Insecticidal composition and use thereof, and insecticide

Abstract

The present invention relates to the field of pesticides. Disclosed are an insecticidal composition and the use thereof, and an insecticide. The composition contains an insecticidal effective amount of component A and an insecticidal effective amount of component B. The weight ratio of the component A to the component B is 1:50-50:1, the component A is compound 1 represented by formula (I); and the component B is selected from at least one of cyantraniliprole, chlorantraniliprole, flubendiamide, emamectin benzoate, cyhalothrin, chlorfenapyr, etc. The insecticidal composition and the insecticide of the present invention can expand the insecticidal spectrum, improve the pest control effect, and delay the occurrence of drug tolerance and drug resistance of pests.

Description

Insecticide composition and its application and insecticide

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Chinese patent application No. 202410062646.6 filed on January 16, 2024, the contents of which are incorporated herein by reference. Technical Field

[0003] The present invention relates to the field of pesticides, and in particular to an insecticide composition, application of the insecticide composition in preventing and controlling crop pests, and an insecticide. Background Art

[0004] Protecting crops from pests remains a recurring challenge in agriculture. To address this issue, researchers in the field of synthetic chemistry have developed numerous different insecticides. However, the long-term, continuous, high-dose use of a single chemical insecticide with a single mode of action can gradually lead to insect resistance. Even increasing the dosage of the insecticide may not achieve the desired control effect. Faced with this situation, compounded insecticides offer advantages, effectively mitigating resistance and broadening the insecticide spectrum, reducing pesticide dosage and effectively increasing pesticide utilization. Summary of the Invention

[0005] The purpose of the present invention is to provide an insecticide composition and an insecticide containing the composition that can expand the insecticide spectrum, improve the pest control effect and delay the occurrence of pest resistance.

[0006] In order to achieve the above-mentioned object, the first aspect of the present invention provides an insecticidal composition, which contains an insecticidal effective amount of component A and an insecticidal effective amount of component B, wherein the weight ratio of the component A to the component B is 1:50-50:1, the component A is compound 1 represented by formula (I); and the component B is selected from cyantraniliprole represented by formula (II-1), chlorfenapyr represented by formula (II-2), flubendiamide represented by formula (II-3), emamectin benzoate represented by formula (II-4), chlorflucythrinate represented by formula (II-5), chlorfenapyr represented by formula (II-6), triazophos represented by formula (II-7), acephate represented by formula (II-8), thiamethoxam represented by formula (II-9), clothianidin represented by formula (II-10), thiamethoxam represented by formula (II-11), dinotefuran represented by formula (II-12), carbosulfan represented by formula (II-13), and avermectin B represented by formula (II-14). 1a , Abamectin B represented by formula (II-15) 1b, lufenuron represented by formula (II-16), spirotetramat represented by formula (II-17), pymetrozine represented by formula (II-18), flonicamid represented by formula (II-19), sulfoxaflor represented by formula (II-20), tolfenpyrad represented by formula (II-21), diafenthiuron represented by formula (II-22), nitenpyram represented by formula (II-23), pyriproxyfen represented by formula (II-24), spinetoram I represented by formula (II-25), spinetoram II represented by formula (II-26), acetamiprid represented by formula (II-27), cyfluthrin represented by formula (II-28), deltamethrin represented by formula (II-29), chlorpyrifos represented by formula (II-30), chlorpyrifos represented by formula (II-31), 1) hexaflumuron, bromofenac represented by formula (II-32), indoxacarb represented by formula (II-33), tebufenozide represented by formula (II-34), fipronil represented by formula (II-35), profenofos represented by formula (II-36), thiacloprid represented by formula (II-37), spirodiclofen represented by formula (II-38), bifenazate represented by formula (II-39), bifenthrin represented by formula (II-40), propargyl represented by formula (II-41), methoxyfenozide represented by formula (II-42), dimehypo represented by formula (II-43), matrine represented by formula (II-44), spinosad A represented by formula (II-45), and spinosad D represented by formula (II-46);

[0007] In formula (II-4), R is a methyl group or an ethyl group.

[0008] The second aspect of the present invention provides use of the insecticide composition described in the first aspect in controlling crop pests.

[0009] The third aspect of the present invention provides an insecticide, which is composed of an active ingredient and an adjuvant, wherein the active ingredient includes the insecticide composition described in the first aspect.

[0010] The insecticide composition provided by the present invention can expand the insecticide spectrum, improve the pest control effect, and delay the occurrence of drug tolerance and drug resistance of crop pests.

