Pyrrole-pentafluorobenzene compound as well as preparation method and application thereof

Abstract

The invention relates to the technical field of insecticides, in particular to a pyrrole-pentafluorobenzene compound as well as a preparation method and application thereof. The invention provides a pyrrole-pentafluorobenzene compound and a preparation method thereof. The pyrrole-pentafluorobenzene compound disclosed by the invention is novel in structure and has good insecticidal activity.

Description

Technical Field

[0001] This invention relates to the field of insecticide technology, and in particular to a pyrrole-pentafluorobenzene compound, its preparation method, and its application. Background Technology

[0002] Insecticides have long been used to manage pests. While they have proven beneficial in controlling pests and disease vectors, they also have a significant drawback: increasing concern about pest resistance. Repeated, long-term use of the same insecticide to control specific pest populations often leads to resistance. Studies have shown that nearly 100 mosquito species have developed resistance to at least one insecticide, further exacerbating this problem. Therefore, designing novel insecticides is crucial for addressing insecticide resistance in pests. Summary of the Invention

[0003] In view of this, the purpose of the present invention is to provide a pyrrole-pentafluorobenzene compound, its preparation method and application, wherein the pyrrole-pentafluorobenzene compound has a novel structure and good insecticidal activity.

[0004] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a pyrrole-pentafluorobenzene compound having the structure shown in Formula 1: Formula 1; In Equation 1, R is , , , , , , , , , , , , , , , , , , , , , , , , , , , , or .

[0005] This invention also provides a method for preparing the pyrrole-pentafluorobenzene compounds described in the above technical solution, comprising the following steps: A compound having the structure shown in Formula a, thionyl chloride, and a first organic solvent were mixed and subjected to an esterification reaction. Methanol was then added to continue the reaction, yielding a compound having the structure shown in Formula b. The compound having the structure shown in formula b, the compound having the structure shown in formula c, aluminum chloride, and a second organic solvent are mixed and subjected to a Friedel-Crafts reaction to obtain the compound having the structure shown in formula d. The compound having the structure shown in formula d, sodium borohydride, and a third organic solvent are mixed and a reduction reaction is carried out to obtain the compound having the structure shown in formula e. The compound having the structure shown in formula e, mercaptoethanol, zinc chloride, and a fourth organic solvent are mixed and subjected to a condensation reaction to obtain a compound having the structure shown in formula f. The compound having the structure shown in formula f, the compound having the structure shown in formula g, 4-dimethylaminopyridine, and a fifth organic solvent were mixed and subjected to an acylation reaction to obtain the pyrrole-pentafluorobenzene compound. Formula a Formula b Formula c Formula d, Formula e Formula f or Formula g; In formula g, R is the same as R in the pyrrole-pentafluorobenzene compound.

[0006] Preferably, the molar ratio of the compound having the structure shown in Formula a to sulfoxide dichloride is 1:(2.5~3.5). The ratio of the compound having the structure shown in Formula a to the first organic solvent is 1 mmol: (15~25) mL; The first organic solvent includes one or more of dichloromethane, THF, and chloroform; The esterification reaction was carried out at room temperature for 2.5 to 3.5 hours. The molar amount of the compound having the structure shown in Formula a and the volume ratio of methanol are 1 mmol: (8~10) mL, and the reaction continues for 10 min.

[0007] Preferably, the molar ratio of the compound having the structure shown in formula b to the compound having the structure shown in formula c is 1:(2.5~3.5). The molar ratio of the compound with the structure shown in formula b to aluminum chloride is 1:(2.5~3.5). The ratio of the compound having the structure shown in formula b to the second organic solvent is 1 mmol: (15~25) mL; The second organic solvent includes one or more of dichloromethane, chloroform, and nitrobenzene; The Friedel-Crafts reaction was carried out at a temperature of 20-25°C for 2.5-3.5 hours.

[0008] Preferably, the molar ratio of the compound having the structure shown in formula d to sodium borohydride is 1:(8~12). The ratio of the compound with the structure shown in formula d to the third organic solvent is 1 mmol: (15~25) mL; The third organic solvent includes one or more of tetrahydrofuran, methanol, and water; The reduction reaction is carried out at a temperature of 15~25℃ for 3.5~4.5h.

[0009] Preferably, the molar ratio of the compound having the structure shown in formula e to mercaptoethanol is 1:(8~12); The molar ratio of the compound with the structure shown in Formula e to zinc chloride is 1:(8~12). The ratio of the compound having the structure shown in formula e to the fourth organic solvent is 1 mmol: (15~25) mL; The fourth organic solvent includes chloroform; The condensation reaction was carried out at room temperature for 10-15 hours.

[0010] Preferably, the molar ratio of the compound having the structure shown in formula f to the compound having the structure shown in formula g is 1:(1.1~1.3). The molar ratio of the compound having the structure shown in formula f to 4-dimethylaminopyridine is 1:(0.05~0.15). The ratio of the compound with the structure shown in formula f to the fifth organic solvent is 1 mmol: (8~12) mL; The fifth organic solvent includes one or more of dichloromethane, chloroform, and THF; The acylation reaction is carried out at a temperature of 15~25℃ for 2.5~3.5h.

[0011] The present invention also provides the application of the pyrrole-pentafluorobenzene compounds described in the above technical solutions or the pyrrole-pentafluorobenzene compounds prepared by the preparation methods described in the above technical solutions in the preparation of insecticides.

[0012] Preferably, the insecticide is a mosquito repellent.

[0013] Preferably, the concentration of pyrrole-pentafluorobenzene compounds in the insecticide is 2.5~20 mg / L.

[0014] This invention provides a pyrrole-pentafluorobenzene compound. The pyrrole-pentafluorobenzene compound has a novel structure, completely different from commercially available insecticides, and possesses a pentafluorobenzene and thioether structure. This type of structure exhibits good biological activity, thus demonstrating excellent mosquito-killing activity. Detailed Implementation

[0015] This invention provides a pyrrole-pentafluorobenzene compound having the structure shown in Formula 1: Formula 1; In Equation 1, R is , , , , , , , , , , , , , , , , , , , , , , , , , , , , or .

