Preparation method of indoloquinoline derivative

Abstract

The invention discloses a method for preparing an indoloquinoline derivative, which comprises the following steps: adding 0.3 mmol of 1-[(2-methylaminophenyl) ethynyl]-2-naphthylamine, 0.45 mmol of aldehyde, 0.015 mmol of gold chloride and 2.5 mL of 1, 2-dichloroethane into a 10mL reaction tube, reacting at room temperature, and detecting that the reaction is complete by TLC (Thin Layer Chromatography). After the reaction is finished, decompressing to remove the solvent, and performing column chromatography to obtain a pure product. The technical scheme provided by the invention has the characteristics of simple synthesis steps, mild reaction conditions, simplicity and convenience in operation, few side reactions, convenience in post-treatment and the like.

Description

Technical Field

[0001] The invention relates to an organic synthesis intermediate, in particular to a preparation method of an indole-quinoline derivative. Background Art

[0002] Indole quinoline compounds are an important class of organic synthesis intermediates that can be used to synthesize organic optoelectronic materials (CN 111247145B). The development of simple and efficient methods to synthesize such compounds is of great significance to the development and research of new materials.

[0003] The preparation methods of indole quinoline derivatives reported in the literature mainly include: using indole boronic acid and o-bromoaniline as raw materials, coupling under the action of palladium catalyst to generate indole substituted aromatic amine. Then react with benzoyl chloride derivatives to generate amide derivatives. Finally, under the action of phosphorus oxychloride, intramolecular cyclization reaction occurs to generate indole quinoline derivatives.

[0004]

[0005] The method has complicated synthesis steps, requires the use of reagents such as phosphorus oxychloride, is inconvenient to operate and has potential safety hazards. Nitrobenzene, a high-boiling-point solvent, is used, and post-processing is complicated. Summary of the invention

[0006] The object of the present invention is to provide a method for preparing an indolequinoline derivative, which has simple synthesis steps, mild reaction conditions, simple operation, few side reactions and convenient post-treatment.

[0007] The technical solution of the present invention is: a certain amount of 1-[(2-methylaminophenyl)ethynyl]-2-naphthylamine, aldehyde, gold chloride and solvent 1,2-dichloroethane are reacted at room temperature. After the reaction is completed, the solvent is removed under reduced pressure, and column chromatography is performed to obtain a pure indole quinoline product.

[0008] Preferably, it comprises the following steps: step 1: adding 1-[(2-methylaminophenyl)ethynyl]-2-naphthylamine (0.3mmol), aldehyde (0.45mmol), gold chloride (0.015mmol), and 1,2-dichloroethane 2.5mL into a 10mL reaction tube, and reacting at room temperature; step 2: after the reaction is completed, removing the solvent under reduced pressure, and obtaining a pure indolequinoline derivative by column chromatography.

[0009] Preferably, the reaction time of step 1 at room temperature is 6-24 hours.

[0010] Preferably, the aldehyde is one of benzaldehyde, 4-bromobenzaldehyde, 4-methylbenzaldehyde, furan-2-carboxaldehyde, pyridine-2-carboxaldehyde, and cinnamaldehyde.

[0011] The above technical scheme has the following beneficial effects: 1. The synthesis steps are simple, the reaction conditions are mild, and the operation is simple; 2. The reaction selectivity is good, the side reactions are few, the purification is easy, and the yield of the product is high. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Attached Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the product obtained in Example 1.

[0013] Attached Figure 2 The hydrogen nuclear magnetic resonance spectrum of the product obtained in Example 2 is shown in FIG.

[0014] Attached Figure 3 The hydrogen nuclear magnetic resonance spectrum of the product obtained in Example 3 is shown in FIG.

[0015] Attached Figure 4 The hydrogen nuclear magnetic resonance spectrum of the product obtained in Example 4 is shown in FIG.

[0016] Attached Figure 5 The hydrogen nuclear magnetic resonance spectrum of the product obtained in step 5 is shown in FIG.

[0017] Attached Figure 6 This is the hydrogen nuclear magnetic resonance spectrum of the product obtained in Example 6. DETAILED DESCRIPTION

[0018] The following is a description of the implementation of the present invention by means of specific embodiments. Those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification.

