Cyclopentene chromene-cinnamate compound as well as preparation method and application thereof

Abstract

The invention provides a cyclopentene chromene-cinnamate compound as well as a preparation method and application thereof, and belongs to the technical field of organic synthesis. According to the invention, mangiferin is taken as a guide, and a cyclopentenochromene structure is designed and synthesized from cyclopentenopyrane and a chromene skeleton by using molecular hybridization and skeleton transition strategies. According to the cyclopentenochromene-cinnamate derivative containing the cinnamic acid active fragment, the cinnamic acid fragment with pesticide activity is grafted to the 8-site of cyclopentenochromene, the cyclopentenochromene-cinnamate derivative containing the cinnamic acid active fragment is synthesized, and the obtained compound has good insecticidal activity, bactericidal activity and plant virus resisting activity.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic synthesis, in particular to a cyclopentenochromene-cinnamate compound and a preparation method and application thereof. BACKGROUND

[0002] The improper use of traditional pesticides not only leads to serious environmental pollution problems such as soil compaction degradation, water eutrophication and sharp reduction of ecosystem diversity, but also causes harmful substance residues in agricultural products that directly threaten food safety and public health. For example, DDT, BHC, carbofuran and temephos are typical representatives. Therefore, it is urgent to develop new environmentally friendly pesticides that can effectively and selectively control agricultural pests.

[0003] Natural products exhibit high selectivity and environmental friendliness in pesticide applications. The active ingredients derived from plants and microorganisms can precisely act on the key physiological links of target organisms, effectively inhibit pests, pathogenic bacteria and weeds, and have low toxicity to non-target organisms and mammals, with outstanding ecological safety. Such compounds can be rapidly degraded in natural conditions, effectively avoiding the problems of persistent residues and biological accumulation of traditional pesticides. It has been proven that natural products and their derivatives are important sources of drugs and play an important role in pesticide research and development. More importantly, the diversified structures of natural products provide a wealth of lead compounds for the development of new green pesticides with novel mechanisms of action. Developing new pesticide types based on natural products as leads is of great significance for alleviating environmental pollution and harmful substance residues in agricultural products. SUMMARY

[0004] Therefore, the purpose of the present application is to provide a cyclopentenochromene-cinnamate compound and a preparation method and application thereof. The cyclopentenochromene-cinnamate derivative obtained based on the natural product hexamorpholide has good insecticidal activity, fungicidal activity and anti-plant virus activity.

[0005] In order to achieve the above-mentioned purpose, the present application provides the following technical solutions: The present application provides a cyclopentenochromene-cinnamate compound having the structure shown in Formula I or Formula II: Formula I; Formula II; In Formula I, R is one or more of H, C1-C4 alkyl, halogen, trifluoromethyl, trifluoromethoxy, dimethylamino, nitro and alkoxy; the number of R is 1-5.

[0006] Preferably, it has the structure shown in any one of Formula 4a-Formula 4ss: .

[0007] This invention provides a method for preparing the above-mentioned cyclopentene-cinnamate compounds, comprising the following steps: 6-Dimethylaminofulne reacts with 2,6-dichloro-1,4-benzoquinone by an addition reaction to give a compound having the structure shown in Formula 3; In the presence of a condensing agent and a catalyst, a compound having the structure shown in Formula 3 undergoes an esterification reaction with a cinnamic acid compound having the structure shown in Formula 4 or Formula 5 to obtain a cyclopentene cinnamic acid ester compound. Formula 3; Equation 4; Formula 5.

[0008] Preferably, the molar ratio of 6-dimethylaminofulne to 2,6-dichloro-1,4-benzoquinone is 1:0.8~2.0; The addition reaction is carried out at a temperature of 0℃ to -60℃ for a time of 0.2 to 4 hours.

[0009] Preferably, the condensing agent comprises 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride; the catalyst comprises 4-dimethylaminopyridine; The molar ratio of the compound having the structure shown in Formula 3 to the cinnamic acid compound is 1:1.2~4.

[0010] Preferably, the esterification reaction is carried out at a temperature of 0~50℃ for 2~10h.

[0011] Preferably, after the esterification reaction, the method further includes post-processing of the resulting esterification product, the post-processing including: The esterification reaction product was quenched with water, diluted with an organic solvent, and the resulting organic phase was dried, concentrated, and purified by column chromatography. The eluent for column chromatography purification is petroleum ether and dichloromethane, with a volume ratio of 4:1.

[0012] This invention provides the application of the above-mentioned cyclopentene-cinnamic acid ester compounds as agricultural insecticides, antiviral agents for plants, or agricultural fungicides.

[0013] This invention provides a cyclopentenyl cinnamic acid ester compound having the structure shown in Formula I or Formula II. Mango aldehyde was first isolated from the bark of the mango tree by Abe et al. This natural product is an iridoid ether compound with anti-TMV, insecticidal, and antifungal biological activities. Chromenes are a class of heterocyclic compounds composed of a benzene ring and a pyran ring, possessing good antibacterial, anti-inflammatory, antitumor, antifungal, and antioxidant biological activities. This invention uses mango aldehyde as a lead compound, and designs and synthesizes a cyclopentenyl cinnamic acid structure by employing molecular hybridization and skeletal transition strategies to combine the cyclopentenyl pyran and cinnamic acid skeletons. Cinnamic acid compounds are a class of organic compounds isolated from cinnamon bark and plants such as benzoin. They possess a wide range of biological activities and pharmacological effects, including antibacterial, antifungal, insecticidal, antioxidant, anti-inflammatory, antidiabetic, and antitumor effects. This invention synthesizes cyclopentene-cinnamic acid ester derivatives containing the pesticide-active cinnamic acid fragment by inserting a cinnamic acid fragment at the 8-position of cyclopentene-cinnamic acid ester. The insecticidal, fungicidal, and antiviral activities of these derivatives were verified. The results of the examples show that the cyclopentene-cinnamic acid ester compounds of this invention, when used as agricultural insecticides, exhibit excellent insecticidal activity against diamondback moth larvae; when used as antiviral agents, they effectively inhibit tobacco mosaic virus; and when used as agricultural fungicides, they effectively inhibit seven pathogens: rapeseed sclerotium, cucumber gray mold, apple ring rot, pepper blight, wheat sheath blight, rice sheath blight, and wheat scab.

[0014] This invention provides a method for preparing the above-mentioned cyclopentene-cinnamic acid ester compounds. Using 6-dimethylaminofulne and 2,6-dichloro-1,4-benzoquinone as raw materials, compound 3 is first synthesized by cycloaddition, and then esterified with cinnamic acid compounds with different substitutions to obtain cyclopentene-cinnamic acid ester compounds. This method has a short synthetic route, simple operation, low cost, high product yield, and is easy to realize industrial mass production. Detailed Implementation

[0015] This invention provides a cyclopentene-cinnamate compound having the structure shown in Formula I or Formula II: Formula I; Formula II; In Formula I, R is one or more of H, C1-C4 alkyl, halogen, trifluoromethyl, trifluoromethoxy, dimethylamino, nitro, and alkoxy; in this invention, the C1-C4 alkyl is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl, the halogen is preferably fluorine, chlorine, or bromine, and the alkoxy is preferably methoxy or ethoxy; in this invention, the number of R is 1 to 5, specifically 1, 2, 3, 4, or 5.

[0016] In this invention, the cyclopentene-cinnamic acid ester compound preferably has the structure shown in any one of formulas 4a to 4ss: .

[0017] This invention provides a method for preparing the above-mentioned cyclopentene-cinnamate compounds, comprising the following steps: 6-Dimethylaminofulne reacts with 2,6-dichloro-1,4-benzoquinone by an addition reaction to give a compound having the structure shown in Formula 3; In the presence of a condensing agent and a catalyst, a compound having the structure shown in Formula 3 undergoes an esterification reaction with a cinnamic acid compound having the structure shown in Formula 4 or Formula 5 to obtain a cyclopentene cinnamic acid ester compound. Formula 3; Equation 4; Formula 5.

[0018] In this invention, 6-dimethylaminofulne undergoes an addition reaction with 2,6-dichloro-1,4-benzoquinone to obtain a compound having the structure shown in Formula 3. In this invention, the 6-dimethylaminofulne has the structure shown in Formula 1, and the 2,6-dichloro-1,4-benzoquinone has the structure shown in Formula 2. Formula 1; Formula 2.

[0019] In this invention, the molar ratio of 6-dimethylaminofulne to 2,6-dichloro-1,4-benzoquinone is preferably 1:0.8~2.0, more preferably 1:1.0~1.5; the organic solvent used in the addition reaction is preferably one or more of dichloromethane, tetrahydrofuran, toluene and acetonitrile; the temperature of the addition reaction is preferably 0℃~-60℃, more preferably -20℃~-40℃; and the time is preferably 0.2~4h, more preferably 0.2~1h.

[0020] Following the addition reaction, the present invention preferably performs post-treatment on the obtained addition reaction product, the post-treatment preferably including the following steps: The addition reaction product was concentrated and purified by column chromatography.

[0021] In this invention, the concentration is preferably vacuum concentration, and the eluent for column chromatography purification is preferably petroleum ether and dichloromethane, with the volume ratio of petroleum ether to dichloromethane preferably being 2:1.