[0016] This invention also provides a method for preparing the pyrrole-pentafluorobenzene compounds described in the above technical solution, comprising the following steps: A compound having the structure shown in Formula a, a first methanol, thionyl chloride and a first organic solvent are mixed and subjected to an esterification reaction. Then, a second methanol is added and the reaction continues to yield a compound having the structure shown in Formula b. The compound having the structure shown in formula b, the compound having the structure shown in formula c, aluminum chloride, and a second organic solvent are mixed and subjected to a Friedel-Crafts reaction to obtain the compound having the structure shown in formula d. The compound having the structure shown in formula d, sodium borohydride, and a third organic solvent are mixed and a reduction reaction is carried out to obtain the compound having the structure shown in formula e. The compound having the structure shown in formula e, mercaptoethanol, zinc chloride, and a fourth organic solvent are mixed and subjected to a condensation reaction to obtain a compound having the structure shown in formula f. The compound having the structure shown in formula f, the compound having the structure shown in formula g, 4-dimethylaminopyridine, and a fifth organic solvent were mixed and subjected to an acylation reaction to obtain the pyrrole-pentafluorobenzene compound. Formula a Formula b Formula c Formula d, Formula e Formula f or Formula g; In formula g, R is the same as R in the pyrrole-pentafluorobenzene compound.

[0017] In this invention, unless otherwise specified, all raw materials used in the preparation are commercially available products well known to those skilled in the art.

[0018] In this invention, the preparation process of the pyrrole-pentafluorobenzene compound is shown in Formula I: Formula I.

[0019] The present invention involves mixing a compound having the structure shown in formula a, a first methanol, thionyl chloride and a first organic solvent, performing an esterification reaction, and then adding a second methanol to continue the reaction to obtain a compound having the structure shown in formula b.

[0020] In this invention, the molar ratio of the compound having the structure shown in Formula a to sulfoxide is preferably 1:(2.5~3.5), more preferably 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3.0, 1:3.1, 1:3.2, 1:3.3, 1:3.4 or 1:3.5. In an embodiment of this invention, the molar ratio of the compound having the structure shown in Formula a to sulfoxide can be 1:3.

[0021] In this invention, the preferred ratio of the compound having the structure shown in Formula a to the first organic solvent is 1 mmol:(15~25) mL, more preferably 1 mmol:15 mL, 1 mmol:20 mL, or 1 mmol:25 mL. In an embodiment of this invention, the ratio of the compound having the structure shown in Formula a to the first organic solvent can be 1 mmol:20 mL.

[0022] In this invention, the first organic solvent preferably includes one or more of dichloromethane, chloroform, and THF. When the first organic solvent is two or more of the above-mentioned specific selections, this invention does not impose any special limitation on the ratio of the above-mentioned specific substances, and they can be mixed in any ratio. In an embodiment of this invention, the first organic solvent may be dichloromethane.

[0023] In this invention, the mixing preferably includes dissolving the compound having the structure shown in formula a in a first organic solvent under ice bath conditions, followed by the addition of thionyl chloride; the addition of thionyl chloride is preferably done dropwise.

[0024] In this invention, the esterification reaction is preferably carried out at room temperature for 2.5 to 3.5 hours, more preferably 2.5 hours, 3 hours, or 3.5 hours. In embodiments of this invention, the esterification reaction can be carried out at room temperature for 3 hours. In this invention, room temperature can be understood as neither additional heating nor additional cooling is required.

[0025] In this invention, the molar ratio of the compound having the structure shown in Formula a to methanol is preferably 1 mmol:(8~10) mL, more preferably 1 mmol:8 mL, 1 mmol:9 mL, or 1 mmol:10 mL. In an embodiment of this invention, the molar ratio of the compound having the structure shown in Formula a to methanol can be 1 mmol:10 mL.

[0026] In this invention, the reaction time is preferably 10 minutes.

[0027] After the esterification reaction is completed, the present invention preferably includes vacuum rotary evaporation. The present invention does not have any special limitations on the vacuum rotary evaporation process, and any process known to those skilled in the art can be used.

[0028] After obtaining the compound with the structure shown in formula b, the present invention mixes the compound with the structure shown in formula b, the compound with the structure shown in formula c, aluminum chloride, and a second organic solvent, and performs a Friedel-Crafts reaction to obtain the compound with the structure shown in formula d.

[0029] In this invention, the molar ratio of the compound having the structure shown in formula b to the compound having the structure shown in formula c is preferably 1:(2.5~3.5), more preferably 1:2.5, 1:3 or 1:3.5. In an embodiment of this invention, the molar ratio of the compound having the structure shown in formula b to the compound having the structure shown in formula c can be 1:3.

[0030] In this invention, the molar ratio of the compound having the structure shown in Formula b to aluminum chloride is preferably 1 (2.5~3.5), more preferably 1:2.5, 1:3 or 1:3.5. In an embodiment of this invention, the molar ratio of the compound having the structure shown in Formula b to aluminum chloride can be 1:3.

[0031] In this invention, the preferred ratio of the compound having the structure shown in formula b to the second organic solvent is 1 mmol:(15~25) mL, more preferably 1 mmol:15 mL, 1 mmol:20 mL, or 1 mmol:25 mL. In an embodiment of this invention, the ratio of the compound having the structure shown in formula b to the second organic solvent can be 1 mmol:20 mL.

[0032] In this invention, the second organic solvent preferably includes one or more of dichloromethane, chloroform, and nitrobenzene. When the second organic solvent is two or more of the above-mentioned specific selections, this invention does not impose any special limitation on the ratio of the above-mentioned specific substances, and they can be mixed in any ratio. In an embodiment of this invention, the second organic solvent can be dichloromethane.

[0033] In this invention, the mixing is preferably performed by mixing a compound having the structure shown in formula b, aluminum chloride, and dichloromethane, and then adding a compound having the structure shown in formula c under ice bath conditions.

[0034] In this invention, the Friedel-Crafts reaction temperature is preferably 20-25°C (room temperature), and the reaction time is preferably 2.5-3.5 h, more preferably 2.5 h, 3 h, or 3.5 h. In embodiments of this invention, the Friedel-Crafts reaction temperature can be room temperature, and the reaction time can be 3 h. In this invention, room temperature can be understood as neither additional heating nor additional cooling is required.

[0035] After the Friedel-Crafts reaction is completed, the present invention preferably includes purification, and the purification method is preferably column chromatography, wherein the eluent used in the column chromatography is preferably petroleum ether and ethyl acetate in a volume ratio of 5:1.

