Insecticide for killing meloidogyne and preparation method thereof

Abstract

The invention relates to the technical field of biological control, and provides a root-knot nematode killing pesticide and a preparation method thereof. The invention provides compounds as shown in a formula 1 to a formula 13. Compared with the prior art, the quinoline type derivative is designed and synthesized, the quinoline type derivative is a small molecule compound which is simple in structure, easy to synthesize and good in nematicidal activity, the nematicidal activity of the compounds is further researched, the compounds are used as root nematode insecticides, and an idea is provided for solving the dilemma of few nematicides at present.

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] Southern root-knot nematode (Meloidogyne incongnita) is a plant parasitic nematode that harms crops and seriously affects the sustainable development of agriculture. Nematicides are mainly divided into two categories: fumigation and non-fumigation. Fumigation nematicides, such as dazomet and dazomet, are mainly applied through soil fumigation. However, the use of fumigation nematicides may damage the soil ecological environment and cause harm to non-target organisms. Non-fumigation nematicides, such as organophosphorus compounds, came out in 1955. At present, the commercialized nematicides mainly include the following: avermectin, thiamethoxam, fluopyram, fluthiamethoxam, avermectin benzoate, etc. Among them, the number of nematicides with three types of active ingredients, avermectin, thiamethoxam and avermectin benzoate, is the largest, accounting for more than 70%. The types of nematicides that can be used in agricultural production are still limited, and the long-term use of a single nematicide may lead to different degrees of resistance in root-knot nematodes.

[0003] Therefore, it is urgent to develop new and environmentally friendly nematicides. 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 as shown in Formula 1 to Formula 13;

[0007]

[0008]

[0009] The present invention also provides a method for preparing the compounds shown in Formula 1 to Formula 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 0.5-2h, cooled to 50-60°C, and then mixed with chloroacetone, and then reacted at 50-60°C for 0.5-1h 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-methylproprrolidone and reacted at 210° C. for 5 h to obtain compounds B1-B8;

[0015]

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

[0017] Preferably, the molar ratio of the compounds B1-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. in 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 shown in Formula 1 to Formula 13 in the control of root-knot nematodes;

[0023]

[0024]

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

[0026] Preferably, the concentration of the compound 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 of the compounds represented by Formula 1 to Formula 13, and acceptable adjuvants.

[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 treatment;

[0029]

[0030]

[0031] Preferably, the antibacterial agent 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 shown in formula 7 in inhibiting wheat fusarium, banana anthracnose fungi, pepper phytophthora, rice blast fungi, rice sheath blight fungi, 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 fusarium, 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 50-100 μg / mL, preferably 50 μg / mL.

[0039]

[0040] Compared with the prior art, 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 way to solve the current dilemma of insufficient nematicides. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0042] Figure 2 The effect of the target compound at a concentration of 200 μg / mL on the root growth of cucumber 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 in vivo protective effect of the target compound of Test Example 6 on cowpea powdery mildew;

[0045] Figure 5 is the hydrogen nuclear magnetic resonance spectrum of compound C1 in the example;

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

[0047] Figure 7 is the hydrogen nuclear magnetic resonance spectrum of compound C2 in the example;

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

[0049] Fig. 9 is the hydrogen nuclear magnetic resonance spectrum of compound C3 in the example;

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

[0051] Fig.11 is the hydrogen nuclear magnetic resonance spectrum of compound C4 in the example;

[0052] Fig.12 is the carbon NMR spectrum of compound C4 in the example;

[0053] Fig.13 is the hydrogen nuclear magnetic resonance spectrum of compound C5 in the example;

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

[0055] Fig.15 is the hydrogen nuclear magnetic resonance spectrum of compound C6 in the example;

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

[0057] Fig.17 is the hydrogen nuclear magnetic resonance spectrum of compound C7 in the examples;

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

[0059] Fig.19 is the hydrogen nuclear magnetic resonance spectrum of compound C8 in the examples;

[0060] Fig. 20 is the hydrogen nuclear magnetic resonance spectrum of compound C9 in the examples;

[0061] Fig.21 is the hydrogen nuclear magnetic resonance spectrum of compound C10 in the example;

[0062] Fig. 22 is the hydrogen nuclear magnetic resonance spectrum of compound C11 in the example;

[0063] Fig.23 is the hydrogen nuclear magnetic resonance spectrum of compound C12 in the example;

[0064] Fig.24 It is the hydrogen nuclear magnetic resonance spectrum of compound C13 in the example. DETAILED DESCRIPTION

[0065] The technical scheme of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments 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 the field without 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 contents:

[0069] Preparation of compound C1:

[0070] (1) Compound A1 (1 mmol) was dissolved in N-methylproprrolidone (NMP, 3 mL), and refluxed at 210°C for 5 h. After the reaction was completed as monitored by TLC, the mixture was cooled to room temperature. Glacial ethyl acetate (EA, 10 mL) was added, and 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), anhydrous potassium carbonate (0.83 g, 6 mmol) and dibromomethane (0.3 mL, 4 mol) were added to the solution, and heated at 120° C. for 2 h under a nitrogen atmosphere. 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 a yellow solid C1 with a yield of 89.7% and a melting point of 97-99° C.

