A tetrahydrocarbazole derivative and a photocatalytic synthesis method thereof

Abstract

The application discloses a kind of tetrahydrocarbazole derivatives and its photocatalytic synthesis method, belong to organic synthesis technical field, 2-arylene phenyl isonitrile compound, cyclopropyl aniline compound and photocatalyst are added to solvent, after photocatalytic reaction, again separation and purification, obtain tetrahydrocarbazole derivative.This method is more simple compared with the method for using no tetrahydrocarbazole synthesis N-substituted tetrahydrocarbazole derivative, and no additional various additives in reaction, the atomic utilization rate of cyclopropyl aniline compound and 2-arylene phenyl isonitrile compound reaches 100%, reflects atomic economy, raw material is cheap and easy to obtain, reaction cost is low, and environment friendly;It is easy to operate, and target product can be efficiently obtained.The photocatalytic synthesis method of the tetrahydrocarbazole derivative is good in universality of raw material, and raw material is widely sourced, under optimized reaction condition, target product is easy to separate, and has potential application value in material and pharmaceutical field.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic synthesis, and particularly relates to a tetrahydrocarbazole derivative and a photocatalytic synthesis method thereof. BACKGROUND

[0002] The tetrahydrocarbazole derivative is a special structural scaffold in a series of candidate drugs and natural indole alkaloids with biological activity, and has an important position in the fields of drug synthesis and biological medicine. Traditional synthesis of the tetrahydrocarbazole is often realized by adopting a synthesis route of carbazole proposed by W.E.Noland, using indole, aldehyde or ketone, and maleimide as raw materials, and realizing condensation and Diels-Alder reaction under acid catalysis [(a) Noland W E, Kuryla W C, Lange RF. J. Am. Chem. Soc., 1995, 81: 601. (b) Noland W E, Sundberg R J. J. Org. Chem., 1963, 28: 844. (c) Noland W E, Kenkel M J, Tempesta M S, Cink R D, Powers D M, Schlemper E O, Barnes C L. J. Heterocyclic Chem., 1993, 30: 81. 1992, 30: 183. (d) Sundberg R J, Cheney R J. J Org. Chem., 1990, 55: 6028. (e) Sundberg R J, Amac M, Fernando AM. J. Org. Chem., 1987, 46: 3151. (f) Ziegler F E, Spitzner E B. J. Am. Chem. Soc., 1970, 92: 3492].

[0003] With the rapid development of photocatalytic reaction, chemists found that isonitrile as a radical acceptor showed good selectivity in photocatalytic reaction; at the same time, cyclopropylamine was easily irreversible ring-opening under photocatalytic conditions due to its inherent three-membered ring tension, forming a radical cation intermediate, and could complete [3+2] cycloaddition with unsaturated bond. Existing literature often provides the reaction process of cyclopropylamine and double bond, triple bond, etc., and the reaction of isonitrile to synthesize tetrahydrocarbazole is rarely reported [(g) Maity S, Zhu M, Shinabery R S, et al. Angew. Chem. Int. Ed. Engl., 2012, 51: 222-226. (h) Nguyen T H, Morris S A, Zheng N. Adv. Synth. &. Catal., 2014, 356: 2831. (i) Cai Y, Wang J, Zhang Y, et al. J. Am. Chem. Soc., 2017, 139: 12259. (j) Kuang Y, Ning Y, Zhu J, et al. Org. Lett, 2018, 20: 2693. (k) Muriel B, Gagnebin A, Waser J. Chem. Sci., 2019, 10: 10716. (l) Pflug N C, Schmitt M, McNeill K. Environ. Sci. Technol., 2019, 53(9), 4813.].

[0004] In view of the problems of traditional tetrahydrocarbazole synthesis method, such as multiple reaction steps, high temperature, low yield and poor functional group tolerance, it is urgent to find a new synthesis method of tetrahydrocarbazole derivative to simplify the synthesis method, optimize the synthesis conditions and improve the yield. SUMMARY

[0005] In order to overcome the above-mentioned defects of the prior art, the purpose of the present application is to provide a tetrahydrocarbazole derivative and a photocatalytic synthesis method thereof, so as to solve the technical problems of traditional tetrahydrocarbazole synthesis method, such as multiple reaction steps, high temperature, low yield and poor functional group tolerance.

[0006] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0007] The application discloses a photocatalytic synthesis method of tetrahydrocarbazole derivative, comprising the following steps: adding 2-arylene phenyl isonitrile compound, cyclopropylamine compound and photocatalyst into a solvent, and then separating and purifying after photocatalytic reaction to obtain tetrahydrocarbazole derivative.

[0008] Preferably, the reaction formula of tetrahydrocarbazole derivative is as follows:

[0009]

[0010] wherein R 1 is selected from hydrogen, alkyl, alkynyl, t-butyl, halogen or ester; R 2 is selected from alkyl, t-butyl, halogen, ester or phenyl; R 3 is selected from alkyl, phenyl, halogen, alkoxy or heterocycle.

[0011] Preferably, the molar ratio of 2-arylenyl phenyl isocyanides: cyclopropyl anilines is 1.0:2.0.

[0012] Preferably, before the catalytic reaction, the air in the reaction system is replaced with nitrogen and sealed.

[0013] Preferably, the conditions for the photocatalytic reaction are: stirring under 15-30 W blue light LED irradiation for 10-15 h at room temperature.

[0014] Preferably, the conditions for separation and purification are: first adding deionized water to quench the reaction, then extracting with ethyl acetate for 2-4 times, collecting the organic phase, then adding anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally performing fast column chromatography to obtain the tetrahydrocarbazole derivative.

[0015] Preferably, the catalyst is an iridium-based catalyst, including [Ir(d t b-bpy)(ppy)2]PF6, Ir(dF(CF3)ppy)2(d t b-bpy)PF6 or [Ir(dF(CF3)ppy)2( 1,10 -Phen)]PF6.

[0016] Preferably, the 2-arylenyl phenyl isocyanides include one of 2-styrylisocyanobenzene, 4-methyl-2-styrylisocyanobenzene, 4-t-butyl-2-styrylisocyanobenzene, 4-chloro-2-styrylisocyanobenzene, 4-fluoro-2-styrylisocyanobenzene, 5-methyl-2-styrylisocyanobenzene, 5-chloro-2-styrylisocyanobenzene, 5-trifluoromethyl-2-styrylisocyanobenzene, 6-methyl-2-styrylisocyanobenzene, 4,6-dimethyl-2-styrylisocyanobenzene, 4,6-dichloro-2-styrylisocyanobenzene, 2-(4-methylstyryl)isocyanobenzene, 2-(4-t-butylstyryl)isocyanobenzene, 2-(4-chlorostyryl)isocyanobenzene, 2-(4-fluorostyryl)isocyanobenzene, 2-(4-methylcarboxylate styryl)isocyanobenzene, 2-biphenylstyrylisocyanobenzene, 2-(ortho-chlorostyryl)isocyanobenzene, 4-nitrile-2-styrylisocyanobenzene, 2-(4-naphthalene styryl)isocyanobenzene and 2-(meta-chlorostyryl)isocyanobenzene.

[0017] Preferably, the cyclopropyl aniline compound includes one of cyclopropyl aniline, 2-methylcyclopropyl aniline, 2-phenylcyclopropyl aniline, 3-methylcyclopropyl aniline, 3-chlorocyclopropyl aniline, 4-oxymethylcyclopropyl aniline, 4-oxyl-tert-butylcyclopropyl aniline, 4-trifluoromethylcyclopropyl aniline, 4-phenylcyclopropyl aniline, 3,5-dimethylcyclopropyl aniline, cyclopropyl naphthalene-2-amine, 4-chlorocyclopropyl aniline, and cyclopropyl pyridine-2-amine.

