A nematicidal insecticide and a method of preparing the same

Abstract

The application relates to the technical field of biological control, and provides a root-knot nematode-killing insecticide and a preparation method thereof. The application provides compounds as shown in formula 1 to formula 13. Compared with the prior art, quinoline type derivatives are designed and synthesized, the derivatives are small-molecule compounds with simple structure, easy synthesis and good nematode-killing activity, the nematode-killing activity of the compounds is researched, the compounds are used as root nematode-killing insecticides, and a thought is provided for solving the current predicament of few nematode-killing insecticides.

Description

Technical Field

[0001] The present invention relates to the technical field of biological control, and more particularly to a root-knot nematode insecticide and a preparation method thereof. Background Art

[0002] The southern root-knot nematode (Meloidogyne incongnita) is a plant-parasitic nematode that harms crops and seriously impacts the sustainable development of agriculture. Nematicides are primarily classified into fumigant and non-fumigant types. Fumigant nematicides, such as dazomet and methamphetamine, are primarily applied through soil fumigation. However, the use of fumigant nematicides can damage the soil ecosystem and harm non-target organisms. Non-fumigant nematicides, such as organophosphorus compounds, were introduced in 1955. Currently, commercialized nematicides primarily include abamectin, thiazolyl, fluopyram, fluthiazolin, and avermectin benzoate. Among these, avermectin, thiazolyl, and avermectin benzoate are the most common active ingredients, accounting for over 70%. The range of nematicides available for agricultural production remains limited, and long-term use of a single nematicide can lead to varying degrees of resistance in root-knot nematodes.

[0003] Therefore, the development of new, environmentally friendly nematicides is urgent. Summary of the Invention

[0004] In view of this, the object of the present invention is to provide a root-knot nematode insecticide and a preparation method thereof. The present invention designs and synthesizes quinoline derivatives, which are small molecule compounds with simple structure, easy synthesis and good nematicidal activity.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] Compounds shown in Formulas 1 to 13;

[0007]

[0008]

[0009] The present invention also provides a method for preparing the compounds shown in Formulas 1 to 8, comprising:

[0010] (1) The compound represented by Formula I is mixed with N,N-dimethylformamide and potassium carbonate, reacted at 100-120°C for 0.5-2 hours, cooled to 50-60°C, and then mixed with chloroacetone, followed by reaction at 50-60°C for 0.5-1 hour to obtain compounds A1-A8;

[0011]

[0012] In formula I, R1 and R2 are independently selected from H, F, Br, I, -CH3, -CF3 or -OCH3;

[0013]

[0014] (2) Compounds A1-A8 were mixed with N-methylpropiolide and reacted at 210°C for 5 h to obtain compounds B1-B8;

[0015]

[0016] (3) Compounds B1 to B8 were mixed with N,N-dimethylformamide, potassium carbonate, and dibromomethane, and heated at 120° C. under a nitrogen atmosphere for 2 h to obtain compounds represented by Formulas 1 to 8.

[0017] Preferably, the molar ratio of the compounds B1 to B8 to potassium carbonate and dibromomethane is 1:(3-5):(1-2), preferably 1:3:2.

[0018] The present invention also provides a method for preparing the compounds shown in Formula 9 to Formula 13, comprising:

[0019] The compound represented by Formula 1 is mixed with 1,4-dioxane, potassium carbonate, R'B(OH)2, and tetrakis(triphenylphosphine)palladium, and reacted at 90° C. under a nitrogen atmosphere for 2 hours to obtain compounds represented by Formulas 9 to 13;

[0020] In R'B(OH)2, R' is selected from phenyl, benzyl, phenylchloro,

[0021] Preferably, the molar ratio of the compound represented by Formula 1 to potassium carbonate, R'B(OH)2, and tetrakis(triphenylphosphine)palladium is 1:(4-5):(1-2):(0.05-0.1), preferably 1:5:1:0.05.

[0022] The present invention also provides the use of compounds represented by Formulas 1 to 13 in controlling root-knot nematodes;

[0023]

[0024]

[0025] Preferably, the root-knot nematode includes Meloidogyne incognita.

[0026] Preferably, the concentration of the compounds represented by Formula 1 to Formula 13 is 50 to 200 μg / mL.

[0027] The present invention also provides a root-knot nematode insecticide, comprising one or more compounds represented by Formula 1 to Formula 13, and acceptable excipients.

