Insecticidal composition containing quinolone compounds and use thereof

Abstract

The application relates to the technical field of biological control, and provides an insecticidal composition containing a quinolone compound and application thereof. The application provides compounds as shown in formula 1 to formula 8. Compared with the prior art, the quinolone derivative is designed and synthesized, is a small-molecule compound with simple structure, easy synthesis and good nematode-killing activity, and the nematode-killing activity of the compound is researched, the compound is used as a root nematode insecticide, and a thought is provided for solving the current predicament of few nematode-killing agents.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of biological control, more particularly to a kind of insecticidal composition containing quinolone compound and application thereof. BACKGROUND

[0002] In the production process of grain, effective prevention and control of pests is particularly important. Plant root-knot nematode (Meloidogyne spp.) is a kind of plant disease that widely harms agricultural production. It can harm more than 3000 kinds of plants, including vegetables, food crops and fruit trees, etc. As a specific fixed endophytic parasitic nematode, the J2 stage of root-knot nematode is the only period of time with invasion ability in its life cycle. At this time, the larvae can move freely in the soil and invade the host plant roots, affecting the lateral root and fine root system, and causing damage to the plant. The harm of root-knot nematode is not only limited to its physical invasion, but also through stimulating the variation of plant root cells to form so-called "giant cells" as a source of nutrition. This parasitic mode seriously affects the normal physiological process of the plant, leading to growth inhibition, such as slow growth, yellowing of leaves and wilting. According to statistics, plant parasitic nematodes cause about 14% reduction in crop yield and economic loss of 80-100 billion US dollars worldwide each year. Among the many control methods of root-knot nematode, chemical control is still the main method due to its high efficiency and convenience. However, there are few nematocides suitable for agricultural production, and the single variety inevitably leads to the development of drug resistance of root-knot nematode. SUMMARY

[0003] Therefore, the purpose of the present application is to provide a kind of insecticidal composition containing quinolone compound and application thereof, the present application is designed to synthesize quinolone derivative, it is simple structure, easy to synthesize, good small molecule compounds of nematicidal activity.

[0004] In order to achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0005] The compound is as shown in formula 1-8;

[0006]

[0007] The present application also provides a preparation method of the compound as shown in formula 1-8, comprising:

[0008] The compound shown in formula I is mixed with N, N-dimethylformamide and potassium carbonate, and reacted at 100-120℃ for 0.5-2h, then cooled to 50-60℃, and then mixed with chloroacetone, and then reacted at 50-60℃ for 0.5-1h to obtain the compound as shown in formula 1-8;

[0009]

[0010] In Formula I, R1 and R2 are independently selected from H, F, Br, I, -CH3, -CF3 or -OCH3.

[0011] Preferably, the molar ratio of the compound represented by Formula I to N,N-dimethylformamide and potassium carbonate is 1:(1.1-1.5):(1.5-2), more preferably 1:1.1:1.5.

[0012] Preferably, the N,N-dimethylformamide is used as a reaction solvent to fully dissolve the raw materials.

[0013] The present invention also provides compounds as shown in Formulas 9 to 21;

[0014]

[0015]

[0016] The present invention also provides a method for preparing compounds as shown in Formulas 9 to 16, comprising:

[0017] The compounds shown in Formulas 1 to 8 were mixed with N-methylproprolidone and reacted at 210°C for 5 h to obtain the compounds shown in Formulas 9 to 16.

[0018]

[0019] The present invention also provides a method for preparing compounds as shown in Formulas 17 to 21, comprising:

[0020] (1) The compound shown in Formula 9 was mixed with N,N-dimethylformamide, potassium carbonate and dibromomethane, and heated at 120°C under a nitrogen atmosphere for 2 hours to obtain the compound shown in Formula II;

[0021]

[0022] (2) The compound shown in Formula II was 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 shown in Formula III.

[0023] In R'B(OH)2, R' is selected from phenyl, benzyl, phenylchloro, ...

[0024] In Formula III, R' is selected from phenyl, benzyl, phenylchloro, ...

[0025] (3) the compound shown in formula III is mixed with hydrochloric acid and acetonitrile, and reacted at 75 DEG C for 6-8 hours to obtain the compound shown in formula 17-21.

[0026] Preferably, the molar ratio of the compound shown in formula 9, potassium carbonate and dibromomethane is 1:(3-5):(1-2), preferably 1:3:2.