[0018] The application also discloses a tetrahydrocarbazole derivative synthesized by the photocatalytic synthesis method.

[0019]

[0020] wherein, R 1 selected from hydrogen, alkyl, acetylenyl, tert-butyl, halogen or ester group; R 2 selected from alkyl, tert-butyl, halogen, ester group or phenyl; R 3 selected from alkyl, phenyl, halogen, alkoxy or heterocycle.

[0021] Compared with the prior art, the application has the following beneficial effects:

[0022] The application discloses a photocatalytic synthesis method of tetrahydrocarbazole derivative, which comprises the following steps: adding 2-aromatic alkenyl phenyl isocyanide compound, cyclopropyl aniline compound and a photocatalyst into a solvent, and then performing photocatalytic reaction, and finally separating and purifying to obtain tetrahydrocarbazole derivative. The cyclopropyl aniline compound and the 2-aromatic alkenyl phenyl isocyanide compound are reacted under a photocatalytic system to synthesize the tetrahydrocarbazole derivative. The reaction can be quickly performed at normal temperature. The 2-aromatic alkenyl phenyl isocyanide compound serves as a free radical acceptor and exhibits good selectivity in the photocatalytic reaction. Meanwhile, the cyclopropyl aniline compound is easily irreversibly opened under the photocatalytic condition due to its inherent three-membered ring tension, so as to form a free radical cation intermediate and complete [3+2] cycloaddition with the unsaturated bond. On the basis of the [3+2] cycloaddition, further cyclization is performed, and the synthesis of tetrahydrocarbazole is completed in one step. The method is performed at normal temperature, does not need to add acid, base and salt as additives, has high reaction efficiency, and has important significance for one-step synthesis of tetrahydrocarbazole and its derivatives. Compared with the method for synthesizing N-substituted tetrahydrocarbazole derivative by using unsubstituted tetrahydrocarbazole (tetrahydrocarbazole needs to be synthesized), the method is simple in operation and can efficiently obtain the target product. The atomic utilization rate of the cyclopropyl aniline compound and the 2-aromatic alkenyl phenyl isocyanide compound reaches 100%, which embodies atomic economy. The raw materials are cheap and easy to obtain, the reaction cost is low, and the method is environment-friendly. The reaction has good universality to raw materials, the raw materials are widely available, the target product is easy to separate under the optimized reaction condition, and the method has potential application value in the fields of materials and medicines.

[0023] Further, before the catalytic reaction, the air in the reaction system is replaced with nitrogen and sealed, and the reaction is carried out under the protection of nitrogen, so that a higher yield can be obtained.

[0024] Further, the photocatalytic reaction is carried out at room temperature under the irradiation of a 15-30 W blue light LED for 10-15 h, so that the raw materials are fully reacted and the yield of the product is maximized.

[0025] The application also discloses the tetrahydrocarbazole derivative synthesized by the synthesis method, the atomic utilization rate of the raw material cyclopropyl aniline compound and the 2-arylene phenyl isonitrile compound reaches 100%, the construction of the nitrogen-containing heterocycle is completed under the requirement of the atomic economy, and the idea of obtaining the polysubstituted tetrahydrocarbazole derivative through secondary ring closure is theoretically feasible. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 The mass spectrum of the product prepared in Example 1 is shown in FIG. 1, wherein (a) is the H NMR spectrum, (b) is the C NMR spectrum, and (c) is the mass spectrum. 1 The H NMR spectrum, (b) is the C NMR spectrum, and (c) is the mass spectrum. 13 The H NMR spectrum, (b) is the C NMR spectrum, and (c) is the mass spectrum.

[0027] Figure 2 The mass spectrum of the product prepared in Example 2 is shown in FIG. 2, wherein (a) is the H NMR spectrum, (b) is the C NMR spectrum, and (c) is the mass spectrum. 1 The H NMR spectrum, (b) is the C NMR spectrum, and (c) is the mass spectrum. 13 The H NMR spectrum, (b) is the C NMR spectrum, and (c) is the mass spectrum.

[0028] Figure 3 The mass spectrum of the product prepared in Example 3 is shown in FIG. 3, wherein (a) is the H NMR spectrum, (b) is the C NMR spectrum, and (c) is the mass spectrum. 1 The H NMR spectrum, (b) is the C NMR spectrum, and (c) is the mass spectrum. 13 The H NMR spectrum, (b) is the C NMR spectrum, and (c) is the mass spectrum.

[0029] Figure 4 The mass spectrum of the product prepared in Example 4 is shown in FIG. 4, wherein (a) is the H NMR spectrum, (b) is the C NMR spectrum, and (c) is the mass spectrum. 1 The H NMR spectrum, (b) is the C NMR spectrum, and (c) is the mass spectrum. 13 The H NMR spectrum, (b) is the C NMR spectrum, and (c) is the mass spectrum.

[0030] Figure 5 The mass spectrum of the product prepared in Example 5 is shown in FIG. 5, wherein (a) is the H NMR spectrum, (b) is the C NMR spectrum, and (c) is the mass spectrum. 1 The H NMR spectrum, (b) is the C NMR spectrum, and (c) is the mass spectrum. 13 The H NMR spectrum, (b) is the C NMR spectrum, and (c) is the mass spectrum.

[0031] Figure 6 The mass spectrum of the product prepared in Example 6 is shown in FIG. 6, wherein (a) is the H NMR spectrum, (b) is the C NMR spectrum, and (c) is the mass spectrum. 1 The H NMR spectrum, (b) is the C NMR spectrum, and (c) is the mass spectrum. 13 The H NMR spectrum, (b) is the C NMR spectrum, and (c) is the mass spectrum.

[0032] Figure 7 Mass spectrum of the product prepared in Example 7, where (a) is the 1 H NMR spectrum, (b) is the 13 C NMR spectrum;

[0033] Figure 8 Mass spectrum of the product prepared in Example 8, where (a) is the 1 H NMR spectrum, (b) is the 13 C NMR spectrum;

[0034] Figure 9 Mass spectrum of the product prepared in Example 9, where (a) is the 1 H NMR spectrum, (b) is the 13 C NMR spectrum;

[0035] Figure 10 Mass spectrum of the product prepared in Example 10, where (a) is the 1 H NMR spectrum, (b) is the 13 C NMR spectrum;

[0036] Figure 11 Mass spectrum of the product prepared in Example 11, where (a) is the 1 H NMR spectrum, (b) is the 13 C NMR spectrum;

[0037] Figure 12 Mass spectrum of the product prepared in Example 12, where (a) is the 1 H NMR spectrum, (b) is the 13 C NMR spectrum;

[0038] Figure 13 Mass spectrum of the product prepared in Example 13, where (a) is the 1 H NMR spectrum, (b) is the 13 C NMR spectrum;

[0039] Figure 14 Mass spectrum of the product prepared in Example 14, where (a) is the 1 H NMR spectrum, (b) is the 13 C NMR spectrum;

[0040] Figure 15 Mass spectrum of the product prepared in Example 15, where (a) is the 1 H NMR spectrum, (b) is the 13 C NMR spectrum. DETAILED DESCRIPTION

[0041] In the following, the technical solutions in the embodiments of the present application will be described clearly and completely with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all the other embodiments obtained by a person of ordinary skill in the art without creative work should belong to the protection scope of the present application.

[0042] It should be noted that the terms "first", "second" and the like in the description and claims of the present application and the above-mentioned drawings are used to distinguish similar objects, and do not necessarily indicate a specific order or sequence. It should be understood that the data thus used can be interchanged under appropriate circumstances, so that the embodiments of the present application described herein can be implemented in an order other than that illustrated or described herein. In addition, the terms "comprise" and "have" and any variations thereof are intended to cover non-exclusive inclusion, for example, a process, method, system, product or device comprising a series of steps or units does not necessarily limit to those steps or units clearly listed, but can include other steps or units not clearly listed or inherent to these processes, methods, products or devices.

