Insecticidal composition containing quinolone compound and application thereof

Abstract

The invention relates to the technical field of biological control, and provides an insecticidal composition containing quinolone compounds and application thereof. The invention provides compounds as shown in formulas 1-8. Compared with the prior art, the quinolone derivatives are designed and synthesized, the quinolone derivatives are small molecule compounds which are simple in structure, easy to synthesize and good in nematicidal activity, the nematicidal activity of the compounds is further researched, the compounds serve as root nematode insecticides, and an idea is provided for solving the problem that few nematicides exist at present.

Description

Technical Field

[0001] The present invention relates to the field of biological control technology, and more specifically to an insecticide composition containing quinolone compounds and application thereof. Background Art

[0002] In the process of food production, effective prevention and control of diseases and pests is particularly important. Plant root-knot nematodes (Meloidogyne spp.) are a type of plant disease that widely harms agricultural production. It can harm more than 3,000 species of plants, including vegetables, food crops and fruit trees. As a specific type of fixed endophytic parasitic nematodes, the second-instar larvae stage (J2) is the only period with infection ability in the life cycle of root-knot nematodes. At this time, the larvae can move freely in the soil and invade the roots of host plants, affecting the lateral roots and fine root systems, causing damage to plants. The harm of root-knot nematodes is not limited to its physical invasion, but also stimulates the mutation of plant root cells to form so-called "giant cells" as a source of nutrition. This parasitic mode seriously affects the normal physiological processes of plants, resulting in stunted plant growth, manifested as slow growth, yellowing of leaves and wilting. According to statistics, plant parasitic nematodes cause about 14% of crop yield reductions worldwide each year, with economic losses as high as 80 billion to 100 billion US dollars. Among the many means of controlling root-knot nematodes, chemical control is still the main means of controlling root-knot nematodes due to its high efficiency and convenience. Currently, there are few nematicides suitable for agricultural production, and the varieties are single, which inevitably causes root-knot nematodes to develop drug resistance. Summary of the invention

[0003] In view of this, the object of the present invention is to provide an insecticidal composition containing quinolone compounds and its application. The present invention designs and synthesizes quinolone derivatives, which are small molecule compounds with simple structure, easy synthesis and good nematicidal activity.

[0004] In order to achieve the above object, the present invention adopts the following technical solutions:

[0005] Compounds as shown in Formula 1 to Formula 8;

[0006]

[0007] The present invention also provides a method for preparing the compounds shown in Formula 1 to Formula 8, comprising:

[0008] 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 the system is mixed with chloroacetone, and then reacted at 50-60°C for 0.5-1h to obtain compounds represented by Formulas 1 to 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), preferably 1:1.1:1.5.

[0012] Preferably, the N,N-dimethylformamide is a reaction solvent, which can fully dissolve the raw materials.

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

[0014]

[0015]

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

[0017] The compounds represented by Formula 1 to Formula 8 are mixed with N-methylproprrolidone, and reacted at 210° C. for 5 hours to obtain compounds represented by Formula 9 to Formula 16;

[0018]

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

[0020] (1) Mixing the compound represented by Formula 9 with N,N-dimethylformamide, potassium carbonate and dibromomethane, and heating at 120° C. for 2 h in a nitrogen atmosphere to obtain the compound represented by Formula II;

[0021]

[0022] (2) mixing the compound represented by formula II with 1,4-dioxane, potassium carbonate, R'B(OH)2, and tetrakis(triphenylphosphine)palladium, and reacting at 90° C. under a nitrogen atmosphere for 2 h to obtain the compound represented by 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 represented by Formula III is mixed with hydrochloric acid and acetonitrile, and reacted at 75° C. for 6 to 8 hours to obtain compounds represented by Formulas 17 to 21.

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

[0027] Preferably, the molar ratio of the compound represented by formula II to potassium carbonate, phenylboric 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 present invention also provides the use of compounds shown in Formula 9 to Formula 21 in the control of root-knot nematodes;

[0030]

[0031]

[0032] Preferably, the root-knot nematode comprises Meloidogyne incognita.

[0033] Meloidogyne incongnita is a plant parasitic nematode that harms crops and seriously affects the sustainable development of agriculture. Currently, there are few nematicides suitable for agricultural production, and the varieties are single, which inevitably causes the root-knot nematodes to develop drug resistance.

[0034] Preferably, the concentration of the compound represented by Formula 9 to Formula 21 is 200 to 300 μg / mL, preferably 200 μg / mL.

