6.9 Hz, 3H), 7.24 (s, 1H), 7.12 (d, J = 8.3 Hz, 2H), 7.00 (dd, J = 8.9 Hz, 2.4 Hz, 1H), 6.73 (d, J = 8.4 Hz, 2H), 3.94 (s, 3H), 3.72 (s, 3H).

[0117] 13 C NMR (151 MHz, CDCl3): δ 158.7, 155.9, 145.4, 142.9, 141.6, 140.3, 138.1, 134.0, 133.2, 131.6, 130.3, 130.2, 130.0, 129.2, 128.9, 128.5, 128.4, 127.6, 126.8, 126.6, 126.5, 126.2, 126.2, 126.1, 123.8, 115.6, 114.2, 113.3, 112.2, 101.0, 56.2, 55.4. HRMS (ESI): m / z calculated for C 38 H 28 N2O4Na + (M + Na) + 599.19413, found 599.19470.

[0118] 2-(4-Fluoro-naphthalen-1-yl)-5-methoxy-1-(4-methoxyphenyl)-3-(4-nitrophenyl)-1H-indole (13)

[0119]

[0120] 1 1H NMR (600 MHz, CDCl3): δ 8.06 (d, J = 8.4 Hz, 1H), 8.02 (d, J = 8.9 Hz, 2H), 7.64 (d, J = 8.5 Hz, 1H), 7.46 (t, J = 7.6 Hz, 1H), 7.40 (d, J = 8.8 Hz, 2H), 7.37 - 7.35 (m, 2H), 7.30 (dd, J = 7.9 Hz, 5.2 Hz, 1H), 7.23 (d, J = 8.9 Hz, 1H), 7.06 - 7.03 (m, 3H), 6.99 (dd, J = 8.9 Hz, 2.4 Hz, 1H), 6.71 (d, J = 8.5 Hz, 2H), 3.92 (s, 3H), 3.71 (s, 3H).

[0121] 13 13C NMR (151 MHz, CDCl3): δ 159.2 (d, J = 255.2 Hz), 158.8, 155.9, 145.5, 142.7, 137.2, 134.2 (d, J = 5.1 Hz), 133.9, 130.5 (d, J = 8.4 Hz), 130.1, 129.1, 128.8, 127.7, 126.7, 126.6, 125.7 (d, J = 2.4 Hz), 125.2 (d, J = 4.4 Hz), 123.8, 123.7 (d, J = 16.4 Hz), 121.0 (d, J = 5.3 Hz), 115.7, 114.3, 113.4, 112.2, 109.1 (d, J = 20.4 Hz), 101.0, 56.2, 55.4.

[0122] 19 19F NMR (565 MHz, CDCl3): δ -120.36 (dd, J = 10.8 Hz, 5.4 Hz).

[0123] HRMS (ESI): m / z calcd for C 32 H 23 FN2O4Na + (M + Na) + 541.15341, found 541.15387.

[0124] (E)-5-Methoxy-1-(4-methoxyphenyl)-3-(4-nitrophenyl)-2-styryl-1H-indole (14)

[0125]

[0126] 1 1H NMR (600 MHz, CDCl3): δ 8.37 (d, J = 8.7 Hz, 2H), 7.79 (d, J = 8.7 Hz, 2H), 7.35 (d, J = 8.8 Hz, 2H), 7.27 (d, J = 7.1 Hz, 1H), 7.25 (s, 1H), 7.22 (t, J = 7.3 Hz, 1H), 7.15 (d, J = 7.3 Hz, 2H), 7.10 - 7.09 (m, 2H), 7.08 (s, 1H), 7.03 (d, J = 8.9 Hz, 1H), 6.93 (d, J = 16.7 Hz, 1H), 6.89 (dd, J = 8.9 Hz, 2.4 Hz, 1H), 6.38 (d, J = 16.6 Hz, 1H), 3.93 (s, 3H), 3.85 (s, 3H).