[0043] The present application will be described in further detail below with reference to the drawings:

[0044] The present application discloses a photocatalytic synthesis method of a tetrahydrocarbazole derivative, comprising:

[0045] The 2-arylene phenyl isocyanide compound and the cyclopropyl aniline compound are added to a solvent, and then a tetrahydrocarbazole derivative is prepared by separation and purification after catalytic reaction of a photocatalyst.

[0046] The reaction formula of the tetrahydrocarbazole derivative is:

[0047]

[0048] wherein, R 1 is selected from hydrogen, alkyl, alkyne, tert-butyl, halogen or ester group; R 2 is selected from alkyl, tert-butyl, halogen, ester group or phenyl; R 3 is selected from alkyl, phenyl, halogen, alkoxy or heterocycle.

[0049] The specific synthesis process of the tetrahydrocarbazole derivative is as follows: 2-arylene phenyl isocyanide compound and photo-reaction catalyst are dissolved in a transparent clamp tube containing a reaction solvent, a ring-cyclopropylamine compound is added by using a pipette, air is replaced by nitrogen and sealed, stirring is performed at room temperature under the irradiation of a 15-30 W blue light LED for 10-15 h, after the reaction is completed, deionized water is added to quench the reaction, ethyl acetate is used for extraction for 2-4 times, the organic phase is collected, dried with anhydrous sodium sulfate to remove water, filtered, and the solvent is removed under reduced pressure, and then fast column chromatography is performed to obtain the tetrahydrocarbazole derivative.

[0050] The molar ratio of the 2-arylene phenyl isocyanide compound to the ring-cyclopropylamine compound is 1.0:2.0.

[0051] The photo-catalyst is an iridium catalyst, including [Ir(d t b-bpy)(ppy)2]PF6, Ir(dF(CF3)ppy)2(d t b-bpy)PF6 or [Ir(dF(CF3)ppy)2( 1,10 -Phen)]PF6.

[0052] The solvent is methanol, acetonitrile or nitromethane, and methanol is preferred.

[0053] The 2-arylene phenyl isocyanide compound includes one of 2-styrylisocyanobenzene, 4-methyl-2-styrylisocyanobenzene, 4-tert-butyl-2-styrylisocyanobenzene, 4-chloro-2-styrylisocyanobenzene, 4-fluoro-2-styrylisocyanobenzene, 5-methyl-2-styrylisocyanobenzene, 5-chloro-2-styrylisocyanobenzene, 5-trifluoromethyl-2-styrylisocyanobenzene, 6-methyl-2-styrylisocyanobenzene, 4,6-dimethyl-2-styrylisocyanobenzene, 4,6-dichloro-2-styrylisocyanobenzene, 2-(4-methylstyryl)isocyanobenzene, 2-(4-tert-butylstyryl)isocyanobenzene, 2-(4-chlorostyryl)isocyanobenzene, 2-(4-fluorostyryl)isocyanobenzene, 2-(4-carboxymethylstyryl)isocyanobenzene, 2-biphenylstyrylisocyanobenzene, 2-(o-chlorostyryl)isocyanobenzene, 4-nitrile-2-styrylisocyanobenzene, 2-(4-naphthalenylstyryl)isocyanobenzene and 2-(m-chlorostyryl)isocyanobenzene.

[0054] The cyclopropyl aniline compound includes one of cyclopropyl aniline, 2-methylcyclopropyl aniline, 2-phenylcyclopropyl aniline, 3-methylcyclopropyl aniline, 3-chlorocyclopropyl aniline, 4-oxymethylcyclopropyl aniline, 4-oxyl-tert-butylcyclopropyl aniline, 4-trifluoromethylcyclopropyl aniline, 4-phenylcyclopropyl aniline, 3,5-dimethylcyclopropyl aniline, cyclopropyl naphthalene-2-amine, 4-chlorocyclopropyl aniline, and cyclopropyl pyridine-2-amine.

[0055] The structural formula of the tetrahydrocarbazole derivative is:

[0056]

[0057] R1 is selected from hydrogen, alkyl, alkyne, tert-butyl, halogen, or ester group; R2 is selected from alkyl, tert-butyl, halogen, ester group, or phenyl; and R3 is selected from alkyl, phenyl, halogen, alkoxy, or heterocycle. 1 R1 is selected from hydrogen, alkyl, alkyne, tert-butyl, halogen, or ester group; R2 is selected from alkyl, tert-butyl, halogen, ester group, or phenyl; and R3 is selected from alkyl, phenyl, halogen, alkoxy, or heterocycle. 2 R1 is selected from hydrogen, alkyl, alkyne, tert-butyl, halogen, or ester group; R2 is selected from alkyl, tert-butyl, halogen, ester group, or phenyl; and R3 is selected from alkyl, phenyl, halogen, alkoxy, or heterocycle. 3 R1 is selected from hydrogen, alkyl, alkyne, tert-butyl, halogen, or ester group; R2 is selected from alkyl, tert-butyl, halogen, ester group, or phenyl; and R3 is selected from alkyl, phenyl, halogen, alkoxy, or heterocycle.

[0058] The application discloses a photocatalytic synthesis method of a tetrahydrocarbazole derivative, and specifically comprises the following steps: adding 2-arylalkenyl phenyl isocyanide compound shown in a formula I and cyclopropyl aniline compound shown in a formula II into a solvent, wherein the molar ratio of the 2-arylalkenyl phenyl isocyanide compound and the cyclopropyl aniline compound is 1.0:2.0; then stirring at room temperature for 12 hours under the conditions of nitrogen atmosphere and 20W blue LED lamp irradiation; and finally separating and purifying to obtain the tetrahydrocarbazole derivative shown in a formula III.

[0059]

[0060] R1 is selected from hydrogen, alkyl, alkyne, tert-butyl, halogen, or ester group; R2 is selected from alkyl, tert-butyl, halogen, ester group, or phenyl; and R3 is selected from alkyl, phenyl, halogen, alkoxy, or heterocycle.

[0061] The following detailed description is a description of the examples, and is intended to provide further details of the application. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the application.

[0062] Example 1

[0063] A preparation method of a tetrahydrocarbazole derivative of N,4-diphenyl-2,3,4,9-tetrahydro-1H-carbazol-3-amine, comprising:

[0064] 0.1 mmol of 2-styrylisocyanobenzene was added to the photocatalyst [Ir(dF(CF3)ppy)2(d t After carefully weighing 0.002 mmol of PF6, a 10 mL translucent clamp tube was added. Following the addition of 1.5 mL of methanol as the reaction solvent, 0.2 mmol of cyclopropylaniline was added using a pipette. The tube was then purged with nitrogen and sealed. The mixture was stirred for 12 h under 20 W blue light irradiation. After the reaction was complete, the reaction was quenched with aqueous solution. Ethyl acetate was extracted three times, and the organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent removed under reduced pressure before being subjected to rapid column chromatography (V). 石油醚 :V 乙酸乙酯 =10:1), yielding 26.4 mg of a colorless oily substance with a yield of 78%. Recrystallization from n-hexane and dichloromethane yielded the pure cis product, the structural formula of which is as follows:

[0065]

[0066] like Figure 1 As shown, the product's NMR characterization: cis isomer: 1 H NMR (400MHz, CDCl3) δ7.84(s,1H),7.34(d,J=8.1Hz,1H),7.30–7.21(m,5H),7.18–7.08(m,4H),6.97(t,J=7.5Hz,1H),6.76(t,J=7. 3Hz, 1H), 6.66 (d, J = 8.0Hz, 2H), 4.72 (d, J = 5.3Hz, 1H), 4.20 (q, J = 6.6Hz, 1H), 3.49 (s, 1H), 3.14–2.97 (m, 2H), 2.01 (h, J = 6.0Hz, 2H). 13 C NMR (101MHz, CDCl3) δ147.08,140.13,136.75,134.34,130.26,129.61,127.99,127.29,126.82,121. 61,119.50,118.48,117.32,113.51,111.74,110.53,52.35,40.96,24.69,22.97.HRMS(ESI)m / z[M+H] + calcdfor C 24 H 22 N2339.1856; found 339.1865.

