A class of naphthoquinone derivatives, their preparation, and their application in the prevention and control of plant diseases and pests.

Abstract

This invention relates to a class of naphthoquinone derivatives, their preparation, and their application in the prevention and control of plant diseases and pests. This invention is the first to discover that juglone derivatives I-1 to I-13 and lancione derivatives II-1 to II-6 can effectively inhibit 14 plant pathogens, including tobacco mosaic virus (TMV), cucumber wilt, peanut brown spot, apple ring rot, wheat sheath rot, corn small spot, watermelon anthracnose, rice seedling blight, tomato early blight, wheat scab, rice blast, pepper blight, rapeseed sclerotium, cucumber gray mold, and rice sheath rot. Furthermore, it exhibits good activity against eight plant pests: armyworm, cotton bollworm, corn borer, cabbage moth, mosquito larvae, aphids, spider mite, and diamondback moth.

Description

Technical Field

[0001] This invention relates to a class of naphthoquinone derivatives, their preparation, and their application in the prevention and control of plant diseases and pests, belonging to the field of agricultural protection technology. Background Technology

[0002] Naphthoquinones have always played a vital role in the discovery of novel drugs, and the design and synthesis of naphthoquinones is an important approach in the search for active lead compounds. Among naphthoquinones, juglone and lanseviquinone typically possess broad biological activities and low toxicity to humans and the environment (Structural Formula 1).

[0003]

[0004] There are many types of naphthoquinone derivatives from natural sources, mostly derived from functional metabolites of various plants, microorganisms, and marine organisms. Among naphthoquinone derivatives, 1,4-naphthoquinone is the most stable and widely reported. The 1,4-naphthoquinone skeleton is widely found in natural products and synthetic drugs, and it has antibacterial, anticancer, and insecticidal biological activities (Bioorg. Med. Chem. Lett., 2016, 26(2): 334-337). Naphthoquinone compounds such as juglone and lansine are the main active ingredients that exert antibacterial, insecticidal, anti-inflammatory, and wound-healing effects, but systematic research in the field of pesticides is lacking. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a class of naphthoquinone derivatives, their preparation methods, and their applications in the prevention and control of plant diseases and pests.

[0006] The present invention comprises a class of naphthoquinone derivatives I and II, specifically juglone derivatives I-1 to I-13 and lancione derivatives II-1 to II-6, wherein R 1 R 2 R 3 The functional groups shown in the structures I-1 to I-13 and II-1 to II-6 are (Structural Formula 2).

[0007]

[0008] The synthetic methods for the above chemical structural formulas I-1 to I-6, II-1 to II-6, and I-9 are as follows:

[0009] Juglone derivatives I-1 to I-6 and lansinoquinone derivatives II-1 to II-6, I-9 were prepared according to the method shown in Equation 1: First, using dichloromethane as a solvent and triethylamine as a base, juglone or lansinoquinone was added, followed by the slow addition of the reaction substrate acyl chloride or sulfonyl chloride. The reaction was carried out at room temperature for 2 hours to generate products I-1 to I-6, II-1 to II-6, I-9. 1 and R2 These are the groups shown in the structures I-1 to I-6 and II-1 to II-6.

[0010]

[0011] Synthesis of Juglone derivative I-7: It was prepared according to the method shown in Equation 2. First, acetone was used as solvent and potassium carbonate as base. Juglone and iodide were heated under reflux for 8 hours to generate I-7.

[0012]

[0013] Synthesis of Juglone derivative I-8: It was prepared according to the method shown in Equation 3, using trifluorotoluene and water in a 1:1 ratio as solvents, and silver nitrate and ammonium persulfate as catalysts. Juglone and cyclohexabolic acid underwent a coupling reaction at room temperature to generate I-8.

[0014]

[0015] Synthesis of Juglone derivatives I-10 to I-13: Prepared according to Equation 4, firstly, using tetrahydrofuran as solvent, triethylamine as base, and tetra-triphenylphosphine palladium as catalyst, 4-bromojuglone undergoes ammoniation reactions with different ammonia sources at 60°C to generate I-10 to I-13. R represents the functional group shown in the structures of I-10 to I-13.