[0127] 13 13C NMR (151 MHz, CDCl3): δ 159.6, 155.7, 146.1, 143.2, 136.9, 135.6, 134.8, 133.6, 130.8, 130.7, 129.7, 128.8, 128.2, 127.2, 126.4, 124.2, 116.7, 115.5, 115.0, 113.9, 111.8, 100.3, 56.1, 55.7.

[0128] HRMS (ESI): m / z calcd for C 30 H 24 N2O4Na + (M + Na) + 499.16283, found 499.16293.

[0129] 5 - Methoxy - 1 - (4 - methoxyphenyl) - 3 - (4 - nitrophenyl) - 2 - (pyren - 1 - yl) - 1H - indole (15)

[0130]

[0131] 11H NMR (600 MHz, CDCl3): δ 8.20 (d, J = 7.7 Hz, 1H), 8.12 (d, J = 7.7 Hz, 1H), 8.10 (d, J = 8.9 Hz, 1H), 8.06 (d, J = 7.8 Hz, 1H), 8.04 - 7.99 (m, 2H), 7.93 - 7.91 (m, 4H), 7.84 (d, J = 7.8 Hz, 1H), 7.43 (d, J = 2.4 Hz, 1H), 7.40 (d, J = 8.9 Hz, 2H), 7.30 (d, J = 8.9 Hz, 1H), 7.11 (d, J = 8.2 Hz, 2H), 7.03 (dd, J = 8.9 Hz, 2.4 Hz, 1H), 6.61 (d, J = 9.1 Hz, 2H), 3.96 (s, 3H), 3.59 (s, 3H).

[0132] 13 13C NMR (151 MHz, CDCl3): δ 158.6, 155.9, 145.3, 142.9, 138.5, 134.1, 131.7, 131.3, 130.9, 130.7, 130.2, 129.7, 129.2, 128.9, 128.4, 128.4, 127.4, 126.9, 126.4, 126.1, 125.8, 125.6, 124.9, 124.7, 124.6, 124.5, 123.8, 116.0, 114.3, 113.4, 112.2, 101.1, 56.3, 55.3.

[0133] HRMS (ESI): m / z calcd for C 38 H 26 N2O4Na + (M + Na) + 597.1784785, found 597.17883.

[0134] 2-(Dibenz[b,d]furan-4-yl)-5-methoxy-1-(4-methoxyphenyl)-3-(4-nitrophenyl)-1H-indole (16)

[0135]

[0136] 11H NMR (600 MHz, CDCl3): δ 8.07 (d, J = 8.9 Hz, 2H), 7.90 - 7.87 (m, 2H), 7.51 (d, J = 8.8 Hz, 2H), 7.41 - 7.38 (m, 1H), 7.34 (dd, J = 5.4 Hz, 2.8 Hz, 2H), 7.32 - 7.30 (m, 1H), 7.25 (d, J = 2.7 Hz, 1H), 7.22 - 7.18 (m, 4H), 6.99 (dd, J = 8.9 Hz, 2.4 Hz, 1H), 6.76 (d, J = 8.7 Hz, 2H), 3.91 (s, 3H), 3.70 (s, 3H).

[0137] 13 13C NMR (151 MHz, CDCl3): δ 158.8, 156.0, 155.8, 154.3, 145.6, 143.0, 134.2, 130.3, 129.9, 129.5, 129.0, 127.6, 126.9, 124.7, 123.8, 123.8, 123.1, 122.9, 121.4, 120.9, 116.0, 115.6, 114.2, 113.6, 112.2, 111.6, 100.9, 56.2, 55.4.

[0138] HRMS (ESI): m / z calcd for C 34 H 24 N2O5Na + (M + Na) + 563.15774, found 563.15790.

[0139] 5-Methoxy-2-(2-methoxynaphthalen-1-yl)-1-(4-methoxyphenyl)-3-(4-nitrophenyl)-1H-indole (17)

[0140]

[0141] 11H NMR (600 MHz, CDCl3): δ 8.00 (d, J = 8.9 Hz, 2H), 7.83 (d, J = 9.1 Hz, 1H), 7.71 - 7.70 (m, 1H), 7.46 (d, J = 8.9 Hz, 2H), 7.39 (dd, J = 6.2 Hz, 3.4 Hz, 2H), 7.25 - 7.24 (m, 2H), 7.22 (d, J = 8.9 Hz, 1H), 7.17 (d, J = 9.1 Hz, 1H), 7.08 (s, 2H), 6.96 (dd, J = 8.9 Hz, 2.4 Hz, 1H), 6.68 (s, 2H), 3.92 (s, 3H), 3.70 (s, 6H).