[0027] Preferably, the molar ratio of the compound shown in formula II, potassium carbonate, phenylboronic acid and tetrakis(triphenylphosphine)palladium is 1:(4-5):(1-2):(0.05-0.1), preferably 1:5:1:0.05.

[0028] Preferably, the concentration of the hydrochloric acid is 3 mol / L.

[0029] The application further provides the application of the compound shown in formula 9-21 in the prevention of root-knot nematode.

[0030]

[0031]

[0032] Preferably, the root-knot nematode includes southern root-knot nematode.

[0033] Southern root-knot nematode (Meloidogyne incongnita) is a kind of plant parasitic nematode that harms crops, and seriously affects the sustainable development of agriculture. At present, there are few nematocides suitable for agricultural production, and the variety is single, which inevitably causes the drug resistance of root-knot nematode.

[0034] Preferably, the concentration of the compound shown in formula 9-21 is 200-300 μg / mL, preferably 200 μg / mL.

[0035] The application further provides an insecticidal composition containing quinolone compounds, which comprises the compound shown in formula 9-21 and acceptable adjuvant.

[0036]

[0037]

[0038] The application further provides the application of one or more of the compound shown in formula 9, the compound shown in formula 10, the compound shown in formula 19, the compound shown in formula 20 and the compound shown in formula 21 in bacteriostasis.

[0039]

[0040] Preferably, the fungistasis comprises inhibiting one or more of Gibberella zeae, Colletotrichum musae, Rhizoctonia solani, Pyricularia grisea, Botrytis cinerea, Colletotrichum gloeosporioides, Phytophthora capsici, Fusarium oxysporum.

[0041] Preferably, the concentration of the compound of formula 9, the compound of formula 10, the compound of formula 19, the compound of formula 20, the compound of formula 21 is 50-100 μg / mL, preferably 50 μg / mL.

[0042] The application also provides the use of the compound of formula 11 in inhibiting Gibberella zeae, Colletotrichum musae, Phytophthora capsici, Fusarium oxysporum, Rhizoctonia solani or Botrytis cinerea.

[0043] Preferably, the concentration of the compound of formula 11 is 50-100 μg / mL, preferably 50 μg / mL.

[0044] The application also provides the use of the compound of formula 12 in inhibiting Gibberella zeae, Colletotrichum musae, Phytophthora capsici, Fusarium oxysporum, Rhizoctonia solani or Botrytis cinerea.

[0045] Preferably, the concentration of the compound of formula 12 is 50-100 μg / mL, preferably 50 μg / mL.

[0046] The application also provides the use of the compound of formula 13 in inhibiting Gibberella zeae, Colletotrichum musae, Phytophthora capsici, Fusarium oxysporum, Rhizoctonia solani or Botrytis cinerea.

[0047] Preferably, the concentration of the compound of formula 13 is 50-100 μg / mL, preferably 50 μg / mL.

[0048] The application also provides the use of the compound of formula 14 in inhibiting Colletotrichum musae, Phytophthora capsici, Fusarium oxysporum, Rhizoctonia solani, Botrytis cinerea, Colletotrichum gloeosporioides or Pyricularia grisea.

[0049] Preferably, the concentration of the compound of formula 14 is 50-100 μg / mL, preferably 50 μg / mL.

[0050] The application also provides the use of the compound of formula 15 in inhibiting Phytophthora capsici, Fusarium oxysporum, Rhizoctonia solani, Botrytis cinerea, Colletotrichum gloeosporioides or Pyricularia grisea.

[0051] Preferably, the concentration of the compound of formula 15 is 50-100 μg / mL, preferably 50 μg / mL.

[0052] The application also provides application of the compound shown in formula 16 in inhibiting Gibberella saubinetii, Phytophthora capsici Leonian, Fusarium oxysporum f.sp.cubense, Colletotrichum gloeosporioides, Pyricularia grisea, Magnaporthe grisea, and Botrytis cinerea.

[0053] Preferably, the concentration of the compound shown in formula 16 is 50-100 μg / mL, preferably 50 μg / mL.

[0054] The application also provides application of the compound shown in formula 17 in inhibiting Gibberella saubinetii, Colletotrichum gloeosporioides, Fusarium oxysporum f.sp.cubense, Magnaporthe grisea, Pyricularia grisea, and Botrytis cinerea.

