A 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compound and a synthesis method thereof

Abstract

The invention discloses a 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compound and a synthesis method thereof. A perfluoroalkyl-3-indole methanol compound is used as a raw material, and a reaction is carried out in a solvent under the catalysis of a catalyst to obtain a 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compound. The compound obtained by the method of the invention has the activity of inhibiting plant pathogenic fungi such as dollar spot pathogen and gray mold pathogen, and is of great significance for the effective prevention and treatment of the diseases of plants such as grassland lawns and field crops. The method of the invention does not require the use of a metal catalyst, reacts at room temperature, and has the advantages of easy availability of raw materials, mild conditions, high yield, wide range of substrates, and atom economy.

Description

Technical Field

[0001] The invention belongs to the technical field of organic compound synthesis, and specifically relates to a 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compound and a synthesis method thereof. Background Art

[0002] Condensed polycyclic indoles are an important class of indole alkaloids. Many of these compounds show diverse and rich biological activities and have wide applications in the fields of medicine, fragrances, pesticides, pigments and materials chemistry. Among them, indeno[1,2-b]indole derivatives have been widely used as precursors for the total synthesis of many natural products and show a wide range of biological activities, such as antioxidant, anticancer, human protein kinase CK2 inhibitors and breast cancer resistance protein inhibitors. In addition, due to their electron-rich properties and strong charge transfer ability, indeno[1,2-b]indole compounds are also used as electron donors in organic optoelectronics and blue light-emitting materials. However, the synthesis methods of indeno[1,2-b]indole compounds are mainly focused on metal-catalyzed ninhydrin cyclization, Japp–Klingemann reaction combined with Fischer indole synthesis, and nitro- or amino-promoted intramolecular reduction-tandem cyclization. However, these methods have many shortcomings, such as the use of expensive transition metal catalysts, the need for multiple steps and difficulty in synthesizing raw materials, and general reaction efficiency.

[0003]

[0004] Fluorinated compounds have very important applications in the fields of chemistry, medicine, pesticides, functional materials, etc. Currently, about 20% of pharmaceuticals and 30% of pesticide molecules contain at least one F atom. Introducing fluorine atoms or fluorine-containing groups into drug molecules can significantly improve the physicochemical properties and biological activities of drugs, such as metabolic stability, lipophilicity, permeability, and interaction with biological targets, and has gradually become a common method for drug screening. Perfluoroalkyl groups have strong electron-withdrawing properties, large steric hindrance, good lipophilicity and stability, and are also important synthons. Therefore, it is extremely important to develop a simple and efficient synthetic method to achieve the efficient synthesis of perfluoroalkyl indeno[1,2-b]indole compounds. Summary of the invention

[0005] The purpose of this section is to summarize some aspects of embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the specification abstract and the invention title of this application to avoid blurring the purpose of this section, the specification abstract and the invention title, and such simplifications or omissions cannot be used to limit the scope of the present invention.

[0006] In view of the above problems or problems existing in the prior art, the present invention is proposed.

[0007] One of the purposes of the present invention is to provide a 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compound. The 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compound prepared by the present invention contains multiple functional groups such as perfluoroalkyl and halogen, and can be further structurally modified and chemically converted into various compounds.

[0008] In order to solve the above technical problems, the present invention provides the following technical solution: a 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compound, whose structural formula is shown in formula (I):

[0009]

[0010] Among them, R 1 One selected from hydrogen, halogen, ester group, sulfonyloxy group, nitro group, cyano group, methoxy group and methyl group;

[0011] R 2 One selected from hydrogen, halogen, phenyl, methyl, methoxy, trifluoromethyl;

[0012] P is selected from the group consisting of p-toluenesulfonyl, benzenesulfonyl, p-methoxybenzenesulfonyl, p-bromobenzenesulfonyl and p-nitrobenzenesulfonyl;

[0013] n is selected from 1, 2, 3 or 4.

[0014] Another object of the present invention is to provide a method for synthesizing the 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compound as described above, wherein the method of the present invention uses inexpensive trifluoromethanesulfonic acid as a catalyst, does not require the use of a metal catalyst, and produces only water as the only byproduct, thereby achieving efficient synthesis of the 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compound. The method of the present invention has the advantages of readily available raw materials, mild conditions, high yield, wide substrate range, and atom economy.

[0015] The specific technical scheme is: using the compound represented by formula (II) as a raw material, reacting in a solvent under the catalysis of a catalyst to obtain the compound represented by formula (I);

[0016]

[0017] Among them, R in formula (II) 1 , R 2 , P, n and R in formula (I) 1 , R 2 , P, and n correspond to each other.

[0018] As a preferred embodiment of the method for synthesizing 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compounds of the present invention, the catalyst is selected from metal Lewis acids or Bronsted acids.

[0019] As a preferred embodiment of the synthesis method of the 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compound of the present invention, the metal Lewis acid comprises one of scandium trifluoromethanesulfonate, copper trifluoromethanesulfonate, aluminum trifluoromethanesulfonate, ferric chloride and indium tribromide.

[0020] As a preferred embodiment of the method for synthesizing 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compounds of the present invention, the Bronsted acid comprises one of p-toluenesulfonic acid and trifluoromethanesulfonic acid.

[0021] As a preferred embodiment of the method for synthesizing the 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compound of the present invention, the molar ratio of the catalyst to the compound represented by formula (II) is 0.1 to 0.3:1.

[0022] As a preferred embodiment of the method for synthesizing the 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compound of the present invention, the concentration of the compound represented by formula (II) in the solvent is 0.05 to 0.2 mol / L.

[0023] As a preferred embodiment of the method for synthesizing 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compounds of the present invention, the solvent comprises one of dichloroethane, toluene and hexafluoroisopropanol.

[0024] As a preferred embodiment of the method for synthesizing 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compounds of the present invention, the solvent is hexafluoroisopropanol.