[0067] Example 2

[0068] A method for preparing a 7-methyl-N,4-diphenyl-2,3,4,9-tetrahydro-1H-carbazol-3- amine tetrahydrocarbazole derivative, which is substantially the same as that of Example 1, except that the 2-arylenylphenyl isothiocyanate compound is selected as 5-methyl-2- phenylethenyl isothiocyanide, to obtain 27.5 mg of colorless oil with a yield of 78%, and the structural formula of the product is as follows:

[0069]

[0070] As shown in Figure 2 , the product nuclear magnetic resonance characterization: cis isomer: 1 H NMR (400 MHz, CDC13) δ 7.75 (s, 1H), 7.31 (s, 2H), 7.25 (d, J = 8.3 Hz, 3H), 7.14 (d, J = 4.7 Hz, 3H), 6.99 (d, J = 7.9 Hz, 1H), 6.83 - 6.74 (m, 2H), 6.67 (d, J = 7.8 Hz, 2H), 4.69 (d, J = 5.3 Hz, 1H), 4.20 (q, J = 6.8 Hz, 1H), 3.06 (q, J = 7.0, 4.5 Hz, 2H), 2.46 (s, 3H), 2.08 - 1.97 (m, 2H). 13 C NMR (151 MHz, CDC13) δ 140.23, 137.30, 133.61, 131.41, 130.29, 129.60, 128.01, 126.80, 125.19, 121.15, 118.18, 117.45, 113.66, 111.61, 110.68, 52.56, 41.15, 24.77, 22.98, 21.83. HRMS (ESI) m / z [M + H] + calcd for C 25 H 24 N 2353.2012; found 353.2022.

[0071] Example 3

[0072] A method for preparing a 7-chloro-N,4-diphenyl-2,3,4,9-tetrahydro-1H-carbazol-3- amine tetrahydrocarbazole derivative, which is substantially the same as that of Example 1, except that the 2-arylenylphenyl isothiocyanate compound is selected as 5-chloro-2- phenylethenyl isothiocyanide, to obtain 28.6 mg of colorless oil with a yield of 77%, and the structural formula of the product is as follows:

[0073]

[0074] As Figure 3 shown, the product was characterized by NMR: cis isomer: 1 H NMR (400 MHz, CDC13) δ 7.85 (s, 1H), 7.30 (d, J = 9.4 Hz, 3H), 7.22 (d, J = 7.5 Hz, 3H), 7.08 (dd, J = 6.8, 2.9 Hz, 2H), 6.98 (d, J = 8.4 Hz, 1H), 6.95 - 6.90 (m, 1H), 6.76 (t, J = 7.3 Hz, 1H), 6.65 (d, J = 8.0 Hz, 2H), 4.66 (d, J = 5.3 Hz, 1H), 4.18 (dt, J = 9.7, 4.9 Hz, 1H), 3.14 - 2.97 (m, 2H), 2.07 - 1.93 (m, 2H). 13 C NMR (101 MHz, CDC13) δ 147.05, 139.89, 137.25, 135.10, 130.20, 129.63, 128.11, 127.52, 127.01, 126.05, 120.23, 119.34, 117.54, 113.64, 112.07, 110.62, 52.48, 41.11, 24.73, 22.96. HRMS (ESI) m / z [M + H] + calcd for C 24 H 21 ClN2 373.1466l; found 373.1479.

[0075] Example 4

[0076] A method for preparing a 6-(tert-butyl)-N,4-diphenyl-2,3,4,9-tetrahydro-1H- carbazol-3-amine tetrahydrocarbazole derivative was substantially the same as that of Example 1, except that the 2-arylenylphenyl isocyanide compound was selected to be 4-tert-butyl-2-styrylisocyanobenzene, and flash column chromatography (V 石油醚 :V 乙酸乙酯 = 8: 1) to obtain 31.5 mg of colorless oil, with a yield of 80%, and the structural formula of the product was as follows:

[0077]

[0078] As Figure 4 shown, the product was characterized by NMR: cis isomer: 1H NMR (400MHz, CDCl3) δ7.78(s,1H),7.32–7.28(m,1H),7.26–7.22(m,4H),7.22–7.11(m,4H),6.89(d,J=1.8Hz,1H),6.70(t,J=7.3Hz,1H),6. 63(d,J=8.0Hz,2H),4.30(d,J=4.1Hz,1H),3.96(ddd,J=6.7,4.4,2.4Hz,1H),2.88(t,J=6.5Hz,2H),2.17(m,1H),2.01(m,1H),1.21(s,9H). 13 C NMR (101MHz, CDCl3) δ143.54,142.48,134.74,134.27,129.46,128.77,128.48,127.66,126.60,119.70, 117.57,114.97,113.77,109.99,109.82,56.09,45.84,34.57,31.96,23.57,19.86.HRMS(ESI)m / z[M+H] + calcd for C 28 H 30 N2 395.2482; found 395.2498.

[0079] Example 5

[0080] The preparation method of a 4-phenyl-3-(phenylamino)-2,3,4,9-tetrahydro-1H-carbazole-6-carbonitrile tetrahydrocarbazole derivative is basically the same as that in Example 1, except that: the 2-arylbenzene isocyanate compound is selected by rapid column chromatography (VLC) of 4-acrylonitrile-2-styrene isocyanophenyl. 石油醚 :V 乙酸乙酯 =8:1), yielding 18.9 mg of a colorless oily substance with a yield of 52%. The structural formula of the obtained product is as follows:

[0081]

[0082] like Figure 5 As shown, the product's NMR characterization: cis isomer: 1H NMR (600 MHz, CDC13) δ 8.21 (s, 1H), 7.38 (s, 1H), 7.35 - 7.32 (m, 2H), 7.25 (d, J = 3.4 Hz, 3H), 7.21 (dd, J = 8.5, 7.3 Hz, 2H), 7.04 (dd, J = 6.6, 3.0 Hz, 2H), 6.79 (t, J = 7.3 Hz, 1H), 6.67 (d, J = 7.9 Hz, 2H), 4.66 (d, J = 5.4 Hz, 1H), 4.15 (m, 1H), 3.05 (m, 2H), 2.08 - 2.01 (m, 2H).13C NMR (101 MHz, CDC13) δ 146.80, 139.26, 138.52, 136.80, 130.06, 129.66, 128.26, 127.30, 127.21, 124.92, 123.89, 117.62, 113.53, 112.78, 111.34, 102.58, 52.15, 40.71, 24.45, 22.92. HRMS (ESI) m / z [M + H] + calcd for C 25 H 21 N3 364.1808; found 364.1821.