[0055] Preferably, the concentration of the compound shown in formula 17 is 50-100 μg / mL, preferably 50 μg / mL.

[0056] The application also provides application of the compound shown in formula 18 in inhibiting Gibberella saubinetii, Colletotrichum gloeosporioides, Phytophthora capsici Leonian, Fusarium oxysporum f.sp.cubense, Magnaporthe grisea, Pyricularia grisea, and Botrytis cinerea.

[0057] Preferably, the concentration of the compound shown in formula 18 is 50-100 μg / mL, preferably 50 μg / mL.

[0058]

[0059] Compared with the prior art, the application has the following beneficial effects:

[0060] The application designs and synthesizes quinolone derivatives, which are small-molecule compounds with simple structure, easy synthesis and good nematocidal activity. BRIEF DESCRIPTION OF DRAWINGS

[0061] Figure 1 The nuclear magnetic resonance hydrogen spectrum of compound A1 in the examples is shown in the figure;

[0062] Figure 2 The nuclear magnetic resonance hydrogen spectrum of compound A2 in the examples is shown in the figure;

[0063] Figure 3 The nuclear magnetic resonance hydrogen spectrum of compound B1 in the examples is shown in the figure;

[0064] Figure 4 The nuclear magnetic resonance carbon spectrum of compound B1 in the examples is shown in the figure;

[0065] Figure 5 The nuclear magnetic resonance hydrogen spectrum of compound B2 in the examples is shown in the figure;

[0066] Figure 6 NMR carbon spectrum of compound B2 in the examples;

[0067] Figure 7 NMR hydrogen spectrum of compound B3 in the examples;

[0068] Figure 8 NMR hydrogen spectrum of compound B4 in the examples;

[0069] Figure 9 NMR carbon spectrum of compound B4 in the examples;

[0070] Figure 10 NMR hydrogen spectrum of compound B5 in the examples;

[0071] Figure 11 NMR carbon spectrum of compound B5 in the examples;

[0072] Figure 12 NMR hydrogen spectrum of compound B6 in the examples;

[0073] Figure 13 NMR carbon spectrum of compound B6 in the examples;

[0074] Figure 14 NMR hydrogen spectrum of compound B7 in the examples;

[0075] Figure 15 NMR carbon spectrum of compound B7 in the examples;

[0076] Figure 16 NMR hydrogen spectrum of compound B8 in the examples;

[0077] Figure 17 NMR carbon spectrum of compound B8 in the examples;

[0078] Figure 18 NMR hydrogen spectrum of compound B9 in the examples;

[0079] Figure 19 NMR carbon spectrum of compound B9 in the examples;

[0080] Figure 20 NMR hydrogen spectrum of compound B10 in the examples;

[0081] Figure 21 NMR carbon spectrum of compound B10 in the examples;

[0082] Figure 22 NMR hydrogen spectrum of compound B11 in the examples;

[0083] Figure 23 NMR spectrum of hydrogen of compound B11 in the example;

[0084] Figure 24 NMR spectrum of hydrogen of compound B12 in the example;

[0085] Figure 25 NMR spectrum of carbon of compound B12 in the example;

[0086] Figure 26 NMR spectrum of hydrogen of compound B13 in the example;

[0087] Figure 27 NMR spectrum of carbon of compound B13 in the example. DETAILED DESCRIPTION

[0088] The technical solutions of the present application will be described clearly and completely below in combination with the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0089] In order to further illustrate the present application, the following examples are used for detailed description. The raw materials used in the following examples and comparative examples of the present application are all commercially available.

[0090] The synthetic routes of compounds A1-8 and compounds B1-13 prepared in the embodiments of the present application are as follows:

[0091]

[0092]

[0093] Examples 1-8

[0094] The present embodiment provides the synthesis of compounds A1-8, which specifically includes the following contents:

[0095] Preparation of compound A1:

[0096] 2-Amino-5-bromobenzoic acid (1 mmol) was dissolved in N,N-dimethylformamide (DMF, 5 mL), and then potassium carbonate (K2CO3, 0.2 g, 1.5 mmol) was added. The mixture was reacted at 120 °C for 30 min, then cooled to 50 °C, and chloroacetone (1.1 mmol) was added dropwise. After the addition was complete, the mixture was reacted at 50 °C for 0.5 h. The reaction was monitored by thin-layer chromatography (TLC) until it was complete. The mixture was then cooled to room temperature, and 30 mL of distilled water was added. A powdery solid was observed to precipitate. After stirring for 10 min, the mixture was filtered to obtain a yellow solid, Al, with a yield of 83.9% and a melting point of 85-87 °C.