[0016]

[0017] The juglone and lansine derivatives I-1 to I-13, II-1 to II-6 of this invention exhibit excellent antiviral and antifungal activity against plant viruses and pathogens. They can effectively inhibit 14 plant pathogens, including tobacco mosaic virus (TMV), cucumber wilt, peanut brown spot, apple ring rot, wheat sheath rot, corn small spot, watermelon anthracnose, rice seedling blight, tomato early blight, wheat scab, rice blast, pepper phytosis, rapeseed sclerotium, cucumber gray mold, and rice sheath rot, as well as good insecticidal activity against plant pests. Detailed Implementation

[0018] The following examples and test results are intended to further illustrate the present invention, but do not imply limitation of the invention.

[0019] Example 1: Synthesis of Juglone and Lanseiquinone derivatives I-1 to I-6, II-1 to II-6, I-9

[0020] In a 50 mL round-bottom flask containing the substrates juglone and lansinoquinone, 0.1 M ultra-dry dichloromethane and triethylamine (0.62 mL, 2 equiv) were added. Benzoyl chloride (0.31 mL, 2.64 mmol, 1.2 equiv) was slowly added under ice bath conditions, and the reaction was carried out at room temperature for 1 h. After the reaction was completed by TLC monitoring, the mixture was extracted with dichloromethane, washed with brine, dried over anhydrous sodium sulfate, concentrated, and the product was obtained by column chromatography.

[0021] I-1 is a pale yellow crystal with a yield of 70% and a melting point of 100-102℃. 1 H NMR (400MHz, CDCl3) δ8.16-8.07 (m, 3H), 7.81 (t, J=7.9Hz, 1H), 7.53 (dd, J=8.1, 1.2Hz, 1H), 7.35 (d, J=8.0Hz, 2H), 6.94 (d, J=10.3Hz, 1H), 6.82 (d, J=10.3Hz, 1H), 2.47 (s, 3H). 13 HRMS C 18 H 13 O4 + [M+H] + cald.293.0808, found 293.0804.

[0022] I-2 is a reddish-brown solid with a yield of 60% and a melting point of 94-96℃. 1 H NMR (400MHz, CDCl3) δ8.04 (dd, J=7.8, 1.2Hz, 1H), 7.76 (t, J=7.9Hz, 1H), 7.41 (dd, J=8.1, 1.2Hz, 1H), 6.94 (d, J= 10.3Hz, 1H), 6.86 (d, J=10.3Hz, 1H), 1.99 (tt, J=8.1, 4.6Hz, 1H), 1.29 (dd, J=4.5, 3.1Hz, 2H), 1.15-1.11 (m, 2H). 13 HRMS C 14 H 10 NaO4 +[M+Na] + cald.265.0471, found 265.0471.

[0023] I-3 is a yellowish-brown solid with a yield of 80% and a melting point of 85-87℃. 1 H NMR (400MHz, CDCl3) δ8.08 (d, J=7.7Hz, 1H), 7.79 (t, J=7.9Hz, 1H), 7.43 (d, J=8.1 Hz, 1H), 6.95 (d, J=10.3Hz, 1H), 6.86 (d, J=10.3Hz, 1H), 4.49 (s, 2H), 3.61 (s, 3H). 13 HRMS C 13 H 10 NaO5 + [M+Na] + cald.269.0420.found 269.0419.

[0024] I-4 is a reddish-brown solid with a yield of 70% and a melting point of 57-59℃. 1 H NMR (400MHz, CDCl3) δ8.03 (d, J=7.7Hz, 1H), 7.73 (t, J=7.9Hz, 1H), 7.33 (m, 5H), 7.24 (d, J=4.0 Hz, 1H), 6.92 (d, J=10.3Hz, 1H), 6.83 (d, J=10.3Hz, 1H), 3.18-3.12 (m, 2H), 3.09-3.04 (m, 2H). 13 HRMS C 19 H 14 NaO4 + [M+Na] + cald.329.0784, found 329.0783.

[0025] I-5 is a yellow crystal with a yield of 70% and a melting point of 102-104℃. 1H NMR (400MHz, CDCl3) δ8.85 (s, 1H), 8.23 ​​(d, J = 8.4Hz, 1H), 8.11 (d, J = 7.6Hz, 1H), 8.05-7.90 (m, 3H), 7.84 (t, J=7.8Hz, 1H), 7.68-7.55 (m, 3H), 6.95 (d, J=10.3Hz, 1H), 6.83 (d, J=10.2Hz, 1H). 13 C NMR (100MHz, CDCl3) δ220.6, 184.3, 183.6, 165.3, 149.9, 140.0, 137.4, 136.0, 134.9, 13 3.6, 132.6, 132.4, 131.2, 130.1, 129.6, 128.8, 128.5, 127.9, 126.9, 125.6, 125.1.HRMS C 21 H 12 NaO4 + [M+H] + cald.351.0628, found 351.0626.