[0028] The present invention also provides the use of one or more of the compounds represented by formulas 1 to 4, the compounds represented by formula 6, the compounds represented by formulas 8 to 9, and the compounds represented by formulas 11 to 13 in antibacterial applications;

[0029]

[0030]

[0031] Preferably, the antibacterial activity includes inhibiting one or more of wheat fusarium, banana anthracnose, rice sheath blight, rice blast, tomato gray mold, rubber anthracnose, pepper phytophthora, and banana wilt.

[0032] Preferably, the concentration of the compound represented by Formulae 1 to 4, the compound represented by Formulae 6, the compound represented by Formulae 8 to 9, or the compound represented by Formulae 11 to 13 is 50 to 100 μg / mL, preferably 50 μg / mL.

[0033] The present invention also provides the use of the compound represented by formula 5 in inhibiting wheat fusarium, pepper phytophthora, banana wilt, rubber anthracnose, rice blast and tomato gray mold.

[0034] Preferably, the concentration of the compound represented by Formula 5 is 50-100 μg / mL, preferably 50 μg / mL.

[0035] The present invention also provides the use of the compound represented by formula 7 in inhibiting wheat gibberella, banana anthracnose, pepper phytophthora, rice blast, rice sheath blight, and tomato gray mold.

[0036] Preferably, the concentration of the compound represented by Formula 7 is 50-100 μg / mL, preferably 50 μg / mL.

[0037] The present invention also provides the use of the compound represented by formula 10 in inhibiting wheat gibberella, banana anthracnose pathogen, pepper phytophthora, banana wilt pathogen, rubber anthracnose pathogen, rice blast pathogen, and tomato gray mold.

[0038] Preferably, the concentration of the compound represented by Formula 10 is 50 to 100 μg / mL, preferably 50 μg / mL.

[0039]

[0040] Compared with the existing technology, the present invention designs and synthesizes quinoline derivatives, which are small molecule compounds with simple structure, easy synthesis and good nematicidal activity. The present invention also studies the nematicidal activity of these compounds and uses them as root nematode insecticides, providing a solution to the current dilemma of limited nematicides. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 This is a graph showing the potted plant control efficacy of the target compound in Experimental Example 2 against southern root-knot nematodes;

[0042] Figure 2 This is the effect of the target compound at a concentration of 200 μg / mL on cucumber root growth in Experimental Example 3;

[0043] Figure 3 This is the experimental result of the live control effect of tomato gray mold in Test Example 5;

[0044] Figure 4 This is the experimental result of the control effect of the target compound on cowpea powdery mildew in Test Example 6;

[0045] Figure 5 is the H NMR spectrum of compound C1 in the examples;

[0046] Figure 6 is the carbon NMR spectrum of compound C1 in the examples;

[0047] Figure 7 is the H NMR spectrum of compound C2 in the examples;

[0048] Figure 8 is the carbon NMR spectrum of compound C2 in the examples;

[0049] Figure 9 is the H NMR spectrum of compound C3 in the examples;

[0050] Figure 10 is the carbon NMR spectrum of compound C3 in the examples;

[0051] Figure 11 is the H NMR spectrum of compound C4 in the examples;

[0052] Figure 12 is the carbon NMR spectrum of compound C4 in the examples;

[0053] Figure 13 is the H NMR spectrum of compound C5 in the examples;

[0054] Figure 14 is the carbon NMR spectrum of compound C5 in the examples;

[0055] Figure 15 is the H NMR spectrum of compound C6 in the examples;

[0056] Figure 16 is the carbon NMR spectrum of compound C6 in the examples;

[0057] Figure 17 is the H NMR spectrum of compound C7 in the examples;

[0058] Figure 18 is the carbon NMR spectrum of compound C7 in the examples;

[0059] Figure 19 is the H NMR spectrum of compound C8 in the examples;

[0060] Figure 20 is the H NMR spectrum of compound C9 in the examples;

[0061] Figure 21 is the H NMR spectrum of compound C10 in the examples;

[0062] Figure 22 is the H NMR spectrum of compound C11 in the examples;

[0063] Figure 23 is the H NMR spectrum of compound C12 in the examples;

[0064] Figure 24 is the hydrogen nuclear magnetic resonance spectrum of compound C13 in the examples. DETAILED DESCRIPTION

[0065] The technical solutions of the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. In order to further illustrate the present invention, the following examples are described in detail. The raw materials used in the following examples and comparative examples of the present invention are all commercially available products. The synthetic routes of compounds C1 to 13 prepared in the embodiments of the present invention are as follows:

[0066]

[0067] Example 1

[0068] This example provides the synthesis of compounds C1 to C13, which specifically includes the following:

[0069] Preparation of compound C1:

[0070] (1) Compound A1 (1 mmol) was dissolved in N-methylpropiodone (NMP, 3 mL) and refluxed at 210°C for 5 h. After the reaction was complete, the mixture was cooled to room temperature and glacial ethyl acetate (EA, 10 mL) was added. A crude precipitate was observed. The mixture was stirred at 0-5°C for 30 min and filtered to obtain a brown solid B1. The yield was 71.7% and the melting point was 181-183°C.