[0011] In particular, the inventors have discovered that the insecticide compositions of the aforementioned preferred embodiments of the present invention have superior pest control efficacy and can significantly delay the development of insecticide resistance and tolerance. These compositions are particularly effective against Plutella xylostella and other Plutella xylostella pests; Noctuidae pests such as Spodoptera exigua, Spodoptera litura, Spodoptera frugiperda, and Cutworm; Pyralidae pests such as Cnaphalocrocis medinalis and Chilo suppressalis; and Codling moth pests such as Codling moth. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] FIG1 is a graph showing the synergistic effect of compound 1 on a population of codling moth susceptible to cyhalothrin;

[0013] FIG2 is a graph showing the synergistic effect of compound 1 on the chlorfenapyr-resistant population of codling moth. DETAILED DESCRIPTION

[0014] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0015] In the present invention, except for the compound represented by formula (II-4), the letters S, R, E, and Z in the structural formulas of the other compounds represent configurations.

[0016] As described above, the first aspect of the present invention provides an insecticidal composition, which contains an insecticidally effective amount of component A and an insecticidally effective amount of component B, wherein the weight ratio of component A to component B is 1:50-50:1, and component A is compound 1 represented by formula (I); and component B is selected from at least one of the compounds represented by the structures of formula (II-1) to formula (II-46) described above;

[0017] And as mentioned above, in formula (II-4), R is a methyl group or an ethyl group.

[0018] Preferably, the weight ratio of the component A to the component B is 1:30-30:1, more preferably 1:20-20:1, and particularly preferably 1:9-9:1.

[0019] The inventors of the present invention have found that the insecticidal composition containing component A and component B in a weight ratio of 1:9-9:1 is used to control crop pests. The formed insecticidal composition has the highest co-toxicity coefficient and has a more excellent control effect on crop pests of the families of Plutellae, Noctuidae, Pyralidae, and Plectropidae.

[0020] As mentioned above, the second aspect of the present invention provides the use of the insecticide composition described in the first aspect in controlling crop pests.

[0021] Preferably, the crop pests are one or more of the family Plutellae, Noctuidae and Pyralidae.

[0022] More preferably, the crop pests are one or more of the group consisting of diamondback moth, beet armyworm, Spodoptera litura, fall armyworm, black cutworm, rice leaf roller, striped stem borer, and codling moth.

[0023] As mentioned above, the third aspect of the present invention provides an insecticide, which is composed of an active ingredient and an adjuvant, wherein the active ingredient includes the insecticide composition described in the first aspect.

[0024] Preferably, based on the total weight of the insecticide, the content of the active ingredient is 5-20%, more preferably 10-15%.

[0025] Preferably, the auxiliary material is at least one of an emulsifier, a dispersant, a wetting agent, a spreader, a stabilizer, a defoaming agent, a synergist, a penetrant, a sticker, a safener, a carrier and a filler.

[0026] Preferably, the formulation of the insecticide is at least one selected from wettable powders, soluble powders, emulsifiable concentrates, aqueous suspensions, dispersible oil suspensions, aqueous emulsions, microemulsions and water-dispersible granules.

[0027] The present invention does not particularly limit the method for forming dosage forms such as wettable powders, soluble powders, emulsifiable concentrates, aqueous suspensions, dispersible oil suspensions, aqueous emulsions, microemulsions, and water-dispersible granules. Those skilled in the art can refer to the methods provided in "Modern Pesticide Formulation Processing Technology" (Edited by Liu Guangwen, Chemical Industry Press) to form various dosage forms provided by the present invention.

[0028] Component B of the present invention may be in other active forms of the aforementioned substances, for example, in the form of esters or salts thereof.

[0029] The components of the insecticide composition provided by the present invention can be stored mixed or separately. According to a preferred embodiment, the insecticide is prepared by storing the components of the pesticide composition forming the active ingredient separately and mixing them in a tank mix for immediate use.

[0030] The pesticides of the present invention include, but are not limited to, application to crops and / or pests by methods such as spraying.

[0031] The present invention does not particularly limit the method for synthesizing component A represented by formula (I). Those skilled in the art can obtain a suitable method for preparing component A represented by formula (I) based on the compound structure provided by the present invention in combination with synthesis methods in the field of chemistry, and the present invention will not be described in detail here.

[0032] The present invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, all raw materials used are commercially available. The amounts of raw materials used in the following examples are by weight unless otherwise specified.