[0083] Example 6

[0084] A method for preparing a 6,8-dimethyl-N,4-diphenyl-2,3,4,9-tetrahydro-1H- carbazol-3-amine tetrahydrocarbazole derivative, which is substantially the same as Example 1, except that the 2-arylenyl phenyl isothiocyanate compound is selected as 4,6-dimethyl-2-styrylisothiocyanobenzene (0.1 mmol), and 24.8 mg of colorless oil is obtained with a yield of 68%, and the structural formula of the product is as follows:

[0085]

[0086] As shown in the product nuclear magnetic characterization: Figure 6 1 H NMR (400 MHz, CDC13) δ 7.69 (d, J = 8.3 Hz, 1H), 7.31 - 7.21 (m, 7H), 7.06 (d, J = 7.2 Hz, 1H), 6.74 (m, 4H), 4.72 - 4.57 (m, 1H), 4.17 - 4.06 (m, 1H), 3.04 (q, J = 8.2 Hz, 2H), 2.57 - 2.39 (m, 3H), 2.28 - 2.20 (m, 3H), 2.00 - 1.90 (m, 2H). 13 ​C NMR (151 MHz, CDC13) δ 147.47, 147.17, 140.32, 134.61, 134.27, 134.13, 134.01, 130.32, 129.60, 129.48, 129.04, 128.99, 128.67, 128.48, 127.97, 127.71, 127.15, 126.74, 126.51, 124.06, 119.36, 119.29, 117.41, 117.28, 116.23, 115.89, 113.61, 113.52, 111.88, 109.29, 60.55, 55.49, 52.46, 45.23, 41.06, 29.84, 24.74, 23.13, 22.31, 21.41, 19.29, 16.73. HRMS (ESI) m / z [M + H] + calcd for C 26 H 26 N2 367.2169; found 367.2181.

[0087] Example 7

[0088] A method for preparing N-phenyl-4-(p-tolyl)-2,3,4,9-tetrahydro-1H-carbazol-3-amine tetrahydrocarbazole derivative, which is substantially the same as Example 1, except that 2-arylenyl phenyl isothiocyanate compound is selected as 2-(4-methylstyryl) isothiocyanobenzene, and fast column chromatography (V 石油醚 :V 乙酸乙酯 = 15:1), 24.9 mg of colorless oil was obtained, the yield was 71%, and the structure of the product is as follows:

[0089]

[0090] As Figure 7 shown, the product nuclear magnetic resonance characterization: cis isomer: 1H NMR(600MHz, CDCl3)δ7.84(s,1H),7.30(dd,J=8.1,0.9Hz,1H),7.22–7.17(m,2H) ,7.09–7.06(m,2H),7.05–7.01(m,2H),6.97(d,J=8.1Hz,2H),6.92(ddd,J=8.0,7 .0,1.0Hz,1H),6.73(t,J=7.3Hz,1H),6.65(d,J=7.9Hz,2H),4.64(d,J=5.3Hz,1H ),4.19–4.05(m,1H),3.08–2.93(m,2H),2.30(s,3H),1.98(dt,J=9.1,4.2Hz,2H). 13 CNMR (151MHz, CDCl3) δ147.46,140.57,136.12,134.12,129.47,129.23,128.51,127.89,121.62,119 .53,118.93,117.44,113.63,110.54,109.73,55.74,45.03,22.87,21.18,19.48.HRMS(ESI)m / z[M+H] + calcd for C 25 H 24 N2 353.2012; found353.2022.

[0091] Example 8

[0092] The preparation method of a 4-([1,1'-biphenyl]-4-yl)-N-phenyl-2,3,4,9-tetrahydro-1H-carbazol-3-amine tetrahydrocarbazole derivative is basically the same as that in Example 1, except that: 2-arylenylphenyl isonitrile is selected as 2-bistyrylisocyanophenyl, and rapid column chromatography (V) is used. 石油醚 :V 乙酸乙酯 =8:1), yielding 24.8 mg of a colorless oily substance with a yield of 60%. The structural formula of the obtained product is as follows:

[0093]

[0094] like Figure 8 As shown, the product's NMR characterization is as follows: 1H NMR (400MHz, CDCl3) δ7.89 (s, 1H), 7.61 (d, J = 7.7Hz, 2H), 7.54–7.42 (m, 4H), 7 .37(d,J=7.8Hz,2H),7.25(t,J=7.8Hz,2H),7.18(t,J=7.3Hz,4H),6.99(t,J=7 .6Hz,1H),6.77(t,J=7.4Hz,1H),6.69(d,J=8.0Hz,2H),4.77(d,J=5.2Hz,1H) ,4.23(q,J=6.7Hz,1H),3.10(q,J=6.2,4.0Hz,2H),2.06(q,J=8.7,6.5Hz,2H). 13 C NMR (101MHz, CDCl3) δ147.05,140.98,139.53,139.27,136.78,134.36,130.67,129.64,128.85,127.30,127.23,127. 10,126.65,121.67,119.54,118.49,117.38,113.56,111.71,110.56,52.45,40.55,24.77,23.04.HRMS(ESI)m / z[M+H] + calcd for C 30 H 26 N2415.2169; found 415.2182.

[0095] Example 9

[0096] The preparation method of a tetrahydrocarbazole derivative of 4-(3-(phenylamino)-2,3,4,9-tetrahydro-1H-carbazol-4-yl)phenylacetate is basically the same as that in Example 1, except that: the 2-arylphenylisocyanate compound selected is 2-(4-methylcarbamate-styryl)isocyanophenyl, and rapid column chromatography (V) is used. 石油醚 :V 乙酸乙酯 =15:1), yielding 24.5 mg of a colorless oily substance with a yield of 62%. The structural formula of the obtained product is as follows:

[0097]

[0098] like Figure 9 As shown, the product's NMR characterization: cis isomer: 1H NMR (400 MHz, CDC13) δ 7.84 (s, 1H), 7.30 (d, J = 8.1 Hz, 1H), 7.20 (t, J = 7.8 Hz, 2H), 7.08 (m, 4H), 6.94 (m, 3H), 6.73 (t, J = 7.4 Hz, 1H), 6.64 (d, J = 7.9 Hz, 2H), 4.70 (d, J = 5.2 Hz, 1H), 4.22 - 4.09 (m, 1H), 3.03 (m, 2H), 2.27 (s, 3H), 1.96 (m, 2H). 13 C NMR (101 MHz, CDC13) δ 169.49, 149.74, 146.92, 137.66, 136.92, 134.31, 131.10, 129.66, 127.32, 121.78, 120.94, 119.66, 118.53, 117.61, 113.72, 111.74, 110.56, 52.68, 40.40, 24.79, 23.07, 21.30. HRMS (ESI) m / z [M + H] + calcd for C 26 H 24 N2O2397.1911; found 397.1924.

[0099] Example 10

[0100] A method for preparing N-([1,1'-biphenyl]-4-yl)-4-phenyl-2,3,4,9-tetrahydro-1H- carbazol-3-amine tetrahydrocarbazole derivative is substantially the same as that of Example 1, except that the cyclopropyl aniline compound is selected as 4-phenylcyclopropyl aniline, and the flash chromatography column is selected as silica gel (V 石油醚 :V 乙酸乙酯 = 8: 1), 35.2 mg of colorless oil is obtained, the yield is 85%, and the structural formula of the obtained product is as follows:

[0101]

[0102] As Figure 10 shown, the product nuclear magnetic resonance characterization: cis isomer: 1H NMR (400MHz, CDCl3) δ7.83(s,1H),7.58(d,J=7.7Hz,2H),7.47(d,J=8.1Hz,2H),7.40(t,J=7.5Hz,2H),7.31(d,J=8.1Hz,1H),7.24(s,4H),7.10(m,4H ),6.94(t,J=7.5Hz,1H),6.69(d,J=8.1Hz,2H),4.71(d,J=5.4Hz,1H),4.27 –4.15(m,1H),3.53(d,J=9.4Hz,1H),3.10–3.00(m,2H),2.05–1.99(m,2H). 13 C NMR (101MHz, CDCl3) δ146.70,141.43,140.20,136.95,134.32,130.32,130.26,128.80,128.26,128.09,127.46,126. 93,126.39,126.18,121.73,119.63,118.60,113.80,111.88,110.57,52.64,41.35,24.92,22.97.HRMS(ESI)m / z[M+H] + calcd for C 30 H 26 N2415.2169; found 415.2180.