[0097] The preparation methods for compounds A2-8 are the same as those for A1.

[0098] The structures and NMR data of compounds A1-8 are as follows: Figures 1-2 As shown:

[0099]

[0100] J=2.4Hz, 1H), 7.36 (dd, J=8.8, 2.4Hz, 1H), 6.58 (d, J=8.8Hz, 1H), 5.74 (s, 2H), 4.84 (s, 2H), 2.23 (s, 4H).

[0101]

[0102] =2.2Hz, 1H), 7.50 (dd, J = 8.7, 2.2Hz, 1H), 6.47 (d, J = 8.7Hz, 1H), 4.83 (s, 2H), 2.23 (s, 3H).

[0103]

[0104] J=2.0, 1.0Hz, 1H), 7.13 (dd, J=8.3, 2.2Hz, 1H), 6.62 (d, J=8.4Hz, 1H), 4.82 (s, 2H), 2.24 (s, 3H), 2.23 (s, 3H).

[0105]

[0106] δ7.69(d,J=9.0Hz,1H), 6.70(s,2H), 6.29(d,J=2.5Hz,1H), 6.17(dd,J=9.0,2.5Hz,1H), 4.88(s,2H), 3.74(s,3H), 2.13(s,3H).

[0107]

[0108] 8.5, 1.7 Hz, 1H), 4.87 (s, 2H), 2.24 (s, 3H).

[0109]

[0110] (dd, J = 11.2, 8.9 Hz, 1H), 6.44 (dd, J = 12.0, 6.6 Hz, 1H), 4.83 (s, 2H), 2.23 (s, 3H).

[0111]

[0112] 7.36 (s, 1H), 6.15 (s, 1H), 4.81 (s, 2H), 3.88 (s, 3H), 3.84 (s, 3H), 2.23 (s, 2H).

[0113]

[0114] (dd, J = 9.5, 3.0 Hz, 1H), 7.09 (ddd, J = 9.1, 7.7, 3.1 Hz, 1H), 6.71 (dd, J = 9.0, 4.5 Hz, 1H), 4.85 (s, 2H), 2.24 (s, 3H).

[0115] Examples 9-21

[0116] This example provides the synthesis of compounds B1-B13, which includes the following:

[0117] Preparation of compound B1:

[0118] Compound A1 (1 mmol) was dissolved in N-methyl pyrrolidone (NMP, 3 mL) and refluxed at 210 °C for 5 h. After the reaction was completed as monitored by TLC, the reaction was cooled to room temperature. Ethyl acetate (EA, 10 mL) was added and a crude precipitated solid was observed. The mixture was stirred at 0-5 °C for 30 min and then filtered to obtain brown solid B1. The yield was 71.7% and the melting point was 181-183 °C.

[0119] The preparation of compounds B2-B8 was performed according to the method of B1.

[0120] Preparation of compound B9:

[0121] (1) Compound B1 (2 mmol) was dissolved in DMF (6 mL), and anhydrous potassium carbonate (0.83 g, 6 mmol) and dibromomethane (CH2Br2, 0.3 mL, 4 mol) were added to the solution. The mixture was heated at 120 °C under a nitrogen atmosphere for 2 h. After the reaction was completed by TLC monitoring, the solution was cooled to room temperature, washed with saturated brine (10 mL × 3, where × 3 means 3 treatments, the same below), extracted with ethyl acetate (EA, 10 mL × 3), dried with anhydrous sodium sulfate (Na2SO4), concentrated to crude product, and then purified by silica gel column chromatography to obtain yellow solid C1, yield: 89.7%, melting point: 97-99 °C.

