Carbazole fused ring compound and synthesis method thereof

Abstract

According to the synthetic method, nitromethane is taken as a solvent for the first time, trifluoromethanesulfonic acid is taken as a catalyst, under the protection of inert gas, 2-alkynyl indole derivatives and alpha, beta-unsaturated ketone derivatives are taken as raw materials, and products and additional products with stable molecular structures and excellent chemical properties are prepared; the reaction system is simple, the reaction raw materials are cheap and easy to obtain, the reaction product is formed through multi-step cascade reaction, the intermediate does not need to be separated, and the reaction atom economy is high. The synthesis method of the substance does not exist at present. Meanwhile, the problems of use of expensive raw materials, complex synthesis steps, environmental pollution caused by the need of transition metal catalysts and the like are avoided. The product can be widely applied to multiple fields of pharmacy, chemical industry, photoelectric materials and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a carbazole condensed ring compound and a synthesis method thereof. Background Art

[0002] As a unique class of nitrogen-containing aromatic heterocyclic compounds, carbazole fused ring compounds and their derivatives exhibit numerous excellent properties and a wide range of biological activities due to their special rigid fused ring structure. These compounds play an important role in many fields such as chemistry, medicine, and optoelectronic materials, and have extremely high application value and potential.

[0003] However, despite the importance of carbazole fused-ring compounds, the types of existing fused-ring carbazole compounds are relatively limited. This is mainly due to the many challenges in the methods of synthesizing such skeletons. Specifically, traditional synthesis methods often rely on expensive raw materials, the synthesis conditions are complex and difficult to control, and the synthesis steps are lengthy and cumbersome, resulting in low overall synthesis efficiency. In addition, these methods usually require the addition of expensive transition metal catalysts and chemically equivalent oxidants, further increasing the synthesis cost and environmental burden.

[0004] Therefore, it is necessary to develop a new synthetic method to achieve low-cost and high-efficiency preparation of carbazole fused-ring compounds while avoiding environmental pollution. Summary of the invention

[0005] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a carbazole fused ring compound to enrich the types of carbazole fused ring compounds and meet the market demand for such compounds.

[0006] Furthermore, a method for synthesizing the above-mentioned carbazole fused ring compound is provided to solve the problems that the existing synthesis technology uses expensive raw materials and has high costs; the conditions are severe and difficult to control; the synthesis steps are lengthy and complicated, and the synthesis efficiency is low; and the use of transition metal catalysts and oxidants further increases the cost and pollutes the environment.

[0007] In order to solve the above problems, the present invention adopts the following technical solutions:

[0008] A carbazole fused ring compound having a structure shown in the following general formula I:

[0009]

[0010] In the general formula I, R 1 is: hydrogen atom, methyl or methoxy; R 2 is methyl or ethyl; R 3 is: hydrogen atom, methyl, methoxy, halogen or trifluoromethyl; R 4is: a hydrogen atom, a halogen, a nitro group, an ester group, an acetyl group or a trifluoromethyl group. Further, its structural formula is any one of the following structures:

[0011]

[0012] The synthesis method of the carbazole fused ring compound, the synthesis process is as follows:

[0013]

[0014] Furthermore, the reaction temperature of the synthesis process is 80-100° C., and the reaction time is 4-8 hours.

[0015] Furthermore, the molar ratio of the substance described in formula II, the substance described in formula III and the Brenster acid catalyst is 1:1-3:0.1-1.

[0016] Further, the substance described in formula II is: 1-methyl-2-(phenylethynyl)-1H-indole, 1-ethyl-2-(phenylethynyl)-1H-indole, 1,5-dimethyl-2-(phenylethynyl)-1H-indole, 1,6-dimethyl-2-(phenylethynyl)-1H-indole, 5-methoxy-1-methyl-2-(phenylethynyl)-1H-indole, 6-methoxy-1-methyl-2-(phenylethynyl)-1H-indole, 2-((4-methoxyphenyl)ethynyl)-1-methyl-1H-indole, 2-((4-fluorophenyl)ethynyl)-1-methyl-1H-indole, 1-methyl-2-((3-(trifluoromethyl)phenyl)ethynyl)-1H-indole or 2-((4-methylphenyl)ethynyl)-1-methyl-1H-indole.