[0035] The present invention also provides an insecticide composition containing quinolone compounds, including compounds represented by Formula 9 to Formula 21, and acceptable adjuvants;

[0036]

[0037]

[0038] The present invention also provides the use of one or more of the compound represented by Formula 9, the compound represented by Formula 10, the compound represented by Formula 19, the compound represented by Formula 20, and the compound represented by Formula 21 in antibacterial treatment;

[0039]

[0040] 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.

[0041] Preferably, the concentration of the compound represented by Formula 9, the compound represented by Formula 10, the compound represented by Formula 19, the compound represented by Formula 20, and the compound represented by Formula 21 is 50 to 100 μg / mL, preferably 50 μg / mL.

[0042] The present invention also provides the use of the compound represented by formula 11 in inhibiting wheat fusarium, banana anthracnose, pepper phytophthora, banana wilt, rice sheath blight or tomato gray mold.

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

[0044] The present invention also provides the use of the compound represented by formula 12 in inhibiting wheat fusarium, banana anthracnose pathogen, pepper phytophthora, banana wilt pathogen and rubber anthracnose pathogen.

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

[0046] The present invention also provides the use of the compound represented by formula 13 in inhibiting wheat fusarium, banana anthracnose pathogen, pepper phytophthora, banana wilt pathogen, rubber anthracnose pathogen and rice blast pathogen.

[0047] Preferably, the concentration of the compound represented by Formula 13 is 50 to 100 μg / mL, preferably 50 μg / mL.

[0048] The present invention also provides the use of the compound represented by formula 14 in inhibiting banana anthracnose, pepper phytophthora, banana wilt, rubber anthracnose, rice blast, rice sheath blight, and tomato gray mold.

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

[0050] The present invention also provides the use of the compound represented by formula 15 in inhibiting pepper phytophthora, banana wilt, rubber anthracnose, rice blast, rice sheath blight and tomato gray mold.

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

[0052] The present invention also provides the use of the compound represented by formula 16 in inhibiting wheat fusarium, pepper phytophthora, banana wilt, rubber anthracnose, rice blast, rice sheath blight, and tomato gray mold.

[0053] Preferably, the concentration of the compound represented by Formula 16 is 50 to 100 μg / mL, preferably 50 μg / mL.

[0054] The present invention also provides the use of the compound represented by formula 17 in inhibiting wheat fusarium, banana anthracnose, banana wilt, rubber anthracnose, rice blast, rice sheath blight, and tomato gray mold.

[0055] Preferably, the concentration of the compound represented by Formula 17 is 50 to 100 μg / mL, preferably 50 μg / mL.

[0056] The present invention also provides the use of the compound represented by formula 18 in inhibiting wheat fusarium, banana anthracnose pathogen, pepper phytophthora, banana wilt pathogen, rice blast pathogen, rice sheath blight pathogen, and tomato gray mold.

[0057] Preferably, the concentration of the compound represented by Formula 18 is 50 to 100 μg / mL, preferably 50 μg / mL.

[0058]

[0059] Compared with the prior art, the beneficial effects of the present invention include:

[0060] The present invention designs and synthesizes quinolone 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

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

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

[0063] Figure 3 is the hydrogen nuclear magnetic resonance spectrum of compound B1 in the example;

[0064] Figure 4 is the carbon NMR spectrum of compound B1 in the example;

[0065] Figure 5 is the hydrogen nuclear magnetic resonance spectrum of compound B2 in the example;

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

[0067] Figure 7 is the hydrogen nuclear magnetic resonance spectrum of compound B3 in the example;

[0068] Figure 8 is the hydrogen nuclear magnetic resonance spectrum of compound B4 in the example;

[0069] Fig. 9 is the carbon NMR spectrum of compound B4 in the example;

[0070] Fig.10 is the hydrogen nuclear magnetic resonance spectrum of compound B5 in the example;

[0071] Fig.11 is the carbon NMR spectrum of compound B5 in the examples;

[0072] Fig.12 is the hydrogen nuclear magnetic resonance spectrum of compound B6 in the example;

[0073] Fig.13 is the carbon NMR spectrum of compound B6 in the example;

[0074] Fig.14 is the hydrogen nuclear magnetic resonance spectrum of compound B7 in the example;

[0075] Fig.15 is the carbon NMR spectrum of compound B7 in the examples;

[0076] Fig.16 is the hydrogen nuclear magnetic resonance spectrum of compound B8 in the example;