[0026] I-6 is a yellow solid with a yield of 70% and a melting point of 145-147℃. 1 H NMR (400MHz, CDCl3) δ8.10 (d, J=7.7Hz, 1H), 8.01 (d, J=7.5Hz, 2H), 7.74 (dt, J=11.4, 7. 8Hz, 2H), 7.58 (dd, J=17.0, 8.2Hz, 3H), 6.93 (d, J=10.3Hz, 1H), 6.82 (d, J=10.3Hz, 1H). 13 HRMS C 16 H 10 NaO5S + [M+Na] + cald.337.0141, found 337.0141.

[0027] II-1 is a yellow oily substance with a yield of 67%. 1H NMR (400MHz, CDCl3) δ8.11 (d, J=8.2Hz, 2H), 8.08 (dd, J=7.8, 1.2Hz, 1H), 7.75 (t, J=7.9Hz, 1H), 7.47 (d d, J=8.1, 1.2Hz, 1H), 7.32 (d, J=8.0Hz, 2H), 6.66 (q, J=1.5Hz, 1H), 2.45 (s, 3H), 2.14 (d, J=1.5Hz, 3H). 13 C NMR (100MHz, CDCl3) δ185.0, 183.5, 165.2, 149.7, 146.8, 144.6, 136.9, 134.4, 133.9, 130.5, 129.7, 129.4, 126.7, 125.1, 124.1, 21.8, 16.0.

[0028] II-2 is a pale yellow oily substance with a yield of 50%. 1 H NMR (400MHz, CDCl3) δ8.85 (s, 1H), 8.23 ​​(dd, J=8.6, 1.7Hz, 1H), 8.14 (dd, J=7.8, 1.2Hz, 1H), 8.05-7 .90 (m, 2H), 7.81 (t, J = 7.9Hz, 1H), 7.69-7.52 (m, 2H), 6.69 (q, J = 1.5Hz, 1H), 2.17 (d, J = 1.5Hz, 3H). 13 C NMR (100MHz, CDCl3) δ184.9, 183.5, 165.3, 149.6, 146.9, 136.9, 136.0, 134.4, 134.0, 132.6, 132.3, 129.7 128.6, 127.9, 126.7, 125.6, 125.2, 123.8, 77.4, 77.1, 76.7, 16.1.

[0029] II-3 is a yellowish-brown crystal with a yield of 70% and a melting point of 125-127℃. 1 H NMR (400MHz, CDCl3) δ8.07 (d, J=7.7Hz, 1H), 7.73 (t, J=7.9Hz, 1H), 7.39 (d, J=8.1Hz, 1H), 6.73 ( s, 1H), 2.18 (s, 3H), 2.05-1.96 (m, 1H), 1.30 (dd, J=7.6, 3.8Hz, 2H), 1.14 (dd, J=7.8, 3.1Hz, 2H). 13HRMS C 15 H 12 NaO4 + [M+Na] + cald.256.736, found 279.0626.

[0030] II-4 is a yellow solid with a yield of 80% and a melting point of 98-100℃. 1 H NMR (400MHz, CDCl3) δ8.09 (d, J=7.7Hz, 1H), 7.75 (t, J=7.9Hz, 1H), 7.39 (d, J=8.0Hz, 1H), 6.71 (s, 1H), 4.49 (s, 2H), 3.61 (s, 3H), 2.17 (s, 3H). 13 HRMS C 15 H 15 O5 + [M+H] + cald.275.918, found 275.0914.

[0031] II-5 is a reddish-brown solid with a yield of 60% and a melting point of 105-107℃. 1 H NMR (400MHz, CDCl3) δ7.99-7.93(m, 2H), 7.69-7.63(m, 1H), 7.55-7.50(m, 2H ), 7.25-7.20 (m, 2H), 6.77 (dd, J=6.4, 2.0Hz, 1H), 6.65 (s, 1H), 2.28 (s, 3H). 13 HRMS C 17 H 13 O5S + [M+H] +cald.329.0478, found 329.0477.