[0033] Cyantraniliprole represented by formula (II-1): purchased from FMC (Shanghai) Agricultural Technology Co., Ltd., product number 736994-63-1;

[0034] Chlorantraniliprole represented by formula (II-2): purchased from Lier Chemical Co., Ltd., product number 500008-45-7;

[0035] Flubendiamide represented by formula (II-3): purchased from Bayer AG, product number 272451-65-7;

[0036] Emamectin benzoate represented by formula (II-4): R=CH2CH3 was purchased from Syngenta Nantong Crop Protection Co., Ltd., product number 137512-74-4;

[0037] Cyfluthrin represented by formula (II-5): purchased from Shandong Weifang Runfeng Chemical Co., Ltd., product number 91465-08-6;

[0038] Chlorfenapyr represented by formula (II-6) was purchased from BASF SE, product number 122453-73-0.

[0039] Preparation Example 1

[0040] Preparation method of compound 1 represented by formula (I):

[0041] Carboxylic acid partial synthesis:

[0042] Amine part synthesis:

[0043] Synthesis of compound 1:

[0044] (i): Synthesis of Intermediate 2

[0045] 4-Bromo-2-methylbenzoic acid (21.50 g), 1,3-bis(diphenylphosphino)propane (0.83 g), palladium acetate (0.23 g), and potassium carbonate (27.64 g) were placed in a Schlenk tube and evacuated with nitrogen three times. Subsequently, n-butyl vinyl ether (30.00 g) and 100 mL of n-butanol were added, and the reaction was refluxed at 120° C. for 6 h. The reaction solution in the reaction tube was cooled and placed in a beaker. Ice water and 1N hydrochloric acid were added and stirred thoroughly to adjust the pH to 2. The organic phases were extracted with ethyl acetate and combined, and then washed three times with saturated NaCl water. The mixture was desiccant-filtered, concentrated, and purified by column chromatography (petroleum ether:ethyl acetate:acetic acid = 60:39.9:0.1) to obtain 15.86 g of intermediate 2 as a white solid in a yield of 89.10%.

[0046] 1 H NMR (600MHz, DMSO-d6) δ13.19(s,1H),7.89(m,1H),7.87-7.84(m,1H),7.84-7.80(m,1H),2.60(s,3H),2.57(s,3H).

[0047] (ii): Synthesis of Intermediate 3

[0048] Intermediate 2 (10.00 g) and 150 mL of methanol were placed in a three-necked flask, and 8 mL of sulfuric acid was slowly added dropwise. The reaction was carried out at 60°C for 4 h, cooled to room temperature, and extracted with ethyl acetate. The organic phase was washed with saturated aqueous NaCl solution, filtered through a funnel, concentrated, and then subjected to column chromatography (petroleum ether:ethyl acetate = 98:2) to obtain 10.30 g of intermediate 3 as a yellow liquid. The yield was 95.69%.

[0049] 1 H NMR (600MHz, DMSO-d6) δ7.91(d,J=8.9Hz,2H),7.85(d,J=8.1Hz,1H),3.86(s,3H),2.61(s,3H),2.57(s,3H).

[0050] (iii): Synthesis of Intermediate 4

[0051] Intermediate 3 (5.77 g), 2,2,2-trifluoro-3′,5′-dichloro-4′-fluoroacetophenone (7.83 g), triethylamine (3.01 g), and 100 mL of n-hexane were placed in a three-necked flask and reacted at 60°C for 8 h. After cooling to room temperature, a white solid precipitated and was filtered to obtain 10.30 g of Intermediate 4 as a white solid, with a yield of 75.75%.

[0052] 1H NMR (600MHz, DMSO-d6) δ7.91-7.78(m,5H),7.12(s,1H),4.47(d,J=18.1Hz,1H),3.91(d,J=18.3Hz,1H),3.86(s,3H),2.56(s,3H).

[0053] (iv): Synthesis of Intermediate 5

[0054] Intermediate 4 (8.16 g), acetic anhydride (3.67 g), 4-dimethylaminopyridine (0.23 g), triethylamine (3.64 g), and 60 ml of toluene were placed in a three-necked flask, reacted at 60°C for 8 h, cooled to room temperature, extracted with ethyl acetate, and the organic phase was washed with saturated aqueous NaCl solution, filtered through a funnel, concentrated, and then column chromatography (petroleum ether:ethyl acetate = 97:3) was performed to obtain 6.31 g of intermediate 5 as a light yellow liquid in a yield of 80.55%.

[0055] 1 H NMR (600MHz, DMSO-d6) δ7.92-7.87(m,2H),7.85(s,1H),7.81(d,J=8.1Hz,1H),7.61(d,J=6.2Hz,2H),3.86(s,3H),2.55(s,3H).