[0036] After obtaining the compound with the structure shown in formula d, the present invention mixes the compound with the structure shown in formula d, sodium borohydride, and a third organic solvent to carry out a reduction reaction to obtain the compound with the structure shown in formula e.

[0037] In this invention, the molar ratio of the compound having the structure shown in formula d to sodium borohydride is preferably 1:(8~12), more preferably 1:8, 1:9, 1:10, 1:11 or 1:12. In an embodiment of this invention, the molar ratio of the compound having the structure shown in formula d to sodium borohydride can be 1:10.

[0038] In this invention, the preferred ratio of the compound having the structure shown in formula d to the third organic solvent is 1 mmol:(15~25) mL, more preferably 1 mmol:15 mL, 1 mmol:20 mL, or 1 mmol:25 mL. In an embodiment of this invention, the ratio of the compound having the structure shown in formula d to the third organic solvent can be 1 mmol:20 mL.

[0039] In this invention, the third organic solvent preferably includes one or more of tetrahydrofuran, methanol, and water. When the third organic solvent is two or more of the above-mentioned specific selections, this invention does not impose any special limitation on the ratio of the above-mentioned specific substances, and they can be mixed in any ratio.

[0040] In this invention, the mixing preferably includes mixing the compound having the structure shown in formula d with a third organic solvent, and then adding the sodium borohydride.

[0041] In this invention, the temperature of the reduction reaction is preferably 15~25℃ (room temperature), and the time is preferably 3.5~4.5h, more preferably 3.5h, 4h, or 4h. In an embodiment of this invention, the temperature of the reduction reaction can be room temperature, and the time can be 4h.

[0042] After the reduction reaction is completed, the present invention preferably includes purification, and the purification method is preferably column chromatography, wherein the eluent used in the column chromatography is preferably petroleum ether and ethyl acetate in a volume ratio of 5:1.

[0043] After obtaining the compound with the structure shown in formula e, the present invention mixes the compound with the structure shown in formula e, mercaptoethanol, zinc chloride and a fourth organic solvent, and performs a condensation reaction to obtain the compound with the structure shown in formula f.

[0044] In this invention, the molar ratio of the compound having the structure shown in Formula e to mercaptoethanol is preferably 1:(8~12), more preferably 1:8, 1:9, 1:10, 1:11 or 1:12. In an embodiment of this invention, the molar ratio of the compound having the structure shown in Formula e to mercaptoethanol can be 1:10.

[0045] In this invention, the molar ratio of the compound having the structure shown in Formula e to zinc chloride is preferably 1:(8~12), more preferably 1:8, 1:9, 1:10, 1:11 or 1:12. In an embodiment of this invention, the molar ratio of the compound having the structure shown in Formula e to zinc chloride can be 1:10.

[0046] In this invention, the preferred ratio of the compound having the structure shown in Formula e to the fourth organic solvent is 1 mmol:(15~25) mL, more preferably 1 mmol:15 mL, 1 mmol:20 mL, or 1 mmol:25 mL. In an embodiment of this invention, the ratio of the compound having the structure shown in Formula e to the fourth organic solvent can be 1 mmol:20 mL.

[0047] In this invention, the fourth organic solvent preferably includes chloroform.

[0048] In this invention, the mixing preferably includes mixing the compound having the structure shown in formula e with a fourth organic solvent, and then adding mercaptoethanol and zinc chloride.

[0049] In this invention, the condensation reaction temperature is preferably 15~25℃ (room temperature), and the time is preferably 10~15h, more preferably 10h, 11h, 12h, 13h, 14h or 15h. In embodiments of this invention, the condensation reaction temperature can be room temperature, and the time can be 12h. In this invention, room temperature can be understood as neither additional heating nor additional cooling is performed.

[0050] After the condensation reaction is completed, the present invention preferably includes purification, and the purification method is preferably column chromatography, wherein the eluent used in the column chromatography is preferably petroleum ether and ethyl acetate in a volume ratio of 6:1.

[0051] After obtaining the compound having the structure shown in formula f, the present invention mixes the compound having the structure shown in formula f, the compound having the structure shown in formula g, 4-dimethylaminopyridine and a fifth organic solvent, and performs an acylation reaction to obtain the pyrrole-pentafluorobenzene compound.

[0052] In this invention, the molar ratio of the compound having the structure shown in formula f to the compound having the structure shown in formula g is preferably 1:(1.1~1.3), more preferably 1:1.1, 1:1.2 or 1:1.3. In an embodiment of this invention, the molar ratio of the compound having the structure shown in formula f to the compound having the structure shown in formula g is specifically 1:1.2.

[0053] In this invention, the molar ratio of the compound having the structure shown in formula f to 4-dimethylaminopyridine is preferably 1:(0.05~0.15), more preferably 1:0.05, 1:0.1 or 1:0.15. In an embodiment of this invention, the molar ratio of the compound having the structure shown in formula f to 4-dimethylaminopyridine can be 1:0.1.

[0054] In this invention, the preferred ratio of the compound having the structure shown in formula f to the fifth organic solvent is 1 mmol: (8~12) mL, more preferably 1 mmol: 8 mL, 1 mmol: 9 mL, 1 mmol: 10 mL, 1 mmol: 11 mL, or 1 mmol: 12 mL. In an embodiment of this invention, the specific ratio of the compound having the structure shown in formula f to the fifth organic solvent is 1 mmol: 10 mL.

[0055] In this invention, the fifth organic solvent preferably includes one or more of dichloromethane, chloroform, and THF. When the fifth organic solvent is two or more of the above-mentioned specific selections, this invention does not impose any special limitation on the ratio of the above-mentioned specific substances, and they can be mixed in any ratio. In an embodiment of this invention, the fifth organic solvent can be dichloromethane.

[0056] In this invention, the temperature of the acylation reaction is preferably 15~25°C, more preferably 15°C, 20°C or 25°C, and the time is preferably 2.5~3.5h, more preferably 2.5h, 3h or 3.5h. In an embodiment of this invention, the temperature of the acylation reaction can be 20°C and the time can be 3h.

[0057] After the acylation reaction is completed, the present invention preferably includes purification, and the purification method is preferably column chromatography. The eluent used in the column chromatography is preferably petroleum ether and ethyl acetate in a volume ratio of 10:1 to 6:1.