[0022] In this invention, in the presence of a condensing agent and a catalyst, a compound having the structure shown in Formula 3 undergoes an esterification reaction with a cinnamic acid compound having the structure shown in Formula 4 or Formula 5 to obtain a cyclopentene-cinnamic acid ester compound. In this invention, the molar ratio of the compound having the structure shown in Formula 3 to the cinnamic acid compound is preferably 1:1.2 to 4, more preferably 1:1.5 to 2.5. In this invention, the condensing agent preferably comprises 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and the molar ratio of the condensing agent to the compound having the structure shown in Formula 3 is preferably 2 to 6:1, more preferably 3 to 5:1; the catalyst preferably comprises 4-dimethylaminopyridine, and the molar ratio of the catalyst to the compound having the structure shown in Formula 3 is preferably 0.2 to 1.0:1, more preferably 0.4 to 0.8:1.

[0023] In this invention, the organic solvent used in the esterification reaction is preferably one or more of dichloromethane, toluene, methanol, and tetrahydrofuran. In this invention, the temperature of the esterification reaction is preferably 0°C to 50°C, more preferably 20°C to 30°C, and the time is preferably 2 to 10 hours, more preferably 4 to 8 hours.

[0024] In this invention, after the esterification reaction, it is preferable to further include post-treatment of the resulting esterification product, the post-treatment preferably including: The esterification reaction product was quenched with water, diluted with an organic solvent, and the resulting organic phase was dried, concentrated, and purified by column chromatography.

[0025] In this invention, the organic solvent is preferably dichloromethane, and the drying is preferably anhydrous sodium sulfate drying; the eluent for column chromatography purification is preferably petroleum ether and dichloromethane, and the volume ratio of petroleum ether to dichloromethane is preferably 4:1.

[0026] This invention provides the application of the above-mentioned cyclopentene-cinnamic acid ester compounds as agricultural insecticides. In this invention, the insects killed by the agricultural insecticide are preferably one or more of the following: diamondback moth larvae, aphids, and brown planthoppers.

[0027] This invention provides the application of the above-mentioned cyclopentene-cinnamic acid ester compounds as antiviral agents for plants. In this invention, the plant virus is preferably one or more of tobacco mosaic virus, cucumber mosaic virus, and tomato spotted wilt virus.

[0028] This invention provides the application of the above-mentioned cyclopentene-cinnamic acid ester compounds as agricultural fungicides. In this invention, the fungi killed by the agricultural fungicide are preferably one or more of the following: rapeseed sclerotium, cucumber gray mold, apple ring rot, pepper blight, wheat sheath blight, rice sheath blight, and wheat scab.

[0029] The following examples illustrate the cyclopentene-cinnamic acid ester compounds, their preparation methods, and applications provided by the present invention, but these should not be construed as limiting the scope of protection of the present invention.

[0030] Example 1 Synthesis of cyclopentene-cinnamate compounds (1) Synthesis of compound 3 1.5 g (1 mmol) of 6-dimethylaminofulne 1 was dissolved in 50 mL of dry dichloromethane and slowly added dropwise to 100 mL of 1-dichloromethane solution of 2,6-dichloro-1,4-benzoquinone 2 (2.6 g, 1.2 mmol) while stirring at -40 °C. After the addition was complete, the reaction was continued at the same temperature for 30 minutes. The reaction solution was concentrated under vacuum and then purified by rapid column chromatography using petroleum ether / dichloromethane (2:1 v / v) as the eluent to obtain compound 3.

[0031] Compound 3: Yield: 88%; mp: 143-145℃; 1 H NMR (400 MHz, DMSO- d 6) δ 10.30(s, 1H), 8.75 (s, 1H), 7.88 (s, 1H), 7.56 (s, 1H), 7.14-7.11 (m, 1H), 6.96-6.93 (m, 1H). 13 C NMR (100 MHz, CDCl3) δ 145.95, 145.39, 142.16, 133.62, 125.17,120.43, 119.51, 118.61, 118.08, 117.83, 116.30, 114.55. HRMS(APCI) calculated for C 12 H6Cl2O2[M+H] + 252.9745 and 254.9715; found 252.9822 and 254.9791. (2) Synthesis of cyclopentene-cinnamic acid esters 4a~4ss Compound 3 (0.2 g, 0.8 mmol) was added to 60 mL of dichloromethane, a cinnamic acid compound selected from any one of formulas a to ss (2 equiv), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI) (0.61 g, 0.32 mmol), and 4-dimethylaminopyridine (DMAP) (0.048 g, 0.4 mmol). The reaction was stirred at room temperature and monitored by TLC until complete. The reaction solution was quenched with water, diluted with dichloromethane, and the organic phase was dried over anhydrous sodium sulfate. After filtration, the obtained organic layer was concentrated by vacuum distillation and purified by column chromatography using petroleum ether / dichloromethane (v / v 4:1) as the eluent to finally obtain the target compounds 4a to 4ss.