[0017] Further, the substance described in formula III is: 4-phenylbut-3-ene-2-one, 4-(p-fluorophenyl)but-3-ene-2-one, 4-(p-chlorophenyl)but-3-ene-2-one, 4-(p-bromophenyl)but-3-ene-2-one, 4-(p-trifluoromethylphenyl)but-3-ene-2-one, 4-(p-acetylphenyl)but-3-ene-2-one, 4-(p-methylphenyl)but-3-ene-2-one, 4-(p-nitrophenyl)but-3-ene-2-one, 4-(2-bromophenyl)but-3-ene-2-one, 4-(2-trifluoromethylphenyl)but-3-ene-2-one, 4-(2-fluorophenyl)but-3-ene-2-one, 4-(3-fluorophenyl)but-3-ene-2-one or 4-(3-trifluoromethylphenyl)but-3-ene-2-one.

[0018] Furthermore, the Brenster acid catalyst is trifluoromethanesulfonic acid, phosphomolybdic acid, phosphotungstic acid, silicotungstic acid, trifluoromethanesulfonamide, p-toluenesulfonic acid, montmorillonite or aminosulfonic acid.

[0019] Furthermore, the organic solvent is nitromethane, nitroethane, 1,4-dioxane, toluene, xylene or trimethylbenzene.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] 1. The carbazole fused ring compound provided by the present invention has the characteristics of stable molecular structure and excellent chemical properties, and can be widely used in multiple fields such as medicine, chemistry, and materials; it is particularly suitable for the research and development of optoelectronic materials.

[0022] 2. The method for synthesizing carbazole fused ring compounds of the present invention innovatively uses nitromethane as a solvent, combines trifluoromethanesulfonic acid as a catalyst and molecular sieves as a dehydrating agent, and directly converts 2-alkynyl indole derivatives and α,β-unsaturated ketone derivatives into carbazole fused ring products and their additional products under the protection of inert gas, thereby achieving efficient and stable preparation. This method not only simplifies the reaction system, avoids raw material pretreatment and intermediate separation and purification, but also significantly reduces the reaction steps, shortens the reaction time, and improves the atom economy through the five-step one-pot cascade reaction of Aldol condensation-dehydration-carbon cation isomerization-alkenyl carbon cation formation-aromatic electrophilic substitution; and the reaction conditions are mild and easy to control. This method also completely abandons transition metal catalysts, reduces production costs and reduces environmental pollution, and is in line with the concept of green chemistry and sustainable development. In addition, the raw materials used in this method are cheap and easily available, the required equipment is simple, the operation is simple and easy, the process is scientific and reasonable, and it is easy to industrialize and promote application. It is particularly suitable for the one-pot efficient and selective synthesis of carbazole fused ring compounds, and provides a new economical and environmentally friendly synthesis route for the scientific research, development and utilization of carbazole fused ring compounds. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is the H NMR spectrum of the product obtained in Example 1;

[0024] Figure 2 is the NMR carbon spectrum of the product obtained in Example 1;

[0025] Figure 3 is the H NMR spectrum of the product obtained in Example 2;

[0026] Figure 4 is the NMR carbon spectrum of the product obtained in Example 2;

[0027] Figure 5 This is the NMR fluorine spectrum of the product obtained in Example 2;

[0028] Figure 6 is the H NMR spectrum of the product obtained in Example 4;

[0029] Figure 7 is the NMR carbon spectrum of the product obtained in Example 4;

[0030] Figure 8 is the H NMR spectrum of the product obtained in Example 5;

[0031] Fig. 9 is the NMR carbon spectrum of the product obtained in Example 5;

[0032] Fig.10 This is the NMR fluorine spectrum of the product obtained in Example 5;

[0033] Fig.11 is the H NMR spectrum of the product obtained in Example 7;

[0034] Fig.12 is the NMR carbon spectrum of the product obtained in Example 7;

[0035] Fig.13 is the H NMR spectrum of the product obtained in Example 9;

[0036] Fig.14 is the NMR carbon spectrum of the product obtained in Example 9;

[0037] Fig.15 This is the NMR fluorine spectrum of the product obtained in Example 9;

[0038] Fig.16 is the H NMR spectrum of the product obtained in Example 13;

[0039] Fig.17 is the NMR carbon spectrum of the product obtained in Example 13;

[0040] Fig.18 This is the NMR fluorine spectrum of the product obtained in Example 13. DETAILED DESCRIPTION

[0041] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention is further described below in conjunction with specific embodiments, but the embodiments of the present invention are not limited thereto.