[0142] 13 13C NMR (151 MHz, CDCl3): δ 158.7, 156.4, 155.6, 145.3, 143.3, 134.9, 134.1, 134.0, 131.6, 130.4, 128.6, 128.6, 128.4, 128.2, 127.4, 126.9, 124.5, 123.9, 123.8, 115.4, 114.1, 113.9, 112.9, 112.6, 112.1, 101.1, 56.3, 56.1, 55.4.

[0143] HRMS (ESI): m / z calcd for C 33 H 26 N2O5Na + (M + Na) + 553.17339, found 553.17383.

[0144] 2-(Cyclohex-1-en-1-yl)-5-methoxy-1-(4-methoxyphenyl)-3-(4-nitrophenyl)-1H-indole (18)

[0145]

[0146] 11H NMR (600 MHz, CDCl3): δ 8.27 (d, J = 8.8 Hz, 2H), 7.70 (d, J = 8.8 Hz, 2H), 7.26 - 7.25 (m, 2H), 7.19 (d, J = 2.4 Hz, 1H), 7.09 (d, J = 8.9 Hz, 1H), 7.00 (d, J = 8.8 Hz, 2H), 6.85 (dd, J = 8.9 Hz, 2.4 Hz, 1H), 5.71 (dt, J = 3.9 Hz, 2.0 Hz, 1H), 3.88 (s, 3H), 3.84 (s, 3H), 1.98 - 1.96 (m, 2H), 1.84 (dd, J = 4.4 Hz, 2.1 Hz, 2H), 1.49 - 1.47 (m, 4H).

[0147] 13 13C NMR (151 MHz, CDCl3): δ 159.0, 155.6, 145.5, 143.8, 142.6, 134.9, 133.3, 130.8, 129.5, 128.9, 128.9, 126.7, 123.9, 114.4, 112.6, 112.5, 111.8, 100.8, 56.2, 55.7, 29.3, 25.8, 22.7, 21.7.

[0148] HRMS (ESI): m / z calcd for C 28 H 26 N2O4Na + (M + Na) + 477.17848, found 477.17871.

[0149] 5 - Methoxy - 7 - methyl - 2 - (naphthalen - 2 - yl) - 3 - (4 - nitrophenyl) - 1 - phenyl - 1H - indole (19)

[0150]

[0151] 11H NMR (600 MHz, CDCl3): δ 8.14 (d, J = 8.9 Hz, 2H), 7.87 (d, J = 6.8 Hz, 1H), 7.77 (d, J = 8.1 Hz, 1H), 7.66 (d, J = 8.5 Hz, 1H), 7.61 (d, J = 9.3 Hz, 2H), 7.55 (d, J = 8.5 Hz, 2H), 7.48 (t, J = 7.5 Hz, 1H), 7.44 - 7.42 (m, 1H), 7.29 (ddd, J = 6.5 Hz, 3.9 Hz, 1.4 Hz, 2H), 7.25 (d, J = 8.6 Hz, 1H), 7.21 (d, J = 8.4 Hz, 1H), 7.05 (d, J = 8.6 Hz, 1H), 6.77 (dd, J = 8.6 Hz, 2.9 Hz, 1H), 6.73 (d, J = 2.8 Hz, 1H), 3.78 (s, 3H), 1.89 (s, 3H).

[0152] 13 13C NMR (151 MHz, CDCl3): δ 159.5, 145.6, 143.0, 139.3, 138.6, 138.24, 133.0, 132.7, 130.8, 130.6, 130.4, 129.2, 128.6, 128.3, 128.2, 128.1, 127.8, 126.8, 126.6, 126.4, 123.9, 123.4, 121.6, 119.1, 116.1, 114.3, 112.2, 111.5, 55.5, 18.1.