[0032] II-6 is a brown solid with a yield of 60% and a melting point of 140-142℃. 1 H NMR (400MHz, CDCl3) δ8.94 (t, J=9.6Hz, 1H), 8.30-8.14 (m, 2H), 8.01 (d, J=10.6Hz, 1H), 7.80-7.73 (m, 1H), 7.69 (dd, J=10.2, 7.4Hz, 1H), 7.55 (dd, J=7.6, 3.2Hz, 1H), 7.30-7.25 (m, 1H), 7.13 (d, J=8.3Hz, 1H), 6.87-6.56 (m, 2H), 2.20 (d, J=11.2Hz, 3H). 13 C NMR (100MHz, CDCl3) δ147.8, 146.3, 137.9, 135.5, 134.2, 133.5, 133.2, 130.9, 129.7, 1 28.2, 128.9, 128.7, 127.4, 125.4, 124.2, 114.8, 112.6, 111.3, 108.8, 102.1, 25.2.HRMS C 21 H 15 O5S + [M+H] + cald.379.0635, found379.0633.

[0033] I-9 is a yellowish-brown solid with a yield of 70% and a melting point of 74-76℃. 1 H NMR (400MHz, CDCl3) δ8.82 (d, J=8.2Hz, 1H), 8.19 (dd, J=7.7, 4.5Hz, 2H), 8.02 (dd, J=13.3, 5.4Hz, 2H), 7.7 8-7.72 (m, 1H), 7.68 (dd, J=12.7, 5.5Hz, 1H), 7.62-7.54 (m, 2H), 7.45 (s, 1H), 7.09 (dd, J=8.2, 1.0Hz, 1H). 13 C NMR (100MHz, CDCl3) δ181.2, 174.9, 148.0, 141.6, 138.8, 136.2, 134.9, 134.3, 134.1 ,133.7,131.6,130.9,129.3,129.1,129.0,128.5,127.5,126.1,125.2,124.1.HRMSC 20 H 11 BrNaO5S+ [M+Na] + cald.464.9403, found 464.9400

[0034] Example 2: Synthesis of Juglone derivative I-7.

[0035] Add iododecane (2 equiv) and potassium carbonate (2 equiv) to the substrate juglone in acetone (0.1 M) and react overnight at room temperature. Remove solvent, extract with ethyl acetate, wash the organic layer with brine, dry to anhydrous sodium sulfate, concentrate, and precipitate by column chromatography to obtain the product as a yellow-green solid, yield 59%, melting point 50-52℃. 1 H NMR (400MHz, CDCl3) δ8.93 (d, J=10.1Hz, 1H), 7.96 (dd, J=7.6, 1.2Hz, 1H), 7.60 (t, J=8.0Hz, 1H), 7.53 (d, J=7.7Hz, 1H), 6.5 5 (d, J=10.1Hz, 1H), 4.39 (t, J=6.7Hz, 2H), 1.87-1.76 (m, 2H), 1.51-1.43 (m, 2H), 1.40-1.26 (m, 12H), 0.90 (t, J=6.8Hz, 3H). 13 C NMR (100MHz, CDCl3) δ165.7, 159.8, 154.7, 141.3, 130.8, 128.1, 127.1, 121 .2, 118.6, 118.0, 66.0, 31.9, 29.5, 29.3, 29.3, 28.6, 26.1, 22.7, 14.1.HRMS C 20 H 27 O3 + [M+H] + cald.315.1955, found 315.1956.

[0036] Example 3: Synthesis of Juglone derivative I-8.

[0037] In a 50 mL round-bottom flask, the substrate reactant juglone, silver nitrate (0.3 equiv), ammonium persulfate (3 equiv), solvent PhCF3∶H2O=1∶1, and reactant borate (2 equiv) were added. The mixture was stirred at room temperature for 8 h. After the reaction was completed by TLC monitoring, the mixture was extracted with dichloromethane, washed with organic phase brine, dried over anhydrous sodium sulfate, dissolved, and subjected to column chromatography to obtain an orange-yellow oil with a yield of 23%. 1H NMR (400MHz, CDCl3) δ11.99 (s, 1H), 7.65-7.58 (m, 2H), 7.25 (s, 1H), 6.69 (s, 1H), 2.90 (t, J=11.9Hz, 1H), 1.85 (d, J=10.4Hz, 6H), 1.45 (d, J=13.2Hz, 2H), 1.28-1.16 (m, 4H). 13 HRMS C 17 H 19 O3 + [M+H] + cald.271.1329, found 271.1333.