[0071] (2) Compound B1 (2 mmol) was dissolved in DMF (6 mL), and anhydrous potassium carbonate (0.83 g, 6 mmol) and dibromomethane (0.3 mL, 4 mol) were added to the solution, followed by heating at 120°C under a nitrogen atmosphere for 2 h. After the reaction was completed as monitored by TLC, the solution was cooled to room temperature, washed with saturated brine (10 mL × 3, where × 3 means treatment 3 times, the same below), extracted with ethyl acetate (EA, 10 mL × 3), dried over anhydrous sodium sulfate, and the mixture was concentrated to a crude product, which was then purified by silica gel flash column chromatography to obtain yellow solid C1 in a yield of 89.7% with a melting point of 97-99°C.

[0072] The preparation methods of compounds C2-8 are the same as C1.

[0073] Preparation of compound C9:

[0074] Compound C1 (1 mmol) was dissolved in 1,4-dioxane (3 mL), and anhydrous potassium carbonate (0.69 g, 5 mmol), phenylboronic acid (R'B(OH)2, 1 mmol), and tetrakis(triphenylphosphine)palladium (Pd[P(C6H5)3]4, 0.05 mmol) were added to the solution. The mixture was refluxed at 90°C under a nitrogen atmosphere for 2 h. After the reaction was complete as monitored by TLC, the solution was cooled to room temperature, washed with saturated brine (10 mL × 3), extracted with ethyl acetate (10 mL × 3), and dried over anhydrous sodium sulfate. The mixture was concentrated to a crude product and then purified by silica gel flash column chromatography to obtain the target product C9 with a yield of 90.8% and a melting point of 114-116°C. In R'B(OH)2, R' is a phenyl group.

[0075] The preparation method of compounds C10~13 is the same as that of C9.

[0076] The structures and NMR data of compounds C1-13 are shown below and in Figure 1:

[0077]

[0078] (d, J=2.2Hz, 1H), 7.80 (d, J=9.1Hz, 1H), 7.58 (dd, J=9.1, 2.3Hz, 1H), 6.25 (s, 2H), 2.62 (s, 3H). 13C NMR(100MHz,CDCl3)δ147.4,144.1,143.8,140.4,131.3,130.5,122.2,119.5,116.5,103.0,19.3。HRMS for C 11 H9BrNO2 + [M+H] + 265.9811,found 265.9818。

[0079]

[0080] J=1.9Hz,1H),7.76(dd,J=9.0,2.0Hz,1H),7.68(d,J=9.1Hz,1H),6.25(s,2H),2.63(s,3H)。 13 C NMR(100MHz,CDCl3)δ147.2,144.3,144.0,140.3,136.6,130.4,128.9,117.2,103.1,90.9,19.3。HRMS for C 11 H9INO2 + [M+H] + 313.9672,found 313.9651。

[0081]

[0082] 8.7Hz,1H),7.51(dt,J=2.0,1.0Hz,1H),7.36(dd,J=8.8,2.0Hz,1H),6.20(s,2H),2.62(s,3H),2.48(s,3H)。 13 C NMR(100MHz,CDCl3)δ147.8,144.0,142.5,139.7,135.6,130.3,128.4,118.5,115.4,102.6,21.6,19.2。HRMS for C 12 H 12 NO2 + [M+H] + 202.0863,found202.0848。

[0083]

[0084] 7.66(d,J=9.1Hz,1H),7.31(d,J=2.4Hz,1H),7.10(dd,J=9.1,2.4 Hz,1H),6.20(s,2H),3.91(s,3H),2.62(s,3H)。 13 C NMR(100 MHz,CDCl3)δ159.7,148.9,147.0,143.1,138.7,121.0,119.3,110.15,106.6,102.5,55.4,19.2。HRMS for C 12 H 12 NO3 + [M+H] + 218.0812,found 218.0811。

[0085]

[0086] 1.7 Hz,1H),6.31(s,2H),2.68(s,3H)。 13 C NMR(100 MHz,CDCl3)δ148.3,145.4,144.0,141.2,129.7(q,J=32.7 Hz),126.7(q,J=4.5 Hz),124.08(d,J=272.3 Hz),121.56–120.54(m,2C)116.9,103.3,19.4。HRMS for C 12 H9F3NO2 + [M+H] + 256.0580,found256.0570。