[0153] HRMS (ESI): m / z calcd for C 32 H 24 N2O3Na + (M + Na) + 507.16791, found 507.16852.

[0154] 5-Methyl-2-(naphthalen-2-yl)-3-(4-nitrophenyl)-1-(p-tolyl)-1H-indole (20)

[0155]

[0156] 11H NMR (600 MHz, CDCl3): δ 8.15 (d, J = 8.5 Hz, 2H), 7.80 (d, J = 8.1 Hz, 1H), 7.68 (d, J = 8.5 Hz, 1H), 7.65 (s, 1H), 7.63 - 7.61 (m, 2H), 7.53 (d, J = 8.4 Hz, 2H), 7.49 (t, J = 7.5 Hz, 1H), 7.45 (t, J = 7.4 Hz, 1H), 7.27 (s, 1H), 7.20 (d, J = 8.5 Hz, 1H), 7.15 (d, J = 9.7 Hz, 5H), 2.54 (s, 3H), 2.36 (s, 3H).

[0157] 13 13C NMR (151 MHz, CDCl3): δ 145.6, 143.0, 138.7, 137.6, 137.0, 135.1, 133.1, 132.7, 131.2, 130.9, 130.5, 130.0, 128.6, 128.4, 128.3, 128.1, 127.8, 127.0, 126.8, 126.4, 125.0, 123.9, 118.6, 114.5, 111.1, 21.7, 21.3.

[0158] HRMS (ESI): m / z calcd for C 32 H 24 N2O2Na + (M + Na) + 491.17300, found 491.17328.

[0159] 5 - Isopropoxy - 1 - (4 - isopropoxyphenyl) - 2 - (naphthalen - 2 - yl) - 3 - (4 - nitrophenyl) - 1H - indole (21)

[0160]

[0161] 11H NMR (600 MHz, CDCl3): δ 8.13 (d, J = 8.8 Hz, 2H), 7.78 (d, J = 8.1 Hz, 1H), 7.66 (d, J = 8.5 Hz, 1H), 7.60 (d, J = 8.1 Hz, 1H), 7.58 (s, 1H), 7.49 (d, J = 8.8 Hz, 2H), 7.48 - 7.46 (m, 1H), 7.44 - 7.41 (m, 1H), 7.33 (d, J = 2.3 Hz, 1H), 7.23 (d, J = 8.9 Hz, 1H), 7.17 (dd, J = 8.4 Hz, 1.7 Hz, 1H), 7.14 (d, J = 8.8 Hz, 2H), 6.95 (dd, J = 8.9 Hz, 2.3 Hz, 1H), 6.83 (d, J = 8.9 Hz, 2H), 4.58 (p, J = 6.1 Hz, 1H), 4.50 (p, J = 6.0 Hz, 1H), 1.39 (s, 3H), 1.38 (s, 3H), 1.33 (s, 3H), 1.32 (s, 3H).

[0162] 13 13C NMR (151 MHz, CDCl3): δ 157.2, 153.7, 145.6, 143.0, 139.3, 134.3, 133.1, 132.7, 130.9, 130.3, 130.1, 129.4, 128.6, 128.3, 128.3, 128.0, 127.8, 127.1, 126.8, 126.4, 123.9, 116.3, 115.3, 114.3, 112.1, 104.9, 71.6, 70.3, 22.3, 22.1.

[0163] HRMS (ESI): m / z calcd for C 36 H 32 N2O4Na + (M + Na) + 579.22543, found 579.22577.