[0038] Example 4: Synthesis of Juglone Derivatives I-10 to I-13

[0039] An aniline-substituted compound (1 equiv), tetrakis(triphenylphosphine)palladium (0.1 equiv), triethylamine (1 equiv), and tetrahydrofuran (0.1 M) solvent were added to the substrate 4-bromojugone. The mixture was purged with argon and reacted at 60 °C for 12 h. After removing the tetrahydrofuran, the mixture was extracted with dichloromethane, washed with brine, dried over anhydrous sodium sulfate, concentrated, and subjected to column chromatography to give products I-10 to I-13.

[0040] I-10 is a reddish-brown crystal with a yield of 50% and a melting point of 65-67℃. 1 H NMR (400MHz, CDCl3) δ12.92 (s, 1H), 8.16 (s, 1H), 7.69 (dd, J=7.5, 1.0Hz, 1H), 7.57-7.52 (m, 1H), 7.31 (dd, J=4.2, 1.1Hz , 1H), 7.03 (d, J=2.9Hz, 1H), 6.91 (d, J=9.0Hz, 1H), 6.70 (dd, J=8.9, 2.9Hz, 1H), 6.44 (s, 1H), 3.90 (s, 3H), 3.83 (s, 3H). 13 C NMR (100MHz, CDCl3) δ189.9, 184.2, 161.0, 153.8, 145.5, 144.4, 134.3, 130. 4, 127.2, 125.9, 119.4, 111.8, 110.1, 109.5, 108.2, 102.9, 56.2, 55.9.HRMS C 18 H16 NO5 + [M+H] + cald.326.1023, found 326.1021.

[0041] I-11 is a reddish-brown crystal with a yield of 70% and a melting point of 120-122℃. 1 H NMR (400MHz, CDCl3) δ12.91 (d, J=2.3Hz, 1H), 7.73-7.65 (m, 2H), 7.55-7.50 (m, 1H), 7.41-7.35 (m, 1H), 7.30 (s, 2H), 7.24 (s, 1H), 7.13 (d, J=7.6Hz, 1H), 6.27 (d, J=2.3Hz, 1H), 1.35 (d, J=2.4Hz, 9H). 13 C NMR (100MHz, CDCl3) δ189.9, 181.6, 161.0, 153.4, 145.7, 136.7, 134.4, 134. 3, 130.3, 129.4, 126.1, 123.3, 120.2, 119.9, 119.4, 102.2, 34.9, 31.3.HRMS C 20 H 20 NO3 + [M+H] + cald.322.1438, found 322.1435.

[0042] I-12 is a reddish-brown crystal with a yield of 80% and a melting point of 175-177℃. 1 H NMR (400MHz, CDCl3) δ12.89 (s, 1H), 7.67 (d, J=7.4Hz, 2H), 7.52 (t, J=8.0Hz, 1H), 7.35-7.28 (m, 2H), 7.10-7.04 (m, 3H), 6.31 (s, 1H), 2.39 (s, 3H). 13 C NMR (100MHz, CDCl3) δ189.9, 184.2, 161.0, 150.1, 141.5, 138.4, 134.3, 129.6, 126.9, 126.1, 123.3, 119.8, 119.4, 116.7, 114.8, 102.3, 21.5.HRMSC 17 H 14 NO3 + [M+H] + cald.280.0968, found 280.0968.

[0043] I-13 is a reddish-brown crystal with a yield of 70% and a melting point of 130-132℃. 1 H NMR (400MHz, CDCl3) δ12.92 (s, 1H), 7.67 (d, J=6.8Hz, 2H), 7.52 (t, J=8.0Hz, 1H), 7 .45 (d, J=8.5Hz, 2H), 7.29 (s, 1H), 7.21 (d, J=8.5Hz, 2H), 6.27 (s, 1H), 1.34 (s, 9H). 13 HRMS C 20 H 20 NO3 + [M+H] + cald.322.1438, found 322.1437.