[0087]

[0088] (dd,J=11.7,7.6 Hz,1H),7.46(dd,J=10.1,8.4 Hz,1H),6.25(s,2H),2.62(s,3H)。 13C NMR(100 MHz,CDCl3)δ151.4(dd,J=252.2,16.3 Hz),149.8(dd,J=252.0,16.4Hz),148.3(dd,J=4.0,2.6 Hz),144.0(d,J=2.6 Hz),142.3(d,J=11.4 Hz),140.1(d,J=2.6 Hz),115.2(dd,J=16.8,1.5 Hz),111.9(d,J=8.4 Hz),105.5(dd,J=19.6,1.5Hz),103.0,19.2。HRMS for C 11 H8F2NO2 + [M+H] + 224.0518,found 224.0485。

[0089]

[0090] 2.59(s,3H)。 13 C NMR(100 MHz,CDCl3)δ146.6,144.7,143.0,137.6,135.5,134.2,105.2,102.8,97.6,92.6,51.3,51.2,14.1。HRMS for C 13 H 14 NO4 + [M+H] + 248.0917,found248.0881。

[0091]

[0092] J=9.3,5.1 Hz,1H),7.39–7.28(m,2H),6.25(s,2H),2.64(s,3H)。 13 C NMR(100MHz,CDCl3)δ155.2(d,J=247.7 Hz),143.5(d,J=5.8 Hz),138.10(d,J=2.6 Hz),137.7,135.6,126.6(d,J=9.4 Hz),113.6(d,J=26.2 Hz),111.0(d,J=10.7 Hz),98.5(d,J=23.9 Hz)。98.2,14.4。HRMS for C 11 H8FNO2 + [M+H] + 206.0605,found 206.0612。

[0093]

[0094] 8.02(dd,J=9.0,0.7 Hz,1H),7.96(dd,J=2.1,0.7 Hz,1H),7.81(dd,J=8.9,2.1 Hz,1H),7.74–7.67(m,2H),7.51–7.43(m,2H),7.41–7.34(m,1H),6.25(d,J=0.8 Hz,2H),2.66(s,3H)。 13 C NMR(100 MHz,CDCl3)δ148.5,144.8,143.5,140.3,140.1,138.3,129.2,128.9,127.7,127.6,127.3,117.5,115.7,102.8,19.4。HRMS for C 17 H 14 NO2 + [M+H] + 264.1019,found 264.1023。

[0095]

[0096] CDCl3)δ8.00(d,J=9.0 Hz,1H),7.93(d,J=2.0 Hz,1H),

[0097] 7.80(dd,J=8.9,2.1 Hz,1H),7.63–7.56(m,2H),7.31–7.26(m,2H),6.24(s,2H),2.65(s,3H),2.41(s,3H)。 13 C NMR(100 MHz,CDCl3)δ148.4,144.7,143.3,140.0,138.2,137.6,137.4,129.7,129.1,127.6,127.1,117.0,115.7,102.8,21.2,19.3。HRMS forC 18 H 16 NO2 + [M+H] + 278.1176,found 278.1183。

[0098]

[0099] Hz,1H),7.75(dd,J=8.9,2.2 Hz,1H),7.61(d,J=8.6 Hz,2H),7.43(d,J=8.5Hz,2H),6.26(s,2H),2.66(s,3H)。 13 C NMR(100 MHz,CDCl3)δ148.5,144.7,143.8,140.2,138.7,137.0,133.9,129.4,129.1,128.5,127.2,117.5,115.6,102.9,19.3。HRMSfor C 17 H 13 ClNO2 + [M+H] + 298.0629,found 298.0631。

[0100]

[0101] (m,1H),7.79(dd,J=8.9,2.1 Hz,1H),7.30–7.24(m,1H),7.21(d,J=2.2 Hz,1H),6.98(d,J=8.3 Hz,1H),6.26(s,2H),3.96(d,J=16.7 Hz,6H),2.66(s,3H)。 13 C NMR(100 MHz,CDCl3)δ149.3,149.0,148.3,144.6,143.3,140.1,138.1,133.2,129.1,127.5,119.7,116.7,115.7,111.6,110.5,102.8,56.0,56.0,19.3。HRMS for C 19 H 18 NO4 + [M+H] + 324.1230,found 324.1245。

[0102]

[0103] CDCl3)δ7.98–7.91(m,2H),7.81(dd,J=9.1,2.0Hz,1H),7.43

[0104] (dd,J=3.6,1.1Hz,1H),7.33(dd,J=5.1,1.1Hz,1H),7.11(dd,J=5.1,3.6Hz,1H),6.25(s,2H),2.64(s,3H)。 13C NMR (100MHz, CDCl3) δ148.4, 144.7, 143.6, 143.4, 140.3, 131.6, 129.3, 128.3, 126.5, 125.6, 124.0, 115.8, 115.7, 102.9, 19.3. HRMS for C 15 H 12 NO2S + [M+H] + 270.0583, found 270.0583.