[0025] As a preferred embodiment of the method for synthesizing 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compounds of the present invention, the reaction temperature is 5 to 60° C. and the reaction time is 0.5 to 48 hours.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] The method of the present invention uses cheap trifluoromethanesulfonic acid as a catalyst, does not require the use of a metal catalyst, and produces only water as the only byproduct, providing a new method for synthesizing 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compounds. The method of the present invention has the advantages of readily available raw materials, mild conditions, high yield, wide substrate range, and atom economy. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative labor. Among them:

[0029] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the target product 1a prepared in Example 1 of the present invention;

[0030] Figure 2 This is the carbon NMR spectrum of the target product 1a prepared in Example 1 of the present invention;

[0031] Figure 3 The NMR fluorine spectrum of the target product 1a prepared in Example 1 of the present invention;

[0032] Figure 4 This is the single crystal diffraction pattern of the target product 1b prepared in Example 2 of the present invention. DETAILED DESCRIPTION

[0033] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the embodiments of the specification.

[0034] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein, and those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0035] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The term "in one embodiment" that appears in different places in this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive with other embodiments.

[0036] The raw material benzenesulfonyl-protected perfluoroalkyl 3-indolemethanol compound used in the example was prepared according to the method reported in the literature (Tetrahedron, 2017, 73(16), 2283-2289; Journal of the American Chemical Society, 2002, 124(44): 13179-13184.).

[0037] Example 1

[0038] Take a 10 mL eggplant-shaped bottle, add p-toluenesulfonyl-protected trifluoromethyl 3-indolemethanol 2a (0.15 mmol) and trifluoromethanesulfonic acid (0.015 mmol) in sequence, add hexafluoroisopropanol (1.5 mL) under atmospheric atmosphere, react at room temperature for 1 h, monitor the reaction by TLC, after the reaction is completed, remove the solvent by rotary evaporation, and separate the crude product by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1 / 100-1 / 50, V / V) to obtain the target product 1a (63.5 mg, white solid, yield 99%).

[0039] The reaction equation is:

[0040]

[0041] The target product 1a was characterized by hydrogen nuclear magnetic resonance spectrum. Figure 1 As shown, the carbon NMR spectrum is Figure 2 As shown, the NMR fluorine spectrum is Figure 3 As shown:

[0042] 1 H NMR (600MHz, CDCl3) δ8.54(d,J=7.9Hz,1H),8.29(d,J=8.4Hz,1H),7.69(d,J=7.7Hz,1H),7.66(d,J=8.4Hz,1H),7.62(d,J=7.7Hz ,1H),7.54(t,J=7.7Hz,1H),7.39–7.34(m,2H),7.31(t,J=7.3Hz,1H),7.11(d,J=8.3Hz,2H),4.45(q,J=8.6Hz,1H),2.27(s,3H);

[0043] 13 C NMR (150MHz, CDCl3) δ145.1,144.6,141.1,140.8,134.8,134.8,129.8,129.5,126.8,126.6,125.9(q,J=2 78.9Hz),125.8,125.7,125.1,124.6,124.4(q,J=2.4Hz),122.5,119.8,115.6,45.9(q,J=30.9Hz),21.5;

[0044] 19 F NMR (565MHz, CDCl3) δ-67.18 (d, J = 8.6Hz, 3F).

[0045] Example 2

[0046] In a 10 mL eggplant-shaped bottle, benzenesulfonyl-protected trifluoromethyl 3-indolemethanol 2b (0.15 mmol) and trifluoromethanesulfonic acid (0.015 mmol) were added in sequence, and hexafluoroisopropanol (1.5 mL) was added under atmospheric atmosphere. The reaction was carried out at room temperature for 1 h and monitored by TLC. After the reaction, the solvent was removed by rotary evaporation. The crude product was separated by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1 / 100-1 / 50, V / V) to obtain the target product 1b (61.4 mg, white solid, yield 99%).

[0047] The reaction equation is:

[0048]

[0049] The target product 1b was characterized as follows:

[0050] 1 H NMR (600MHz, CDCl3) δ8.54(d,J=7.9Hz,1H),8.30(d,J=8.4Hz,1H),7.78(d,J=7.6Hz,2H),7.69(d,J=7.5Hz,1H),7.62(d,J=7 .7Hz,1H),7.55(t,J=7.7Hz,1H),7.45(t,J=7.5Hz,1H),7.37(t,J=7.7Hz,2H),7.32(t,J=7.8Hz,3H),4.46(q,J=8.6Hz,1H);

[0051] 13 C NMR (150MHz, CDCl3) δ144.6,141.0,140.8,137.6,134.7,133.9,129.5,129.2,126.8,126.5, 125.9(q,J=279.1Hz),125.8,125.8,125.2,124.7,122.4,119.9,115.6,45.9(q,J=30.7Hz);

[0052] 19 F NMR (565MHz, CDCl3) δ-67.16 (d, J = 8.7Hz, 3F).

[0053] The structure of compound 1b was confirmed by single crystal diffraction, as shown in Figure 4 shown.

[0054] Example 3

[0055] Take a 10 mL eggplant-shaped bottle, add p-nitrobenzenesulfonyl-protected trifluoromethyl 3-indolemethanol 2c (0.15 mmol) and trifluoromethanesulfonic acid (0.015 mmol) in sequence, add hexafluoroisopropanol (1.5 mL) under atmospheric atmosphere, react at room temperature for 4 h, monitor the reaction by TLC, after the reaction is completed, remove the solvent by rotary evaporation, and separate the crude product by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1 / 100-1 / 50, V / V) to obtain the target product 1c (53.1 mg, yellow solid, yield 85%).