[0032] Compound 4a: Yield: 90%; mp: 184-186 °C; 1 H NMR (400 MHz, CDCl3) δ 8.19 (d, J = 1.4 Hz, 1H), 8.02 (d, J = 16.0 Hz, 1H), 7.67-7.62 (m, 4H), 7.45 (dd, J = 5.0, 1.7 Hz, 3H), 7.19 (dd, J = 4.9, 2.7 Hz, 1H), 6.91 (dd, J = 4.9, 1.2 Hz, 1H), 6.77(d, J = 16.0 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ163.55, 148.35, 145.89, 145.08, 141.93, 134.11, 131.22, 129.21, 128.69, 125.84, 125.61, 125.01, 120.29, 120.00, 119.63, 117.92, 115.79, 114.79. HRMS(APCI) calculated for C 21 H 12 Cl2O3[M+H] + 383.0163 and 385.0134; found 383.0234 and 385.0217. Compound 4b: Yield: 80 %; mp: 194 - 196 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.18 (s,1H), 7.99 (d, J = 16.0 Hz, 1H), 7.64 (s, 2H), 7.54 (d, J = 7.7 Hz, 2H), 7.26 (s,1H), 7.25 - 7.16 (m, 2H), 6.90 (d, J = 4.8 Hz, 1H), 6.72 (d, J = 16.0 Hz, 1H), 2.41(s, 3H). 13 C NMR (100 MHz, CDCl3) δ 163.74, 148.38, 145.83, 145.05, 141.98, 141.81, 134.06, 131.41, 129.93, 128.69, 125.84, 125.57, 125.03, 120.30, 119.96, 119.58, 117.88, 114.75, 114.59, 21.72. HRMS(APCI) calculated for C 22 H 14 Cl2O3[M+H] + 397.0320 and 399.0290; found 397.0390 and 399.0371. Compound 4c: Yield: 86 %; mp: 156 - 159 ℃; 1 H NMR (400 MHz, CDCl3)δ 8.19 (d, J J = 1.3 Hz, 1H), 8.00 (d, J J = 16.0 Hz, 1H), 7.65 (s, 2H), 7.58 (d, J J = 8.1 Hz, 2H),7.31 (d, J J = 8.0 Hz, 2H), 7.19 (dd, J J = 4.9, 2.7 Hz, 1H), 6.91 (dd, J J = 4.9, 1.1Hz, 1H), 6.72 (d, J J = 16.0 Hz, 1H), 2.97 (p, J J = 6.9 Hz, 1H), 1.29 (d, J J = 6.9 Hz,6H). 13 C NMR (100MHz, CDCl3) δ 163.76, 152.71, 148.40, 145.85, 145.08, 142.00,134.09, 131.78, 128.84, 127.34, 125.87, 125.59, 125.05, 120.33, 119.99,119.61, 117.90, 114.75, 114.66, 34.34, 23.90. HRMS(APCI) calculated forC 24 H 18 Cl2O3[M+H] + 425.0633 and 427.0603; found 425.0705 and 427.0684. Compound 4d: Yield: 90 %; mp: 189-191 ℃; 1 H NMR (400 MHz,CDCl3) δ 8.18 (d, J J=1.3 Hz, 1H), 8.01 (d, J J = 16.0 Hz, 1H), 7.64 (s, 2H), 7.59 (d, J J = 8.4 Hz, 2H),7.47 (d, J J = 8.3 Hz, 2H), 7.18 (dd, J J = 4.9, 2.7 Hz, 1H), 6.90 (dd,J = 4.9, 1.1 Hz, 1H), 6.73 (d, J = 16.0 Hz, 1H), 1.36 (s, 9H). 13 C NMR (100 MHz, CDCl3) δ 163.75, 154.95, 148.28, 145.84, 145.06, 141.99, 134.07, 131.38, 128.57, 126.18, 125.86, 125.59, 125.04, 120.31, 119.98, 119.60, 117.89, 114.76, 35.16, 31.30. HRMS(APCI) calculated for C 25 H 20 Cl2O3[M + H] + 439.0789 and 441.0760; found 439.0863 and 441.0845. Compound 4e: Yield: 90 %; mp: 206 - 207 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.18 (d, J = 1.4 Hz, 1H), 7.96 (d, J = 16.0 Hz, 1H), 7.64 (s, 2H), 7.57 (d, J = 8.3 Hz, 2H), 7.42 (d, J = 8.4 Hz, 2H), 7.18 (dd, J = 4.9, 2.7 Hz, 1H), 6.93 - 6.88 (m, 1H), 6.73(d, J = 16.0 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 163.30, 146.79, 145.91, 145.07, 141.84, 137.23, 134.10, 132.61, 129.81, 129.52, 125.78, 125.61, 124.91, 120.26, 120.02, 119.67, 117.94, 116.38, 114.83. HRMS(APCI) calculated for C 21 H11 Cl3O3[M+H] + 416.9774 and 418.9744; found 416.9852 and 418.9833. Compound 4f: Yield: 84 %; mp: 171 - 173 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.18 (s,1H), 7.97 (d, J = 16.0 Hz, 1H), 7.63 (d, J = 9.4 Hz, 4H), 7.20 - 7.11 (m, 3H), 6.91(d, J = 4.9 Hz, 1H), 6.69 (d, J = 16.0 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 164.54( J c-f = 251 Hz), 163.42, 146.96, 145.88, 145.08, 141.86, 134.09, 130.70,130.61, 130.38, 125.80, 125.59, 124.93, 120.26, 120.00, 119.64, 117.92,116.53, 116.31, 115.53, 114.81. 19 F NMR (376 MHz, CDCl3) δ -108.13. HRMS(APCI)calculated for C 21 H 11 Cl2FO3[M+H] + 401.0069 and 403.0040; found 401.0142 and403.0122. Compound 4g: Yield: 76 %; mp: 169 - 171 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.18 (d, J = 1.4 Hz, 1H), 8.02 (d, J = 16.1 Hz, 1H), 7.74 (d, J = 8.3 Hz, 2H), 7.70 (d,J = 8.2 Hz, 2H), 7.64 (d, J = 2.5 Hz, 2H), 7.19 (dd, J = 4.9, 2.7 Hz, 1H), 6.91 (dd, J = 4.9, 1.2 Hz, 1H), 6.84 (d, J = 16.1 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 163.00, 146.29, 145.91, 145.07, 141.70, 137.39, 134.11, 132.75, 132.43, 128.77, 126.14 (q, J c-f = 3.7 Hz), 125.70, 125.57, 125.25, 124.79, 122.54, 120.18, 120.02, 119.70, 118.40, 117.96, 114.88. 19 F NMR (376 MHz, CDCl3) δ -62.92. HRMS(APCI) calculated for C 22 H 11 Cl2F3O3[M + H] + 451.0037 and 453.0008; found 451.0110 and 453.0092. Compound 4h: Yield: 90 %; mp: 232 - 235 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.18 (d, J = 1.3 Hz, 1H), 7.94 (d, J = 15.7 Hz, 1H), 7.66 - 7.62 (m, 2H), 7.53 (d, J = 8.8 Hz, 2H), 7.18 (dd, J = 4.9, 2.7 Hz, 1H), 6.90 (dd, J = 4.9, 1.1 Hz, 1H), 6.70 (d, J = 8.8 Hz, 2H), 6.52 (d, J = 15.8 Hz, 1H), 3.06 (s, 6H). 13 C NMR (100MHz, CDCl3) δ164.43, 152.44, 148.95, 145.76, 145.06, 142.33, 134.04, 130.59, 126.04, 125.58, 125.31, 121.92, 120.44, 119.95, 119.49, 117.82, 114.63, 111.94, 109.47, 40.25. HRMS(APCI) calculated for C 23 H 17 Cl2NO3[M + H] + 426.0585 and 428.0556; found 426.0658 and 428.0640. Compound 4i: Yield: 74%; mp: 226 - 228 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.31 (d, J J = 8.8 Hz, 2H), 8.20 (d, J J = 1.5 Hz, 1H), 8.03 (d, J J = 16.1 Hz, 1H), 7.79 (d, J J = 8.7 Hz, 2H), 7.66 (s, 1H), 7.65 (dt, J J = 2.7, 1.3 Hz, 1H), 7.19 (dd, J J = 4.9, 2.7 Hz, 1H), 6.92 (dd, J J = 4.9, 1.2 Hz, 1H), 6.88 (d, J J = 16.0 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 162.65, 149.12, 145.99, 145.11, 142.35, 141.60, 140.03, 134.17, 129.25, 125.66, 125.62, 124.72, 124.42, 120.16, 120.12, 120.07, 119.77, 118.01, 114.96. HRMS(APCI) calculated for C 21 H 11 Cl2NO5[M + Na] +450.0014 and 451.9985; found 449.9912 and 451.9894. Compound 4j: Yield: 80 %; mp: 159 - 161 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.73 (d, J J = 5.5 Hz, 2H), 8.19 (d, J J = 1.4 Hz, 1H), 7.92 (d, J J = 16.0 Hz, 1H), 7.68 - 7.62 (m, 2H), 7.49 - 7.45 (m, 2H), 7.19 (dd, J J = 4.9, 2.7 Hz, 1H), 6.95 - 6.89 (m, 2H). 13 C NMR (100 MHz, CDCl3) δ 162.62, 150.95, 145.99, 145.26, 145.09, 141.59, 141.17, 134.15, 125.66, 125.62, 124.73, 122.15, 120.53, 120.18, 120.07, 119.76, 118.00, 114.92. HRMS(APCI) calculated for C 20 H 11 Cl2NO3[M + H] + 384.0116 and 386.0086; found 384.0188 and 386.0152. Compound 4k: Yield: 85 %; mp: 143 - 145 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.18 (d, J J = 1.3 Hz, 1H), 7.99 (d, J J = 16.0 Hz, 1H), 7.68 - 7.61 (m, 2H), 7.45 (d, J J = 8.2 Hz, 2H), 7.38 - 7.27 (m, 2H), 7.18 (dd, J J = 4.9, 2.7 Hz, 1H), 6.90 (dd, J J = 4.9, 1.1 Hz, 1H), 6.75 (d,J = 16.0 Hz, 1H), 2.41 (s, 3H). 