[0077] Fig.17 is the carbon NMR spectrum of compound B8 in the example;

[0078] Fig.18 is the hydrogen nuclear magnetic resonance spectrum of compound B9 in the example;

[0079] Fig.19 is the carbon NMR spectrum of compound B9 in the example;

[0080] Fig. 20 is the hydrogen nuclear magnetic resonance spectrum of compound B10 in the example;

[0081] Fig.21 is the carbon NMR spectrum of compound B10 in the example;

[0082] Fig. 22 is the hydrogen nuclear magnetic resonance spectrum of compound B11 in the example;

[0083] Fig.23 is the carbon NMR spectrum of compound B11 in the example;

[0084] Fig.24 is the hydrogen nuclear magnetic resonance spectrum of compound B12 in the example;

[0085] Fig.25 is the carbon NMR spectrum of compound B12 in the example;

[0086] Fig.26 is the hydrogen nuclear magnetic resonance spectrum of compound B13 in the example;

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

[0088] The technical solution 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, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0089] In order to further illustrate the present invention, the following examples are used to explain it in detail. The raw materials used in the following examples and comparative examples of the present invention are all commercially available products.

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

[0091]

[0092]

[0093] Examples 1-8

[0094] This example provides the synthesis of compounds A1 to A8, which specifically include the following contents:

[0095] Preparation of compound A1:

[0096] 2-Amino-5-bromo-benzoic acid (1 mmol) was dissolved in N,N-dimethylformamide (DMF, 5 mL), and potassium carbonate (K2CO3, 0.2 g, 1.5 mmol) was then added. After reacting at 120°C for 30 min, the temperature was lowered to 50°C, and chloroacetone (1.1 mmol) was added dropwise. After the addition was completed, the mixture was reacted at 50°C for 0.5 h. After the reaction was completed as monitored by thin layer chromatography (TLC), the temperature was lowered to room temperature, 30 mL of distilled water was added, and precipitation of a powdery solid was observed. After stirring for 10 min, the mixture was filtered to obtain a yellow solid A1 with a yield of 83.9% and a melting point of 85-87°C.

[0097] The preparation methods of compounds A2-8 were carried out according to the method of A1.

[0098] The structures and NMR data of compounds A1 to 8 are as follows: Figure 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] 8.5,1.7Hz,1H), 4.87(s,2H), 2.24(s,3H).

[0109]

[0110] (dd,J=11.2,8.9Hz,1H), 6.44 (dd,J=12.0,6.6Hz,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] Embodiment 9-21

[0116] This example provides the synthesis of compounds B1 to 13, which specifically includes the following contents:

[0117] Preparation of compound B1:

[0118] 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.

[0119] The preparation methods of compounds B2-8 were carried out according to the method of B1.

[0120] Preparation of compound B9:

[0121] (1) Compound B1 (2 mmol) was dissolved in DMF (6 mL), anhydrous potassium carbonate (0.83 g, 6 mmol) and dibromomethane (CH2Br2, 0.3 mL, 4 mol) were added to the solution, and heated at 120°C under 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, × 3 here means 3 times, the same below), extracted with ethyl acetate (EA, 10 ml × 3), dried over anhydrous sodium sulfate (Na2SO4), 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.

[0122] (2) 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 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 (Na2SO4), 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. The preparation method of compounds C10-13 is the same as that of C9; in R'B(OH)2, R' is phenyl.

[0123] (3) A suspension of compound C9 (1 mmol) in 5 mL of dilute hydrochloric acid (HCl / H2O, 3 mol / L) was heated to 75°C. After 0.5 h, acetonitrile (10 mL) was added to the suspension. The solution was heated to reflux for 6 hours. 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 in vacuo to obtain the target product B9 with a yield of 51.4% and a melting point of >300°C. The preparation method of compounds B10-13 is the same as that of B9.

[0124] The structures and NMR data of compounds B1 to 13 are as follows: Figure 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(100MHz,DMSO-d6)δ167.9,139.1,136.4,133.1,133.0,127.0,124.3,120.8,114.5,14.6。HRMS forC 10 H9BrNO2 + [M+H] + 253.9811,found 253.9815。

[0127]