[0103] Example 11

[0104] The preparation method of an N-(4-methoxyphenyl)-4-phenyl-2,3,4,9-tetrahydro-1H-carbazol-3-amine tetrahydrocarbazole derivative is basically the same as that in Example 1, except that: 4-oxymethylcyclopropylaniline is selected as the cyclopropylaniline compound, and rapid column chromatography (V) is used. 石油醚 :V 乙酸乙酯 =15:1), yielding 28.7 mg of a colorless oily substance with a yield of 78%. The structural formula of the obtained product is as follows:

[0105]

[0106] like Figure 11 As shown, the product's NMR characterization: cis isomer: 1H NMR (400MHz, CDCl3) δ7.83 (s, 1H), 7.31 (d, J = 8.1Hz, 1H), 7.24 (d, J = 7.1Hz, 3 H),7.10(q,J=7.7Hz,5H),6.93(t,J=7.6Hz,1H),6.30(d,J=8.3Hz,1H),6.23 (d,J=8.3Hz,1H),6.19(s,1H),4.68(d,J=5.4Hz,1H),4.20–4.09(m,1H),3.7 8(s,3H),3.45(d,J=9.8Hz,1H),3.03(q,J=6.5Hz,2H),1.99(t,J=6.9Hz,2H). 13 C NMR (101MHz, CDCl3) δ161.27,148.64,140.24,136.91,134.31,130.32,128.03,127.44,126.86,121.67,119 .57,118.58,111.86,110.53,106.74,102.57,99.60,55.27,52.59,41.28,24.86,22.95.HRMS(ESI)m / z[M+H] + calcd for C 25 H 24 N2O 369.1961; found 369.1972.

[0107] Example 12

[0108] The preparation method of an N-(4-chlorophenyl)-4-phenyl-2,3,4,9-tetrahydro-1H-carbazol-3-amine tetrahydrocarbazole derivative is basically the same as that in Example 1, except that: 4-chlorocyclopropylaniline is selected as the cyclopropylaniline compound, and rapid column chromatography (V) is used. 石油醚 :V 乙酸乙酯 =8:1), yielding 33.4 mg of a colorless oily substance with a yield of 90%. The structural formula of the obtained product is as follows:

[0109]

[0110] like Figure 12 As shown, the product's NMR characterization: cis isomer: 1H NMR (400 MHz, CDC13) δ 7.86 (s, 1H), 7.34 (d, J = 8.2 Hz, 1H), 7.26 (s, 3H), 7.20 - 7.07 (m, 6H), 6.97 (t, J = 7.5 Hz, 1H), 6.64 - 6.51 (m, 2H), 4.69 (d, J = 5.2 Hz, 1H), 4.13 (m, 1H), 3.07 (q, J = 6.2 Hz, 2H), 2.10 - 1.91 (m, 2H). 13 CNMR (101 MHz, CDC13) δ 145.78, 140.02, 136.91, 134.19, 130.22, 129.43, 128.10, 127.37, 126.97, 121.87, 121.76, 119.63, 118.54, 114.65, 111.69, 110.57, 52.79, 41.11, 24.78, 22.91. HRMS (ESI) m / z [M + H] + calcd for C 24 H 21 ClN2 373.1466; found 373.1478.

[0111] Example 13

[0112] A method for preparing N-(3,5-dimethylphenyl)-4-phenyl-2,3,4,9-tetrahydro-1H- carbazol-3-amine tetrahydrocarbazole derivative, which is substantially the same as Example 1, except that the cyclopropyl aniline compound is selected as 3,5-dimethylcyclopropyl aniline, and flash column chromatography (V 石油醚 :V 乙酸乙酯 = 15: 1) to obtain 27.4 mg of colorless oil, with a yield of 75%, and the structure of the product is as follows:

[0113]

[0114] As Figure 13 shown, the product nuclear magnetic resonance characterization: cis isomer: 1H NMR (400 MHz, CDC13) δ 7.87 (s, 1H), 7.35 (d, J = 8.1 Hz, 1H), 7.28 (m, 4H), 7.13 (t, J = 8.6 Hz, 4H), 6.97 (t, J = 7.4 Hz, 1H), 6.42 (s, 1H), 6.30 (s, 2H), 4.69 (d, J = 5.3 Hz, 1H), 4.18 (q, J = 6.7 Hz, 1H), 3.08 (q, J = 6.8 Hz, 2H), 2.28 (s, 6H), 2.04 - 1.97 (m, 2H). 13 C NMR (101 MHz, CDC13) δ 147.21, 140.30, 139.20, 136.94, 134.40, 130.37, 127.99, 127.49, 126.81, 121.68, 119.59, 119.48, 118.60, 114.81, 111.56, 110.54, 52.59, 41.39, 24.93, 23.05, 21.67. HRMS (ESI) m / z [M + H] + calcd for C 26 H 26 N2 367.2196; found 367.2197.

[0115] Example 14

[0116] A method for preparing N-(naphthalen-2-yl)-4-phenyl-2,3,4,9-tetrahydro-1H- carbazol-3-amine tetrahydrocarbazole derivative, which is basically the same as Example 1, the difference is that the cyclopropyl aniline compound is selected as cyclopropyl naphthalene-2-amine, and the fast chromatographic column is selected as silica gel (V 石油醚 :V 乙酸乙酯 = 8: 1), 33.3 mg of colorless oil was obtained, the yield was 86%, and the structure of the product is as follows:

[0117]

[0118] As Figure 14 shown, the product nuclear magnetic resonance characterization: cis isomer: 1H NMR (400MHz, CDCl3) δ7.79 (s, 1H), 7.72 (d, J = 8.1Hz, 1H), 7.66 (dd, J = 12.6, 8.5Hz, 2H) ,7.40(t,J=7.5Hz,1H),7.33(d,J=8.1Hz,1H),7.28–7.24(m,4H),7.13(dt,J=8.9,5.3H z,4H),6.98(t,J=3.4Hz,2H),6.80(dt,J=8.9,1.6Hz,1H),4.82(d,J=5.4Hz,1H),4.32 (h,J=6.5,5.7Hz,1H),3.63(d,J=9.8Hz,1H),3.17–2.98(m,2H),2.07(h,J=4.6Hz,2H). 13 C NMR (101MHz, CDCl3) δ144.90,140.22,136.94,135.60,134.35,130.28,129.34,128.04,127.81,127.68,127.46,126.88,126. 51,126.04,122.08,121.71,119.61,118.57,118.54,111.78,110.58,105.25,52.61,40.78,24.80,22.97.HRMS(ESI)m / z[M+H] + calcd for C 28 H 24 N2 389.2012; found 389.2023.