13 C NMR (100 MHz, CDCl3) δ 163.61, 148.55, 145.86, 145.06, 141.95, 138.90, 134.08, 132.06, 129.31, 129.07, 125.91, 125.85, 125.59, 125.01, 120.30, 119.98, 119.61, 117.90, 115.51, 114.76, 21.47. HRMS(APCI) calculated for C 22 H 14 Cl2O3[M+H] + 397.0320 and 399.0290; found 397.0392 and 399.0373. Compound 4l: Yield: 86 %; mp: 134 - 135 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.17 (d, J = 1.5 Hz, 1H), 7.98 (d, J = 16.0 Hz, 1H), 7.64 (d, J = 2.3 Hz, 2H), 7.35 (t, J = 7.9 Hz, 1H), 7.22 (d, J = 7.6 Hz, 1H), 7.18 (dd, J = 4.9, 2.7 Hz, 1H), 7.15 (t, J = 2.0 Hz, 1H), 6.99 (dd, J = 8.3, 2.5 Hz, 1H), 6.90 (dd, J = 4.9, 1.2 Hz, 1H), 6.74(d, J = 16.0 Hz, 1H), 4.09 (q, J = 7.0 Hz, 2H), 1.45 (t, J = 7.0 Hz, 3H). 13 C NMR(100 MHz, CDCl3) δ163.52, 159.55, 148.36, 145.86, 145.06, 141.92, 135.41, 134.08, 130.17, 125.82, 125.59, 124.98, 121.29, 120.29, 119.99, 119.63, 117.90, 117.78, 115.94, 114.78, 114.01, 63.79, 14.94. HRMS(APCI) calculated for C 23 H 16 Cl2O4[M+H] + 427.0426 and 429.0396; found 427.0497 and 429.0481. Compound 4m: Yield: 92 %; mp: 167 - 168 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.17 (d, J J = 1.3 Hz, 1H), 7.94 (d, J J = 16.0 Hz, 1H), 7.63 (s, 3H), 7.50 (d, J J = 7.3 Hz, 1H), 7.39 (dt, J J = 15.4, 7.9 Hz, 2H), 7.18 (dd, J J = 4.9, 2.7 Hz, 1H), 6.90 (d, J J = 4.8Hz, 1H), 6.76 (d, J J = 16.0 Hz, 1H). 13 C NMR (100MHz, CDCl3) δ 163.14, 146.60, 145.88, 145.07, 141.76, 135.87, 135.26, 134.10, 131.02, 130.42, 128.36, 126.81, 125.73, 125.57, 124.85, 120.21, 119.99, 119.65, 117.92, 117.29, 114.83. HRMS(APCI) calculated for C 21 H 11 Cl3O3[M+H] +416.9774 and 418.9744; found 416.9845 and 418.9821. Compound 4n: Yield: 87 %; mp: 196 - 197 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.18 (s,1H), 7.97 (d, J = 16.0 Hz, 1H), 7.65 (s, 2H), 7.42 (s, 2H), 7.34 (d, J = 9.6 Hz,1H), 7.17 (d, J = 9.9 Hz, 2H), 6.91 (d, J = 4.8 Hz, 1H), 6.76 (d, J = 16.0 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 163.19, 146.84, 145.92, 145.08, 141.79, 136.30 (d, J c-f = 7.8 Hz), 134.13, 130.78(d, J c-f = 8 Hz), 125.78, 125.60, 124.89, 124.68 (d, J c-f = 3.0 Hz), 120.26, 120.03, 119.68, 118.19, 117.95, 117.24, 115.00, 114.83, 114.78. 19 F NMR (376 MHz, CDCl3) δ -112.12. HRMS(APCI) calculated for C 21 H 11 Cl2FO3[M + H] + 401.0069 and 403.0040; found 401.0140 and 403.0122. Compound 4o: Yield: 80 %; mp: 138 - 140 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.19 (d, J= 1.4 Hz, 1H), 8.03 (d, J = 16.0 Hz, 1H), 7.90 (s, 1H), 7.82 (d, J = 7.8 Hz, 1H),7.71 (d, J = 7.8 Hz, 1H), 7.68 - 7.64 (m, 2H), 7.59 (t, J = 7.8 Hz, 1H), 7.19 (dd, J = 4.9, 2.7 Hz, 1H), 6.91 (dd, J = 4.9, 1.2 Hz, 1H), 6.83 (d, J = 16.0 Hz, 1H). 13 13C NMR (100 MHz, CDCl3) δ 163.02, 146.36, 145.96, 145.09, 141.76, 134.91, 134.14, 131.70, 131.62, 129.80, 127.55, 125.76, 125.63, 125.23, 124.85, 122.53, 120.25, 120.05, 119.72, 117.97, 117.88, 114.86. 19 19F NMR (376 MHz, CDCl3) δ -62.91. HRMS(APCI) calculated for C 22 H 11 Cl2F3O3[M + H] + 451.0037 and 453.0008; found 451.0109 and 453.0088. Compound 4p: Yield: 78 %; mp: 129 - 130 ℃; 1 1H NMR (400 MHz, CDCl3) δ 8.18 (d, J = 1.4 Hz, 1H), 7.98 (d, J = 16.0 Hz, 1H), 7.65 (d, J = 1.7 Hz, 2H), 7.57 (d, J= 7.8 Hz, 1H), 7.51 - 7.46 (m, 2H), 7.34 - 7.28 (m, 1H), 7.19 (dd, J = 4.9, 2.7 Hz, 1H), 6.91 (dd, J = 4.9, 1.2 Hz, 1H), 6.78 (d, J = 16.0 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 163.06, 149.93, 146.41, 145.93, 145.08, 141.74, 136.16, 134.12, 130.65, 126.99, 125.74, 125.59, 124.84, 123.32, 120.65, 120.23, 120.03, 119.69, 117.96, 117.68, 114.85. 19 F NMR (376 MHz, CDCl3) δ -57.78. HRMS(APCI) calculated for C 22 H 11 Cl2F3O4 [M + H] + 466.9986 and 468.9957; found 467.0057 and 469.0041. Compound 4q: Yield: 77 %; mp: 202 - 204 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.50 (s, 1H), 8.30 (d, J = 8.2 Hz, 1H), 8.19 (s, 1H), 8.04 (d, J = 16.0 Hz, 1H), 7.94 (d, J = 7.7 Hz, 1H), 7.69 - 7.61 (m, 3H), 7.19 (dd, J = 4.9, 2.7 Hz, 1H), 6.93 - 6.86 (m, 2H). 13 C NMR (100 MHz, CDCl3) δ162.75, 148.92, 145.95, 145.23, 145.09, 141.62, 135.78, 134.14, 134.08, 130.28, 125.67, 125.59, 125.33, 124.75, 123.01, 120.16, 120.04, 119.73, 119.05, 117.98, 114.92. HRMS(APCI) calculated for C 21 H 11 Cl2NO5[M+H] + 428.0014 and 429.9985; found 428.0087 and 429.0112. Compound 4r: Yield: 91 %; mp: 178 - 180 °C; 1 H NMR (400 MHz, CDCl3) δ 8.31 (d, J J = 16.1 Hz, 1H), 8.18 (d, J J = 1.3 Hz, 1H), 7.66 - 7.61 (m, 3H), 7.44 - 7.39 (m, 1H), 7.18 (dd, J J = 4.9, 2.7 Hz, 1H), 7.04 - 6.95 (m, 2H), 6.91 - 6.86 (m, 2H), 3.94 (s, 3H). 13 C NMR (100 MHz, CDCl3) δ 164.13, 158.99, 145.81, 145.07, 143.91, 142.12, 134.04, 132.47, 129.87, 125.91, 125.57, 125.12, 123.08, 120.96, 120.35, 119.95, 119.54, 117.85, 116.18, 114.71, 111.43, 55.69. HRMS(APCI) calculated for C 22 H 14 Cl2O4[M+H] + 413.0269 and 415.0240; found 413.0343 and 415.0322. Compound 4s: Yield: 92 %; mp: 178 - 200 °C; 11H NMR (400 MHz, CDCl3) δ 8.44 (d, J J = 16.0 Hz, 1H), 8.19 (d, J J = 1.4 Hz, 1H), 7.78 (dd, J J = 7.3, 2.2 Hz, 1H), 7.65(s, 2H), 7.48 (dd, J J = 7.7, 1.8 Hz, 1H), 7.37 (pd, J J = 7.3, 1.8 Hz, 2H), 7.19(dd, J J = 5.0, 2.7 Hz, 1H), 6.91 (dd, J J = 4.9, 1.2 Hz, 1H), 6.77 (d, J J = 16.0 Hz,1H). 13 13C NMR (100 MHz, CDCl3) δ 163.07, 145.93, 145.07, 143.95, 141.85, 135.62,134.13, 132.38, 131.92, 130.54, 128.12, 127.37, 125.83, 125.63, 124.96,120.30, 120.03, 119.67, 118.35, 117.94, 114.81. HRMS(APCI) calculated forC 21 H 11 Cl3O3[M+H] + 416.9774 and 418.9744; found 416.9850 and 418.9824. Compound 4t: Yield: 90 %; mp: 213-215 ℃; 1 1H NMR (400 MHz, CDCl3) δ 8.40 (d, J J = 16.0 Hz, 1H), 8.19 (s, 1H), 7.77 (d, J J = 7.8 Hz, 1H), 7.67 (d, J J = 9.8 Hz, 3H),7.40 (t, J J = 7.5 Hz, 1H), 7.30 (t, J= 7.6 Hz, 1H), 7.19 (dd, J = 4.9, 2.7 Hz, 1H),6.91 (d, J = 4.9 Hz, 1H), 6.72 (d, J = 15.9 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 162.96, 146.50, 145.93, 145.08, 141.86, 134.17, 134.12, 133.82, 132.05,128.23, 128.00, 125.97, 125.84, 125.62, 124.96, 120.29, 120.03, 119.67,118.53, 117.93, 114.81. HRMS(APCI) calculated for C 21 H 11 BrCl2O3[M+H] + 460.9269and 462.9248; found 460.9342 and 462.9308. Compound 4u: Yield: 94 %; mp: 168 - 170 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.19 (d, J = 1.3 Hz, 1H), 8.14 (d, J = 16.2 Hz, 1H), 7.65 (s, 3H), 7.46 - 7.41 (m, 1H),7.25 - 7.14 (m, 3H), 6.91 (dd, J = 4.8, 1.1 Hz, 1H), 6.88 (d, J = 16.2 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 163.44, 161.80 (d, J c-f = 255.1 Hz), 145.88, 145.09,141.84, 140.96 (d, J c-f = 2.9 Hz), 134.10, 132.69 (d, J c-f= 9.0 Hz), 129.70 (d, J c-f = 2.4 Hz), 125.79, 125.57, 124.93, 124.77 (d, J c-f = 2.0 Hz), 122.23 (d, J c-f =12.0 Hz), 120.28, 119.99, 119.62, 118.33 (d, J c-f = 8.0Hz), 117.93,116.54 (d, J c-f = 22.0Hz), 114.79. 