[0128] 1H),7.34(d,J=8.7Hz,1H),2.37(s,3H)。 13 C NMR(100MHz,DMSO-d6)δ167.6,139.0,138.3,136.7,133.4,133.1,124.8,120.7,86.2,14.6。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)δ169.1,161.2,139.5,138.0,131.1,126.8,117.3,113.0,98.3,55.7,14.4。HRMSfor 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)δ168.5,139.9,136.8,133.73,130.2(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。HRMSfor 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)δ168.1(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=10.7Hz),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)δ168.0,152.5,146.3,137.7,133.6,130.1,116.7,103.8,98.8,56.0,55.9,14.4。HRMS forC 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)δ173.0(d,J=3.1 Hz),162.6(d,J=239.9 Hz),143.1,139.2,137.7,128.4(d,J=6.9Hz),125.6(d,J=8.4 Hz),124.4(d,J=26.1 Hz),113.1(d,J=22.1 Hz),19.3。HRMS forC 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(150MHz,DMSO-d6)δ157.6,147.0,139.0,138.6,136.9,134.9,131.0,129.7,128.8,127.6,120.4,120.3,120.2,16.3。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=8.0Hz,2H),2.68(s,3H),2.38(s,3H)。 13 C NMR(150 MHz,DMSO-d6)δ144.0,138.2,137.7,137.3,136.3,135.2,130.6,130.3,127.3,120.9,120.1,120.0,21.2,16.0。HRMS forC 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=8.2Hz,2H),2.39(s,3H)。 13 C NMR(150 MHz,DMSO-d6)δ144.9,138.0,137.3,136.4,135.3,133.6,130.5,129.6,129.2,120.8,120.7,120.3,16.1。HRMS forC 16 H 13 ClNO2 + [M+H] + 286.0629,found 286.0633。

[0147]

[0148] 2.0Hz,1H),8.15(dd,J=8.9,2.0Hz,1H),8.05(d,J=8.8Hz,1H),7.40(d,J=2.2Hz,1H),7.36(dd,J=8.3,2.2Hz,1H),7.10(d,J=8.4Hz,1H),3.90(s,3H),3.83(s,3H),2.71(s,3H)。 13 C NMR(150MHz,DMSO-d6)δ157.7,149.8,149.7,146.2,138.3,137.0,134.7,131.6,130.8,120.5,120.2,120.0,119.4,112.7,111.0,56.5,56.1,16.2。HRMS forC 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=3.7Hz,1H),7.66(d,J=4.9Hz,1H),7.21(dd,J=5.1,3.6Hz,1H),2.66(s,3H)。13 C NMR (150MHz, DMSO-d6) δ158.8, 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. HRMSforC 14 H 12 NO2S + [M+H] + 258.0583, found 258.0553.

[0151] Comparative Examples 1-6

[0152] Comparative Examples 1-6 Referring to Example 1, the conditions such as the amount of reactants, reaction temperature, reaction time, etc. were changed, and the reaction yields were calculated. The results are shown in Table 1.

[0153] Table 1

[0154]

[0155] It can be seen from Table 1 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, change the amount of reactants, reaction temperature, reaction time and other conditions, calculate the reaction yield, the results are shown in Table 2.

[0158] Table 2

[0159]

[0160] It can be seen from Table 2 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 immersion method to determine the lethal activity of the target compound at different concentrations against southern root-knot nematodes, which specifically includes the following steps:

[0163] The test was carried out by the insect immersion method. 5 mg of the test compound was weighed, DMF (0.1 mL) was added to prepare a 50000 μg / mL mother solution, and distilled water was added to dilute the test compound concentration to 400 μg / mL. At the same time, the nematodes were prepared into a nematode solution of 100 / mL. A clean 12-well plate was taken, and 1 mL of nematode solution and 1 mL of the test compound solution were added to each well. The corrected mortality rate of the target compound at a concentration of 200 μg / mL was determined. 2 / 1000 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 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 was counted respectively. The corrected mortality rates of 24h, 48h, and 72h were calculated. The experimental results are shown in Table 3.

[0164] Mortality rate (%) = number of nematodes killed / total number of nematodes × 100%

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

[0166] Table 3

[0167]

[0168]

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

[0170] Test Example 2

[0171] 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:

[0172] 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 after the solution becomes clear and transparent, add the solution of the dissolved test compound to 300 mL of PDA medium, shake well, and prepare a PDA medium containing 50 μg / mL of the test compound, add 1 mL of distilled water to the PDA medium as a blank control, 0.2% DMF without the drug as a solvent control, and 50 μg / mL of azoxystrobin as a positive control, and pour them into 9 cm culture dishes, each treatment is repeated 3 times, and after the PDA solidifies, the bacterial cake is inoculated, the sealing film is sealed, and it is placed in a 25°C incubator for 2-5 days. When the diameter of the colony in the culture dish reaches 8 cm, it is measured with a ruler to calculate the inhibition rate. The experimental results are shown in Table 4.