[0058] The present invention also provides the application of the pyrrole-pentafluorobenzene compounds described in the above technical solutions or the pyrrole-pentafluorobenzene compounds prepared by the preparation methods described in the above technical solutions in the preparation of insecticides.

[0059] In this invention, the insecticide is preferably a mosquito repellent.

[0060] In this invention, the concentration of pyrrole-pentafluorobenzene compounds in the insecticide is preferably 2.5~20 mg / L, more preferably 2.5 mg / L, 5 mg / L, 10 mg / L or 20 mg / L.

[0061] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0062] Example 1 In a 100 mL round-bottom flask, under ice bath conditions, 1 mmol of the compound with the structure shown in formula a was dissolved in 20 mL of dichloromethane, and 3 mmol of dichlorosulfoxide was added dropwise. After reacting at room temperature for 3 h, 10 mL of methanol was added, and after reacting for 10 min, the mixture was evaporated under reduced pressure to obtain the compound with the structure shown in formula b (yield of 85%). In a 100 mL round-bottom flask, 1 mmol of the compound with the structure shown in formula b and 3 mmol of aluminum chloride were dissolved in 20 mL of dichloromethane. 3 mmol of the compound with the structure shown in formula c was added under ice bath conditions. After reacting at room temperature for 3 h, the mixture was purified by column chromatography using petroleum ether and ethyl acetate in a volume ratio of 5:1 to obtain the compound with the structure shown in formula d (brown crystals, yield 79%). In a 100 mL round-bottom flask, 1 mmol of the compound having the structure shown in formula d was dissolved in 20 mL of tetrahydrofuran, and 10 mmol of sodium borohydride was added. After reacting at 20 °C for 4 h, the compound was purified by column chromatography using petroleum ether and ethyl acetate in a volume ratio of 5:1 as eluents to obtain the compound having the structure shown in formula e (white crystals, yield 94%). In a 100 mL round-bottom flask, 1 mmol of the compound with the structure shown in formula e was dissolved in 20 mL of chloroform, and 10 mmol of mercaptoethanol and 10 mmol of zinc chloride were added. After reacting at room temperature for 12 h, the compound was purified by column chromatography using petroleum ether and ethyl acetate in a volume ratio of 6:1 as eluents to obtain the compound with the structure shown in formula f (yellow liquid, yield 88%). In a 500 mL round-bottom flask, 1 mmol of the compound having the structure shown in formula f was dissolved in 10 mL of dichloromethane, and 1.2 mmol of [unspecified ingredient] was added. (R is) ) and 0.1 mmol of 4-dimethylaminopyridine, reacted at 20 °C for 3 h, and then purified by column chromatography using petroleum ether and ethyl acetate in a volume ratio of 10:1 → 6:1 as eluents to obtain pyrrole-pentafluorobenzene compounds ( ); The pyrrole-pentafluorobenzene compounds were analyzed by 1D / 2D NMR (one-dimensional and two-dimensional NMR spectroscopy) combined with HRMS. The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: 1H NMR (400 MHz, CDCl3) δ 9.12 (s, 1H), 7.82 (dd, J = 8.2, 1.5 Hz, 1H), 7.39-7.31 (m, 1H), 7.19-7.16 (m, 2H), 6.98-6.90 (m, 1H), 6.83-6.75 (m, 1H), 5.42 (s, 1H), 4.37 (t, J = 1.3 Hz, 2H), 3.75 (s, 3H), 2.83 (t, J = 6.6 Hz, 2H). 2.51 (s, 3H).19FNMR (376 MHz, CDCl3) δ-140.47, -155.23, -161.18. HR-MS (m / z) calcd forC 23 H 18 F5NO4S [M-Na] + : 499.09; found: 522.0769.

[0063] Example 2 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.31 (s, 1H), 7.56 (s, 2H), 7.12 (s, 1H), 6.97–6.91 (m, 1H), 6.80–6.75 (m, 1H), 5.44 (s, 1H), 4.38 (t, J = 6.6 Hz, 2H), 3.74 (s, 3H), 2.82 (t, J = 6.7 Hz, 2H), 2.28 (s, 6H). ¹⁹F NMR (376 MHz, CDCl₃) δ -140.42, -155.23, -161.28. HR-MS (m / z) calcd for C 24 H 20 F5NO4S [M-Na] + : 513.10; found: 536.0925.

[0064] Example 3 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.09 (s, 1H), 7.16 (d, J=2.4 Hz, 2H), 7.03 (t, J=2.3 Hz, 1H), 6.88-6.78 (m, 1H), 6.71-6.62 (m, 1H), 5.50 (s, 1H), 4.46 (t, J= 6.8 Hz, 2H), 3.83 (s, 9H), 2.90 (t, J= 6.7 Hz, 2H). ¹³C NMR (101 MHz, CDCl₃) δ 166.04, 166.02, 161.16, 160.68, 131.63, 123.10, 122.96, 121.61, 114.37, 107.25, 105.87, 77.33, 63.49, 55.58,51.62, 36.09, 31.44.HR-MS (m / z) calcd for C 24 H 20 F5NO6S [M-Na] + : 545.09; found:568.0824.

[0065] Example 4 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.57 (s, ¹H), 8.88 (d, J = 8.6 Hz, ¹H), 8.17 (d, J = 7.2 Hz, ¹H), 8.02 (d, J = 8.2 Hz, ¹H), 7.88 (d, J = 8.1 Hz, ¹H), 7.59–7.46 (m, 3H), 6.77–6.72 (m, 1H), 6.58–6.50 (m, ¹H), 5.44 (s, 1H), 4.53 (t, J = 6.6 Hz, 2H), 3.54 (s, 3H), 2.92 (t, J = 6.6 Hz, 2H). ¹⁹F NMR (376 MHz, CDCl3)δ-140.36, -155.28, -161.31.HR-MS (m / z) calcd forC 26 H 18 F5NO4S [M-Na] + : 535.09; found: 558.0769.