[0042] 1. The present invention provides a carbazole fused ring compound having a structure shown in the following general formula I:

[0043]

[0044] In the general formula I, R 1 is: hydrogen atom, methyl or methoxy; R 2 is methyl or ethyl; R 3 is: hydrogen atom, methyl, methoxy, halogen or trifluoromethyl; R 4 is: a hydrogen atom, a halogen, a nitro group, an ester group, an acetyl group or a trifluoromethyl group.

[0045] 2. The present invention also provides a method for synthesizing the above-mentioned carbazole fused ring compound

[0046] The reaction equation is:

[0047]

[0048] Wherein, the Brenster acid catalyst is trifluoromethanesulfonic acid, phosphomolybdic acid, phosphotungstic acid, silicotungstic acid, trifluoromethanesulfonamide, p-toluenesulfonic acid, montmorillonite or aminosulfonic acid. Preferably, trifluoromethanesulfonic acid is used as the catalyst. The organic solvent is nitromethane, nitroethane, 1,4-dioxane, toluene, xylene or trimethylbenzene. Preferably, nitromethane is used as the acid catalyst.

[0049] MS Type molecular sieve. In the reaction formula, T represents the reaction temperature.

[0050] In a specific implementation, in an inert gas atmosphere, a 2-alkynyl indole derivative shown in formula II, an α,β-unsaturated ketone derivative shown in formula III, an organic solvent, an acid catalyst and After the molecular sieve is fully mixed, the reaction is carried out at 80-100°C for 4-8 hours, and the obtained product is purified to obtain a carbazole fused ring compound. The molar ratio of the 2-alkynyl indole derivative shown in formula II, the α,β-unsaturated ketone derivative shown in formula III, and the acid catalyst is 1:1-3:0.1-1; for example, it can be 1:1-2:0.1-0.5, 1:1-2.5:0.1-0.8, 1:2-3:0.5-1, 1:2:0.1, 1:3:0.2. Preferably, it is 1:2:0.1.

[0051] 3. Embodiment

[0052] Examples 1 to 22 respectively provide a method for synthesizing a carbazole fused ring compound. The reactants, reaction conditions, reaction products and yields of each example are shown in Table 1.

[0053] Table 1 Comparison of reactants, reaction conditions, reaction products and yields in Examples 1 to 22

[0054]

[0055]

[0056]

[0057]

[0058] 4. The NMR data of the products obtained in some examples are:

[0059] The present invention provides NMR data of products generated in some typical embodiments to illustrate the structure of the carbazole fused ring compound obtained by the present invention. The following data have proved that the carbazole fused ring compound was obtained by the synthesis method of the present invention. Other embodiments not mentioned will not be repeated.

[0060] 1. The product of Example 1 is:

[0061]

[0062] Combination Figure 1 and Figure 2 The NMR spectrum of the product can prove that the obtained product has the above structure.

[0063] The NMR, IR and high resolution mass spectrometry data of the product of Example 1 are as follows:

[0064] 1 H NMR (400MHz, CDCl3): δ = 8.00 (ddd, J = 2.4, 1.6, 0.8Hz, 1H), 7.93-7.90 (m, 2H), 7.53-7.45 (m, 2H), 7.43 (dt, J = 8.0, 1.2Hz, 1H), 7 .37(dt,J=8.0,0.8Hz,1H),7.24-7.13(m,6H),7.05-7.01(ddd,J=8.0,7.2,0.8Hz,1H),5.21(s,1H),4.16(s,3H),2.42(s,3H). 13 CNMR (101MHz, CDCl3): δ=147.97,142.44,142.38,141.88,133.74,133.68,131.63,130 .85,128.64,128.37,127.86,127.55,126.29,125.72,125.11,123.94,123.44,121.88, 119.74,118.98,113.92,109.76,48.21,31.26,15.07.IR(UATR):2921.0,1588.6,1515. 8,1489.9,1451.6,1214.8,1074.6,1013.9,950.9,867.5,838.2,738.3,698.6,541.6cm -1 .HRMS(ESI)m / z:[M+H] + Calculate for C 27 H 22 N360.1752, found 360.1735.

[0065] 2. The product of Example 2 is:

[0066]

[0067] Combination Figure 3 , Figure 4 , Figure 5 The NMR spectrum of the product can prove that the obtained product has the above structure.