[0122] (2) Compound C1 (1 mmol) was dissolved in 1,4-dioxane (3 mL). 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 the mixture was refluxed at 90 °C under a nitrogen atmosphere for 2 h. After the reaction was completed by TLC monitoring, the solution was cooled to room temperature, washed with saturated brine (10 mL × 3), extracted with ethyl acetate (10 mL × 3), dried with anhydrous sodium sulfate (Na2SO4), and the mixture was concentrated to a crude product. Then, it was purified by silica gel column chromatography to obtain the target product C9, with a yield of 90.8% and a melting point of 114-116 °C. The preparation methods of compounds C10-13 were the same as those for C9; in R'B(OH)2, R' is phenyl.

[0123] (3) The suspension of compound C9 (1 mmol) in 5 mL of dilute hydrochloric acid (HCl / H2O, 3 mol / L) was heated to 75 °C for 0.5 h, and then acetonitrile (10 mL) was added to the suspension. The solution was heated under reflux for 6 h. A crude solid precipitate was observed. The mixture was then adjusted to pH 7 with saturated sodium carbonate solution. The precipitate was filtered, washed with water (3 mL), ethanol (3 mL), and dichloromethane (4 mL), and dried under vacuum to obtain the target product B9, yield: 51.4%, melting point > 300 °C. The preparation methods of compounds B10–13 were the same as those for B9.

[0124] The structures and NMR data of compounds B1-13 are as follows: Figures 3-27 As shown:

[0125]

[0126] J=8.9, 2.4Hz, 1H), 7.48 (d, J=8.9Hz, 1H), 2.37 (s, 3H). 13C NMR (100 MHz, DMSO-d6) δ 167.9, 139.1, 136.4, 133.1, 133.0, 127.0, 124.3, 120.8, 114.5, 14.6. HRMS for C 10 H9BrNO2 + [M+H] + 253.9811, found 253.9815.

[0127]

[0128] 1H), 7.34 (d, J = 8.7 Hz, 1H), 2.37 (s, 3H). 13 C NMR (100 MHz, DMSO-d6) δ 167.6, 139.0, 138.3, 136.7, 133.4, 133.1, 124.8, 120.7, 86.2, 14.6. HRMS for C 10 H9INO2 + [M+H] + 301.9672, found 301.9651.

[0129]

[0130] 2.35 (s, 3H). HRMS for C 11 H 12 NO2 + [M+H] + 190.0863, found 190.0835.

[0131]

[0132] (m, 2H), 3.83 (s, 3H), 2.33 (s, 3H). 13 C NMR (100 MHz, DMSO-d6) δ 169.1, 161.2, 139.5, 138.0, 131.1, 126.8, 117.3, 113.0, 98.3, 55.7, 14.4. HRMS for C 11 H 12 NO3 + [M+H] + 206.0812, found 206.0789.

[0133]

[0134] (s, 1H), 7.57 - 7.28 (m, 1H), 2.41 (d, J = 1.6 Hz, 3H). 13 C NMR (100 MHz, DMSO-d6) δ 168.5, 139.9, 136.8, 133.73, 130.2 (d, J = 31.6 Hz), 127.1, 124.8, 124.5 (q, J = 270 Hz), 117.37 (q, J = 3.2 Hz), 115.83 (q, J = 4.6 Hz) 14.74. HRMS for C 11 H9F3NO2 + [M+H] + 244.0580, found 244.0558.

[0135]

[0136] 6.8 Hz, 1H), 2.36 (s, 3H). 13 C NMR (100 MHz, DMSO-d6) δ 168.1 (d, J = 2.8 Hz), 151.7 (dd, J = 249.3, 16.0 Hz), 146.45 (dd, J = 243.5, 14.7 Hz), 138.5, 134.4 (d, J = 10.7 Hz), 133.2, 119.7 (d, J = 5.0 Hz), 111.66 (dd, J = 16.3, 2.0 Hz), 105.8 (d, J = 20.6 Hz), 14.6. HRMS for C 10 H8F2NO2 + [M+H] + 212.0518, found 212.0489.

[0137]

[0138] = 5.6 Hz, 6H), 2.32 (s, 3H). 13 C NMR (100 MHz, DMSO-d6) δ 168.0, 152.5, 146.3, 137.7, 133.6, 130.1, 116.7, 103.8, 98.8, 56.0, 55.9, 14.4. HRMS for C 12 H 14 NO4 + [M+H] + 236.0917, found 236.0893.