[0056] The reaction equation is:

[0057]

[0058] The target product 1c was characterized as follows:

[0059] 1 H NMR (600MHz, CDCl3) δ8.46(d,J=7.9Hz,1H),8.25(d,J=8.4Hz,1H),8.14(d,J=8.9Hz,2H),7.90(d,J=8.9Hz,2H),7.70(d,J =7.5Hz,1H),7.61(d,J=7.7Hz,1H),7.55(t,J=7.7Hz,1H),7.39(t,J=7.8Hz,2H),7.37–7.32(m,1H),4.46(q,J=8.5Hz,1H);

[0060] 13 C NMR (150MHz, CDCl3) δ150.6,144.4,142.4,141.0,140.7,134.3,129.7,127.9,127.2,126.12,126.1(q, J=2.6Hz),126.0,125.8,125.7(q,J=279.3Hz),125.5,124.4,122.2,120.3,115.7,46.0(q,J=31.3Hz);

[0061] 19 F NMR (565MHz, CDCl3) δ-67.19 (d, J = 8.5Hz, 3F).

[0062] Example 4

[0063] In a 10 mL eggplant-shaped bottle, trifluoromethyl 3-indolemethanol 2d (0.15 mmol) and trifluoromethanesulfonic acid (0.015 mmol) were added in sequence, and hexafluoroisopropanol (1.5 mL) was added under atmospheric atmosphere. The reaction was reacted at room temperature for 2 h. The reaction was monitored by TLC. After the reaction was completed, the solvent was removed by rotary evaporation. The crude product was separated by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1 / 100 to 1 / 50, V / V) to obtain the target product 1d (69.0 mg, white solid, yield 98%).

[0064] The reaction equation is:

[0065]

[0066] The target product 1d was characterized as follows:

[0067] 1 H NMR (600MHz, CDCl3) δ8.52(d,J=7.9Hz,1H),8.20(dd,1H),7.65(d,J=7.5Hz,1H),7.62(d,J=8.4Hz,2H),7.53(t,J=7.7Hz,1H),7 .37(td,J=7.6,0.7Hz,1H),7.29–7.26(m,1H),7.23(t,J=8.1Hz,1H),7.10(d,J=8.2Hz,2H),4.71(q,J=7.4Hz,1H),2.27(s,3H);

[0068] 13 C NMR (150MHz, CDCl3) δ146.3,145.5,142.4,141.5,134.3,134.1,129.8,129.5,127.1,126.6,126.0,125.6 ,125.5,125.3,125.1(q,J=280.7Hz),124.9,123.4(q,J=1.8Hz),122.8,114.2,46.6(q,J=29.8Hz),21.5;

[0069] 19 F NMR (565MHz, CDCl3) δ-66.10 (d, J = 7.4Hz, 3F).

[0070] Example 5

[0071] Take a 10 mL eggplant-shaped bottle, add trifluoromethyl 3-indolemethanol 2e (0.15 mmol) and trifluoromethanesulfonic acid (0.015 mmol) in sequence, add hexafluoroisopropanol (1.5 mL) under atmospheric atmosphere, react for 2 h at room temperature, monitor the reaction by TLC, after the reaction is completed, remove the solvent by rotary evaporation, and separate the crude product by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1 / 100-1 / 20, V / V) to obtain the target product 1e (75.4 mg, white solid, yield 99%).

[0072] The reaction equation is:

[0073]

[0074] The target product 1e was characterized as follows:

[0075] 1 H NMR (600MHz, CDCl3) δ8.52(d,J=7.9Hz,1H),8.33–8.27(m,2H),8.03(d,J=8.1Hz,1H),7.69(d,J=7.5Hz,1H),7.66(d,J=8.3H z,2H),7.54(t,J=7.6Hz,1H),7.38(t,J=7.5Hz,1H),7.12(d,J=8.2Hz,2H),4.48(q,J=8.4Hz,1H),3.93(s,3H),2.27(s,3H);

[0076] 13 C NMR (150MHz, CDCl3) δ166.8,145.9,145.5,143.2,141.1,134.5,134.3,130.0,129.6,127.2,126.6,126.5 ,126.1,125.8,125.7(q,J=278.8Hz),125.5,124.2,122.6,121.7,115.2,52.2,45.9(q,J=30.6Hz),21.5;

[0077] 19 F NMR (565MHz, CDCl3) δ-67.14 (d, J = 8.5Hz, 3F).

[0078] Example 6

[0079] Take a 10 mL eggplant-shaped bottle, add trifluoromethyl 3-indolemethanol 2f (0.15 mmol) and trifluoromethanesulfonic acid (0.015 mmol) in sequence, add hexafluoroisopropanol (1.5 mL) under atmospheric atmosphere, react at room temperature for 5 h, monitor the reaction by TLC, after the reaction is completed, remove the solvent by rotary evaporation, and separate the crude product by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1 / 50 ~ 1 / 5, V / V) to obtain the target product 1f (107.7 mg, white solid, yield 90%).

[0080] The reaction equation is:

[0081]

[0082] The above target product 1f was characterized:

[0083] 1 H NMR (600MHz, CDCl3) δ8.50(d,J=7.9Hz,1H),8.17(d,J=9.1Hz,1H),7.68(d,J=8.3 Hz,2H),7.66(d,J=7.6Hz,1H),7.63(d,J=8.4Hz,2H),7.53(t,J=7.7Hz,1H),7.38 (t,J=7.6Hz,1H),7.28(d,J=8.1Hz,2H),7.15(d,J=8.3Hz,2H),7.10(d,J=1.9Hz, 1H),7.01(dd,J=9.1,2.4Hz,1H),4.36(q,J=8.5Hz,1H),2.44(s,3H),2.30(s,3H);

[0084] 13 C NMR (150MHz, CDCl3) δ146.6,146.1,145.5,145.5,141.0,138.8,134.6,134.3,132.0,130.0,129.7,129.6,128.5,127.3,1 26.6,126.2,125.8,125.5(q,J=250.5Hz),123.5(q,J=1.7Hz),122.7,119.4,116.4,113.4,45.8(q,J=30.1Hz),21.6,21.5;

[0085] 19 F NMR (565MHz, CDCl3) δ-67.29 (d, J = 8.4Hz, 3F).