[0066] Example 5 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.23 (s, ¹H), 7.54 (dt, J=7.7, 1.2 Hz, ¹H), 7.46 (dd, J=2.7, 1.5 Hz, ¹H), 7.27 (t, J=7.9 Hz, ¹H), 7.03 (ddd, J=8.3, 2.7, 1.0 Hz, ¹H), 6.98–6.92 (m, ¹H), 6.81–6.75 (m, ¹H), 5.43 (s, ¹H), 4.39 (t, J=6.7 Hz, 2H), 3.76 (d, J=6.4 Hz, 6H), 2.84 (t, J=6.7 Hz, 2H). 2H).13C NMR (101 MHz, CDCl3)δ165.14, 165.12, 160.26, 160.24,158.57, 158.56, 130.05, 130.03, 128.43, 128.42, 122.02, 122.01, 121.01,121.00, 120.70, 118.64, 118.62, 113.39, 113.10, 62.40, 62.39, 54.41, 54.41,50.60, 50.59, 35.07, 35.05, 30.44, -0.00.HR-MS (m / z) calcd for: C 23 H 18 F5NO5S[M-Na] + : 515.45; found: 538.0718.

[0067] Example 6 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.20 (s, ¹H), 8.01–7.94 (m, 2H), 7.68–7.61 (m, 2H), 6.98–6.93 (m, ¹H), 6.81–6.76 (m, ¹H), 5.42 (s, ¹H), 4.41 (t, J = 6.6 Hz, 2H), 3.76 (s, 3H), 2.84 (t, J = 6.6 Hz, 2H). ¹³C NMR (101 MHz, CDCl₃) δ 165.25, 161.25, 135.55, 131.79, 130.27, 122.82, 121.67. 114.39, 76.71, 63.64, 51.65, 36.08, 31.40.HR-MS (m / z) calcdfor : C 23 H 15 F8NO4S2[M-Na] + : 585.48; found: 608.0207.

[0068] Example 7 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.12 (s, ¹H), 8.35 (t, J=1.7 Hz, ¹H), 7.98 (dt, J=7.9, 1.4 Hz, ¹H), 7.90 (dt, J=7.9, 1.1 Hz, ¹H), 7.19 (t, J=7.8 Hz, ¹H), 7.06–7.00 (m, ¹H), 6.89–6.78 (m, ¹H), 5.49 (s, ¹H), 4.47 (t, J =1.3 Hz, 2H), 3.83 (s, 3H), 2.90 (t, J = 6.7 Hz, 2H). ¹³C NMR (101 MHz, CDCl₃) δ164.79, 161.17, 142.02, 138.50, 131.66, 130.12,128.83, 122.90, 121.60, 114.38, 93.80, 63.64, 51.65, 36.05, 31.36.HR-MS (m / z)calcd for : C 22 H 15 F5INO4S [M-Na] + : 611.32; found: 633.9579.

[0069] Example 8 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.16 (s, ¹H), 7.85–7.78 (m, ¹H), 7.69 (dt, J = 9.2, 2.0 Hz, ¹H), 7.42 (td, J = 8.0, 5.5 Hz, ¹H), 7.26 (s, ¹H), 7.06–7.00 (m, ¹H), 6.88–6.84 (m, ¹H), 5.49 (s, ¹H), 4.47 (t, J = 6.7 Hz, 2H), 3.83 (s, 3H), 2.92 (t, J = 6.7 Hz, 2H). ¹³C NMR (101 MHz, CDCl₃) δ 165.16, 163.77, 161.19, 131.96, 130.13, 125.38, 122.90, 121.61,120.39, 116.44, 114.38, 63.58, 51.64, 36.07, 31.41.HR-MS (m / z) calcd for :C 22 H 15 F6NO4S [M-Na] + : 503.42; found: 526.0518.

[0070] Example 9 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.39 (s, ¹H), 7.97–7.90 (m, ¹H), 7.74–7.61 (m, 3H), 7.07–7.02 (m, ¹H), 6.88–6.82 (m, ¹H), 5.46 (s, ¹H), 4.46 (t, J = 6.8 Hz, 2H), 3.84 (s, 3H), 2.87 (t, J = 6.8 Hz, 2H). 13C NMR (101 MHz, CDCl3)δ165.21, 161.33, 148.02, 133.06, 131.88,129.51, 127.42, 124.01, 123.04, 122.78, 121.88, 114.40, 64.55, 51.64, 36.07,30.87.HR-MS (m / z) calcd for : C 22 H 15 F5INO4S [M-Na] + : 611.32; found: 633.9579.

[0071] Example 10 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.35 (s, ¹H), 7.99 (dd, J = 8.0, 1.2 Hz, ¹H), 7.78 (dd, J = 7.8, 1.7 Hz, ¹H), 7.40 (td, J = 7.6, 1.2 Hz, ¹H), 7.16 (td, J = 7.7, 1.7 Hz, ¹H), 7.07–7.01 (m, ¹H), 6.89–6.83 (m, ¹H), 5.50 (s, ¹H), 4.48 (t, J = 1.9 Hz, 2H), 3.83 (s, 3H), 2.93 (t, J = 6.7 Hz, 2.93). 2H).13C NMR (101 MHz, CDCl3)δ166.17, 161.32, 141.37, 132.84,131.00, 127.95, 123.04, 121.83, 116.33, 114.46, 94.11, 63.84, 51.65, 36.08,31.32.HR-MS (m / z) calcd for : C 22 H 15 F5N2O6S [M-Na] + : 530.42; found: 553.0463.

[0072] Example 11 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.16 (s, ¹H), 7.07-7.01 (m, ¹H), 6.88-6.82 (m, ¹H), 5.48 (s, ¹H), 4.51 (t, J = 4.4 Hz, 2H), 3.84 (s, 3H), 2.88 (t, J = 6.6 Hz, 2H). ¹³C NMR (101 MHz, CDCl₃) δ 161.16, 123.15, 122.77, 121.60, 114.32, 77.33, 64.91, 51.65, 36.06, 31.04. ¹⁹F NMR (376 MHz, CDCl3)δ-137.75, -140.58, -147.83, -154.67, -160.05, -161.23.HR-MS(m / z) calcd for : C 22 H 11 F 10 NO4S [M-Na] + : 575.38; found: 598.0141.