[0044] Example 5: Determination of activity against tobacco mosaic virus, the determination procedure is as follows:

[0045] 1. Virus purification and concentration determination:

[0046] Virus purification and concentration determination were performed in accordance with the SOP (Standard Operating Procedure) for tobacco mosaic virus prepared by the Bioassay Laboratory of the Institute of Elementochemistry, Nankai University. The crude virus extract was centrifuged twice with polyethylene glycol, and the concentration was determined. It was then stored at 4°C for later use.

[0047] 2. Preparation of compound solutions:

[0048] After weighing, the original drug was dissolved in DMF to obtain 1×10 5 The stock solution was diluted to μg / mL with an aqueous solution containing 1‰ Tween 80 to the required concentration; the Ningnanmycin preparation was diluted directly with water.

[0049] 3. In vivo protection:

[0050] Select uniformly growing *Nicotiana santalinus* plants at the 3-5 leaf stage and spray the entire plant with the pesticide. Each treatment was repeated three times, with a 1‰ Tween 80 aqueous solution as a control. 24 hours later, sprinkle emery (500 mesh) on the leaves. Using a brush dipped in the virus solution, gently rub the entire leaf surface along the veins twice, supporting the underside of the leaf with the palm of your hand. The virus concentration was 10 μg / mL. Rinse with running water after inoculation. Record the number of lesions after 3 days and calculate the control efficacy.

[0051] 4. In vivo therapeutic effects:

[0052] Select uniformly growing *Nicotiana sambac* plants at the 3-5 leaf stage. Inoculate the entire leaf with the virus using a paintbrush at a concentration of 10 μg / mL. Rinse with running water after inoculation. After the leaves have dried, spray the entire plant with the pesticide. Each treatment is replicated three times, with a 1‰ Tween 80 aqueous solution as a control. Record the number of lesions after 3 days and calculate the control efficacy.

[0053] 5. In vivo passivation effect:

[0054] Select uniformly growing 3-5 leaf stage *Nicotiana sambac* plants. Mix the pesticide with an equal volume of virus sap, inactivate for 30 minutes, and then inoculate by friction. The virus concentration is 20 μg / mL. Rinse immediately with running water after inoculation. Repeat 3 times. Include a 1‰ Tween 80 aqueous solution as a control. Count the number of lesions after 3 days and calculate the results.

[0055] Inhibition rate (%) = [(Number of control necrotic spots - Number of treated necrotic spots) / Number of control necrotic spots] × 100%

[0056] First, the in vivo inactivation activity against tobacco mosaic virus (TMV) of all compounds was tested at a treatment dose of 500 μg / mL. Compounds with a relative inhibition rate greater than 40% were further tested for in vivo therapeutic and protective activity at a treatment dose of 500 μg / mL, and for in vivo inactivation, therapeutic, and protective activity against TMV at a treatment dose of 100 μg / mL. Positive controls were the commercially available antiviral agents ribavirin and ningnanmycin.

[0057] Table 1. Results of anti-Tobacco Mosaic Virus (TMV) activity tests of juglone-lansine derivatives 1-1 to I-13 and II-1 to II-6:

[0058]

[0059]

[0060] The data in the table show that the juglone-lansine derivatives I-1 to I-13 and II-1 to II-6 all exhibited good anti-TMV activity at a treatment concentration of 500 μg / mL. Among them, derivatives II-5, I-6, and I-10 showed anti-TMV activity comparable to that of ribavirin.

[0061] Example 6: Antibacterial activity test, the measurement procedure is as follows:

[0062] In vitro sterilization test, bacterial growth rate determination method (plate method):

[0063] A certain amount of the drug was dissolved in an appropriate amount of acetone, and then diluted to the required concentration with an aqueous solution containing 200 μg / mL emulsifier. 1 mL of the drug solution was then injected into each petri dish, followed by 9 mL of culture medium. After mixing, a 50 μg / mL drug-containing plate was prepared. A plate with 1 mL of sterile water added served as a blank control. Mycelial discs were cut along the outer edge of the hyphae using a 4 mm diameter punch and transferred to the drug-containing plate. Each treatment was repeated three times. The petri dishes were incubated in a constant temperature incubator at 24 ± 1℃. After 48 hours, the diameter of the mycelial discs in each treatment was observed, and the average value was calculated. The relative inhibition rate was then compared with the blank control.