[0019] Example embodiments will now be described more fully with reference to the accompanying drawings. However, example embodiments can be implemented in a variety of forms and should not be construed as being limited to the examples set forth herein; on the contrary, these embodiments are provided so that the present invention will be more comprehensive and complete, and the concept of the example embodiments will be fully conveyed to those skilled in the art. The described features, structures, or characteristics may be combined in one or more embodiments in any suitable manner. In the following description, many specific details are provided to provide a full understanding of the embodiments of the present invention. However, those skilled in the art will appreciate that the technical solutions of the present invention may be practiced while omitting one or more of the specific details, or other methods, components, devices, steps, etc. may be adopted. In other cases, known technical solutions are not shown or described in detail to avoid obscuring various aspects of the present invention.

[0020] Embodiment 1:

[0021] Step 1: Add 1-[(2-methylaminophenyl)ethynyl]-2-naphthylamine (0.3 mmol), benzaldehyde (0.45 mmol), gold chloride (0.015 mmol), and 2.5 mL of 1,2-dichloroethane into a 10 mL reaction tube and react at room temperature for 12 hours;

[0022] Step 2: After the reaction is completed, the solvent is removed under reduced pressure and column chromatography is performed to obtain 13-methyl-8-phenyl-13H-benzo[f]indole[3,2-c]

[0023] The molecular formula of pure quinoline is:

[0024]

[0025] Yield: 72%; the product is a white solid; the H NMR spectrum of the product is as follows Figure 1 Shown: (CDCl3, 400 MHz) (δ, ppm): 8.55 (d, J = 8.0 Hz, 1H), 8.26 (s, 1H), 8.09-8.01 (m, 2H), 7.94 (d, J = 7.2 Hz, 2H), 7.77-7.70 (m, 1H), 7.69-7.64 (m, 2H), 7.64-7.61 (m, 3H), 7.61-7.57 (m, 1H), 7.57-7.51 (m, 1H), 7.24-7.18 (m, 1H), 3.96 (s, 3H).

[0026] Carbon NMR: (CDCl3, 100 MHz) (δ, ppm): 155.1, 146.4, 145.1, 144.9, 140.5, 132.1, 129.5, 129.4, 129.1, 128.8, 128.2, 128.0, 126.4, 126.2, 125.6, 122.9, 122.0, 121.5, 117.3, 112.2, 110.9, 37.4.

[0027] Infrared spectrum (KBr, ν, cm-1): 3053, 1601, 1556, 1466, 1387, 914, 828, 745, 701.

[0028] High Resolution Mass Spectrometry (ESI) m / z calcd for (ESI) m / z calcd for C 26 H 18 N2(M+H) + :359.1548;Found:359.1544.

[0029] Embodiment 2:

[0030] Step 1: Add 1-[(2-methylaminophenyl)ethynyl]-2-naphthylamine (0.3 mmol), 4-bromobenzaldehyde (0.45 mmol), gold chloride (0.015 mmol), and 2.5 mL of 1,2-dichloroethane into a 10 mL reaction tube and react at room temperature for 12 hours;

[0031] Step 2: After the reaction is completed, the solvent is removed under reduced pressure and column chromatography is performed to obtain 8-(4-bromophenyl)-13-methyl-13H-benzo[f][3,2-c]

[0032] The molecular formula of pure quinoline is:

[0033]

[0034] Yield: 78%; the product is a yellow solid; the H NMR spectrum of the product is as follows Figure 2 Shown: (CDCl3, 400 MHz) (δ, ppm): 8.54 (d, J = 8.0 Hz, 1H), 8.21 (d, J = 8.8 Hz, 1H), 8.07-8.00 (m, 2H), 7.84 (d, J = 7.6 Hz, 2H), 7.80-7.61 (m, 6H), 7.61-7.53 (m, 1H), 7.26-7.20 (m, 1H), 3.95 (s, 3H).

[0035] Carbon NMR: (CDCl3, 100 MHz) (δ, ppm): 145.2, 144.9, 132.1, 132.0, 131.2, 129.8, 128.3, 128.2, 127.8, 126.7, 126.4, 125.8, 123.6, 122.6, 121.8, 121.7, 117.1, 112.3, 111.1, 37.5.

[0036] Infrared spectrum (KBr, ν, cm-1): 2830, 1631, 1593, 1483, 1448, 1384, 826, 776.

[0037] High resolution mass spectrometry (ESI) m / z calcd for C 26 H 17 BrN2(M+H) + :437.0653;Found:437.0649.