[0073] Example 12 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.17 (s, ¹H), 8.15 (t, J = 1.8 Hz, ¹H), 7.95 (dt, J = 7.8, 1.3 Hz, ¹H), 7.70 (dt, J = 8.0, 1.1 Hz, ¹H), 7.32 (t, J = 7.9 Hz, ¹H), 7.06–7.00 (m, ¹H), 6.89–6.78 (m, ¹H), 5.49 (s, ¹H), 4.47 (t, J = 1.3 Hz, 2H), 3.83 (s, 3H), 2.91 (t, J = 6.7 Hz, 2H). ¹⁹F NMR (376 MHz, CDCl3)δ-140.49, -154.79, -161.23.HR-MS (m / z) calcdfor : C 22 H 15 BrF5NO4S [M-Na] + : 564.32; found: 585.9718.

[0074] Example 13 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.02 (s, ¹H), 7.94–7.87 (m, 2H), 7.26–7.23 (m, 2H), 7.04–6.99 (m, ¹H), 6.87–6.83 (m, ¹H), 5.50 (s, ¹H), 4.45 (t, J = 6.7 Hz, 2H), 3.83 (s, 3H), 2.90 (t, J = 6.7 Hz, 2H), 2.41 (s, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ -140.42, -155.15, -161.34. HR-MS (m / z) calcd for: C 23 H 18 F5NO4S [M-Na] + : 499.45; found: 522.0769.

[0075] Example 14 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.30 (s, ¹H), 8.00–7.91 (m, 2H), 7.46–7.37 (m, 2H), 7.05–7.00 (m, ¹H), 6.88–6.82 (m, ¹H), 5.49 (s, 1H), 4.47 (t, J = 6.6 Hz, 2H), 3.83 (s, 3H), 2.91 (t, J = 6.7 Hz, 2H). ¹³C NMR (101 MHz, CDCl₃) δ 165.43, 161.27, 139.69, 131.04, 128.80, 128.22, 123.07. 121.70, 114.41, 64.00, 51.65, 36.07, 31.45.19F NMR (376 MHz, CDCl3)δ-140.50, -155.07, -161.12.HR-MS (m / z) calcd for : C 22 H 15 ClF5NO4S [M-Na] + :519.87; found: 542.0223.

[0076] Example 15 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.23 (s, ¹H), 7.92 (td, J=7.6, 1.9 Hz, ¹H), 7.58–7.48 (m, ¹H), 7.26–7.09 (m, 2H), 7.07–7.02 (m, 1H), 6.89–6.83 (m, 1H), 5.53 (s, ¹H), 4.49 (t, J = 2.4 Hz, 2H), 3.83 (s, 3H), 2.91 (t, J = 6.6 Hz, 2H). ¹³C NMR (101 MHz, CDCl₃) δ 164.11, 163.28, 161.25, 134.79, 132.15, 124.04, 123.00, 121.75, 116.92, 114.42,63.78, 51.62, 36.04, 31.31.19F NMR (376 MHz, CDCl3)δ-108.91, -140.45, -154.87, -161.38.HR-MS (m / z) calcd for : C 22 H 15 F6NO4S [M-Na] + : 503.42; found:526.0518.

[0077] Example 16 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.26 (s, ¹H), 7.86–7.79 (m, 2H), 7.41–7.27 (m, 2H), 7.06–7.00 (m, ¹H), 6.89–6.83 (m, ¹H), 5.51 (s, ¹H), 4.46 (t, J = 6.6 Hz, 2H), 3.83 (s, 3H), 2.91 (t, J = 6.7 Hz, 2H), 2.40 (s, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 166.47, 161.27, 138.26, 133.96, 130.16, 128.32, 126.79, 123.05, 121.72, 114.42, 63.34, 51.62, 36.09,31.48, 21.24.19F NMR (376MHz, CDCl3)δ-138.26,-140.46,-154.85.HR-MS (m / z)calcd for : C 23 H 18 F5NO4S [M-Na] + : 499.45; found: 522.0769.

[0078] Example 17 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.10 (s, ¹H), 8.02–7.92 (m, 2H), 7.05–6.99 (m, ¹H), 6.94–6.90 (m, 2H), 6.86–6.84 (m, ¹H), 5.50 (s, ¹H), 4.44 (t, J = 6.6 Hz, 2H), 3.86 (s, 3H), 3.83 (s, 3H), 2.90 (t, J = 6.7 Hz, 2H). ¹⁹F NMR (376 MHz, CDCl₃) δ -140.46, -155.15, -161.20. HR-MS (m / z) calcd for: C 23 H 18 F5NO5S [M-Na] +: 515.45; found: 538.0718.

[0079] Example 18 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.13 (s, ¹H), 8.33–8.25 (m, 2H), 8.24–8.15 (m, 2H), 7.06–7.00 (m, ¹H), 6.88–6.82 (m, ¹H), 5.49 (s, ¹H), 4.52 (t, 2H), 3.83 (s, 3H), 2.93 (t, J = 6.6 Hz, 2H). ¹⁹F NMR (376 MHz, CDCl₃) δ -140.49, -154.78, -160.98. HR-MS (m / z) calcd for :C 22 H 15 F5N2O6S [M-Na] + : 530.42; found: 553.0463.

[0080] Example 19 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.22 (s, ¹H), 8.62-8.57 (m, ¹H), 8.03 (dd, J = 8.6, 1.7 Hz, ¹H), 7.98-7.91 (m, ¹H), 7.88 (d, J = 8.4 Hz, 2H), 7.57 (dddd, J = 20.8, 8.1, 6.8, 1.3 Hz, 2H), 7.06-7.00 (m, ¹H), 6.89-6.84 (m, ¹H), 5.55 (s, ¹H), 4.54 (t, J = 6.7 Hz, 2H), 3.81 (s, 3H), 2.96 (t, J = 6.7 Hz, 2H).19F NMR (376 MHz, CDCl3)δ-140.45, -154.79, -161.15.HR-MS (m / z) calcd for : C 26 H 18 F5NO4S [M-Na] + : 535.49; found:558.0769.

[0081] Example 20 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.12 (s, ¹H), 8.12–8.07 (m, 4H), 7.07–6.98 (m, ¹H), 6.89–6.79 (m, ¹H), 5.50 (s, ¹H), 4.49 (t, J = 6.6 Hz, 2H), 3.95 (s, 3H), 3.83 (s, 3H), 2.92 (t, J = 6.7 Hz, 2H). ¹⁹F NMR (376 MHz, CDCl₃) δ -140.47, -155.09, -161.24. HR-MS (m / z) calcd for: C 24 H 18 F5NO6S [M-Na] + : 543.46; found: 566.0667.