[0086] Example 7

[0087] Take a 10 mL eggplant-shaped bottle, add 2 g (0.15 mmol) of trifluoromethyl 3-indole methanol and trifluoromethanesulfonic acid (0.045 mmol) in sequence, add hexafluoroisopropanol (1.5 mL) under atmospheric atmosphere, react at room temperature for 12 h, monitor the reaction by TLC, and after the reaction, remove the solvent by rotary evaporation. The crude product is separated by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1 / 50 to 1 / 25, V / V) to obtain 1 g (61.1 mg, white solid, yield 90%) of the target product.

[0088] The reaction equation is:

[0089]

[0090] The above target product 1g was characterized:

[0091] 1 H NMR (600MHz, CDCl3) δ8.53(d,J=7.9Hz,1H),8.36(d,J=8.8Hz,1H),7.92(s,1H),7.71(d,J=7.5Hz,1H),7.67(d,J =8.3Hz,2H),7.60–7.54(m,2H),7.42(t,J=7.5Hz,1H),7.17(d,J=8.2Hz,2H),4.49(q,J=8.4Hz,1H),2.31(s,3H);

[0092] 13 C NMR (150MHz, CDCl3) δ146.7,146.0,142.2,141.2,134.4,133.8,130.2,129.7,127.8,126.6,126. 0,125.7,124.7,124.6(q,J=1.0Hz),124.4,122.9,119.0,116.2,108.3,45.9(q,J=31.2Hz),21.6;

[0093] 19 F NMR (565MHz, CDCl3) δ-67.19 (d, J = 8.5Hz, 3F).

[0094] Example 8

[0095] Take a 10 mL eggplant-shaped bottle, add trifluoromethyl 3-indolemethanol 2h (0.15 mmol) and trifluoromethanesulfonic acid (0.015 mmol) in sequence, add hexafluoroisopropanol (1.5 mL) under atmospheric atmosphere, react at room temperature for 2.5 h, monitor the reaction by TLC, and after the reaction, remove the solvent by rotary evaporation. The crude product is separated by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1 / 100-1 / 30, V / V) to obtain the target product 1h (67.7 mg, white solid, yield 99%).

[0096] The reaction equation is:

[0097]

[0098] The above target product 1h was characterized:

[0099] 1 H NMR (600MHz, CDCl3) δ8.50(d,J=7.7Hz,1H),8.10(s,1H),7.66(d,J=7.4Hz,3H),7.52(t,J=7.5Hz,1H),7.49 (d,J=7.8Hz,1H),7.34(t,J=7.3Hz,1H),7.18–7.05(m,3H),4.42(q,J=8.2Hz,1H),2.52(s,3H),2.28(s,3H);

[0100] 13 C NMR (150MHz, CDCl3) δ145.0,143.9,141.3,140.9,135.4,135.0,134.9,129.8,129.4,126.5,126.4,126.0,1 25.9(q,J=278.7Hz),125.7,124.5(q,J=2.8Hz),123.5,122.2,119.4,115.7,45.9(q,J=31.0Hz),22.1,21.5;

[0101] 19 F NMR (565MHz, CDCl3) δ-67.21 (d, J = 8.7Hz, 3F).

[0102] Example 9

[0103] Take a 10 mL eggplant-shaped bottle, add trifluoromethyl 3-indolemethanol 2i (0.15 mmol) and trifluoromethanesulfonic acid (0.015 mmol) in sequence, add hexafluoroisopropanol (1.5 mL) under atmospheric atmosphere, react for 3 h at room temperature, monitor the reaction by TLC, after the reaction, remove the solvent by rotary evaporation, and separate the crude product by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1 / 100-1 / 50, V / V) to obtain the target product 1i (46.3 mg, light yellow solid, yield 70%).

[0104] The reaction equation is:

[0105]

[0106] The target product 1i was characterized as follows:

[0107] 1 H NMR (600MHz, CDCl3) δ8.26(d,J=7.8Hz,1H),7.59(d,J=7.5Hz,1H),7.51(t,J=7.6Hz,1H),7.32(t,J=7.5Hz,1H),7.28(d,J=7 .5Hz,1H),7.22(t,J=7.5Hz,1H),7.19–7.16(m,3H),6.92(d,J=8.2Hz,2H),4.26(q,J=8.7Hz,1H),2.79(s,3H),2.23(s,3H);

[0108] 13 C NMR (150MHz, CDCl3) δ149.3,144.7,143.3,140.3,136.2,132.4,130.5,129.6,129.5(q,J=2.7Hz),129.2,12 9.1,128.9,126.6,126.6,126.0,125.7(q,J=304.3Hz),125.4,122.9,117.4,46.1(q,J=30.9Hz),21.7,21.4;

[0109] 19 F NMR (565MHz, CDCl3) δ-66.95 (d, J = 8.8Hz, 3F).

[0110] Example 10

[0111] Take a 10 mL eggplant-shaped bottle, add trifluoromethyl 3-indolemethanol 2j (0.15 mmol) and trifluoromethanesulfonic acid (0.015 mmol) in sequence, add hexafluoroisopropanol (1.5 mL) under atmospheric atmosphere, react at room temperature for 5 h, monitor the reaction by TLC, after the reaction, remove the solvent by rotary evaporation, and separate the crude product by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1 / 100-1 / 30, V / V) to obtain the target product 1j (70.1 mg, white solid, yield 91%).