19 F NMR (377 MHz, CDCl3) δ -113.28. HRMS(APCI) calculated for C 21 H 11 Cl2FO3[M+H] + 401.0069 and 403.0040; found 401.0144 and 403.0124. Compound 4v: Yield: 73 %; mp: 172 - 174 ℃; 1 1H NMR (400 MHz, CDCl3) δ 8.41 (d, J = 15.8 Hz, 1H), 8.18 (s, 1H), 7.86 (d, J = 7.8 Hz, 1H), 7.76 (d, J = 7.8 Hz, 1H),7.65 (s, 3H), 7.55 (t, J = 7.7 Hz, 1H), 7.19 (dd, J = 4.9, 2.7 Hz, 1H), 6.91 (d, J = 4.9 Hz, 1H), 6.73 (d, J = 15.8 Hz, 1H). 13 13C NMR (100 MHz, CDCl3) δ 162.63,145.94, 145.08, 143.59,J c-f = 30.8 Hz), 128.28, 126.53 (m, J c-f = 11.0 Hz), 125.78, 125.60, 125.38, 124.89, 120.25, 120.14, 120.02, 119.67, 117.93, 114.82. 19 19F NMR (376 MHz, CDCl3) δ -58.70. HRMS(APCI) calculated for C 22 H 11 Cl2F3O3[M+H] + 451.0037 and 453.0008; found 451.0112 and 453.0094. Compound 4w: Yield: 79 %; mp: 211 - 212 ℃; 1 1H NMR (400 MHz, CDCl3) δ 8.50 (d, J = 15.8 Hz, 1H), 8.20 (d, J = 1.3 Hz, 1H), 8.12 (dd, J = 8.2, 1.2 Hz, 1H), 7.80 (d, J = 7.5 Hz, 1H), 7.73 (t, J = 7.5 Hz, 1H), 7.68 - 7.60 (m, 3H), 7.19 (dd, J = 4.9, 2.7 Hz, 1H), 6.92 (dd, J = 4.9, 1.2 Hz, 1H), 6.68 (d, J = 15.8 Hz, 1H). 13 13C NMR (100 MHz, CDCl3) δ162.35, 148.59, 146.00, 145.08, 143.54, 141.68, 134.16, 133.82, 131.07, 130.31, 129.49, 125.79, 125.64, 125.26, 124.88, 120.90, 120.26, 120.07, 119.73, 117.97, 114.85. HRMS(APCI) calculated for C 21 H 11 Cl2NO5[M + H] + 428.0014 and 429.9985; found 428.0086 and 430.0068. Compound 4x: Yield: 94 %; mp: 198 - 200 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.28 (d, J J = 15.9 Hz, 1H), 8.18 (d, J J = 1.3 Hz, 1H), 7.63 (d, J J = 13.1 Hz, 3H), 7.18 (dd, J J = 4.9, 2.7 Hz, 1H), 7.08 (d, J J = 8.8 Hz, 2H), 6.90 (dd, J J = 4.9, 1.2 Hz, 1H), 6.66(d, J J = 15.9 Hz, 1H), 2.48 (s, 3H), 2.37 (s, 3H). 13 C NMR (100 MHz, CDCl3) δ 163.83, 145.88, 145.84, 145.06, 142.03, 141.46, 138.43, 134.08, 131.93, 130.18, 127.48, 126.88, 125.88, 125.59, 125.06, 120.32, 119.97, 119.58, 117.87, 115.33, 114.74, 21.55, 19.89. HRMS(APCI) calculated for C 23 H 16 Cl2O3[M + H] +411.0476 and 413.0447; found 411.0549 and 413.0531. Compound 4y: Yield: 90 %; mp: 233-234 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.35 (d, J = 16.0 Hz, 1H), 8.20 (d, J = 1.3 Hz, 1H), 7.71 (d, J = 8.5 Hz, 1H), 7.67-7.63 (m,2H), 7.50 (d, J = 2.0 Hz, 1H), 7.34 (dd, J = 8.5, 2.1 Hz, 1H), 7.19 (dd, J = 4.9,2.7 Hz, 1H), 6.91 (dd, J = 4.9, 1.1 Hz, 1H), 6.75 (d, J = 16.0 Hz, 1H). 13 C NMR(100 MHz, CDCl3) δ 162.87, 145.97, 145.09, 142.68, 141.78, 137.38, 136.20,134.16, 130.98, 130.40, 128.85, 127.90, 125.80, 125.64, 124.90, 120.28,120.06, 119.72, 118.77, 117.97, 114.85. HRMS(APCI) calculated for C 21 H 10 Cl4O3[M+H] + 452.9355 and 450.9384; found 452.9434 and 450.9460. Compound 4z: Yield: 90 %; mp: 215-217 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.36 (d, J = 16.0 Hz, 1H), 8.19 (d, J = 1.4 Hz, 1H), 7.77 (dd, J= 8.8, 5.9 Hz, 1H), 7.65(d, J = 3.0 Hz, 2H), 7.23 (dd, J = 8.3, 2.6 Hz, 1H), 7.19 (dd, J = 4.9, 2.7 Hz,1H), 7.09 (td, J = 8.4, 2.6 Hz, 1H), 6.91 (dd, J = 4.9, 1.2 Hz, 1H), 6.71 (d, J =16.0 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 163.87 (d, J c-f = 255.7 Hz), 162.97,145.93, 145.09, 142.76, 141.78, 136.66 (d, J c-f = 9.9 Hz), 134.13, 129.52 (d, J c-f = 9.3 Hz), 128.79 (d, J c-f = 3.4 Hz), 125.79, 125.60, 124.90, 120.27, 120.02,119.67, 118.03, 117.95, 117.79, 115.15 (d, J c-f = 21.9 Hz), 114.83. 19 F NMR (376MHz, CDCl3) δ -106.76. HRMS(APCI) calculated for C 21 H 10 Cl3FO3[M+H] + 434.9680 and436.9650; found 434.9752 and 436.9726. Compound 4aa: Yield: 92 %; mp: 224 - 225 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.33 (d, J = 16.0 Hz, 1H), 8.19 (d,J = 1.4 Hz, 1H), 7.77 (dd, J = 8.8, 5.9 Hz, 1H), 7.65(d, J = 3.4 Hz, 2H), 7.42 (dd, J = 8.1, 2.6 Hz, 1H), 7.19 (dd, J = 4.9, 2.7 Hz,1H), 7.13 (td, J = 8.4, 2.6 Hz, 1H), 6.91 (dd, J = 4.9, 1.2 Hz, 1H), 6.67 (d, J =15.9 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 163.67 (d, J c-f = 256.7 Hz), 162.86,145.94, 145.24, 145.09, 141.78, 134.14, 130.53 (d, J c-f = 3.2 Hz), 129.48 (d, J c-f = 7.9 Hz), 126.40 (d, J c-f = 9.4 Hz), 125.80, 125.61, 124.91, 121.06 (d, J c-f =24.6 Hz), 120.27, 120.02, 119.67, 118.28, 117.94, 115.66 (d, J c-f = 21.6 Hz),114.83. 19 F NMR (376 MHz, CDCl3) δ -107.02. HRMS(APCI) calculated forC 21 H 10 BrCl2FO3[M+H] + 478.9174 and 480.9154; found 478.9249 and 480.9221. Compound 4bb: Yield: 52 %; mp: 195 - 196 ℃; 1H NMR (400 MHz, CDCl3) δ 8.18 (d, J = 1.3 Hz, 1H), 8.04 (d, J = 16.2 Hz, 1H), 7.64 (d, J = 1.9 Hz, 2H), 7.51 (t, J =8.1 Hz, 1H), 7.40-7.34 (m, 2H), 7.18 (dd, J = 4.9, 2.7 Hz, 1H), 6.91 (dd, J =4.9, 1.2 Hz, 1H), 6.86 (d, J = 16.2 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 163.20,161.31 (d, J c-f = 259.0 Hz), 145.91, 145.08, 141.75, 139.75, 134.11, 130.50 (d, J c-f = 3.9 Hz),128.31 (d, J c-f = 4.0 Hz), 125.70 (d, J c-f = 9.5 Hz), 125.57 (d, J c-f =4.2 Hz), 124.84, 121.38 (d, J c-f = 11.5 Hz), 120.28 (d, J c-f = 24.8 Hz), 120.23,120.15, 119.67, 118.94, 118.87, 117.94, 114.84. 19 F NMR (376 MHz, CDCl3) δ -110.87. HRMS(APCI) calculated for C 21 H 10 BrCl2FO3[M+H] + 478.9174 and 480.9154;found 478.9246 and 480.9215. Compound 4cc: Yield: 87 %; mp: 187 - 189 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.18 (d, J J = 1.4 Hz, 1H), 8.10 (d, J J = 16.2 Hz, 1H), 7.64 (s, 2H), 7.55 (ddd, J J = 7.8, 6.3,1.6 Hz, 1H), 7.52 - 7.46 (m, 1H), 7.20 - 7.14 (m, 2H), 6.93 - 6.84 (m, 2H). 13 C NMR(100 MHz, CDCl3) δ 163.07, 157.09 (d, J c-f J = 257.1 Hz), 145.93, 145.08, 141.74,139.87, 134.12, 132.88, 127.75, 125.73, 125.59, 125.05 (d, J c-f J = 4.7 Hz),124.84, 123.78 (d, J c-f J = 12.1 Hz), 122.49 (d, J c-f J = 17.3 Hz), 120.23, 120.01,119.68, 119.61, 117.95, 114.84. 