[0068] The NMR, IR and high resolution mass spectrometry data of the product of Example 2 are as follows:

[0069] 1 H NMR (400MHz, CDCl3): δ = 8.00 (dd, J = 7.6, 1.6Hz, 1H), 7.92-7.90 (m, 1H), 7.90 (s, 1H), 7.54-7.46 (m, 2H), 7.39 (t, J = 7.6Hz, 2H ),7.23-7.19(m,1H),7.16-7.13(m,2H),7.07(t,J=8.4Hz,1H),6.93(t,J=8.4Hz,2H),5.16(s,1H),4.14(s,3H),2.40(s,3H). 13 CNMR (101MHz, CDCl3): δ = 162.62 (d, J = 244.8Hz), 147.81, 142.46 (d, J = 10.6Hz), 137.61 (d, J = 3.3Hz), 133.71, 133.52, 131.63, 130.80, 129.31 ( d, J=7.9Hz),128.40,127.30,125.82,125.21,123.92,123.33,121.99, 119.83,118.80,115.56,115.35,114.03,109.83,47.36,31.24,15.02. 19 F NMR (376MHz, CDCl3): δ = -116.82.IR (UATR): 2950.0, 1604.6, 1506.0, 1351.7, 1217.3, 1157.5, 1012.3, 950.8, 835.1, 768.3, 732.0, 538.6cm -1 .HRMS(ESI)m / z:[M+H]+calcd for C 27 H 21 FN 378.1658, found 378.1652.

[0070] 3. The product of Example 3 is:

[0071]

[0072] The NMR, IR and high resolution mass spectrometry data of the product of Example 3 are as follows:

[0073] 1 H NMR (400MHz, CDCl3): δ=8.00-7.98(m,1H),7.93-7.90(m,1H),7.88(s,1H),7.55-7.48(m,2H),7.39-7.34(m,2H),7.24-7.20(m, 2H),7.19(t,J=2.0Hz,1H),7.12(t,J=2.8Hz,1H),7.10-7.08(m,1H),7.07-7.04(m,1H),5.07(s,1H),4.07(s,3H),2.39(s,3H). 13 C NMR (101MHz, CDCl3): δ=147.54,142.44,142.40,140.59,133.73,133.50,131.85,131.61,1 30.81,129.23,128.81,128.42,126.98,125.87,125.26,123.94,123.28,122.04,119.87,1 18.78,114.08,109.85,47.43,31.18,15.09.IR(UATR):2922.3,1625.9,1588.0,1487.8,13 51.3,1214.3,1088.1,1014.4,830.4,767.1,727.3,554.8,529.9cm-1.HRMS(ESI)m / z:[M+H] + Calculate for C 27 H 21 ClN 394.1363, found 394.1367.

[0074] 4. The product of Example 4 is:

[0075]

[0076] Combination Figure 6 , Figure 7 The NMR spectrum of the product can prove that the obtained product has the above structure.

[0077] The NMR, IR and high resolution mass spectrometry data of the product of Example 4 are as follows:

[0078] 1H NMR (400MHz, CDCl3): δ=8.00-7.98(m,1H),7.92(dd,J=7.6,1.6Hz,1H),7.87(s,1H),7.55-7.48(m,2 H),7.39-7.33(m,4H),7.24-7.20(m,1H),7.08-7.03(m,3H),5.04(s,1H),4.08(s,3H),2.38(s,3H). 13 C NMR (101MHz, CDCl3): δ=147.46,142.42,142.40,141.14,133.72,133.48,131.75,131.5 9,130.81,129.63,128.42,126.87,125.89,125.28,123.95,123.25,122.04,119.91,11 9.88,118.78,114.09,109.86,47.47,31.19,15.13.IR(UATR):2922.9,1626.0,1587.2, 1520.0,1484.0,1421.7,1259.8,1213.1,1069.5,1010.1,800.6,725.7,553.9,526.7cm -1 .HRMS(ESI)m / z:[M+H] + Calculate for C 27 H 21 BrN 438.0857, found 438.0865.

[0079] 5. The product of Example 5 is:

[0080]

[0081] Combination Figure 8 , Fig. 9 , Fig.10 The NMR spectrum of the product can prove that the obtained product has the above structure.