[0112] The reaction equation is:

[0113]

[0114] The target product 1j was characterized as follows:

[0115] 1 H NMR (600MHz, CDCl3) δ8.82(s,1H),8.29(d,J=8.3Hz,1H),7.75(t,J=8.1Hz,3H),7.68(d,J=8.4Hz,2H),7.63(d,J=7.7Hz,1H),7.61(dd,J=7.9,1.4Hz,1H ),7.52(t,J=7.7Hz,2H),7.42(t,J=7.4Hz,1H),7.37(t,J=7.3Hz,1H),7.33 (t,J=7.3Hz,1H),7.12(d,J=8.2Hz,2H),4.51(q,J=8.5Hz,1H),2.27(s,3H);

[0116] 13 C NMR (150MHz, CDCl3) δ145.2,144.4,142.6,140.9,140.8,140.0,135.5,134.8,129.9,128.9,127.7,127.4,1 26.6,125.9,125.8,125.6,125.2,125.0(q,J=2.0Hz),124.6,121.3,119.9,115.7,45.8(q,J=31.0Hz),21.5;

[0117] 19 F NMR (565MHz, CDCl3) δ-67.13 (d, J = 8.6Hz, 3F).

[0118] Embodiment 11

[0119] Take a 10 mL eggplant-shaped bottle, add trifluoromethyl 3-indolemethanol 2k (0.15 mmol) and trifluoromethanesulfonic acid (0.015 mmol) in sequence, add hexafluoroisopropanol (1.5 mL) under atmospheric atmosphere, react for 10 h at room temperature, monitor the reaction by TLC, and after the reaction, remove the solvent by rotary evaporation. The crude product is separated by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1 / 100-1 / 30, V / V) to obtain the target product 1k (49.8 mg, white solid, yield 67%).

[0120] The reaction equation is:

[0121]

[0122] The above target product 1k was characterized:

[0123] 1 H NMR (600MHz, CDCl3) δ8.78(s,1H),8.28(d,J=8.4Hz,1H),7.77(d,J=7.8Hz,1H),7.63(d,J=8.1Hz,4H), 7.40(t,J=7.8Hz,1H),7.34(t,J=7.5Hz,1H),7.14(d,J=8.2Hz,2H),4.52(q,J=8.4Hz,1H),2.29(s,3H);

[0124] 13 C NMR (150MHz, CDCl3) δ145.5,144.5,143.1,141.0,135.6,134.6,132.0(q,J=32.2Hz),130.0,126.6,125.9,125.8,125.6(q,J=2.3Hz),125.5 (q,J=279.5Hz),125.3,124.8,124.1(q,J=272.9Hz),123.7(dd,J=7.5,3.8Hz),120.1,119.3(q,J=3.9Hz),115.6,46.1(q,J=31.7Hz),21.5;

[0125] 19 F NMR (565MHz, CDCl3) δ-62.34 (s, 3F), -66.94 (d, J = 8.5Hz, 3F).

[0126] Example 12

[0127] Take a 10 mL eggplant-shaped bottle, add trifluoromethyl 3-indolemethanol 2l (0.15 mmol) and trifluoromethanesulfonic acid (0.015 mmol) in sequence, add hexafluoroisopropanol (1.5 mL) under atmospheric atmosphere, react at room temperature for 3.5 h, monitor the reaction by TLC, after the reaction is completed, remove the solvent by rotary evaporation, and separate the crude product by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1 / 100 ~ 1 / 30, V / V) to obtain the target product 1l (48.0 mg, white solid, yield 68%).

[0128] The reaction equation is:

[0129]

[0130] The target product 11 was characterized as follows:

[0131] 1 H NMR (600MHz, CDCl3) δ8.32(d,J=8.0Hz,1H),7.83(d,J=2.2Hz,1H),7.64(d,J=8.4Hz,2H),7.48–7.42(m,2H),7.30(d,J=8. 0Hz,1H),7.11(d,J=8.2Hz,2H),6.92(dd,J=8.6,2.3Hz,1H),4.35(q,J=8.7Hz,1H),3.91(s,3H),2.45(s,3H),2.27(s,3H);

[0132] 13 C NMR (150MHz, CDCl3) δ158.0,145.0,143.4,141.8,140.9,136.3,134.8,132.5,129.9,129.8,126.6,126.5,126. 0(q,J=279.2Hz),123.8(q,J=2.5Hz),121.5,120.1,119.9,113.2,100.4,55.8,45.7(q,J=30.9Hz),21.5,21.4;

[0133] 19 F NMR (565MHz, CDCl3) δ-67.29 (d, J = 8.7Hz, 3F).

[0134] Embodiment 13

[0135] Take a 10 mL eggplant-shaped bottle, add pentafluoroethyl 3-indolemethanol 2m (0.15 mmol) and trifluoromethanesulfonic acid (0.015 mmol) in sequence, add hexafluoroisopropanol (1.5 mL) under atmospheric atmosphere, react at room temperature for 0.5 h, monitor the reaction by TLC, and after the reaction, remove the solvent by rotary evaporation, and separate the crude product by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1 / 100-1 / 50, V / V) to obtain the target product 1m (71.0 mg, yellow solid, yield 99%).

[0136] The reaction equation is:

[0137]

[0138] The above target product 1m was characterized:

[0139] 1 H NMR (600MHz, CDCl3) δ8.55(d,J=7.9Hz,1H),8.29(d,J=8.4Hz,1H),7.67(d,J=7.1Hz,1H),7.59(d,J=8.2Hz,3H),7.53(t,J= 7.7Hz,1H),7.35(dd,J=13.2,6.9Hz,2H),7.31(t,J=7.4Hz,1H),7.07(d,J=8.2Hz,2H),4.49(t,J=10.8Hz,1H),2.26(s,3H);

[0140] 13 C NMR (150MHz, CDCl3) δ145.0, 144.4, 141.0, 140.7 (d, J = 9.7Hz), 134.6, 134.5, 129.6, 129.4, 126.6, 126.5, 126. 1,126.0(d,J=4.1Hz),125.2,124.8,124.7,122.5,119.8(d,J=6.1Hz),115.8,45.2(t,J=24.7Hz),21.4,carbon signals corresponding to theC2F5group cannot be identified due to CF coupling;

[0141] 19 F NMR (565MHz, CDCl3) δ-80.29–-80.45(m,3F),-105.04–-105.69(m,1F),-108.96–-109.56(m,1F).