19 F NMR (376 MHz, CDCl3) δ -115.44. HRMS(APCI)calculated for C 21 H 10 Cl3FO3[M + H] + 434.9680 and 436.9650; found 434.9755 and436.9728. Compound 4dd: Yield: 70 %; mp: 196 - 198 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.19 (d, J J = 1.4 Hz, 1H), 8.11 (d, J= 16.4 Hz, 1H), 7.65 (s, 2H), 7.38 (p, J = 7.8 Hz,1H), 7.19 (dd, J = 4.8, 2.7 Hz, 1H), 7.09 (d, J = 16.5 Hz, 1H), 7.00 (t, J = 8.8Hz, 2H), 6.91 (d, J = 4.8 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 163.49, 163.39 (d, J c-f = 6.4 Hz), 160.84 (d, J c-f = 6.4 Hz), 145.94, 145.07, 141.87, 134.29, 134.13,132.23 (d, J c-f = 12.1 Hz), 132.06, 125.81, 125.63, 124.94, 121.78 (t, J c-f = 9.3Hz), 120.31, 120.03, 119.67, 117.94, 114.81,112.27 (d, J c-f = 15.0 Hz), 112.17(d, J c-f = 25.0 Hz). 19 F NMR (376 MHz, CDCl3) δ -109.33. HRMS(APCI) calculated forC 21 H 10 Cl2F2O3[M+H] + 418.9975 and 420.9946; found 419.0049 and 421.0031. Compound 4ee: Yield: 89 %; mp: 206-207 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.25 (d, J = 16.4 Hz, 1H), 8.19 (d, J= 1.4 Hz, 1H), 7.65 (d, J = 2.2 Hz, 2H), 7.32 (dd, J =7.2, 4.3 Hz, 2H), 7.19 (dd, J = 4.9, 2.7 Hz, 1H), 7.15 - 7.10 (m, 1H), 7.08 (d, J =16.4 Hz, 1H), 6.91 (dd, J = 4.9, 1.1 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 163.45,162.54 ( J c-f = 256 Hz), 145.93, 145.09, 141.86, 138.18, 136.69, 134.13, 131.66,126.34, 125.81, 125.62, 124.94, 122.74, 121.37, 120.30, 120.02, 119.66,117.93, 115.21, 114.80. 19 F NMR (376 MHz, CDCl3) δ -106.79. HRMS(APCI) calculatedfor C 21 H 10 Cl3FO3[M + H] + 434.9680 and 436.9650; found 434.9753 and 436.9724. Compound 4ff: Yield: 91 %; mp: 212 - 213 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.21 - 8.14 (m, 2H), 7.66 (d, J = 2.3 Hz, 2H), 7.42 (d, J = 8.1 Hz, 2H), 7.26 - 7.22 (m,1H), 7.19 (dd, J = 4.9, 2.7 Hz, 1H), 6.99 (d, J = 16.4 Hz, 1H), 6.91 (dd, J = 4.9,1.1 Hz, 1H). 1313C NMR (100 MHz, CDCl3) δ 162.89, 145.97, 145.08, 143.47, 141.84, 141.50, 135.56, 134.15, 131.53, 130.56, 129.17, 125.83, 125.64, 124.94, 124.45, 120.30, 120.05, 119.69, 117.95, 114.81. HRMS(APCI) calculated for C 21 H 10 Cl4O3 [M+H] + 452.9355 and 450.9384; found 452.9428 and 450.9457. Compound 4gg: Yield: 90 %; mp: 181 - 182 ℃; 1 1H NMR (400 MHz, CDCl3) δ 8.18 (d, J J = 1.5 Hz, 1H), 8.07 (d, J J = 16.2 Hz, 1H), 7.65 (s, 2H), 7.34 (t, J J = 6.6 Hz, 1H), 7.19 (dd, J J = 4.9, 2.6 Hz, 1H), 7.16 - 7.10 (m, 2H), 6.91 (d, J J = 4.5 Hz, 1H), 6.84 (d, J J = 16.2 Hz, 1H). 13 13C NMR (100 MHz, CDCl3) δ 163.01, 145.93, 145.07, 141.72, 139.58, 134.12, 125.73, 125.59, 124.83, 120.23, 120.01, 119.53 (d, J c-f J = 6.7 Hz), 119.49, 119.30 (d, J c-f J = 8.8 Hz), 119.06 (d, J c-f J = 8.5 Hz), 117.93 (d, J c-f= 4.6 Hz), 117.82, 117.61 (d, J c-f = 8.7 Hz), 115.33 (d, J c-f = 3.0 Hz), 115.08(d, J c-f = 3.3 Hz), 114.84. 19 F NMR (376 MHz, CDCl3) δ -117.81 (d, J = 17.0 Hz), -119.34 (d, J = 17.7 Hz). HRMS(APCI) calculated for C 21 H 10 Cl2F2O3[M + H] + 418.9975and 420.9946; found 419.0046 and 421.0029. Compound 4hh: Yield: 83 %; mp: 204-206 ℃; 1 1H NMR (400 MHz, CDCl3) δ 8.18 (d, J = 1.3 Hz, 1H), 8.03 (d, J = 16.2 Hz, 1H), 7.78 (dd, J = 6.4, 2.5 Hz, 1H), 7.64(d, J = 2.5 Hz, 2H), 7.52 (ddd, J = 8.8, 4.6, 2.5 Hz, 1H), 7.19 (dd, J = 4.9, 2.7Hz, 1H), 7.06 (dd, J = 10.0, 8.8 Hz, 1H), 6.91 (dd, J = 4.9, 1.2 Hz, 1H), 6.86(d, J = 16.2 Hz, 1H). 13 13C NMR (100 MHz, CDCl3) δ 162.96, 160.65 (d, J c-f= 254.5 Hz), 145.94, 145.08, 141.72, 139.25, 135.22 (d, J c-f = 9.1 Hz), 134.13, 132.08 (d, J c-f = 2.4 Hz), 125.74, 125.60, 124.83, 124.18 (d, J c-f = 13.2 Hz), 120.24, 120.03, 119.73, 119.69, 118.30 (d, J c-f = 24.0 Hz), 117.96, 117.36 (d, J c-f = 3.9 Hz), 114.84. 19 F NMR (376 MHz, CDCl3) δ -115.60. HRMS(APCI) calculated for C 21 H 10 BrCl2FO3 [M+H] + 478.9174 and 480.9154; found 478.9248 and 480.9218. Compound 4ii: Yield: 84 %; mp: 204 - 205 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.33 (d, J = 16.0 Hz, 1H), 8.19 (d, J = 1.3 Hz, 1H), 7.74 (d, J = 2.4 Hz, 1H), 7.65 (d, J = 3.0 Hz, 2H), 7.41 (d, J = 8.6 Hz, 1H), 7.35 (dd, J = 8.6, 2.4 Hz, 1H), 7.19 (dd, J = 4.9, 2.7 Hz, 1H), 6.91 (dd, J = 4.9, 1.1 Hz, 1H), 6.76 (d, J = 16.0 Hz, 1H). 13CNMR (100 MHz, CDCl3) δ 162.70, 145.96, 145.08, 142.59, 141.70, 134.14, 133.80,133.68, 133.44, 131.70, 131.59, 127.89, 125.74, 125.60, 124.83, 120.23,120.03, 119.70, 119.61, 117.96, 114.84. HRMS(APCI) calculated for C 21 H 10 Cl4O3[M+H] + 452.9355 and 450.9384; found 452.9435 and 450.9462. Compound 4jj: Yield: 93 %; mp: 177 - 178 ℃; 1 H NMR (400 MHz,CDCl3) δ 8.29 (d, J = 16.1 Hz, 1H), 8.17 (s, 1H), 7.63 (s, 2H), 7.20 - 7.12 (m, 2H), 6.98 (dd, J =9.2, 2.9 Hz, 1H), 6.93 - 6.81 (m, 3H), 3.86 (d, J = 25.7 Hz, 6H). 13 C NMR (100 MHz,CDCl3) δ 163.99, 153.74, 153.50, 145.84, 145.06, 143.63, 142.11, 134.06,125.91, 125.60, 125.11, 123.56, 120.35, 119.96, 119.57, , 118.42, 117.86,116.36, 114.72, 113.88, 112.75, 56.25, 56.01. HRMS(APCI) calculated forC 23 H 16 Cl2O5[M+H] + 443.0375 and 445.0345; found 443.0449 and 445.0433. Compound 4kk: Yield: 92 %; mp: 176 - 177 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.19 (d, J J = 1.4 Hz, 1H), 7.96 (d, J J = 15.9 Hz, 1H), 7.65 (s, 2H), 7.22 (dd, J J = 8.3, 2.0Hz, 1H), 7.20 - 7.16 (m, 2H), 6.94 - 6.90 (m, 2H), 6.63 (d, J J = 15.9 Hz, 1H), 3.95(d, J J = 3.2 Hz, 6H). 13 C NMR (100 MHz, CDCl3) δ 163.78, 152.01, 149.54, 148.28,145.83, 145.06, 142.03, 134.07, 127.13, 125.88, 125.59, 125.06, 123.62,120.31, 119.98, 119.59, 117.89, 114.76, 113.28, 111.28, 110.09, 56.17, 56.12.HRMS(APCI) calculated for C 23 H 16 Cl2O5[M + H] + 443.0375 and 445.0345; found443.0447 and 445.0427. Compound 4ll: Yield: 73 %; mp: 190 - 192 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.18 (s,1H), 7.90 (d, J J = 15.9 Hz, 1H), 7.64 (s, 2H), 7.46 (t, J J = 9.4 Hz, 1H), 7.37 (d, J J = 8.3 Hz, 1H), 7.20 (d, J J = 16.5 Hz, 2H), 6.91 (d, J J = 3.4 Hz, 1H), 6.67 (d, J= 15.8 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 163.04, 152.76 (dd, J c-f = 131.0, 13.7 Hz), 150.25 (dd, J c-f = 126.4, 12.5 Hz), 145.92, 145.79, 145.07, 141.75, 134.12, 131.33 (t, J c-f = 5.0 Hz), 125.74, 125.53 (dd, J c-f = 9.2, 5.9 Hz), 124.84, 120.22, 120.02, 119.69, 118.28, 118.10, 117.95, 117.00 (d, J c-f = 4.9 Hz), 116.85, 114.86. 