[0164] 3-(2-Chloro-4-nitrophenyl)-5-methoxy-1-(4-methoxyphenyl)-2-(naphthalen-1-yl)-1H-indole (22)

[0165]

[0166] 11H NMR (600 MHz, CDCl3): δ 8.36 (s, 1H), 8.01 (dd, J = 8.5 Hz, 2.3 Hz, 1H), 7.74 (d, J = 8.1 Hz, 1H), 7.60 (d, J = 8.5 Hz, 1H), 7.58 (d, J = 8.2 Hz, 1H), 7.49 (s, 1H), 7.46 - 7.43 (m, 2H), 7.41 (t, J = 7.5 Hz, 1H), 7.24 (s, 1H), 7.22 (d, J = 7.7 Hz, 2H), 7.10 (d, J = 8.5 Hz, 1H), 6.94 (d, J = 8.8 Hz, 1H), 6.89 (d, J = 9.6 Hz, 3H), 3.85 (s, 3H), 3.80 (s, 3H).

[0167] 13 13C NMR (151 MHz, CDCl3): δ 158.8, 155.4, 147.0, 142.1, 139.4, 135.7, 134.1, 133.6, 133.0, 132.5, 130.6, 130.2, 129.3, 128.7, 128.2, 127.9, 127.7, 127.3, 126.7, 126.4, 125.4, 121.6, 114.6, 113.5, 112.7, 112.1, 101.2, 56.0, 55.5.

[0168] HRMS (ESI): m / z calcd for C 32 H 23 ClN2O4Na + (M + Na) + 557.12386, found 557.12415.

[0169] 5-Methoxy-1-(4-methoxyphenyl)-2-(naphthalen-2-yl)-3-(4-nitro-3-(trifluoromethyl)phenyl)-1H-indole (23)

[0170]

[0171] 11H NMR (600 MHz, CDCl3): δ 7.95 (s, 1H), 7.80 (d, J = 3.9 Hz, 1H), 7.78 (d, J = 4.3 Hz, 1H), 7.70 (d, J = 8.5 Hz, 1H), 7.65 (d, J = 8.1 Hz, 1H), 7.60 (s, 1H), 7.52 - 7.49 (m, 2H), 7.48 (d, J = 8.7 Hz, 1H), 7.45 (d, J = 7.0 Hz, 1H), 7.22 (d, J = 8.9 Hz, 1H), 7.18 - 7.16 (m, 3H), 6.97 (dd, J = 8.9 Hz, 2.4 Hz, 1H), 6.86 (d, J = 8.8 Hz, 2H), 3.90 (s, 3H), 3.78 (s, 3H).

[0172] 13 13C NMR (151 MHz, CDCl3): δ 159.0, 156.0, 145.0, 141.6, 139.8, 134.0, 133.3, 133.0, 132.8, 130.8, 130.1, 129.4, 128.6 (q, J = 5.5 Hz), 128.4, 128.3, 128.0 (d, J = 3.2 Hz), 127.8, 127.0, 126.6, 125.8, 124.2 (d, J = 33.6 Hz), 122.2 (d, J = 273.5 Hz), 114.6, 113.6, 113.0, 112.4, 100.2, 56.1, 55.5.

[0173] 19 19F NMR (565 MHz, CDCl3): δ -60.01.

[0174] HRMS (ESI): m / z calcd for C 33 H 23 F3N2O4Na + (M + Na) + 591.15021, found 591.15057.

[0175] 5-Methoxy-1-(4-methoxyphenyl)-3-(3-methyl-4-nitrophenyl)-2-(naphthalen-1-yl)-1H-indole (24)

[0176]

[0177] 11H NMR (600 MHz, CDCl3): δ 7.93 (d, J = 8.5 Hz, 1H), 7.78 (d, J = 8.1 Hz, 1H), 7.67 (d, J = 8.5 Hz, 1H), 7.63 (d, J = 8.1 Hz, 1H), 7.60 (s, 1H), 7.47 (t, J = 7.7 Hz, 1H), 7.44 (d, J = 9.6 Hz, 2H), 7.29 (d, J = 2.4 Hz, 1H), 7.23 (t, J = 8.7 Hz, 2H), 7.20 - 7.16 (m, 3H), 6.96 (dd, J = 8.9 Hz, 2.4 Hz, 1H), 6.86 (d, J = 8.8 Hz, 2H), 3.91 (s, 3H), 3.78 (s, 3H), 2.56 (s, 3H).