[0082] Example 21 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.16 (s, ¹H), 7.83–7.78 (m, 2H), 7.74–7.70 (m, 2H), 7.04–7.00 (m, ¹H), 6.87–6.83 (m, ¹H), 5.48 (s, ¹H), 4.46 (t, J = 6.6 Hz, 2H), 3.83 (s, 3H), 2.90 (t, J = 6.6 Hz, 2H). ¹⁹F NMR (376 MHz, CDCl₃) δ -140.45, -155.05, -161.09. HR-MS (m / z) calcd for :C 22 H 15 F5INO4S [M-Na] + : 611.32; found: 633.9579.

[0083] Example 22 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.27 (s, ¹H), 8.13–8.05 (m, 2H), 7.68–7.61 (m, 4H), 7.49–7.39 (m, 3H), 7.07–7.01 (m, ¹H), 6.89–6.84 (m, ¹H), 5.52 (s, ¹H), 4.50 (t, J = 6.6 Hz, 2H), 3.82 (s, 3H), 2.93 (t, J = 6.6 Hz, 2H). ¹⁹F NMR (376 MHz, CDCl₃) δ -140.44, -154.84, -161.15. HR-MS (m / z) calcd for: C 28 H 20 F5NO4S [M-Na] + : 561.52; found: 584.0932.

[0084] Example 23 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.00 (s, ¹H), 7.83–7.75 (m, 2H), 6.98–6.92 (m, ¹H), 6.81–6.76 (m, ¹H), 6.59–6.55 (m, 2H), 5.44 (s, ¹H), 4.35 (t, J = 6.7 Hz, 2H), 3.76 (s, 3H), 2.98 (s, 6H), 2.82 (t, J = 6.6 Hz, 2H). ¹⁹F NMR (376 MHz, CDCl₃) δ -140.37, -155.31, -161.27. HR-MS (m / z) calcd for: C 24 H 21 F5N2O4S [M-Na] + : 528.49; found: 551.1034.

[0085] Example 24 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.09 (s, ¹H), 8.07–8.01 (m, 2H), 7.72–7.67 (m, 2H), 6.95 (t, J = 2.3 Hz, ¹H), 6.78 (d, J = 2.1 Hz, 1H), 5.41 (s, ¹H), 4.43 (t, J = 6.6 Hz, 2H), 3.77 (s, 3H), 2.85 (t, J = 6.6 Hz, 2H). ¹⁹F NMR (376 MHz, CDCl₃) δ -140.50, -154.69, -161.11. HR-MS (m / z) calcd for: C 23 H 15 F5N2O4S [M-Na] + : 510.44; found: 533.0565.

[0086] Example 25 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.24 (t, J = 2.2 Hz, ¹H), 9.23 (s, ¹H), 9.14 (d, J = 2.1 Hz, 2H), 7.10–6.97 (m, ¹H), 6.91–6.76 (m, ¹H), 5.50 (s, ¹H), 4.60 (t, J = 4.1 Hz, 2H), 3.83 (s, 3H), 2.97 (t, J = 6.6 Hz, 2H). ¹⁹F NMR (376 MHz, CDCl₃) δ -140.57, -154.39, -160.85. HR-MS (m / z) calcd for: C 22 H 14 F5N3O8S [M-Na] + : 575.42; found: 598.0314.

[0087] Example 26 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.14 (s, ¹H), 7.23–7.18 (m, 2H), 6.97–6.92 (m, ¹H), 6.80–6.74 (m, ¹H), 5.43 (s, ¹H), 4.40 (t, J = 6.7 Hz, 2H), 3.85–3.82 (m, 9H), 3.76 (s, 3H), 2.84 (t, J = 6.7 Hz, 2H). ¹⁹F NMR (376 MHz, CDCl₃) δ -140.43, -154.81, -160.96. HR-MS (m / z) calcd for: C 25 H 22 F5NO7S [M-Na] + : 575.50; found: 598.0929.

[0088] Example 27 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.28 (s, ¹H), 6.85 (d, J = 2.8 Hz, ¹H), 6.79–6.73 (m, 3H), 5.38 (s, ¹H), 4.36 (t, J = 6.6 Hz, 2H), 3.74 (s, 3H), 2.80 (t, J = 6.7 Hz, 2H), 2.20 (d, J = 5.7 Hz, 9H). ¹⁹F NMR (376 MHz, CDCl₃) δ -140.55, -154.89, -161.38. HR-MS (m / z) calcd for: C 25 H 22 F5NO4S [M-Na] + : 527.51; found: 550.1082.

[0089] Example 28 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.16 (s, ¹H), 7.78 (dd, J = 7.1, 2.4 Hz, ¹H), 7.66 (dd, J = 7.2, 2.0 Hz, ¹H), 7.41–7.29 (m, 2H), 7.06–7.00 (m, ¹H), 6.89–6.83 (m, ¹H), 5.49 (s, ¹H), 4.48 (t, J = 3.1 Hz, 2H), 3.83 (s, 3H), 2.92 (t, J = 6.6 Hz, 2H). ¹⁹F NMR (376 MHz, CDCl₃) δ -140.44, -154.79, -161.26. HR-MS(m / z)calcd for : C 22 H 15 BrF5NO4S [M-Na] +:564.32; found: 585.9718.

[0090] Example 29 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, CDCl₃) δ 9.07 (s, ¹H), 7.98–7.88 (m, 2H), 7.45–7.32 (m, 2H), 7.00–6.88 (m, ¹H), 6.83–6.71 (m, ¹H), 5.43 (s, ¹H), 4.54 (s, 2H), 4.40 (t, J = 6.7 Hz, 2H), 3.76 (s, 3H), 2.84 (t, J = 6.6 Hz, 2H). ¹⁹F NMR (376 MHz, CDCl₃) δ -140.49, -154.80, -161.19. HR-MS (m / z) calcd for: C 23 H 17 ClF5NO4S [M-Na] + : 533.89; found: 556.0379.