[0139]

[0140] Hz, 1H), 7.46 (ddd, J = 9.1, 8.2, 3.0 Hz, 1H), 2.39 (s, 3H). 13 C NMR (100 MHz, DMSO-d6) δ 173.0 (d, J = 3.1 Hz), 162.6 (d, J = 239.9 Hz), 143.1, 139.2, 137.7, 128.4 (d, J = 6.9 Hz), 125.6 (d, J = 8.4 Hz), 124.4 (d, J = 26.1 Hz), 113.1 (d, J = 22.1 Hz), 19.3. HRMS for C 10 H8FNO2 + [M+H] + 194.0608, found 195.0612.

[0141]

[0142] 2H), 7.54 (t, J = 7.5 Hz, 2H), 7.44 (t, J = 7.2 Hz, 1H), 2.70 (s, 2H). 13 C NMR (150 MHz, DMSO-d6) δ 157.6, 147.0, 139.0, 138.6, 136.9, 134.9, 131.0, 129.7, 128.8, 127.6, 120.4, 120.3, 120.2, 16.3. HRMS for C 16 H 14 NO2 + [M+H] + 252.1019, found 252.1022.

[0143]

[0144] J = 8.9, 2.0 Hz, 1H), 8.02 (d, J = 8.9 Hz, 1H), 7.82 - 7.61 (m, 2H), 7.34 (d, J = 8.0 Hz, 2H), 2.68 (s, 3H), 2.38 (s, 3H). 13 C NMR (150 MHz, DMSO-d6) δ 144.0, 138.2, 137.7, 137.3, 136.3, 135.2, 130.6, 130.3, 127.3, 120.9, 120.1, 120.0, 21.2, 16.0. HRMS for C 17 H 16 NO2 + [M+H] +266.1176, found 266.1153.

[0145]

[0146] 8.6 Hz, 1H), 7.77 (d, J = 8.1 Hz, 2H), 7.61 (d, J = 8.7 Hz, 1H), 7.54 (d, J = 8.2 Hz, 2H), 2.39 (s, 3H). 13 C NMR (150 MHz, DMSO-d6) δ 144.9, 138.0, 137.3, 136.4, 135.3, 133.6, 130.5, 129.6, 129.2, 120.8, 120.7, 120.3, 16.1. HRMS for C 16 H 13 ClNO2 + [M+H] + 286.0629, found 286.0633.

[0147]

[0148] 2.0 Hz, 1H), 8.15 (dd, J = 8.9, 2.0 Hz, 1H), 8.05 (d, J = 8.8 Hz, 1H), 7.40 (d, J = 2.2 Hz, 1H), 7.36 (dd, J = 8.3, 2.2 Hz, 1H), 7.10 (d, J = 8.4 Hz, 1H), 3.90 (s, 3H), 3.83 (s, 3H), 2.71 (s, 3H). 13 C NMR (150 MHz, DMSO-d6) δ 157.7, 149.8, 149.7, 146.2, 138.3, 137.0, 134.7, 131.6, 130.8, 120.5, 120.2, 120.0, 119.4, 112.7, 111.0, 56.5, 56.1, 16.2. HRMS for C 18 H 19 NO4 + [M+H] + 312.1230, found 312.1231.

[0149]

[0150] 8.07 (m, 1H), 8.01 - 7.96 (m, 1H), 7.70 (d, J = 3.7 Hz, 1H), 7.66 (d, J = 4.9 Hz, 1H), 7.21 (dd, J = 5.1, 3.6 Hz, 1H), 2.66 (s, 3H).13 C NMR (150 MHz, DMSO-d6) δ 158.8, 144.3, 142.6, 137.5, 135.2, 131.4, 129.4, 129.3, 127.4, 125.6, 121.1, 120.4, 118.7, 15.9. HRMS for C 14 H 12 NO2S + [M+H] + 258.0583, found 258.0553.

[0151] Comparative Examples 1-6

[0152] Comparative Examples 1-6 refer to Example 1, changing the amount of reactants, reaction temperature, reaction time and other conditions, the reaction yield is calculated, and the results are shown in Table 1.

[0153] Table 1

[0154]

[0155] From Table 1, it can be seen that adjusting the amount of reactants, reaction temperature or reaction time will reduce the yield of compound A1.

[0156] Comparative Examples 7-11

[0157] Comparative Examples 7-11 refer to Example 9, changing the amount of reactants, reaction temperature, reaction time and other conditions, the reaction yield is calculated, and the results are shown in Table 2.