[0082] The NMR, IR and high resolution mass spectrometry data of the product of Example 5 are as follows:

[0083] 1H NMR (400MHz, CDCl3): δ=8.00-7.98(m,1H),7.94(dd,J=8.8,2.0Hz,1H),7.90(s,1H),7.57-7.50(m,2H),7.49(d,J=8.0Hz,2H),7.38-7.35( m,2H),7.29(d,J=8.4Hz,2H),7.25(ddd,J=8.0,6.8,1.2Hz,1H),7.07(ddd,J=8.0,7.2,0.8Hz,1H),5.15(s,1H),4.10(s,3H),2.37(s,3H). 13 C NMR (101MHz, CDCl3): δ = 147.21, 146.44, 142.53 (d, J = 9.3Hz), 133.77, 133.43, 131.59, 130.85, 128.75, 128.45 (d, J = 2.7Hz), 128.16, 126.58,125.98,125.72(q,J=3.7Hz),125.36,123.96,123.22,122.92,122.12,119.95,118.69,114.22,109.91,47.78,31.19,15.17. 19 F NMR (376MHz, CDCl3): δ = -62.30. IR (UATR): 2923.0, 1618.1, 1532.0, 1460.7, 1418.7, 1322.5, 1161.3, 1105.9, 1065.2, 1018.0, 836.1, 740.0, 599.7cm -1 .HRMS(ESI)m / z:[M+H] + Calculate for C 28 H 21 F3N 428.1626, found 428.1622.

[0084] 6. The product of Example 7 is:

[0085]

[0086] Combination Fig.11 , Fig.12 The NMR spectrum of the product can prove that the obtained product has the above structure.

[0087] The NMR, IR and high resolution mass spectrometry data of the product of Example 7 are as follows:

[0088] 1H NMR (400MHz, CDCl3): δ=7.99-7.97(m,1H),7.93-7.91(m,1H),7.90(d,J=6.0Hz,2H),7.6-7.48(m,2H),7.37(t ,J=7.2Hz,2H),7.26-7.20(m,3H),7.07(t,J=7.6Hz,1H),5.09(s,1H),4.06(s,3H),3.88(s,3H),2.35(s,3H). 13 C NMR (101MHz, CDCl3): δ=167.04,147.80,147.33,142.50,142.41,133.76,133.49,131.59 ,130.85,130.12,128.45,128.33,127.91,126.64,125.92,125.30,123.97,123.28,122.0 6,119.92,118.75,114.15,109.86,52.00,47.99,31.16,15.14.IR(UATR):2950.8,1725.7 ,1608.7,1525.7,1434.9,1342.7,1274.7,1176.0,1099.2,1020.8,740.7,724.3,703.6cm -1 .HRMS(ESI)m / z:[M+H] + Calculate for C 29 H 24 NO2418.1807, found 418.1810.

[0089] 7. The product of Example 9 is:

[0090]

[0091] Combination Fig.13 , Fig.14 , Fig.15 The NMR spectrum of the product can prove that the obtained product has the above structure.

[0092] The NMR, IR and high resolution mass spectrometry data of the product of Example 9 are as follows:

[0093] 1H NMR (400MHz, CDCl3): δ = 7.97 (q, J = 8.0Hz, 3H), 7.78 (d, J = 8.0Hz, 1H), 7.54 (ddd, J = 19.2, 14.4, 6.8Hz, 3H), 7.35 (d, J = 8.0Hz, 1H), 7.2 4(dt,J=15.2,7.2Hz,2H),7.11(t,J=8.0Hz,1H),7.04(t,J=7.6Hz,1H),6.58(d,J=8.0Hz,1H),5.57(s,1H),4.14(s,3H),2.28(s,3H). 13 C NMR (101MHz, CDCl3): δ = 148.57, 142.74, 142.40, 141.53, 133.69 (d, J = 8.5Hz), 132.21, 131.70, 130.82, 129.29, 128.41, 127.32, 12 6.30,125.89,125.66(q,J=5.9Hz),125.24,124.00,123.26,122.04,119.91,119.17,119.14,114.01,109.66,43.61,31.21,14.29. 19 F NMR (376MHz, CDCl3): δ = -56.84.IR (UATR): 2958.8, 1608.2, 1526.5, 1455.71310.2, 1157.8, 1119.5, 1035.6, 952.0, 769.5, 738.2, 558.7cm -1 .HRMS(ESI)m / z:[M+H] + Calculate for C 28 H 21 F3N 428.1626, found 428.1620.