[0064]

[0065] Table 2. Results of anti-plant pathogen activity tests of juglone-lansine derivatives I-1~I-13, II-1~II-6:

[0066]

[0067]

[0068] Juglone-lansine derivatives exhibited broad-spectrum and excellent inhibitory activity against 14 tested bacteria at a test concentration of 50 μg / mL. Among them, the antibacterial activity against peanut brown spot was particularly good, with compounds II-4 and I-1 showing inhibition rates exceeding 60%, and compound I-2 achieving 100% inhibition. They also showed good antibacterial activity against rice sheath blight and apple ring rot, with some compounds exhibiting superior inhibitory activity against certain strains compared to commercially available fungicides such as carbendazim and pyrimethanil.

[0069] Example 7: Insecticidal Activity Test Method

[0070] 1. Activity test against armyworm (Mythimna separata Walker), cotton bollworm (Helicoverpa armigera), fall armyworm (Spodoptera frugiperda), and corn borer (Ostrinia nubilalis Hubner): All insects were normal populations reared indoors. The leaf-dip method was used. The active ingredient was dissolved in acetone to prepare a stock solution. Corn leaves were immersed in the acetone-prepared stock solution. After the solution dried, 10 third-instar larvae were introduced. The main effects were stomach poison and contact killing. Larval feeding was observed. Mortality was checked after three days. Each experiment was repeated two or three times, and the average value was taken.

[0071] 2. Mosquito larval activity test: The mosquito larvae were Culex pipiens pallens,

[0072] The larvae were a normal population raised indoors. The original drug was dissolved in acetone to prepare a stock solution, which was then diluted with water to a specific concentration to prepare a rearing solution. Ten third-instar Culex mosquito larvae were placed in the rearing solution, and the mortality rate was checked after three days. An aqueous solution containing 1 mL of the test solvent was used as a blank control. Each experiment was repeated three times, and the average value was taken.

[0073] Table 3. Insecticidal activity test results of juglone-lansine derivatives I-1~I-13, II-1~II-6:

[0074]

[0075]

[0076] Most compounds exhibited good activity against *Tetranychus carmine* at specific concentrations (600 μg / mL or 200 μg / mL); most compounds showed excellent activity against *Dalbergia odorifera* at a concentration of 600 μg / mL, with half of the compounds showing good activity at 200 μg / mL. However, the phenylpropionyl-substituted compound I-4 of juglone still showed a lethality greater than 60% against *Dalbergia odorifera* at 100 μg / mL and 10 μg / mL, while I-11 showed a 100% lethality against *Dalbergia odorifera* at 600 μg / mL and 200 μg / mL, and a 70% lethality at 100 μg / mL. These compounds show promising application potential.

Claims

1. A naphthoquinone derivative having the structure shown in Formula I, wherein the compound of Formula I is selected from one of compounds I-10 to I-13; 2. The method for preparing the naphthoquinone derivative according to claim 1: Synthesis of naphthoquinone derivatives I-10 to I-13: Prepared according to the method shown in Equation 4. First, using tetrahydrofuran as solvent, triethylamine as base, and tetra(triphenylphosphine)palladium as catalyst, bromojugolone 1 undergoes ammoniation reaction with different ammonia at 60°C to generate naphthoquinone derivatives I-10 to I-13.

3. The application of the naphthoquinone derivative of claim 1 in the prevention and control of tobacco mosaic virus disease.

4. The application of the naphthoquinone derivative of claim 1 in the prevention and control of plant pathogenic diseases, characterized in that... The plant pathogens mentioned are cucumber wilt, peanut brown spot, apple ring rot, wheat sheath blight, corn leaf spot, watermelon anthracnose, rice bakanae disease, tomato early blight, wheat scab, rice blast, pepper blight, rapeseed sclerotinia, cucumber gray mold, or rice sheath blight.

5. The application of compound I-10 of claim 1 in the control of plant pests, characterized in that... The plant pests mentioned are armyworms, cotton bollworms, corn borers, or diamondback moths.

6. The application of compound I-11 of claim 1 in the control of plant pests, characterized in that... The plant pests mentioned are aphids, spider mites, or diamondback moths.

7. The use of compound I-12 of claim 1 in the control of plant pests, characterized in that... The plant pests mentioned are armyworms, corn borers, spider mites, or diamondback moths.

8. The application of compound I-13 of claim 1 in the control of plant pests, characterized in that... The plant pests mentioned are armyworms, bollworms, or diamondback moths.

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