[0119] Example 15

[0120] The preparation method of a 4-phenyl-N-(pyridin-2-yl)-2,3,4,9-tetrahydro-1H-carbazol-3-amine tetrahydrocarbazole derivative is basically the same as that in Example 1, except that: cyclopropylpyridine-2-amine is selected as the cyclopropylaniline compound, and rapid column chromatography (V) is used. 石油醚 :V 乙酸乙酯 =8:1), yielding 18.3 mg of a colorless oily substance with a yield of 54%. The structural formula of the obtained product is as follows:

[0121]

[0122] like Figure 15 As shown, the product's NMR characterization: cis isomer: 1H NMR (400 MHz, CDC13) δ 8.09 (d, J = 5.0 Hz, 1H), 7.96 (s, 1H), 7.46 - 7.36 (m, 1H), 7.30 (d, J = 8.1 Hz, 1H), 7.22 (d, J = 7.3 Hz, 3H), 7.12 - 7.00 (m, 4H), 6.91 (t, J = 7.4 Hz, 1H), 6.57 (dd, J = 7.1, 5.1 Hz, 1H), 6.34 (d, J = 8.4 Hz, 1H), 4.64 (d, J = 5.5 Hz, 1H), 4.54 (dd, J = 10.8, 6.5 Hz, 1H), 4.28 (s, 1H), 3.17 - 2.94 (m, 2H), 2.00 (pt, J = 9.4, 4.5 Hz, 2H). 13 CNMR (101 MHz, CDC13) δ 157.88, 140.30, 137.65, 136.70, 134.28, 130.14, 128.15, 127.32, 126.85, 121.48, 119.36, 118.60, 112.82, 111.52, 110.49, 107.90, 50.82, 41.60, 24.88, 22.65. HRMS (ESI) m / z [M + H] + calcd for C 23 H 21 N3 340.1808; found 340.1818.

[0123] Example 16

[0124] A method for preparing a N,4-diphenyl-7-(trifluoromethyl)-2,3,4,9-tetrahydro-1H- carbazol-3-amine tetrahydrocarbazole derivative, which is substantially the same as Example 1, except that the 2-arylenylphenyl isothiocyanate compound is selected as 5- trifluoromethyl-2-styrylisothiocyanobenzene, and the photo-catalyst is selected as [Ir(d t b-bpy)(ppy)2]PF6, to obtain 26.4 mg of colorless oil, with a yield of 65%, and the structural formula of the product obtained is as follows:

[0125]

[0126] Example 17

[0127] A method for preparing a 6,8-dichloro-N,4-diphenyl-2,3,4,9-tetrahydro-1H- carbazol-3-amine tetrahydrocarbazole derivative, which is substantially the same as that of Example 1, except that the 2-arylenylphenyl isothiocyanate compound is selected as 4,6-dichloro-2-phenylstyrylisothiocyanobenzene, and the photo-catalyst is selected as [Ir(dF(CF3)ppy)2 1,10 -Phen)]PF6, to obtain 27.6 mg of colorless oil with a yield of 68%, and the structural formula of the obtained product is as follows:

[0128]

[0129] Example 18

[0130] A method for preparing a 4-(4-(tert-butyl)phenyl)-N-phenyl-2,3,4,9-tetrahydro-1H- carbazol-3-amine tetrahydrocarbazole derivative, which is substantially the same as that of Example 1, except that the 2-arylenylphenyl isothiocyanate compound is selected as 2-(4-tert-butylphenylstyryl)isothiocyanobenzene, and the stirring is performed under the irradiation of 15 W blue light for 15 h, and the fast column chromatography is performed with a V 石油醚 :V 乙酸乙酯 = 15:1) to obtain 26.4 mg of colorless oil with a yield of 67%, and the structural formula of the obtained product is as follows:

[0131]

[0132] Example 19

[0133] A method for preparing a 4-(4-chlorophenyl)-N-phenyl-2,3,4,9-tetrahydro-1H-carbazol- 3-amine tetrahydrocarbazole derivative, which is substantially the same as that of Example 1, except that the 2-arylenylphenyl isothiocyanate compound is selected as 2-(4-chlorophenylstyryl)isothiocyanobenzene, and the stirring is performed under the irradiation of 25 W blue light for 10 h, and the fast column chromatography is performed with a V 石油醚 :V 乙酸乙酯 = 15:1) to obtain 24.8 mg of colorless oil with a yield of 67%, and the structural formula of the obtained product is as follows:

[0134]

[0135] Example 20

[0136] A method for preparing a 4-(naphthalen-2-yl)-N-phenyl-2,3,4,9-tetrahydro-1H- carbazol-3-amine tetrahydrocarbazole derivative is substantially the same as that of Example 1, except that the 2-arylenylphenyl isonitrile compound is selected as 2-(4- naphthalene phenylethenyl) isonitrile, and the stirring under 30W blue light irradiation is performed for 10h, and the flash column chromatography (V 石油醚 :V 乙酸乙酯 = 8:1) to obtain 22.3mg of colorless oil with a yield of 71%, and the structure of the obtained product is as follows:

[0137]

[0138] Example 21

[0139] A method for preparing a N-(4-(tert-butoxy)phenyl)-4-phenyl-2,3,4,9-tetrahydro-1H- carbazol-3-amine tetrahydrocarbazole derivative is substantially the same as that of Example 1, except that the cyclopropyl aniline compound is selected as 4-oxo tert-butyl cyclopropyl aniline, and the stirring under 30W blue light irradiation is performed for 10h, and the flash column chromatography (V 石油醚 :V 乙酸乙酯 = 15:1) to obtain 33.6mg of colorless oil with a yield of 82%, and the structure of the obtained product is as follows:

[0140]

[0141] Example 22

[0142] A method for preparing a 4-phenyl-N-(4-(trifluoromethyl)phenyl)-2,3,4,9-tetrahydro-1H- carbazol-3-amine tetrahydrocarbazole derivative is substantially the same as that of Example 1, except that the cyclopropyl aniline compound is selected as 4-trifluoromethyl cyclopropyl aniline, and the ethyl acetate extraction is performed twice, and the flash column chromatography (V 石油醚 :V 乙酸乙酯 = 8:1) to obtain 30.4mg of colorless oil with a yield of 75%, and the structure of the obtained product is as follows:

[0143]

[0144] Example 23

[0145] A method for preparing a 4-phenyl-N-(m-tolyl)-2,3,4,9-tetrahydro-1H-carbazol-3- amine tetrahydrocarbazole derivative, which is substantially the same as that of Example 1, except that the 2-arylideneaniline compound is selected from 3-methyl-2- phenylprop-2-enenitrile, and the product is obtained as 24.6 mg of colorless oil in a yield of 70%, and the structure of the product is as follows: 石油醚 :V 乙酸乙酯 = 15:1), to obtain 24.6 mg of colorless oil in a yield of 70%, and the structure of the product is as follows:

[0146]

[0147] Example 24

[0148] A method for preparing a 6-methyl-N,4-diphenyl-2,3,4,9-tetrahydro-1H-carbazol-3- amine tetrahydrocarbazole derivative, which is substantially the same as that of Example 1, except that the 2-arylideneaniline compound is selected from 4-methyl-2- phenylprop-2-enenitrile, to obtain 27.4 mg of colorless oil in a yield of 78%, and the structure of the product is as follows:

[0149]

[0150] Example 25

[0151] A method for preparing a 6-fluoro-N,4-diphenyl-2,3,4,9-tetrahydro-1H-carbazol-3- amine tetrahydrocarbazole derivative, which is substantially the same as that of Example 1, except that the 2-arylideneaniline compound is selected from 4-fluoro-2- phenylprop-2-enenitrile, to obtain 25.6 mg of colorless oil in a yield of 72%, and the structure of the product is as follows:

[0152]

[0153] Example 26

[0154] A method for preparing a 6-chloro-N,4-diphenyl-2,3,4,9-tetrahydro-1H-carbazol-3- amine tetrahydrocarbazole derivative, which is substantially the same as that of Example 1, except that the 2-arylideneaniline compound is selected from 4-chloro-2- phenylprop-2-enenitrile, to obtain 27.9 mg of colorless oil in a yield of 75%, and the structure of the product is as follows:

[0155]

[0156] Example 27

[0157] A method for preparing a 8-methyl-N,4-diphenyl-2,3,4,9-tetrahydro-1H-carbazol-3-amine tetrahydrocarbazole derivative, which is substantially the same as that of Example 1, except that the 2-arylenyl phenyl isothiocyanate compound is selected as 6-methyl-2-styrylisothiocyanobenzene, to obtain 23.9 mg of colorless oil at a yield of 68%, and the structure of the obtained product is as follows:

[0158]

[0159] Example 28

[0160] A method for preparing a 4-(2-chlorophenyl)-N-phenyl-2,3,4,9-tetrahydro-1H-carbazol-3-amine tetrahydrocarbazole derivative, which is substantially the same as that of Example 1, except that the 2-arylenyl phenyl isothiocyanate compound is selected as 2-(o-chlorostyryl)isothiocyanobenzene, and fast column chromatography (V 石油醚 :V 乙酸乙酯 = 8:1) is performed four times, to obtain 23.8 mg of colorless oil at a yield of 64%, and the structure of the obtained product is as follows:

[0161]

[0162] Example 29

[0163] A method for preparing a 4-(3-chlorophenyl)-N-phenyl-2,3,4,9-tetrahydro-1H-carbazol-3-amine tetrahydrocarbazole derivative, which is substantially the same as that of Example 1, except that the 2-arylenyl phenyl isothiocyanate compound is selected as 2-(m-chlorostyryl)isothiocyanobenzene, and fast column chromatography (V 石油醚 :V 乙酸乙酯 = 8:1) is performed four times, to obtain 22.3 mg of colorless oil at a yield of 60%, and the structure of the obtained product is as follows:

[0164]

[0165] Example 30

[0166] A method for preparing a N-(3-chlorophenyl)-4-phenyl-2,3,4,9-tetrahydro-1H-carbazol-3-amine tetrahydrocarbazole derivative, which is substantially the same as that of Example 1, except that the cyclopropyl aniline compound is selected as 3-chlorocyclopropyl aniline, and ethyl acetate extraction is performed four times, and fast column chromatography (V石油醚 :V 乙酸乙酯 = 8: 1), to obtain 31.2 mg of colorless oil, the yield was 84%, the structure of the product is as follows:

[0167]

[0168] Example 31

[0169] A method for preparing a 4-phenyl-N-(o-tolyl)-2,3,4,9-tetrahydro-1H-carbazol-3-amine tetrahydrocarbazole derivative, which is basically the same as Example 1, the difference is that the cyclopropyl aniline compound is selected as 2-methylcyclopropyl aniline, and the rapid chromatographic column is used for chromatography (V 石油醚 :V 乙酸乙酯 = 15: 1), to obtain 27.4 mg of colorless oil, the yield was 78%, the structure of the product is as follows:

[0170]

[0171] Example 32

[0172] A method for preparing a N-([1,1'-biphenyl]-2-yl)-4-phenyl-2,3,4,9-tetrahydro-1H-carbazol-3-amine tetrahydrocarbazole derivative, which is basically the same as Example 1, the difference is that the cyclopropyl aniline compound is selected as 2-phenylcyclopropyl aniline, and the rapid chromatographic column is used for chromatography (V 石油醚 :V 乙酸乙酯 = 15: 1), to obtain 18.6 mg of colorless oil, the yield was 45%, the structure of the product is as follows:

[0173]

[0174] The above is only to illustrate the technical idea of the present application, and cannot be used to limit the protection scope of the present application. Any modification made according to the technical idea of the present application on the basis of the technical scheme falls within the protection scope of the claims of the present application.

Claims

1. A method for photocatalytic synthesis of a tetrahydrocarbazole derivative, characterized by, The application relates to a method for preparing a tetrahydrocarbazole derivative. The 2-arylene phenyl isonitrile compound comprises one of 2-styrylisocyanobenzene, 4-methyl-2-styrylisocyanobenzene, 4-tert-butyl-2-styrylisocyanobenzene, 4-chloro-2-styrylisocyanobenzene, 4-fluoro-2-styrylisocyanobenzene, 5-methyl-2-styrylisocyanobenzene, 5-chloro-2-styrylisocyanobenzene, 5-trifluoromethyl-2-styrylisocyanobenzene, 6-methyl-2-styrylisocyanobenzene, 4,6-dimethyl-2-styrylisocyanobenzene, 4,6-dichloro-2-styrylisocyanobenzene, 2-(4-methylstyryl)isocyanobenzene, 2-(4-tert-butylstyryl)isocyanobenzene, 2-(4-chlorostyryl)isocyanobenzene, 2-(4-fluorostyryl)isocyanobenzene, 2-(4-methylcarboxylate styryl)isocyanobenzene, 2-biphenylstyrylisocyanobenzene, 2-(o-chlorostyryl)isocyanobenzene, 4-nitrile-2-styrylisocyanobenzene, 2-(4-naphthalene styryl)isocyanobenzene and 2-(m-chlorostyryl)isocyanobenzene. The cyclopropyl aniline compound comprises one of cyclopropyl aniline, 2-methylcyclopropyl aniline, 2-phenylcyclopropyl aniline, 3-methylcyclopropyl aniline, 3-chlorocyclopropyl aniline, 4-oxymethylcyclopropyl aniline, 4-oxo-tert-butylcyclopropyl aniline, 4-trifluoromethylcyclopropyl aniline, 4-phenylcyclopropyl aniline, 3,5-dimethylcyclopropyl aniline, cyclopropyl naphthalene-2-amine, 4-chlorocyclopropyl aniline and cyclopropyl pyridine-2-amine. The molar ratio of the 2-arylene phenyl isonitrile compound to the cyclopropyl aniline compound is 1.0:2.

0. The catalyst is an iridium catalyst. The light catalytic reaction is carried out at room temperature under the irradiation of a 15-30 W blue light LED for 10-15 h. The reaction formula of the tetrahydrocarbazole derivative is shown in the description.

2. The method of photocatalytic synthesis of tetrahydrocarbazole derivatives according to claim 1, characterized in that, Before the catalytic reaction, the air in the reaction system is replaced by nitrogen and the system is sealed. ； wherein R is selected from hydrogen, methyl, tert-butyl, halogen, cyano or trifluoromethyl; R 1 is selected from hydrogen, methyl, tert-butyl, halogen, methylformate or phenyl; R 2 is selected from hydrogen, methyl, tert-butyl, halogen, methylformate or phenyl; R 3 is selected from hydrogen, methyl, tert-butyl, halogen, methylformate or phenyl; R 3. The method of photocatalytic synthesis of tetrahydrocarbazole derivatives according to claim 1, characterized in that, The separation and purification are carried out by adding deionized water to quench the reaction, then extracting the reaction system with ethyl acetate for 2-4 times, collecting the organic phase, adding anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure and finally carrying out fast column chromatography to obtain the tetrahydrocarbazole derivative.

4. The method of photocatalytic synthesis of tetrahydrocarbazole derivatives according to claim 1, characterized in that, The structural formula of the tetrahydrocarbazole derivative is shown in the description.

5. The method of photocatalytic synthesis of tetrahydrocarbazole derivatives according to claim 1, characterized in that, The catalyst is an iridium-based catalyst, including [Ir(d t b-bpy)(ppy)2]PF6, Ir(dF(CF3)ppy)2(d t b-bpy)PF6 or [Ir(dF(CF3)ppy)2(1, 10 -Phen)]PF6.

6. The tetrahydrocarbazole derivative synthesized by the photocatalytic synthesis method according to any one of claims 1 to 5, characterized in that, ​ ， wherein R is selected from hydrogen, methyl, tert-butyl, halogen, cyano or trifluoromethyl; R 1 is selected from hydrogen, methyl, tert-butyl, halogen, cyano or trifluoromethyl; R 2 is selected from hydrogen, methyl, tert-butyl, halogen, cyano or trifluoromethyl; R 3 is selected from hydrogen, methyl, tert-butyl, halogen, cyano or trifluoromethyl.

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