[0094] 8. The product of Example 10 is:

[0095]

[0096] The NMR, IR and high resolution mass spectrometry data of the product of Example 10 are as follows:

[0097] 1H NMR (400MHz, CDCl3): δ=8.01-7.99(m,1H),7.94-7.92(m,1H),7.90(s 1H),7.56-7.48(m,3H),7.36(d,J=8.4Hz,1H),7.43-7.20(m,1H),7.19-7.13(m,2H),7.11-7.07( m,1H),6.83(td,J=7.6,1.6Hz,1H),6.64(t,J=7.6Hz,1H),5.54(s,1H),4.10(s,3H),2.39(s,3H). 13 C NMR (101MHz, CDCl3): δ = 162.32 (d, J = 245.0Hz), 147.12, 142.67 (d, J = 24.9Hz), 133.74,133.73,131.60,130.64,128.62(qm,4C),128.44,127.92(d,J=8.1Hz) ,126.47,125.79,125.19,124.48(d,J=3.5Hz),123.97,123.28,121.97,119.8 8,119.18(d,J=2.9Hz),115.52,115.29,114.10,109.75,39.65,31.19,14.87. 19 FNMR (376MHz, CDCl3): δ = -118.98.IR (UATR): 2923.5, 1625.6, 1586.6, 1488.0, 1455.2, 1229.6, 1089.3, 942.7, 868.6, 806.9, 733.5, 529.1cm -1 .HRMS(ESI)m / z:[M+H] + Calculate for C 27 H 21 FN 378.1658, found 378.1654.

[0098] 9. The product of Example 13 is:

[0099]

[0100] Combination Fig.16 , Fig.17 , Fig.18 The NMR spectrum of the product can prove that the obtained product has the above structure.

[0101] The NMR, IR and high resolution mass spectrometry data of the product of Example 13 are as follows:

[0102] 1H NMR (400MHz, CDCl3): δ=8.01 (dd, J=7.6, 1.6Hz, 1H), 7.93 (dd, J=7.2, 1.6Hz, 1H), 7.89 (s, 1H), 7.55-7.48 (m, 2H), 7.42 (d, J=8.0 Hz,1H),7.37(d,J=8.4Hz,1H),7.24-7.18(m,2H),7.09-7.03(m,2H),6.88-6.79(m,2H),5.12(s,1H),4.11(s,3H),2.40(s,3H). 13 C NMR (101MHz, CDCl3): δ = 164.26 (d, J = 246.5Hz), 147.35, 144.79 (d, J = 6.9Hz), 142.46 ( d,J=2.4Hz),133.75,133.49,131.63,130.88,130.11(d,J=8.4Hz),128.42,126.80,12 5.88,125.26,123.96,123.67(d,J=2.8Hz),123.32,122.01,119.87,118.83,114.60(d ,J=21.5Hz),114.10,113.40(d,J=21.0Hz),109.84,47.76(d,J=1.7Hz),31.20,15.08. 19 F NMR (376MHz, CDCl3): δ = -58.58.IR (UATR): 2961.1, 1615.6, 1521.5, 1491.7, 1438.7, 1375.5, 1259.4, 1217.4, 960.7, 861.7, 732.9, 699.2, 557.7cm -1 .HRMS(ESI)m / z:[M+H] + Calculate for C 27 H 21 FN 378.1658, found 378.1653.

[0103] 10. The product of Example 14 is:

[0104]

[0105] The NMR, IR and high resolution mass spectrometry data of the product of Example 14 are as follows:

[0106] 1H NMR (400MHz, CDCl3): δ=8.02 (dd, J=8.0, 1.6Hz, 1H), 7.96 (dd, J=7.6, 1.6Hz, 1H), 7.86 (s, 1H), 7.55-7.47 (m, 2H), 7.46 (dd, J=8.0, 0.8Hz, 1H),7.40(d,J=8.4Hz,1H),7.25-7.16(m,6H),7.07(m,1H).5.23(s,1H),4.62(qd,J=7.2,2.8Hz,2H),2.44(s,3H),1.64(t,J=7.2Hz,3H). 13 C NMR (101MHz, CDCl3): δ=148.08,141.90,141.52,141.43,133.79,133.58,131.66,130. 84,128.65,128.40,127.92,127.84,126.30,125.73,125.13,123.97,123.61,121.86,1 19.70,119.10,113.89,109.74,48.28,39.49,15.92,15.08.IR(UATR):2978.9,1626.9 ,1590.7,1515.5,1489.0,1450.6,1341.4,1073.8,829.1,739.4,699.1,543.1,428.9cm -1 .HRMS(ESI)m / z:[M+H] + Calculate for C 28 H 24 N 374.1909, found 374.1906.