[0038] Embodiment 3:

[0039] Step 1: Add 1-[(2-methylaminophenyl)ethynyl]-2-naphthylamine (0.3 mmol), 4-methylbenzaldehyde (0.45 mmol), gold chloride (0.015 mmol), and 2.5 mL of 1,2-dichloroethane into a 10 mL reaction tube and react at room temperature for 12 hours;

[0040] Step 2: After the reaction is completed, the solvent is removed under reduced pressure and column chromatography is performed to obtain pure 13-methyl-8-(p-tolyl)-13H-benzo[f]indole[3,2-c]quinoline, the molecular formula of which is:

[0041]

[0042] Yield: 78%; the product is a white solid; the H NMR spectrum of the product is as follows Figure 3 Shown as: (CDCl3, 400MHz) (δ, ppm): 8.52 (d, J = 8.0Hz, 1H), 8.22 (d, J = 8.8Hz, 1H), 8.07-7.96 (m, 2H), 7.86 (d, J = 7.6Hz, 2H), 7.75 (d, J = 8.0H z,1H),7.73-7.66(m,1H),7.66-7.58(m,2H),7.57-7.50(m,1H),7.45(d,J=8.0Hz,2H),7.25-7.18(m,1H),3.91(s,3H),2.55(s,3H).

[0043] Carbon NMR: (CDCl3, 100 MHz) (δ, ppm): 155.2, 146.4, 145.1, 144.9, 139.0, 137.6, 132.0, 129.5, 129.4, 129.3, 128.9, 128.2, 128.2, 128.0, 126.3, 126.1, 125.6, 123.0, 122.1, 121.5, 117.3, 112.1, 110.9, 37.4, 21.7.

[0044] Infrared spectrum (KBr, ν, cm-1): 2833, 1632, 1596, 1505, 1465, 1363, 1348, 826, 742.

[0045] High resolution mass spectrometry (ESI) m / z calcd for C 27 H 20 N2(M+H) + :373.1705;Found:373.1706.

[0046] Embodiment 4:

[0047] Step 1: Add 1-[(2-methylaminophenyl)ethynyl]-2-naphthylamine (0.3 mmol), furan-2-carbaldehyde (0.45 mmol), gold chloride (0.015 mmol), and 1,2-dichloroethane 2.5 mL into a 10 mL reaction tube and react at room temperature for 12 hours;

[0048] Step 2: After the reaction is completed, the solvent is removed under reduced pressure and column chromatography is performed to obtain 8-(2-furyl)-13-methyl-13H-benzo[f]indole

[0049] [3,2-c] Quinoline pure product, its molecular formula is:

[0050]

[0051] Yield: 81%; the product is a white solid; the H NMR spectrum of the product is as follows Figure 4 Shown: (CDCl3, 400 MHz) (δ, ppm): 8.50-8.43 (m, 2H), 8.17 (d, J = 8.8 Hz, 1H), 8.03-7.97 (m, 2H), 7.83 (s, 1H), 7.72-7.66 (m, 1H), 7.66-7.59 (m, 3H), 7.42-7.34 (m, 2H), 6.75 (s, 1H), 3.90 (s, 3H).

[0052] Carbon NMR: (CDCl3, 100 MHz) (δ, ppm): 153.5, 146.2, 145.5, 145.0, 144.0, 143.5, 132.0, 129.7, 128.6, 128.2, 128.2, 127.9, 126.6, 126.3, 125.7, 123.1, 122.5, 121.8, 116.6, 112.2, 112.2, 112.1, 110.9, 37.5.

[0053] Infrared spectrum (KBr, ν, cm-1): 2831, 1633, 1593, 1484, 1445, 1364, 1348, 1118, 827, 738.

[0054] High resolution mass spectrometry (ESI) m / z calcd for C 24 H 16 N2O(M+H) + :349.1341;Found:349.1342.

[0055] Embodiment 5:

[0056] Step 1: Add 1-[(2-methylaminophenyl)ethynyl]-2-naphthylamine (0.3 mmol), pyridine-2-carboxaldehyde (0.45 mmol), gold chloride (0.015 mmol), and 1,2-dichloroethane 2.5 mL into a 10 mL reaction tube and react at room temperature for 12 hours;

[0057] Step 2: After the reaction is completed, the solvent is removed under reduced pressure and column chromatography is performed to obtain 13-methyl-8-(2-pyridyl)-13H-benzo[f]indole

[0058] [3,2-c] Quinoline pure product, its molecular formula is:

[0059]

[0060] Yield: 60%; the product is a white solid; the H NMR spectrum of the product is as follows Figure 5 Shown as: (CDCl3, 400MHz) (δ, ppm): 8.92 (d, J = 4.8Hz, 1H), 8.55 (d, J = 8.0Hz, 1H), 8.30 (s, 1H), 8.24 (d, J = 7.6Hz, 1H), 8.09-7.98 (m, 3H), 7.91(d,J=8.0Hz,1H),7.77-7.70(m,1H),7.70-7.61(m,2H),7.61-7.55(m,1H),7.55-7.49(m,1H),7.30-7.26(m,1H),3.96(s,3H).