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

[0174] Note: The diameter of the mushroom cake is 5mm

[0175] Based on the data in Table 4, EC analysis was performed on target compounds with a pathogen inhibition rate of more than 70%. 50 The results are shown in Table 5.

[0176] Table 4

[0177]

[0178]

[0179] 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.

[0180] Table 5

[0181]

[0182] Note: -a means not tested

[0183] It can be seen from Tables 4 and 5 that in compounds B9-13, when a substituted benzene or thiophene heterocycle is introduced at the 6-position, the fungicidal activity of the compound remains at a low level, and there is no significant improvement in the fungicidal activity compared with compounds B1-8.

[0184] 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. The compounds shown in Formula 1 to Formula 8; 2. A method for preparing the compound according to claim 1, It is characterized in that include: 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 the system is mixed with chloroacetone, and then reacted at 50-60°C for 0.5-1h to obtain the compound represented by formula I; In Formula I, the R 1 , R 2 Independently selected from H, F, Br, I, -CH 3 , -CF 3 or -OCH 3 .

3. Compounds as shown in Formula 9 to Formula 21; 4. A method for preparing the compound according to claim 3, It is characterized in that The method for preparing the compounds represented by Formula 9 to Formula 16 comprises: The compounds represented by Formula 1 to Formula 8 are mixed with N-methylproprrolidone, and reacted at 210° C. for 5 hours to obtain compounds represented by Formula 9 to Formula 16; 5. A method for preparing the compound according to claim 3, It is characterized in that The method for preparing the compounds represented by Formula 17 to Formula 21 comprises: (1) Mixing the compound represented by Formula 9 with N,N-dimethylformamide, potassium carbonate and dibromomethane, and heating at 120° C. for 2 h in a nitrogen atmosphere to obtain the compound represented by Formula II; (2) The compound represented by formula II is mixed with 1,4-dioxane, potassium carbonate, R'B(OH) 2 , tetrakis(triphenylphosphine)palladium, react at 90° C. in a nitrogen atmosphere for 2 h to obtain a compound of formula III; R'B(OH) 2 In which R' is selected from phenyl, benzyl, phenylchloro, In formula III, R' is selected from phenyl, benzyl, phenylchloro, (3) The compound represented by Formula III is mixed with hydrochloric acid and acetonitrile, and reacted at 75° C. for 6 to 8 hours to obtain compounds represented by Formulas 17 to 21.

6. Use of the compound according to claim 3 in controlling root-knot nematodes.

7. An insecticidal composition containing a quinolone compound, It is characterized in that Including compounds represented by formula 9 to formula 21, and acceptable auxiliary materials; 8. Use of one or more of the compound represented by Formula 9, the compound represented by Formula 10, the compound represented by Formula 19, the compound represented by Formula 20, and the compound represented by Formula 21 in antibacterial treatment; 9. The use according to claim 8, It is 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.

10. Use of the compound represented by formula 11 in inhibiting wheat fusarium, banana anthracnose, pepper phytophthora, banana wilt, rice sheath blight or tomato gray mold; Use of the compound represented by formula 12 in inhibiting wheat fusarium, banana anthracnose pathogen, pepper phytophthora, banana wilt pathogen, and rubber anthracnose pathogen; Application of the compound represented by formula 13 in inhibiting wheat fusarium, banana anthracnose, pepper phytophthora, banana wilt, rubber anthracnose and rice blast; Use of the compound represented by formula 14 in inhibiting banana anthracnose, pepper phytophthora, banana wilt, rubber anthracnose, rice blast, rice sheath blight, and tomato gray mold; Use of the compound represented by formula 15 in inhibiting pepper phytophthora, banana wilt, rubber anthracnose, rice blast, rice sheath blight, and tomato gray mold; Application of the compound represented by formula 16 in inhibiting wheat fusarium, pepper phytophthora, banana wilt, rubber anthracnose, rice blast, rice sheath blight, and tomato gray mold; Use of the compound represented by formula 17 in inhibiting wheat fusarium, banana anthracnose, banana wilt, rubber anthracnose, rice blast, rice sheath blight, and tomato gray mold; Application of the compound represented by formula 18 in inhibiting wheat fusarium, banana anthracnose, pepper phytophthora, banana wilt, rice blast, rice sheath blight, and tomato gray mold;

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