[0107] In summary, the method for synthesizing carbazole fused ring compounds of the present invention uses trifluoromethanesulfonic acid as a catalyst for the first time, nitromethane as a solvent under the protection of an inert gas, and uses two simple and easily available components, 2-alkynyl indole derivatives and α, β-unsaturated ketones, as raw materials for the first time, to selectively synthesize carbazole fused ring compounds in multiple steps in series; the disadvantages of using expensive raw materials, complicated synthesis steps, requiring transition metal catalysts, and requiring separation of intermediates are avoided; the carbazole fused ring compounds can be widely used in multiple fields such as pharmaceuticals, chemical industry, optoelectronics, printing and dyeing, supramolecular recognition, etc., and are particularly suitable for the research and development of optoelectronic multifunctional materials.

[0108] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the technical solution. Those skilled in the art should understand that those modifications or equivalent substitutions of the technical solution of the present invention that do not depart from the purpose and scope of the technical solution should be included in the scope of the claims of the present invention.

Claims

1. A carbazole fused ring compound, characterized in that: It has the structure shown in the following general formula I: In the general formula I, R 1 is: hydrogen atom, methyl or methoxy; R 2 is methyl or ethyl; R 3 is: hydrogen atom, methyl, methoxy, halogen or trifluoromethyl; R 4 is: a hydrogen atom, a halogen, a nitro group, an ester group, an acetyl group or a trifluoromethyl group.

2. The carbazole fused ring compound according to claim 1, characterized in that: Its structural formula is any one of the following structures:

3. The method for synthesizing the carbazole fused ring compound according to claim 1 or 2, characterized in that: The synthesis process is as follows:

4. The method for synthesizing the carbazole fused ring compound according to claim 3, characterized in that: The reaction temperature of the synthesis process is 80-100° C., and the reaction time is 4-8 hours.

5. The method for synthesizing the carbazole fused ring compound according to claim 3, characterized in that: The molar ratio of the substance described in formula II, the substance described in formula III and the Brenster acid catalyst is 1:1-3:0.1-1.

6. The method for synthesizing the carbazole fused ring compound according to claim 3, characterized in that: The substance described in formula II is: 1-methyl-2-(phenylethynyl)-1H-indole, 1-ethyl-2-(phenylethynyl)-1H-indole, 1,5-dimethyl-2-(phenylethynyl)-1H-indole, 1,6-dimethyl-2-(phenylethynyl)-1H-indole, 5-methoxy-1-methyl-2-(phenylethynyl)-1H-indole, 6-methoxy-1-methyl-2-(phenylethynyl)-1H-indole, 2-((4-methoxyphenyl)ethynyl)-1-methyl-1H-indole, 2-((4-fluorophenyl)ethynyl)-1-methyl-1H-indole, 1-methyl-2-((3-(trifluoromethyl)phenyl)ethynyl)-1H-indole or 2-((4-methylphenyl)ethynyl)-1-methyl-1H-indole.

7. The method for synthesizing the carbazole fused ring compound according to claim 3, characterized in that: The substance described in formula III is: 4-phenylbut-3-en-2-one, 4-(p-fluorophenyl)but-3-en-2-one, 4-(p-chlorophenyl)but-3-en-2-one, 4-(p-bromophenyl)but-3-en-2-one, 4-(p-trifluoromethylphenyl)but-3-en-2-one, 4-(p-acetylphenyl)but-3-en-2-one, 4-(p-methylphenyl)but-3-en-2-one, 4-(p-nitrophenyl)but-3-en-2-one, 4-(2-bromophenyl)but-3-en-2-one, 4-(2-trifluoromethylphenyl)but-3-en-2-one, 4-(2-fluorophenyl)but-3-en-2-one, 4-(3-fluorophenyl)but-3-en-2-one or 4-(3-trifluoromethylphenyl)but-3-en-2-one.

8. The method for synthesizing the carbazole fused ring compound according to claim 3, characterized in that: The Brenster acid catalyst is trifluoromethanesulfonic acid, phosphomolybdic acid, phosphotungstic acid, silicotungstic acid, trifluoromethanesulfonamide, p-toluenesulfonic acid, montmorillonite or aminosulfonic acid.

9. The method for synthesizing the carbazole fused ring compound according to claim 3, characterized in that: The organic solvent is nitromethane, nitroethane, 1,4-dioxane, toluene, xylene or trimethylbenzene.

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