19 F NMR (376 MHz, CDCl3) δ -132.68 (d, J = 21.3 Hz), -136.09 (d, J = 20.5 Hz). HRMS(APCI) calculated for C 21 H 10 Cl2F2O3[M + H] + 418.9975 and 420.9946; found 419.0048 and 421.0031. Compound 4mm: Yield: 80 %; mp: 160 - 161 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.16 (s, 1H), 7.89 (d, J = 15.9 Hz, 1H), 7.83 (d, J = 6.4 Hz, 1H), 7.62 (s, 2H), 7.56 - 7.51 (m, 1H), 7.17 (q, J = 7.9, 5.4 Hz, 2H), 6.90 (d, J = 4.7 Hz, 1H), 6.68 (d,J = 15.9 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 163.03, 160.67 (d, J c-f = 253.6 Hz), 145.90, 145.43, 145.07, 141.73, 134.11, 133.64, 131.84 (d, J c-f = 4.2 Hz), 129.37 (d, J c-f = 7.6 Hz), 125.73, 125.58, 124.83, 120.21, 120.01, 119.67, 117.95, 117.29 (d, J c-f = 22.8 Hz), 116.93 (d, J c-f = 2.1 Hz), 114.85, 110.22 (d, J c-f = 22.0 Hz). 19 F NMR(376 MHz, CDCl3) δ -102.68. HRMS(APCI) calculated for C 21 H 10 BrCl2FO3[M + H] + 478.9174 and 480.9154; found 478.9249 and 480.9225. Compound 4nn: Yield: 90 %; mp: 200 - 202 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.19 (d, J = 1.3 Hz, 1H), 7.89 (d, J = 16.0 Hz, 1H), 7.72 (d, J = 2.0 Hz, 1H), 7.65 (d, J = 2.5 Hz, 2H), 7.52 (d, J = 8.3 Hz, 1H), 7.46 (dd, J = 8.4, 2.0 Hz, 1H), 7.19 (dd, J= 4.9, 2.7 Hz, 1H), 6.91 (dd, J = 4.9, 1.2 Hz, 1H), 6.74 (d, J = 16.0 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 162.96, 145.96, 145.42, 145.07, 141.74, 135.24, 134.15, 134.12, 133.69, 131.23, 130.21, 127.54, 125.75, 125.63, 124.85, 120.24, 120.05, 119.73, 117.97, 117.74, 114.87. HRMS(APCI) calculated for C 21 H 10 Cl4O3[M+H] + 452.9355 and 450.9384; found 452.9429 and 450.9461. Compound 4oo: Yield: 86 %; mp: 209 - 210 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.20 (d, J = 1.4 Hz, 1H), 8.13 (d, J = 2.0 Hz, 1H), 7.95 (d, J = 16.0 Hz, 1H), 7.76 (dd, J =8.4, 2.1 Hz, 1H), 7.67 - 7.63 (m, 3H), 7.19 (dd, J = 4.9, 2.7 Hz, 1H), 6.92 (dd, J = 4.9, 1.2 Hz, 1H), 6.83 (d, J = 16.0 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ162.54, 148.56, 146.01, 145.10, 143.96, 141.57, 134.17, 132.83, 132.27, 129.26, 125.65, 125.63, 125.10, 124.71, 120.17, 120.08, 119.77, 119.47, 118.03, 114.95. HRMS(APCI) calculated for C 21 H 10 Cl3NO5[M+Na] + 483.9625 and 485.9595; found 483.9524 and 485.9499. Compound 4pp: Yield: 88 %; mp: 206 - 208 ℃; 1 H NMR (400 MHz, CDCl3) δ 8.19 (d, J J = 1.3 Hz, 1H), 7.89 (d, J J = 16.0 Hz, 1H), 7.65 (d, J J = 2.5 Hz, 2H), 7.21 - 7.13(m, 3H), 6.95 - 6.88 (m, 2H), 6.75 (d, J J = 16.0 Hz, 1H). 13 C NMR (100 MHz, CDCl3) δ 164.70 (d, J c-f J = 13.6 Hz), 162.81, 162.22 (d, J c-f J = 14.0 Hz), 145.97, 145.52, 145.08, 141.67, 137.29, 134.16, 125.72, 125.63, 124.80, 120.22, 120.07, 119.73, 118.66, 117.98, 114.89, 111.30 (d, J c-f J = 26.2 Hz), 111.29 (d, J c-f J = 12.1Hz), 106.31 (t, J c-f J = 25.3 Hz). 1919F NMR (376 MHz, CDCl3) δ -108.55. HRMS(APCI) calculated for C 21 H 10 Cl2F2O3 [M+H] + 418.9975 and 420.9946; found 419.0052 and 421.0029. Compound 4qq: Yield: 87 %; mp: 156 - 157 ℃; 1 1H NMR (400 MHz, CDCl3) δ 8.18 (d, J J = 1.4 Hz, 1H), 8.02 (d, J J = 16.2 Hz, 1H), 7.64 (d, J J = 2.6 Hz, 2H), 7.39 (dtd, J J = 9.4, 7.6, 6.6, 2.4 Hz, 1H), 7.19 (dd, J J = 4.9, 2.7 Hz, 1H), 7.07 (tdd, J J = 9.1, 6.9, 2.1 Hz, 1H), 6.91 (dd, J J = 4.9, 1.2 Hz, 1H), 6.84 (d, J J = 16.2 Hz, 1H). 13 13C NMR (100 MHz, CDCl3) δ 162.94, 145.95, 145.07, 141.70, 138.95, 134.13, 125.73, 125.62, 124.81, 123.58, 123.54, 123.50, 123.46, 120.21, 120.04, 119.72, 119.35 (d, J c-f J = 6.7 Hz), 117.96, 114.88, 113.11 (d, J c-f J = 4.6 Hz), 112.93 (d, J c-f J = 4.2 Hz). 19 19F NMR (376 MHz, CDCl3) δ -129.01 (dd, J= 20.1, 9.9 Hz), -134.05 (dd, J = 19.4, 9.9 Hz), -158.98 (t, J = 19.7 Hz). HRMS(APCI) calculated for C 21 H9Cl2F3O3[M+H] + 436.9881 and 438.9851; found 436.9955 and 438.9935. Compound 4rr: Yield: 90 %; mp: 188 - 190 ℃; 1 1H NMR (400 MHz, CDCl3) δ 8.19 (d, J = 1.5 Hz, 1H), 7.83 (d, J = 15.9 Hz, 1H), 7.67 - 7.61 (m, 2H), 7.28 (s, 1H), 7.24 (s, 1H), 7.19 (dd, J = 4.9, 2.7 Hz, 1H), 6.91 (dd, J = 4.9, 1.2 Hz, 1H), 6.68 (d, J = 15.9 Hz, 1H). 13 13C NMR (100 MHz, CDCl3) δ 162.67, 152.99 (dd, J c-f = 10.2, 3.7 Hz), 150.49 (dd, J c-f = 10.5, 3.5 Hz), 145.98, 145.08, 144.74, 141.63, 140.13, 134.16, 130.22 (dd, J <00​​​​​​​​19F NMR (376 MHz, CDCl3) δ -132.62, -132.68, -155.30 (t, J J = 20.0 Hz). HRMS(APCI) calculated for C 21 H9Cl2F3O3[M+H] + 436.9881 and 438.9851; found 436.9956 and 438.9939. Compound 4ss: Yield: 86 %; mp: 187 - 188 °C; 1 1H NMR (400 MHz, CDCl3) δ 8.19 (d, J J = 1.4 Hz, 1H), 7.93 (d, J J = 15.9 Hz, 1H), 7.65 (d, J J = 3.3 Hz, 2H), 7.19 (dd, J J = 4.9, 2.7 Hz, 1H), 6.91 (dd, J J = 4.9, 1.1 Hz, 1H), 6.87 (s, 2H), 6.67 (d, J J = 15.9 Hz, 1H), 3.93 (d, J J = 3.2 Hz, 9H). 13 13C NMR (100 MHz, CDCl3) δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ 163.52, 153.70, 148.30, 145.86, 145.07, 141.92, 141.07, 134.08, 134.04, 129.53, 125.82, 125.59, 124.97, 120.27, 120.00, 119.63, 117.91, 114.89, 114.81, 105.97, 61.16, 56.39. HRMS(APCI) calculated for C 24 H 18 Cl2O6[M+H] + 473.0480 and 475.0451; found 473.0554 and 475.0535. Test Example 1 Using commercially available agrochemical rotenone as a control, the insecticidal activity of the compound against diamondback moth larvae was evaluated using the leaf-dipping method recommended by the International Resistivity Action Committee (IRAC). The specific procedure was as follows: 2 mg of the test compound was weighed into a 10 mL beaker, dissolved in 50 µL of analytical grade DMF, and then an appropriate amount of distilled water was added to prepare a solution of the desired concentration. Cabbage leaves were picked up with straight ophthalmic forceps and immersed in the solution for 2–3 seconds, then removed gently to remove excess droplets. Three leaves were used in each treatment, with each leaf immersed individually. The treated leaves were placed on treatment paper in numerical order, and after the solution on the leaf surface had air-dried naturally, they were transferred to marked 10 cm straight tubes. Second-instar diamondback moth larvae were inoculated into each tube, and the tube openings were sealed with gauze. All treatments were placed under standard culture conditions, and the results were observed and recorded after 96 hours. Three replicates were set for each compound. The control group was prepared by adding equal volumes of emulsifier and solvent to distilled water, mixing well, and then treating the control group using the same method.