[0142] Embodiment 14

[0143] Take a 10 mL eggplant-shaped bottle, add heptafluoropropyl 3-indolemethanol 2n (0.15 mmol) and trifluoromethanesulfonic acid (0.015 mmol) in sequence, add hexafluoroisopropanol (1.5 mL) under atmospheric atmosphere, react at room temperature for 2 h, monitor the reaction by TLC, and after the reaction, remove the solvent by rotary evaporation. The crude product is separated by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1 / 100 to 1 / 50, V / V) to obtain the target product 1n (71.5 mg, yellow solid, yield 90%).

[0144] The reaction equation is:

[0145]

[0146] The above target product 1n was characterized:

[0147] 1 H NMR (600MHz, CDCl3) δ8.54(d,J=7.9Hz,1H),8.30(d,J=8.4Hz,1H),7.67(d,J=7.4Hz,1H),7.57(d,J=8.3Hz ,3H),7.53(t,J=7.7Hz,1H),7.39–7.28(m,3H),7.06(d,J=8.3Hz,2H),4.50(t,J=11.5Hz,1H),2.24(s,3H);

[0148] 13 C NMR (150MHz, CDCl3) δ145.0,144.5,141.1,140.7(dd,J=9.4,1.6Hz),134.5,129.6,129.3,126.6,126.5,126.3,125.9(d,J=2 .8Hz),125.2,124.9(dd,J=10.7,1.7Hz),124.8,122.5,119.8(d,J=5.9Hz),116.0,46.1(t,J=25.0Hz),21.3,carbonsignals corresponding to the C3F7group cannot be identified due to C-Fcoupling;

[0149] 19F NMR(565MHz, CDCl3)δ-81.10(t,J=10.9Hz,3F),-101.40–-102.05(m,1F),-106.09–-106.71 (m,1F),-123.62(ddd,J=289.5,14.6,7.6Hz,1F),-124.88(ddd,J=289.7,14.8,5.3Hz,1F).

[0150] Embodiment 15

[0151] Take a 10 mL eggplant-shaped bottle, add nonafluorobutyl 3-indolemethanol 2o (0.15 mmol) and trifluoromethanesulfonic acid (0.015 mmol) in sequence, add hexafluoroisopropanol (1.5 mL) under atmospheric atmosphere, react at room temperature for 2 h, monitor the reaction by TLC, and after the reaction, remove the solvent by rotary evaporation. The crude product is separated by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1 / 100-1 / 80, V / V) to obtain the target product 1o (85.5 mg, yellow solid, yield 96%).

[0152] The reaction equation is:

[0153]

[0154] The target product 1o was characterized as follows:

[0155] 1 H NMR (600MHz, CDCl3) δ8.54(d,J=7.6Hz,1H),8.31(d,J=8.1Hz,1H),7.67(d,J=6.5Hz,1H),7.6 1–7.49(m,4H),7.40–7.28(m,3H),7.04(d,J=7.7Hz,2H),4.50(t,J=11.6Hz,1H),2.23(s,3H);

[0156] 13C NMR (150MHz, CDCl3) δ145.0, 144.5, 141.2, 140.7 (d, J = 8.8Hz), 134.5, 129.6, 129.3, 126.6, 126.5, 126.3, 125.9 (d ,J=3.3Hz),125.2,125.0(d,J=10.1Hz),124.8,122.5,119.8(d,J=6.1Hz),116.0,46.4(t,J=25.1Hz),21.3,carbon signalscorresponding to the C4F9group cannot be identified due to CF coupling;

[0157] 19 F NMR(565MHz, CDCl3)δ-81.02(t,J=9.0Hz,3F),-100.27–-101.07(m,1F),-105.58–-106.50(m,1F),-1 20.12–-120.76(m,1F),-121.01–-121.67(m,1F),-125.37–-126.05(m,1F),-126.60–-127.29(m,1F).

[0158] Example 16

[0159] In order to verify the potential industrial scale-up application of the present invention, the present invention also carried out a ten-gram scale-up experiment, and the specific steps are as follows.

[0160] Take a 250mL round-bottom flask, add trifluoromethyl 3-indolemethanol 2a (22.5mmol, 10.023g) and trifluoromethanesulfonic acid (2.25mmol) in sequence, add hexafluoroisopropanol (75mL) under atmospheric atmosphere, react at room temperature for 2h, monitor the reaction by TLC, after the reaction is completed, remove the solvent by rotary evaporation, and separate the crude product by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1 / 100 ~ 1 / 50, V / V) to obtain the target product 1a (9.487g, white solid, yield 98%).

[0161] The reaction equation is:

[0162]

[0163] It can be seen that when the raw material trifluoromethyl 3-indolemethanol 2a is enlarged to 22.5 mmol (10.023 g), when the trifluoromethanesulfonic acid catalyst loading is 10 mol%, the reaction can still obtain the expected product with a yield of 98%, which fully demonstrates that the present invention is suitable for industrial application.

[0164] Embodiment 17

[0165] The 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compounds prepared in Examples 1 to 16 can be used as intermediates and can be further structurally modified and chemically converted into various compounds. The following experiments were performed in this example:

[0166] In a 10 mL round-bottom flask, 10-trifluoromethyl-5,10-dihydroindeno[1,2-b]indole compound 1a (0.3 mmol) was dissolved in dry dichloroethane (3 mL) under atmospheric atmosphere, and then trifluoromethanesulfonic acid (2.1 mmol) was added to react at room temperature for 0.5 h (TLC tracking reaction until the reaction was complete). After the reaction was completed, 2 mL of saturated sodium bicarbonate was added to quench, and ethyl acetate was extracted twice. The organic phases were combined, washed with saturated sodium chloride aqueous solution, dried over anhydrous magnesium sulfate, filtered, and concentrated by rotary evaporation to remove the solvent. The crude product was separated by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1 / 100 to 1 / 30, V / V) to obtain the de-Ts product 3 (65.6 mg, white solid, yield 45%).