[0178] 13 13C NMR (151 MHz, CDCl3): δ 158.8, 155.7, 146.5, 141.4, 139.1, 134.3, 134.0, 133.7, 133.0, 132.6, 130.8, 130.5, 129.4, 128.6, 128.4, 128.3, 128.2, 127.9, 127.8, 127.2, 126.7, 126.4, 125.3, 114.5, 114.3, 113.1, 112.1, 101.0, 56.2, 55.5, 21.2.

[0179] HRMS (ESI): m / z calcd for C 33 H 26 N2O4Na + (M + Na) + 537.17848, found 537.17896.

[0180] Example 3

[0181] Four 2,3 - diarylindole compounds with different substitution types were selected from the products prepared in Example 2, namely Compound 3, Compound 1, Compound 23, and Compound 14 in Table 2. 0.01 mmol of the product was weighed and dissolved in 2 ml of DCM to prepare a solution with a concentration of 0.005 M, as follows Figure 1 shown, the compound solutions were all yellow and the color depth could be adjusted by different substituents, and they could be used as organic colorants and applied in fields such as textiles and printing.

[0182] Furthermore, Compound 14 was selected from the products prepared in Example 2 for a dyeing experiment. 0.04 mmol of the product was weighed and dissolved in 4 ml of DCM to prepare a solution with a concentration of 0.01 M as the dyeing solution, as followsFigure 2 As shown Figure 2 in which g is the dyeing solution and the cotton fabric to be dyed, and one of them is cut for dyeing. As Figure 2 shown in h, the cotton fabric is immersed in the dyeing solution for five minutes, Figure 2 and i, j, and k in are the dyeing states at different time points after dyeing. Among them, Figure 2 j in is the state after five minutes of dyeing, Figure 2 and k in is the state after half an hour of dyeing. It can be seen that the compound 14 has a good dyeing effect and uniform dyeing, and this compound can be used as an organic colorant and applied in the textile field.

Claims

1. A method for preparing 2,3-diaryl indole compounds, characterized in that: The method comprises the following steps: using aniline compounds (1), aromatic ketone aldehyde compounds (2) and aromatic boronic acid compounds (3) as raw materials in a reaction solvent, reacting in the presence of a copper catalyst and an oxidant to generate 2,3-diaryl indole compounds (4); The reaction formula is as follows: Wherein R1 and R2 are electron-donating substituents; R3 is an aromatic group with a para-nitro group; and R4 is a halogen, an electron-donating group, a polycyclic aromatic hydrocarbon, a heteroaryl group or a vinyl group.

2. The preparation method according to claim 1, characterized in that: The aniline compound (1) is preferably selected from any one of the following compounds:

3. The preparation method according to claim 1, characterized in that: The aromatic ketone aldehyde compound (2) is selected from any one of the following compounds:

4. The preparation method according to claim 1, characterized in that: The aromatic boronic acid compound (3) is selected from any one of the following compounds:

5. The preparation method according to claim 1, characterized in that: The copper catalyst is preferably any one or more of CuBr, CuCl, Cu(TFA)2·xH2O, and Cu(CF3SO3)2.

6. The preparation method according to claim 1, characterized in that: The oxidant is preferably any one or more of CoPyCl, Co(salen), DDQ, and Na2S2O8.

7. The preparation method according to claim 1, characterized in that: The reaction solvent is any one or more of 1,2-dichloroethane, dichloromethane or toluene.

8. The preparation method according to claim 1, characterized in that: The molar ratio of the aniline compound (1), the aromatic ketone aldehyde compound (2), and the aromatic boronic acid compound (3) is 1:2:2-5, and the concentration of the aniline compound is 0.05-0.15 mol / L.

9. The preparation method according to claim 1, characterized in that: The molar ratio of the aniline compound (1) to the copper catalyst is 4:1-10:1, and the molar ratio of the aniline compound (1) to the oxidant is 4:1-10:

1.

10. The preparation method according to claim 1, characterized in that: The reaction temperature in the reaction system is 60-80°C, the reaction time is 4-8h, and the reaction system needs to be carried out under air.

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