[0105] Test Example 1

[0106] This test example employed the insect immersion method to determine the lethal activity of the target compound against southern root-knot nematodes at various concentrations. The assay specifically involved the following steps: Using the insect immersion method, 5 mg of the test compound was weighed and added to 0.1 mL of DMF to prepare a 50,000 μg / mL stock solution. Distilled water was then added to dilute the test compound to a concentration of 400 μg / mL. The nematodes were then diluted to a concentration of 100 nematodes / mL. In a clean 12-well plate, 1 mL of the nematode solution and 1 mL of the test compound solution were added to each well. The corrected mortality rate at a concentration of 200 μg / mL of the target compound was determined. 0.02% DMF without the drug was used as a solvent control, and 50 μg / mL of avermectin was used as a positive control. Each treatment was replicated three times. The 12-well plate was incubated at 25°C, and the number of dead and live nematodes was counted at 24, 48, and 72 hours. The corrected mortality rates for 24, 48, and 72 hours were calculated. The experimental results are shown in Table 1.

[0107] Mortality rate (%) = number of dead nematodes / total number of nematodes × 100%

[0108] Corrected mortality rate (%) = (mortality rate of treatment group - mortality rate of control group) / (1 - mortality rate of control group) × 100%

[0109] Table 1

[0110]

[0111]

[0112] As shown in Table 1, compounds C1 to C3, C8, and C13 at a concentration of 200 μg / mL had nematicidal activities of 90% at 72 h.

[0113] Based on the above target compound killing data, the target compound with a nematicidal activity of more than 90% at a concentration of 200 μg / mL at 72 h was selected for EC 50 Determination of its EC 50 The results of the value determination are shown in Table 2.

[0114] Table 2

[0115]

[0116] As shown in Table 2, among compounds C1-C3, C8, and C13, C13 has the poorest activity, and its EC 50 The / 72h value was 68.153 μg / mL, and the activities of the remaining compounds were higher.

[0117] Test Example 2

[0118] This test example is a potted plant control experiment of the target compounds (C1, C3, and C13) against southern root-knot nematodes, which specifically includes the following steps:

[0119] Select plump cucumber seeds and place them in a Petri dish containing filter paper. Moisten the filter paper with sterile water overnight. After the cucumber seeds germinate, select cucumber seedlings of uniform growth and plant them in 10 cm diameter planting cups, one per cup. Simultaneously, fresh oocysts are harvested from cucumber roots infected with root-knot nematodes and hatched to obtain J2 southern root-knot nematodes of uniform vigor. After the cucumbers have grown for two weeks in the planting cups and established roots, prepare solutions of the test compound at concentrations of 100 μg / mL and 200 μg / mL. Drill 3-5 wells at a depth of 5-7 cm around the rhizosphere of the plants and inject the prepared solutions. Each plant receives 10 mL of the test solution. 10 μg / mL avermectin is used as a positive control, and water is used as a control solution. Each treatment is replicated three times. On the second day after root irrigation, 3-5 holes were drilled again around the root zone of each cucumber plant, with a depth of 6-8 cm, and about 1000 J2 were inoculated on each plant. After 30 days, the number of root knots produced on the cucumber roots was counted and the control effect was calculated. The experimental results are shown in Table 3 and Figure 1 .

[0120] Inhibitory effect (%) = (number of root knots in the control group - number of root knots in the treatment group) / number of root knots in the control group × 100%

[0121] Table 3

[0122]

[0123] Note: Lowercase letters represent the results of one-way ANOVA between different groups at the same time point (Duncan analysis P≤

[0124] 0.05).

[0125] From Table 3 and Figure 1It can be seen that the potted control efficacy of compounds C1, C3, and C13 against southern root-knot nematodes increases with increasing concentration. The potted control efficacy of compound C1 against southern root-knot nematodes at concentrations of 100 μg / mL and 200 μg / mL is 32.18% and 62.57%, respectively. The nematicidal activity of compound C1 at a concentration of 200 μg / mL is equivalent to that of the positive control abamectin at a concentration of 10 μg / mL. The control efficacy of compounds C3 and C13 at concentrations of 100 μg / mL and 200 μg / mL are 21.8%, 44.8%, 9.1%, and 27.5%, respectively. At a concentration of 100 μg / mL, the potted activities of compounds C1 and C3 are 32.18% and 21.83%, respectively, while the nematicidal activity of compound C13 at the same concentration is only 9.19%.