[0033] The results are shown in Table 1.

[0034] Table 1. Insecticidal activity (lethality) test results of compounds 4a-4ss, compound 3, and rotenone.

[0035] In Table 1, - indicates that it was not measured.

[0036] As shown in Table 1, the overall activity was very good at a concentration of 600 mg / kg. Among them, 19 compounds showed higher activity against diamondback moth larvae at a concentration of 200 μg / mL than the parent compound 3, especially compounds 4f, 4p, 4v, 4cc, 4ll, and 4oo, which had a lethality of more than 80% against diamondback moth larvae.

[0037] Further LC analysis of these compounds 50 The values ​​are tested, as shown in Table 2.

[0038] Table 2. LC-100 of compounds with a lethality greater than 80% against diamondback moth larvae at a concentration of 100 mg / kg. 50 value

[0039] LC 50 Measurements showed that 4f and 4ll exhibited the strongest activity, LC... 50 The values ​​were 71.99 μg / mL and 73.31 μg / mL, respectively, both below 100 μg / mL. In contrast, the LC50 of the positive control rotenone... 50 The concentration was 35.63 μg / mL. Although the active compounds were less potent than rotenone, their LC50 was [not specified]. 50The values ​​show promising insecticidal potential. Furthermore, the compounds of this invention are derived from the natural product mango aldehyde, exhibiting good environmental friendliness and significant advantages over existing pesticides.

[0040] Test Example 2 Using commercially available ribavirin and ningnanmycin as controls, the antiviral activity of the compounds against tobacco mosaic virus (TMV) was tested. The in vivo antiviral activity of compounds 3, 4a~4ss against TMV is shown in Table 3.

[0041] The specific method is as follows: all tests for each compound were performed in triplicate. The inhibition rate of the compound was calculated using the following formula: Inhibition rate (%) = [(Number of control necrotic spots - Number of treated necrotic spots) / Number of control necrotic spots] × 100% First, the compound is dissolved in an appropriate amount of DMF, then diluted with water containing 0.1% Tween-80 to a concentration of 500 µg / mL, and then further diluted to 100 µg / mL.

[0042] In vivo inactivation of TMV by the compound: To test the inhibitory effect on the virus, equal volumes of virus extract and compound solution were mixed together for 30 minutes. The mixture was then inoculated onto tobacco leaves of the same age, with another group using the solvent and virus extract mixture as a control. The number of lesions was recorded 3-4 days after inoculation.

[0043] In vivo treatment of TMV with compounds: TMV (concentration of 6.0 × 10⁻⁶) was applied. -3 The test compound solution (µg / mL) was inoculated onto tobacco leaves of the same age. The leaves were then washed with water and air-dried. The solution was then applied to the inoculated leaves, while another group was inoculated with the solvent as a control. The number of local lesions was recorded 3-4 days after inoculation.

[0044] In vivo protection of TMV by the compounds: The compound solution was applied to at least 3 leaves of growing tobacco of the same age. In another group, the leaves were applied with the solvent as a control. After 12 h, TMV was inoculated onto the leaves by sap-leaf rubbing, followed by washing with water. The total number of local lesions appearing on the leaves 3-4 days after inoculation was recorded. Each compound was tested in triplicate.

[0045] Table 3. In vivo antiviral activity of compounds 3, 4a-4ss against TMV

[0046] In Table 3, - indicates that it was not measured.

[0047] It can be seen that at a concentration of 500 μg / mL, nine compounds exhibited higher inactivation effects than ribavirin. Among them, compounds 4f, 4s, 4t, 4u, and 4p showed higher in vivo inactivation, therapeutic, and protective activities than ribavirin. Compound 4s exhibited the highest inactivation activity (51.6±1.2%), compound 4f had the strongest protective effect (50.2±2.1%), and compound 4u showed the best therapeutic effect (49.5±2.5%). Compound 4f demonstrated the most outstanding overall activity, with an inactivation effect of 48.0±3.1%, a protective effect of 50.2±2.1%, and a therapeutic effect of 41.4±3.5%.

[0048] Test Example 3 Using the commercial fungicide chlorothalonil as a control, the in vitro antibacterial activity of each compound against seven plant pathogens at a concentration of 50 μg / mL was tested by the cell growth rate assay (plate method). The specific method is as follows: Dissolve the test agent in an appropriate amount of DMSO, and then dilute it to the required concentration with an aqueous solution containing 200 μg / mL emulsifier; add 1 mL of drug solution and 9 mL of culture medium to the petri dish, mix well and prepare a 50 μg / mL drug-containing plate. A plate with 1 mL of sterile water added is used as a blank control. Use a 4 mm diameter punch to cut the mycelial cake along the edge of the colony and inoculate it on the drug-containing plate. Each treatment is repeated 3 times. Place the plate in a constant temperature incubator at (24±1)℃ for 72 h, measure the expansion diameter of the colonies in each treatment, take the average value, and calculate the relative inhibition rate according to the following formula (1): Relative antibacterial rate = [(D) CK -D) / D CK ]×100% formula (1); In the formula: D and D CK The values ​​are the average diameter of the bacterial disc expansion in the treatment group and the control group, respectively, in cm.

[0049] The fungicidal activities of compounds 4a-4s, compound 3, and chlorothalonil against seven plant pathogens are shown in Table 4. The EC50 of compounds 4f and chlorothalonil against *Phytophthora capsici* is also shown in Table 4. 50 As shown in Table 5.

[0050] Table 4. Fungicidal activity of compounds 4a-4s, compound 3, and chlorothalonil against seven plant pathogens.

[0051] Table 5. EC5 of compound 4f and chlorothalonil against Phytophthora capsici. 50

[0052] Overall, most compounds showed good fungicidal activity against rapeseed sclerotinia, cucumber gray mold, and apple ring rot fungus. In particular, compound 4f exhibited 100% inhibition against *Phytophthora capsici* at the initial screening concentration, and also showed good EC50 activity against *Phytophthora capsici*. 50 The concentration is 12.95 μg / mL, which is close to that of the commercially available chlorothalonil. Furthermore, the compound of this invention is derived from the natural product mango aldehyde, exhibiting good environmental friendliness and demonstrating significant advantages over chlorothalonil.

[0053] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle 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 cyclopentene-cinnamic acid ester compound, characterized in that, It has the structure shown in Equation I or Equation II: Formula I; Formula II; In Formula I, R is one or more of H, C1-C4 alkyl, halogen, trifluoromethyl, trifluoromethoxy, dimethylamino, nitro and alkoxy; the number of R is 1 to 5.

2. The cyclopentene-cinnamate compound according to claim 1, characterized in that, It has the structure shown in any one of Equations 4a to 4ss: 。 3. The method for preparing the cyclopentene-cinnamate ester compound according to claim 1 or 2, characterized in that, Includes the following steps: 6-Dimethylaminofulne reacts with 2,6-dichloro-1,4-benzoquinone by an addition reaction to give a compound having the structure shown in Formula 3; In the presence of a condensing agent and a catalyst, a compound having the structure shown in Formula 3 undergoes an esterification reaction with a cinnamic acid compound having the structure shown in Formula 4 or Formula 5 to obtain a cyclopentene cinnamic acid ester compound. Formula 3; Equation 4; Formula 5.

4. The preparation method according to claim 3, characterized in that, The molar ratio of 6-dimethylaminofulne to 2,6-dichloro-1,4-benzoquinone is 1:0.8~2.0; The addition reaction is carried out at a temperature of 0℃ to -60℃ for a time of 0.2 to 4 hours.

5. The preparation method according to claim 3, characterized in that, The condensing agent comprises 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride; the catalyst comprises 4-dimethylaminopyridine. The molar ratio of the compound having the structure shown in Formula 3 to the cinnamic acid compound is 1:1.2~4.

6. The preparation method according to claim 3 or 5, characterized in that, The esterification reaction is carried out at a temperature of 0℃ to 50℃ for a time of 2 to 10 hours.

7. The preparation method according to claim 3, characterized in that, The esterification reaction is followed by a post-processing of the resulting esterification product, the post-processing including: The esterification reaction product was quenched with water, diluted with an organic solvent, and the resulting organic phase was dried, concentrated, and purified by column chromatography. The eluent for column chromatography purification is petroleum ether and dichloromethane, with a volume ratio of 4:

1.

8. The application of the cyclopentene-cinnamate compound according to claim 1 or 2, or the cyclopentene-cinnamate compound prepared by any one of claims 3 to 7, as an agricultural insecticide.

9. The application of the cyclopentene-cinnamate compound according to claim 1 or 2, or the cyclopentene-cinnamate compound prepared by any one of claims 3 to 7, as an antiviral agent for plants.

10. The application of the cyclopentene-cinnamic acid ester compound according to claim 1 or 2, or the cyclopentene-cinnamic acid ester compound prepared by the preparation method according to any one of claims 3 to 7, as an agricultural fungicide.

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