[0167] The above target product 3 was characterized:

[0168] 1 H NMR (600MHz, CDCl3) δ8.39(s,1H),7.74(dd,J=5.5,3.1Hz,1H),7.70(d,J=7.5Hz,1 H),7.44–7.38(m,3H),7.32–7.28(m,1H),7.27–7.23(m,2H),4.51(q,J=8.8Hz,1H);

[0169] 13 C NMR(150MHz, CDCl3)δ144.3,141.9(q,J=2.2Hz),140.5,135.2,128.7,126.6(q,J=278.4Hz),12 6.1,126.0,124.1,122.4,121.1,119.3,117.9,116.0(q,J=3.0Hz),112.2,46.5(q,J=30.9Hz);

[0170] 19 F NMR (565MHz, CDCl3) δ-67.73 (d, J=8.8Hz, 3F).

[0171] It can be seen that, taking the 10-trifluoromethyl-5,10-dihydroindeno[1,2-b]indole compound 1a prepared in Example 16 as an example, the p-toluenesulfonyl protecting group can be removed by trifluoromethanesulfonic acid catalysis to obtain product 3. The reaction equation is as follows:

[0172]

[0173] Embodiment 18

[0174] The 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compounds prepared in Examples 1 to 16 can be used as intermediates and can be further structurally modified and chemically converted into various compounds. The following experiments were performed in this example:

[0175] Take a 25 mL round-bottom flask, dissolve 10-trifluoromethyl-5,10-dihydroindeno[1,2-b]indole compound 1a (0.3 mmol) in methanol (10 mL) under atmospheric environment, add magnesium chips (6.0 mmol), react for 5 h under ultrasonic conditions (TLC tracking reaction until the reaction is complete), add dilute hydrochloric acid (0.5 M) dropwise after the reaction is completed to quench, extract twice with dichloromethane, combine the organic phases, wash with saturated sodium bicarbonate solution, dry the organic phase with anhydrous magnesium sulfate, filter, and concentrate by rotary evaporation to remove the solvent, and separate the crude product by silica gel column chromatography (eluent:

[0176] Ethyl acetate:petroleum ether=1 / 50~1 / 8, V / V) to give product 4 (103.6 mg, yellow solid, yield 80%).

[0177] The above target product 4 was characterized:

[0178] 1 H NMR (600MHz, CDCl3) δ8.53(d,J=7.8Hz,1H),8.31(d,J=8.0Hz,1H),7.97(d,J=7.7Hz,1H),7.92(d,J=7.5Hz,1H),7.63(d ,J=8.0Hz,2H),7.35(t,J=7.6Hz,1H),7.32–7.27(m,3H),7.05(d,J=8.1Hz,2H),4.02(s,3H),4.01(s,3H),2.24(s,3H);

[0179] 13C NMR (150MHz, CDCl3) δ159.6,144.4,141.4,139.3,138.7,135.0,130.0,129.6,126.6,125. 8,125.7,125.2,124.7,124.2,124.0,123.0,121.5,121.0,115.6,97.8,57.7,57.6,21.4.

[0180] It can be seen that, taking the 10-trifluoromethyl-5,10-dihydroindeno[1,2-b]indole compound 1a prepared in Example 16 as an example, the 10-trifluoromethyl-5,10-dihydroindeno[1,2-b]indole compound 1a can also be selectively defluoromethoxylated by magnesium chips and methanol under ultrasonic conditions to obtain product 4. The reaction equation is as follows:

[0181]

[0182] Embodiment 19

[0183] The 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compounds prepared in Examples 1 to 16 can be used as intermediates and can be further structurally modified and chemically converted into various compounds. The following experiments were performed in this example:

[0184] Take a 10 mL round-bottom flask, add 10-trifluoromethyl-5,10-dihydroindeno[1,2-b]indole compound 1a (0.3 mmol) and sodium hydroxide (2.1 mmol), add methanol (3 mL) under atmospheric atmosphere, react for 2.5 h under reflux conditions (trace the reaction by thin layer chromatography until the reaction is complete), add 2 mL of saturated ammonium chloride solution to quench the reaction, extract twice with dichloromethane, combine the organic phases, wash with saturated sodium chloride solution, dry the organic phase with anhydrous magnesium sulfate, filter, and concentrate by rotary evaporation to remove the solvent. The crude product is separated by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1 / 50 to 1 / 6, V / V) to obtain product 5 (80.0 mg, white solid, yield 96%).

[0185] The above target product 5 was characterized:

[0186] 1 H NMR(600MHz, CDCl3)δ8.64(s,1H),7.68–7.63(m,1H),7.54(d,J=7.3Hz,1H),7.37–7.34(m,1H),7.3 2–7.27(m,2H),7.23(td,J=7.3,1.2Hz,1H),7.18(dd,J=6.0,3.1Hz,2H),3.69(s,3H),3.12(s,3H);

[0187] 13 C NMR (150MHz, DMSO) δ166.4,143.2,140.8,136.1,130.1,125.0,122.1,120.0,119.3,117.1,116.1,114.0,114.0,113.0,108.4,74.7,47.8,47.7.