[0126] Test Example 3

[0127] This test example is a potted experiment to determine the effect of the target compound on cucumber growth, which specifically includes the following steps: select cucumber seeds with full grains, place them in a culture dish containing filter paper, moisten the filter paper on the culture dish with sterile water overnight, and after the cucumber seeds germinate, select cucumber seedlings with consistent growth and plant them in 10 cm diameter planting cups, one per cup. The target compound to be tested was configured to a target concentration of 200 μg / mL, with distilled water treatment as a blank control and 10 μg / mL of avermectin as a positive control. The cucumber seedlings were root-irrigated, and after 14 days, the root fresh weight, dry weight, root length and number of lateral roots were counted to calculate the inhibition rate. The experimental results are shown in Tables 4 and Figure 2 .

[0128] Inhibition rate = (control group value - treatment group value) / control group value × 100%

[0129] Table 4

[0130]

[0131] From Table 4 and Figure 2 As can be seen, when the three compounds C1, C3, and C13 were irrigated at a concentration of 200 μg / mL on cucumber seedlings grown in cultivation cups for two weeks, the experimental data showed that compared with the CK group treated with clear water as the control, compounds C1 and C3 had a certain degree of inhibitory effect on the cucumber root system, resulting in a certain degree of reduction in the dry weight and fresh weight of the cucumber root system. At the same time, there was also a certain degree of inhibitory effect on the root length and number of lateral roots of the cucumber. Compound C13 had a significant inhibitory effect on the growth of the cucumber root system. The fresh weight, dry weight, root length, and number of lateral roots of the cucumber root system treated with compound C13 were all significantly inhibited. Among them, the inhibition rate of compound C13 on the growth of cucumber lateral roots reached 50%.

[0132] Test Example 4

[0133] This test example uses the mycelial growth rate method to determine the in vitro antibacterial activity of the target compound, which specifically includes the following:

[0134] Weigh 15 mg of the test compound using a 1 / 10,000 balance, place it in a 1.5 mL centrifuge tube, add 0.5 mL of DMF to dissolve the test compound, and after the solution becomes clear, add the dissolved solution of the test compound to 300 mL of PDA medium, shake well, and prepare a PDA medium containing 50 μg / mL of the test compound. Use 1 mL of distilled water as a blank control, 0.02% DMF without the drug as a solvent control, and 50 μg / mL of azoxystrobin as a positive control. Pour them into 9 cm culture dishes, and repeat 3 times for each treatment. After the PDA solidifies, insert the bacterial cake, seal it with a sealing film, and culture it in a 25 ° C incubator for 2-5 days. When the diameter of the colony in the culture dish reaches 8 cm, measure it with a ruler and calculate the inhibition rate. The experimental results are shown in Table 5. Based on the data in Table 4, EC was performed on the target compound with an inhibition rate of more than 70% of pathogens. 50 The results are shown in Table 6.

[0135] Mycelial growth inhibition rate (%) = ((control colony diameter - treated colony diameter) / (control colony diameter - cake diameter)) * 100

[0136] Note: The diameter of the mushroom cake is 5mm

[0137] Table 5

[0138]

[0139] Note: FG: Gibberella graminearum; CM: Colletotrichum oxysporum; PC: Phytophthora capsici; FO: Fusarium wilt; CS: Colletotrichum rubrum; PO: Rice blast; RS: Sheath blight; BC: Botrytis cinerea.

[0140] Table 6

[0141]

[0142]