[0072] The preparation method of compounds C2~8 is 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, and refluxed at 90°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), extracted with ethyl acetate (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 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 C9.

[0076] The structures and NMR data of compounds C1-13 are as follows and shown in Figure ~:

[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 adopts the insect immersion method to determine the lethal activity of the target compound to southern root-knot nematodes at different concentrations, specifically including the following steps: using the insect immersion method for determination, weighing 5 mg of the test compound, adding DMF (0.1 mL) to prepare a 50000 μg / mL stock solution, adding distilled water to dilute the test compound concentration to 400 μg / mL, and at the same time, preparing the nematodes into a nematode solution of 100 / mL, taking a clean 12-well plate, adding 1 mL of nematode solution and 1 mL of the test compound solution to each well, and determining the corrected mortality rate of the target compound at a concentration of 200 μg / mL, using 0.2% DMF without the agent as a solvent control, and 50 μg / mL of avermectin as a positive control, each treatment was repeated 3 times, and the 12-well plate was cultured at 25°C, and the number of dead and live worms at 24h, 48h, and 72h were counted respectively. And the corrected mortality rates of 24h, 48h, and 72h were calculated. The experimental results are shown in Table 1.

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

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

[0109] Table 1

[0110]

[0111]

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

[0113] Based on the nematicidal data of the above target compounds, the compounds with nematicidal activity of more than 90% at 72 h at a concentration of 200 μg / mL were selected for EC 50 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 remaining compounds had higher activities.

[0117] Test Example 2

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

[0119] 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 planting cups with a diameter of 10 cm, one per cup. At the same time, pick fresh egg capsules from the roots of cucumbers infected with root-knot nematodes for hatching to obtain southern root-knot nematodes J2 with consistent vitality. After the cucumbers grow and take root in the planting cups for 2 weeks, prepare the test compound into 100 μg / mL and 200 μg / mL concentrations of liquid, make 3-5 holes around the root zone of the plant with a depth of 5-7 cm, and pour the prepared liquid into it. Each plant is poured with 10 mL of the test liquid, with 10 μg / mL avermectin as the positive control and clean water as the control solution, and each treatment is repeated 3 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 effects of compounds C1, C3, and C13 on southern root-knot nematodes increase with increasing concentrations. The potted control effects of compound C1 on southern root-knot nematodes at concentrations of 100 μg / mL and 200 μg / mL are 32.18% and 62.57%, respectively. The nematicidal activity of compound C1 at a concentration of 200 μg / mL is equivalent to the control effect of avermectin at a concentration of 10 μg / mL, which is the positive control. The control effects 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 plant 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 planting cups with a diameter of 10 cm, one per cup. The target compound to be tested was configured to a target concentration of 200 μg / mL, and distilled water treatment was used as a blank control, and 10 μg / mL of avermectin was used as a positive control. The cucumber seedlings were treated with root irrigation. After 14 days, the root fresh weight, dry weight, root length and number of lateral roots were counted, and the inhibition rate was calculated. 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 It can be seen that the three compounds C1, C3, and C13 were used to irrigate the roots of cucumber seedlings grown in cultivation cups for two weeks at a concentration of 200μg / mL. The experimental data showed that compared with the CK group treated with clean 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 lateral root number 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 lateral root number of the cucumber root system treated with compound C13 were significantly inhibited, and the growth inhibition rate of compound C13 on the lateral root of cucumber 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 contents:

[0134] Weigh 15 mg of the test compound with a 1 / 10,000 balance, place it in a 1.5 mL centrifuge tube, add 0.5 mL DMF to dissolve the test compound, and when the solution is clear and transparent, 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 place 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] Mycelium 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 oxysporum; PO: Magnaporthe oryzae; 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 5.56 μg / mL, 3.85 μg / mL, 29.0 μg / mL, 6.59 μg / mL, 7.76 μg / mL, and 2.98 μg / mL, respectively. 50 The value is significantly lower than that of azoxystrobin, and its protective effect is better than the positive control. In addition, when the Br of the substituent at the 6th position 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, the compound does not change significantly, but still maintains a high antibacterial activity. When the substituent at the 6th position is replaced by F atom, the fungicidal activity of the compound is still greatly improved. Its fungicidal activity against wheat fusarium, banana anthracnose, pepper phytophthora, and rice blast at a concentration of 50μg / mL is better than the fungicidal activity of the commercial drug azoxystrobin at the same concentration, and its compound C8 has an EC of 1.3477 for tomato gray mold. 50 The values ​​were 3.41μg / mL, both lower than 4.35μg / mL and 13.19μg / mL of azoxystrobin. 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, had a 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 introduction of an electron-donating group did not significantly change the fungicidal activity of the compound. 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 1.344 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, which specifically includes 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 3 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 mother 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. DMF that does not contain one thousandth of the drug is used as a negative control. Use a sterile needle to make a 2 mm deep wound at the equatorial part of the fruit, take 10 μL of the test solution and titrate it into the wound, place it in a clean bench to blow dry the solution, and after the solution is dry, use a 5 mm puncher to punch 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 large to small according to the inhibition rate.

[0152] From Table 7 and Figure 3 It can be seen that the in vivo protective effects of C1 and C13 compounds against Botrytis cinerea at the concentrations of 100 μg / mL and 200 μg / mL were higher than those of pyrimethanil (EC 50 After treatment with 100 μg / mL of compound C1, the control effect 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 an experiment on the efficacy of the target compounds (C1, C13) against cowpea powdery mildew potted plants, which specifically includes the following contents: cowpea seeds are placed in warm water for 5 hours to germinate, and then the cowpea seeds are wiped dry and placed in a cultivation cup, watered and fertilized once every 3 days, and when the cowpea seedlings grow to two leaves that are fully unfolded, the target compounds to be tested are prepared into target concentrations of 100 μg / mL and 200 μg / mL, and propiconazole is used as a positive control and 1 / 1000 DMF aqueous solution is used as a negative control, and sprayed onto cowpea leaves. After 1 day, a powdery mildew spore suspension (5×10 6 CFU mL -1 ), sprayed on the leaves of cowpea powder, and the diseased area was counted 14 days after the spraying was completed, and the disease index and prevention effect were calculated. The results are shown in Table 8 and Figure 4 .

[0155] Grading Standard:

[0156] Level 0: No lesions

[0157] Level 1: Powdery mildew 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: 40% < powdery mildew spot area accounts for the total leaf area

[0162]

[0163]

[0164] Table 8

[0165]

[0166] From Table 8 and Figure 4 It can be seen that in the in vivo control experiment of compounds C1 and C13 at a concentration of 100μg / mL against cowpea powdery mildew, it was found that the in vivo control effects of compounds C1 and C13 at a concentration of 100μg / mL against cowpea powdery mildew were 91.1% and 88.9% respectively; compound C1 had the same control effect as the commercial drug propiconazole at the same concentration. However, after further testing at a higher concentration, it was found that spraying compounds C1 and C13 on cowpea leaves at a concentration of 200μg / mL would cause cowpea leaves to shrink, wilt, and burn.

[0167] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those 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 will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. Compounds as shown in Formula 1 to Formula 13; 2. The method for preparing the compound according to claim 1, characterized in that: The method for preparing the compounds represented by Formula 1 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 0.5-2h, cooled to 50-60°C, and then mixed with chloroacetone, and then reacted at 50-60°C for 0.5-1h to obtain compounds A1-A8; In formula I, R1 and R2 are independently selected from H, F, Br, I, -CH3, -CF3 or -OCH3; (2) Compounds A1-A8 were mixed with N-methylproprrolidone and reacted at 210° C. for 5 h to obtain compounds B1-B8; (3) Compounds B1 to B8 are mixed with N,N-dimethylformamide, potassium carbonate and dibromomethane, and heated at 120° C. for 2 h in a nitrogen atmosphere to obtain compounds represented by Formulas 1 to 8.

3. The method for preparing the compound according to claim 1, characterized in that: The method for preparing the compounds represented by Formula 9 to 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. in a nitrogen atmosphere for 2 hours to obtain compounds represented by Formulas 9 to 13; In R'B(OH)2, R' is selected from phenyl, benzyl, phenylchloro, 4. Use of one or more of the compounds described in claim 1 in controlling root-knot nematodes.

5. The use according to claim 4, characterized in that: The concentration of the compounds represented by Formula 1 to Formula 13 is 50 to 200 μg / mL.

6. A root-knot nematode insecticide, characterized in that: The invention comprises one or more of the compounds described in claim 1, and acceptable auxiliary materials.

7. Use of one or more of the compounds represented by formulae 1 to 4, the compounds represented by formulae 6, the compounds represented by formulae 8 to 9, and the compounds represented by formulae 11 to 13 in antibacterial treatment; 8. The use according to claim 7, characterized in that: The antibacterial agent 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.

9. The use according to claim 7, 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.

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

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