[0158] Table 2

[0159]

[0160] From Table 2, it can be seen that adjusting the amount of reactants, reaction temperature or reaction time will reduce the yield of compound B1.

[0161] Test Example 1

[0162] This test example adopts the insect dipping method to determine the lethal activity of the target compound on southern root-knot nematodes at different concentrations, which specifically includes the following steps:

[0163] The test is carried out by the immersion method. 5 mg of the test compound is weighed, dissolved in 0.1 mL of DMF to obtain a 50,000 μg / mL mother solution, and then diluted with distilled water to obtain a 400 μg / mL test compound solution. Meanwhile, 100 nematodes / mL of nematode solution is prepared. A clean 12-well plate is prepared, 1 mL of nematode solution and 1 mL of test compound solution are added to each well, and the corrected mortality of the target compound at a concentration of 200 μg / mL is determined. Distilled water without 0.01% DMF is used as a solvent control, and 50 μg / mL of abamectin is used as a positive control. Each treatment is repeated three times. The 12-well plate is incubated at 25°C, and the number of dead and live nematodes is counted at 24 h, 48 h, and 72 h, respectively. The corrected mortality at 24 h, 48 h, and 72 h is calculated. The experimental results are shown in Table 3.

[0164] Mortality (%) = number of dead nematodes / total number of nematodes x 100%

[0165] Corrected mortality (%) = (treatment group mortality - control group mortality) / (1 - control group mortality) x 100%

[0166] Table 3

[0167]

[0168]

[0169] As shown in Table 3, compounds B1-B13 have a certain mortality rate on southern root-knot nematodes. Among them, compounds B1-B8 have the highest insecticidal activity.

[0170] Test Example 2

[0171] In this test example, the in vitro antibacterial activity of the target compound is determined by the mycelial growth rate method, which includes the following contents:

[0172] 15 mg of the test compound is weighed with a 1 / 10,000 balance and placed in a 1.5 mL centrifuge tube. 0.5 mL of DMF is added to dissolve the test compound. After the solution is clear and transparent, the dissolved test compound solution is added to 300 mL of PDA medium and shaken to obtain a PDA medium containing 50 μg / mL of the test compound. A PDA medium containing 1 mL of distilled water is used as a blank control, a 0.01% DMF solution without the test compound is used as a solvent control, and 50 μg / mL of azoxystrobin is used as a positive control. Each treatment is repeated three times, and the PDA medium is poured into a 9 cm Petri dish. After the PDA solidifies, a bacterial cake is inoculated, sealed with a sealing film, and incubated in a 25°C incubator for 2-5 days. When the diameter of the colonies in the Petri dish reaches 8 cm, a ruler is used to measure the diameter, and the inhibition rate is calculated. The experimental results are shown in Table 4.

[0173] Myceilial growth inhibition rate (%) = ((control colony diameter - treated colony diameter) / (control colony diameter - mycelium cake diameter))*100

[0174] Note: Mycelium cake diameter is 5mm

[0175] Based on the data in Table 4, the target compounds whose pathogenic fungi inhibition rate reached more than 70% were determined for EC 50 , and the results are shown in Table 5.

[0176] Table 4

[0177]

[0178]

[0179] Note: F.G: Fusarium graminearum; C.M: Colletotrichum musae; P.C: Phytophthora capsici; F.O: Fusarium oxysporum; C.S: Colletotrichum gloeosporioides; P.O: Pyricularia oryzae; R.S: Rhizoctonia solani; B.C: Botrytis cinerea.

[0180] Table 5

[0181]

[0182] Note: -a represents not tested

[0183] From Table 4 and Table 5, it can be seen that in compounds B9-B13, when a substituted benzene or a thienyl heterocycle is introduced at the 6-position, the fungicidal activity of the compounds remains at a low level, and compared with compounds B1-B8, the fungicidal activity does not obviously increase.

[0184] The above description of disclosed embodiments enables one skilled in the art to make or use the present application. Numerous modifications to these embodiments will be apparent to those skilled in the art, and the generic principles defined herein can be applied to other embodiments without departing from the spirit or scope of the application. Therefore, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. Use of a compound represented by formula 9 in inhibiting Mycosphaerella fijiensis: ###0001### Formula 9.

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