[0091] Example 30 Referring to Example 1, the difference is: R in The structural formula of the obtained pyrrole-pentafluorobenzene compound is as follows: ; The NMR data of the pyrrole-pentafluorobenzene compounds are as follows: ¹H NMR (400 MHz, Chloroform-d) δ 9.20 (s, 1H), 8.42–8.31 (m, 2H), 8.00 (s, 1H), 6.96 (t, J = 2.4 Hz, 1H), 6.79 (t, J = 2.2 Hz, 1H), 5.43 (s, 1H), 4.47 (td, J = 6.8, 1.8 Hz, 2H), 3.76 (s, 3H), 2.87 (t, J = 6.7 Hz, 2H). ¹⁹F NMR (376 MHz, CDCl₃) δ -63.19, -140.54, -154.62, -161.02. HR-MS (m / z) calcd for: C 24 H14 F11NO4S [M-Na] + : 621.42; found:644.0360.

[0092] Test Example 1 Fourth-instar larvae and pupae of the harassing mosquito were selected as research subjects. Ten larvae were placed in sterile tubes containing 3 mL of pyrrole-pentafluorobenzene compound solutions of different concentrations (20 mg / L, 10 mg / L, 5 mg / L, and 2.5 mg / L, respectively, in a 0.1% Tween 80 aqueous solution). Each experiment was performed in triplicate at 25°C, and the results were observed after 72 hours. Rotenone and pyrethroids were selected as positive controls. The test results are shown in Tables 1 and 2. Table 1. Anti-harassment activity of the pyrrole-pentafluorobenzene compound solutions described in Examples 1-30 against 4th instar larvae of *Aedes aegypti*.

[0093] Table 2. Anti-harassment activity of the pyrrole-pentafluorobenzene compound solutions described in Examples 6, 10, 11, 18, 20, 24, 25 and 30 against *Aedes aegypti* pupae.

[0094] As shown in Tables 1 and 2, the pyrrole-pentafluorobenzene compounds described in this invention all have good mosquito-killing activity. In Example 25, the activity against fourth-instar larvae and pupae of Aedes mosquitoes exceeded that of the positive control rotenone.

[0095] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A pyrrole-pentafluorobenzene compound, characterized in that, It has the structure shown in Equation 1: Formula 1; In Equation 1, R is , , , , , , , , , , , , , , , , , , , , , , , , , , , , or .

2. The method for preparing the pyrrole-pentafluorobenzene compound according to claim 1, characterized in that, Includes the following steps: A compound having the structure shown in Formula a, thionyl chloride, and a first organic solvent were mixed and subjected to an esterification reaction. Methanol was then added to continue the reaction, yielding a compound having the structure shown in Formula b. The compound having the structure shown in formula b, the compound having the structure shown in formula c, aluminum chloride, and a second organic solvent are mixed and subjected to a Friedel-Crafts reaction to obtain the compound having the structure shown in formula d. The compound having the structure shown in formula d, sodium borohydride, and a third organic solvent are mixed and a reduction reaction is carried out to obtain the compound having the structure shown in formula e. The compound having the structure shown in formula e, mercaptoethanol, zinc chloride, and a fourth organic solvent are mixed and subjected to a condensation reaction to obtain the compound having the structure shown in formula f. The compound having the structure shown in formula f, the compound having the structure shown in formula g, 4-dimethylaminopyridine, and a fifth organic solvent were mixed and subjected to an acylation reaction to obtain the pyrrole-pentafluorobenzene compound. Formula a Formula b Formula c Formula d, Formula e Formula f or Formula g; In formula g, R is the same as R in the pyrrole-pentafluorobenzene compound.

3. The preparation method according to claim 2, characterized in that, The molar ratio of the compound having the structure shown in Formula a to sulfoxide dichloride is 1:(2.5~3.5). The ratio of the compound having the structure shown in Formula a to the first organic solvent is 1 mmol: (15~25) mL; The first organic solvent includes one or more of dichloromethane, THF, and chloroform; The esterification reaction was carried out at room temperature for 2.5 to 3.5 hours. The molar amount of the compound having the structure shown in Formula a and the volume ratio of methanol are 1 mmol: (8~10) mL, and the reaction continues for 10 min.

4. The preparation method according to claim 2, characterized in that, The molar ratio of the compound having the structure shown in formula b to the compound having the structure shown in formula c is 1:(2.5~3.5). The molar ratio of the compound with the structure shown in formula b to aluminum chloride is 1:(2.5~3.5). The ratio of the compound having the structure shown in formula b to the second organic solvent is 1 mmol: (15~25) mL; The second organic solvent includes one or more of dichloromethane, chloroform, and nitrobenzene; The Friedel-Crafts reaction was carried out at a temperature of 20-25°C for 2.5-3.5 hours.

5. The preparation method according to claim 2, characterized in that, The molar ratio of the compound with the structure shown in formula d to sodium borohydride is 1:(8~12). The ratio of the compound with the structure shown in formula d to the third organic solvent is 1 mmol: (15~25) mL; The third organic solvent includes one or more of tetrahydrofuran, methanol, and water; The reduction reaction is carried out at a temperature of 15~25℃ for 3.5~4.5h.

6. The preparation method according to claim 2, characterized in that, The molar ratio of the compound having the structure shown in formula e to mercaptoethanol is 1:(8~12); The molar ratio of the compound with the structure shown in Formula e to zinc chloride is 1:(8~12). The ratio of the compound having the structure shown in formula e to the fourth organic solvent is 1 mmol: (15~25) mL; The fourth organic solvent includes chloroform; The condensation reaction was carried out at room temperature for 10-15 hours.

7. The preparation method according to claim 2, characterized in that, The molar ratio of the compound having the structure shown in formula f to the compound having the structure shown in formula g is 1:(1.1~1.3). The molar ratio of the compound having the structure shown in formula f to 4-dimethylaminopyridine is 1:(0.05~0.15). The ratio of the compound with the structure shown in formula f to the fifth organic solvent is 1 mmol: (8~12) mL; The fifth organic solvent includes one or more of dichloromethane, chloroform, and THF; The acylation reaction is carried out at a temperature of 15~25℃ for 2.5~3.5h.

8. The use of the pyrrole-pentafluorobenzene compound of claim 1 or the pyrrole-pentafluorobenzene compound prepared by any one of claims 2 to 7 in the preparation of insecticides.

9. The application as described in claim 8, characterized in that, The insecticide is a mosquito repellent.

10. The application as described in claim 8 or 9, characterized in that, The concentration of pyrrole-pentafluorobenzene compounds in the insecticide is 2.5~20 mg / L.

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