[0188] It can be seen that, taking the 10-trifluoromethyl-5,10-dihydroindeno[1,2-b]indole compound 1a prepared in Example 16 as an example, the 10-trifluoromethyl-5,10-dihydroindeno[1,2-b]indole compound 1a can also be catalyzed by sodium hydroxide and heated under reflux in a methanol solution to obtain the product 5. The reaction equation is as follows:

[0189]

[0190] Embodiment 20

[0191] Based on Example 1, the reaction conditions such as acid catalyst, solvent, and reaction time were optimized. The specific optimization results are shown in Table 1 below:

[0192] Table 1

[0193] Catalyst (10 mol%) Solvent (0.1M) Time (h) Yield (%) 1 <![CDATA[Sc(OTf)3]]> PhMe 24 - 2 <![CDATA[Sc(OTf)3]]> DCE 24 - 3 <![CDATA[Sc(OTf)3]]> HFIP 5 77 4 <![CDATA[Cu(OTf)2]]> HFIP 12 94 5 <![CDATA[Al(OTf)3]]> HFIP 15 91 6 <![CDATA[FeCl3]]> HFIP 48 87 7 <![CDATA[InBr3]]> HFIP 48 96 8 TxD HFIP 6 97 9 TxD HFIP 1 99 10 TxH DCE 24 17 11 TxD PhMe 24 10 12 TxD THF 24 NR 13 - HFIP 24 NR

[0194] From the data in Table 1, it can be seen that when Sc(OTf)3 (10 mol%) was used as a catalyst in toluene and 1,2-dichloroethane at room temperature, no reaction occurred. When hexafluoroisopropanol (HFIP) was used as a solvent, the expected product 1a was obtained with an isolated yield of 77%. Other metal Lewis acid catalysts, such as Cu(OTf)2, Al(OTf)3, FeCl3 and InBr3, can also obtain 1a with a yield of 87-96%. When the Bronsted acids p-toluenesulfonic acid (TsOH) and trifluoromethanesulfonic acid (TfOH) were used, the expected product 1a was obtained with excellent yields, among which trifluoromethanesulfonic acid (TfOH) had the best effect when used as a catalyst. Using trifluoromethanesulfonic acid (TfOH) as a catalyst, in other common solvents such as dichloroethane, toluene and tetrahydrofuran, the effect was extremely poor or even no reaction. The blank control test showed that no reaction occurred in the absence of a catalyst.

[0195] Embodiment 21

[0196] The antibacterial activity of the obtained compounds was determined by mycelium growth rate inhibition method. The test was conducted on Sclerotinia homoeocarpa and Botrytis cinerea.

[0197] Dollar spot pathogen (Sclerotinia homoeocarpa) can infect almost all cool-season and warm-season turfgrasses. It is also an important plant pathogen that causes the most serious economic losses to the turfgrass industry. Dollar spot pathogen is widely distributed worldwide. In recent years, more than 20 provinces and regions across the country have experienced varying degrees of dollar spot disease. It is a devastating disease on lawns. It can cause large-scale death of lawn grasses in a short period of time, forming bald spots, greatly damaging the lawn landscape. It can infect all parts of lawn grasses, causing bud rot, seedling rot, damping off, root rot, leaf rot, etc. Therefore, it is of great significance to effectively prevent and control this disease on grassland lawns.

[0198] Botrytis cinerea is a broad-host pathogen that can cause damping-off, leaf fall, flower rot, fruit rot and cellar rot in seedlings, fruits and storage organs of many plants. When it is humid, a large amount of gray mold is produced on the surface of the diseased part, which is called gray mold. It is widely distributed in the air and can not only infect field crops, but also cause huge losses to plants in the post-harvest stage.

[0199] The specific test method is: weigh different compounds and dissolve them in dimethyl sulfoxide (DMSO) and sonicate them to completely dissolve them to make a 10 mg / mL drug solution, filter them through a 0.22 μm sterile filter membrane, and add them to the sterilized PSA medium under sterile conditions to make a drug-containing medium with a concentration of 10 mg / L. Take a 5 mm diameter bacterial cake from the edge of the test colony after 6 days of culture, and inoculate it in the center of the PSA plate containing different drug solutions. Use a PSA plate without drug solution as a control, and set up three replicates for each treatment. The mycelium face is facing down and cultured at 25+2°C. After 72 hours, the colony diameter is determined by the cross-cross method, and the mycelium growth inhibition rate is calculated. Three replicates are set for each treatment. The calculation formula is as follows:

[0200]

[0201] The test results of the inhibition rate (10 ppm) / % of different compounds on plant pathogens Sclerotinia homoeocarpa (dollar spot pathogen) and Botrytis cinerea (gray mold pathogen) are shown in Table 2.

[0202] Table 2

[0203]

[0204] As can be seen from Table 2, the tested compounds 1a~1l and compounds 3 and 5 have the activity of inhibiting plant pathogenic fungi Pathogen Pathogen and Botrytis cinerea. Compounds 1e, 1g, 1h, 1i, 1k, 1l and 3 and 5 have a certain inhibitory effect on Pathogen Pathogen, and the effect is better than the positive control substance thiram. Among them, compounds containing cyano group (1g), trifluoromethyl group (1k) and methoxy group (1l) on the benzene ring have better activity, and compounds 3 and 5 with TS protecting group removed have the best activity, and the inhibitory effect on Pathogen Pathogen is stronger than the positive control substance (thiram), but slightly inferior to the positive control substance methyl thiophanate.

[0205] The inhibitory effects of compounds 1a-1l and compounds 3 and 5 on Botrytis cinerea were better than those of the positive control methylthiophanate, and the inhibitory effects of compounds containing trifluoromethyl (1k) and methoxy (1l) on the benzene ring were better than those of the positive control thiram. The inhibitory effects of compounds 3 and 5 with the TS protecting group removed on Botrytis cinerea were significantly improved, which were significantly better than those of the positive controls thiram and methylthiophanate.

[0206] The method of the present invention uses cheap trifluoromethanesulfonic acid as a catalyst, does not require the use of a metal catalyst, and only produces water as the only byproduct, thereby achieving efficient synthesis of 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compounds. The compounds obtained by the method of the present invention have the activity of inhibiting plant pathogenic fungi such as dollar spot fungus and gray mold fungus, and are of great significance for the effective prevention and control of such diseases in plants such as grassland lawns and field crops. The method of the present invention has the advantages of easy availability of raw materials, mild conditions, a wide range of substrates, high yield, and atom economy.

[0207] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.

Claims

1. Use of a 10-perfluoroalkyl-5,10-dihydroindeno[1,2-b]indole compound in inhibiting dollar spot fungus and gray mold, characterized in that: Its structural formula is shown in formula (I): The compound is selected from one of the following compounds:

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