[0143] Note:- a Represents untested

[0144] As shown in Tables 5 and 6, compound C1 has better fungicidal activity and a wider fungicidal spectrum. Its antibacterial activity against Gibberella zeae, Colletotrichum syringae, Phytophthora capsici, Magnaporthe oryzae, Rhizoctonia solani, and Botrytis cinerea is better than that of its positive control azoxystrobin at a concentration of 50 μg / mL. 50The EC values ​​of target compound C1 against Botrytis cinerea were 5.56μg / mL, 3.85μg / mL, 29.0μg / mL, 6.59μg / mL, 7.76μg / mL and 2.98μg / mL, respectively. 50 The value is significantly lower than that of azoxystrobin, and its control effect is better than the positive control. In addition, if the Br at the 6-position substituent is replaced by I, the fungicidal spectrum of the compound becomes narrower and the antibacterial activity of the compound is reduced to a certain extent. When Br is replaced by F, there is no significant change in the compound, but it still maintains a high antibacterial activity. When the substituent at the 6-position is replaced by F atom, the fungicidal activity of the compound is still greatly improved. At a concentration of 50 μg / mL, its fungicidal activity against wheat fusarium, banana anthracnose, pepper phytophthora, and rice blast fungus is better than that of the commercial drug azoxystrobin at the same concentration. In addition, the EC value of compound C8 against tomato gray mold is 2.34. 50 The values ​​were 3.41μg / mL, which were lower than 4.35μg / mL and 13.19μg / mL of myclobutanil. When an electron-withdrawing aldehyde group was introduced at the 6-position, the fungicidal activity of compound C14 was improved to a certain extent compared with that of C15, but there was still a big gap compared with the improvement of the fungicidal activity of the compound after the introduction of halogen at the 6-position. Compound C6, in which F atoms were introduced at both the 6- and 7-positions of the compound, showed significantly better improvement in the fungicidal activity than compound C5, in which CF3 was introduced at the 7-position. After the introduction of a benzene ring at the 6-position, it was found that the fungicidal activity of the compound could be improved to a certain extent by increasing the electron-withdrawing group on the benzene ring, while the fungicidal activity of the compound did not change significantly when an electron-donating group was introduced. At the same time, when compounds C10~12 were compared with compound C13, the fungicidal activity of the compound was significantly improved by introducing a thiophene heterocycle at the 6-position substituent. Among them, compound C13 had an EC of 1.574 for rice sheath blight pathogen. 50 It was only 1.31 μg / mL, slightly worse than the positive control of 0.76 μg / mL.

[0145] Test Example 5

[0146] This test example is an experiment on the efficacy of target compounds (C1, C13) against tomato gray mold, specifically including the following contents:

[0147] Pick fresh and healthy tomatoes of uniform size, wash them with clean water, soak them in a 50-fold diluted sodium hypochlorite solution, disinfect the surface for 1 minute, then wash them three times with sterile water and blow dry them in a clean bench. Accurately weigh 5 mg of the compound to be tested, add DMF (10 μL) to dissolve it, add 5 mL of distilled water to prepare a 5000 μg / mL stock solution, and dilute it to 100 μg / mL and 200 μg / mL for activity testing. Use 200 μg / mL of pyrimethanil as a positive control. 1 / 1000th of DMF without the drug is used as a negative control. Use a sterile needle to make a 2 mm deep wound at the equator of the fruit, take 10 μL of the test solution and titrate it into the wound, place it in a clean bench and blow dry the solution. After the solution is dry, use a 5 mm punch to punch out the bacterial cake and inoculate it into the wound part of the fruit. The inoculated tomato fruits were placed in an artificial incubator with a humidity of 80%-90% and a constant temperature of 22°C. The diameter of the lesions was measured after 4 days. The results are shown in Table 7 and Figure 3 .

[0148] Inhibition rate (%) = (CK lesion area - treatment group lesion area) / CK lesion area × 100%

[0149] Table 7

[0150]

[0151] Lowercase letters represent the results of one-way ANOVA between different groups at the same time point (Duncan analysis P ≤ 0.05). a, b, c, d, e, f, g indicate significant differences between different groups, and a, b, c, d, e, f, g are marked from highest to lowest inhibition rate.

[0152] From Table 7 and Figure 3 It can be seen that the C1 and C13 compounds have a better control effect on tomato gray mold at the concentrations of 100 μg / mL and 200 μg / mL than the pyrimethanil (its EC 50 After treatment with 100 μg / mL of compound C1, the control efficiency was 66.16%, which was slightly worse than that of 100 μg / mL pyrimethanil; while 200 μg / mL of compound C1 was better than pyrimethanil.

[0153] Test Example 6

[0154] This test example is a potted test of the target compounds (C1, C13) against powdery mildew in cowpea. The test includes the following steps: soak cowpea seeds in warm water for 5 hours to accelerate germination, then wipe the cowpea seeds dry and place them in a cultivation cup. Water and fertilize once every three days. After the cowpea seedlings grow to two fully expanded leaves, the target compound to be tested is prepared into a target concentration of 100 μg / mL and 200 μg / mL. At the same time, propiconazole is used as a positive control and 1 / 1000 DMF aqueous solution is used as a negative control. The compounds are sprayed on the cowpea leaves. One day later, a powdery mildew spore suspension (5×10 6 CFU mL -1 ), sprayed on the leaves of cowpea powder, the affected area was counted 14 days after the spraying was completed, and the disease index and control effect were calculated. The results are shown in Table 8 and Figure 4 .