[0061] Carbon NMR: (CDCl3, 100 MHz) (δ, ppm): 149.4, 145.7, 145.2, 137.3, 132.2, 129.8, 128.3, 128.2, 127.8, 126.8, 126.5, 125.8, 124.9, 124.1, 123.3, 122.6, 121.8, 117.6, 112.7, 110.9, 37.5.

[0062] Infrared spectrum (KBr, ν, cm-1): 2830, 1612, 1555, 1470, 1384, 773, 749, 734.

[0063] High resolution mass spectrometry (ESI) m / z calcd for C 25 H 17 N3(M+H) + :360.1501;Found:360.1501.

[0064] Embodiment 6:

[0065] Step 1: Add 1-[(2-methylaminophenyl)ethynyl]-2-naphthylamine (0.3 mmol), cinnamaldehyde (0.45

[0066] mmol), gold chloride (0.015 mmol), and 1,2-dichloroethane 2.5 mL, react at room temperature for 12 hours;

[0067] Step 2: After the reaction is completed, the solvent is removed under reduced pressure and column chromatography is performed to obtain pure (E)-13-methyl-8-phenylvinyl-13H-benzo[f]indole[3,2-c]quinoline, the molecular formula of which is:

[0068]

[0069] Yield: 70%; the product is a yellow solid; the H NMR spectrum of the product is as follows Figure 6 Shown: (CDCl3, 400 MHz) (δ, ppm): 8.50-8.42 (m, 2H), 8.22 (s, 2H), 8.18 (d, J = 8.8 Hz, 1H), 8.03-7.98 (m, 2H), 7.81 (d, J = 7.6 Hz, 2H), 7.74-7.57 (m, 5H), 7.52-7.46 (m, 3H), 7.42-7.37 (m, 1H), 3.92 (s, 3H).

[0070] Carbon NMR: (CDCl3, 100 MHz) (δ, ppm): 153.6, 146.5, 144.8, 144.3, 141.3, 133.2, 132.2, 131.0, 130.5, 129.6, 128.9, 128.3, 128.2, 128.2, 127.9, 126.6, 126.4, 125.7, 123.1, 122.6, 121.9, 121.6, 118.1, 112.9, 111.0, 37.4.

[0071] Infrared spectrum (KBr, ν, cm-1): 2832, 1632, 1592, 1493, 1446, 1382, 1364, 1347, 826, 776, 732.

[0072] High resolution mass spectrometry (ESI) m / z calcd for C 28 H 20 N2(M+H) + :385.1705;Found:385.1707.

[0073] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A method for preparing an indoloquinoline derivative, characterized in that: It includes the following steps: Step 1: reacting a certain amount of 1-[(2-methylaminophenyl)ethynyl]-2-naphthylamine, aldehyde, gold chloride and solvent 1,2-dichloroethane at room temperature; Step 2: After the reaction is completed, the solvent is removed under reduced pressure and the pure indolequinoline derivative is obtained by column chromatography.

2. A method for preparing an indoloquinoline derivative, characterized in that: It includes the following steps: Step 1: Add 1-[(2-methylaminophenyl)ethynyl]-2-naphthylamine (0.3 mmol), aldehyde (0.45 mmol), gold chloride (0.015 mmol), and 2.5 mL of 1,2-dichloroethane into a 10 mL reaction tube and react at room temperature; Step 2: After the reaction is completed, the solvent is removed under reduced pressure and the pure indolequinoline derivative is obtained by column chromatography.

3. The method for preparing an indoloquinoline derivative according to claim 1 or 2, characterized in that: The reaction time of step 1 is 6-24 hours at room temperature.

4. The method for preparing an indoloquinoline derivative according to claim 1 or 2, characterized in that: The aldehyde is one of benzaldehyde, 4-bromobenzaldehyde, 4-methylbenzaldehyde, furan-2-carboxaldehyde, pyridine-2-carboxaldehyde and cinnamaldehyde.

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