[0155] Grading standards:

[0156] Level 0: No lesions

[0157] Level 1: Powdery mildew spot area accounts for ≤5% of the total leaf area

[0158] Level 3: 5% < Powdery mildew spot area accounts for ≤ 10% of the total leaf area

[0159] Level 5: 10< Powdery mildew spot area accounts for ≤ 20% of the total leaf area

[0160] Level 7: 20% < Powdery mildew spot area accounts for ≤ 40% of the total leaf area

[0161] Level 9: Powdery mildew spot area less than 40% of the total leaf area

[0162]

[0163]

[0164] Table 8

[0165]

[0166] From Table 8 and Figure 4 In vivo efficacy tests of compounds C1 and C13 against cowpea powdery mildew at a concentration of 100 μg / mL revealed that compounds C1 and C13 demonstrated efficacy of 91.1% and 88.9%, respectively, against the fungus. Compound C1 demonstrated comparable efficacy to the commercial drug propiconazole at the same concentration. However, further testing at a higher concentration revealed that spraying compounds C1 and C13 at a concentration of 200 μg / mL on cowpea leaves caused wrinkling, wilting, and burns.

[0167] The above description of the disclosed embodiments will enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not limited to the embodiments shown herein but is to be construed in the widest manner consistent with the principles and novel features disclosed herein.

Claims

1. The compound shown below: Formula 1; Formula 2; Formula 3; Formula 5; Formula 7; Formula 8; Formula 13.

2. The method for preparing the compound according to claim 1, wherein The preparation method of the compounds represented by Formula 1 to Formula 3, Formula 5 and Formula 7 to Formula 8 comprises: (1) The compound represented by formula I is mixed with N,N-dimethylformamide and potassium carbonate, reacted at 100-120°C for 0.5-2 h, cooled to 50-60°C, and then mixed with chloroacetone, followed by reaction at 50-60°C for 0.5-1 h to obtain compounds A1-A3, A5, A7 and A8; Formula I; In formula I, R1 and R2 are independently selected from H, F, Br, I, -CH3, -CF3 or -OCH3; A1; A2; A3; A5; A7; A8; (2) Compounds A1-A3, A5, A7, and A8 were mixed with N-methylpropiolide and reacted at 210 °C for 5 h to obtain compounds B1-B3, B5, B7, and B8; B1; B2; B3; B5; B7; B8; (3) Compounds B1-B3, B5, B7, and B8 were mixed with N,N-dimethylformamide, potassium carbonate, and dibromomethane, and heated at 120°C under a nitrogen atmosphere for 2 h to obtain the compounds represented by Formulas 1-3, 5, and 7-8.

3. The method for preparing the compound according to claim 1, wherein The method for preparing the compound represented by Formula 13 comprises: The compound represented by Formula 1 is mixed with 1,4-dioxane, potassium carbonate, R'B(OH)2, and tetrakis(triphenylphosphine)palladium, and reacted at 90°C under a nitrogen atmosphere for 2 h to obtain the compound represented by Formula 13; In R'B(OH)2, R' is selected from .

4. Use of the compound according to claim 1 in the preparation of a root-knot nematode insecticide, characterized in that: The concentration of the compounds represented by Formulae 1 to 3, Formulae 5, and Formulae 7 to 8 is 50 to 200 μg / mL.

5. A root-knot nematode insecticide, characterized in that: The invention comprises one or more compounds according to claim 1, and acceptable excipients.

6. Use of one or more of the compounds represented by Formulas 1 to 4, 6, 8 to 9, and 11 to 13 in antibacterial activities; wherein the antibacterial activity is selected from one or more of the group consisting of: wheat fusarium, banana anthracnose, rice sheath blight, rice blast, tomato gray mold, and pepper phytophthora; Formula 1; Formula 2; Formula 3; Formula 4; Formula 6; Formula 8; Formula 9; Formula 11; Formula 12; Formula 13.

7. The use according to claim 6, characterized in that The concentration of the compound represented by Formulae 1 to 4, the compound represented by Formulae 6, the compound represented by Formulae 8 to 9, or the compound represented by Formulae 11 to 13 is 50 to 100 μg / mL.

8. Use of the compound represented by formula 5 in inhibiting tomato gray mold; Application of the compound represented by formula 7 in inhibiting wheat fusarium and rice sheath blight pathogen; Use of the compound represented by formula 10 in inhibiting wheat fusarium, banana wilt pathogen, rice blast pathogen, and tomato gray mold; Formula 5; Formula 7; Formula 10.

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