[0056] (v): Synthesis of Intermediate 6

[0057] Intermediate 5 (6.31 g), 50% aqueous hydroxylamine solution (1.91 g), tetrabutylammonium bromide (0.93 g), and 100 ml of dichloromethane were placed in a three-necked flask, and 30 mL of aqueous sodium hydroxide solution (2.32 g) was added dropwise at 0°C. The mixture was reacted at room temperature for 12 h. The pH was adjusted to 5, and the mixture was extracted with dichloromethane. The organic phase was washed with saturated aqueous NaCl solution, filtered through a funnel, concentrated, and then purified by column chromatography (petroleum ether:ethyl acetate = 97:4) to obtain 5.00 g of intermediate 6 as a yellow solid in a yield of 76.59%.

[0058] 1 H NMR(600MHz,DMSO-d6)δ7.91(d,J=8.0Hz,1H),7.81(d,J=6.0Hz,2H),7.70-7.64( m,2H),4.40(d,J=18.4Hz,1H),4.33(d,J=18.3Hz,1H),3.85(s,3H),2.55(s,3H).

[0059] (vi): Synthesis of Intermediate 7

[0060] Intermediate 6 (5.00 g) and 50 mL of methanol were placed in a reaction flask, 15% aqueous sodium hydroxide solution (1.56 g) was added, and the reaction was refluxed for 3 h. After the reaction solution was cooled, it was placed in a beaker, water and concentrated hydrochloric acid were added and stirred thoroughly, and the pH was adjusted to 2. The organic phases were extracted with ethyl acetate and combined, and then washed three times with saturated NaCl water. The mixture was dehydrated with a desiccant, filtered through a funnel, concentrated, and purified by column chromatography to obtain 4.45 g of intermediate 7 as a white solid, with a yield of 91.90%.

[0061] 1 H NMR (600MHz, DMSO-d6) δ13.12(s,1H),7.90(d,J=8.0,3.0Hz,1H),7.83-7.61(m,4H),4.40(d,J=18.4Hz,1H),4.31(d,J=18.3Hz,1H),2.56(s,3H).

[0062] (vii): Synthesis of Intermediate 9

[0063] 4-Nitropyrazole (100.00 g), potassium carbonate (146.67 g), and 1000 mL of N,N-dimethylformamide were placed in a reaction flask, and 2-bromopropane (130.52 g) was added in batches. The reaction was carried out at 50°C for 6 h. The organic phases were combined and extracted with ethyl acetate, then washed three times with saturated NaCl water, dehydrated with a desiccant, and concentrated by column chromatography (petroleum ether:ethyl acetate = 97:3) to obtain 131.85 g of intermediate 9 as a white solid in a yield of 96.09%.

[0064] 1 H NMR (600MHz, DMSO-d6) δ8.93 (s, 1H), 8.26 (s, 1H), 4.59 (m, 1H), 1.45 (d, J = 6.6Hz, 6H).

[0065] (viii): Synthesis of Intermediate 10

[0066] Intermediate 9 (10.00 g, 64.45) and 100 mL of methanol were placed in a reaction flask, and 10% palladium carbon (1.00 g) was added. The mixture was reacted under H2 atmosphere for 24 h, filtered through diatomaceous earth, and the filter cake was rinsed with ethyl acetate. After spin drying, 7.81 g of red oily intermediate 10 was obtained, with a yield of 96.80%.

[0067] 1H NMR (600MHz, DMSO-d6) δ7.03 (s, 1H), 6.88 (s, 1H), 4.26 (m, 1H), 3.76 (s, 2H), 1.32 (d, J = 6.5Hz, 6H).

[0068] (ix): Synthesis of Compound 1:

[0069] Intermediate 7 (100 g) and 500 mL of dichloromethane were placed in a reaction flask, and oxalyl chloride (58.21 g) and a few drops of N,N-dimethylformamide were added. After reacting for 5 h, the solvent was dried by spin drying to obtain the acid chloride. Intermediate 10 (31.57 g), 200 mL of dichloromethane, and triethylamine (46.40 g) were added dropwise at 0°C. The reaction was allowed to proceed overnight at room temperature. After a large amount of solvent was dried by spin drying, a white solid precipitated. The solid was filtered and the filter cake was rinsed with 100 mL of petroleum ether. The filter cake was slurried with 500 mL of water overnight, filtered, and dried. The dried filter cake was placed in a 500 mL eggplant-shaped flask and 40 mL of tetrahydrofuran was added. At this time, some white solid did not dissolve. After heating under reflux, tetrahydrofuran was slowly added until the system became a yellow transparent solution. Heating was stopped and 250 mL of petroleum ether was added dropwise. After cooling to room temperature, filtration was performed to obtain 108.74 g of the white target compound 1 with a purity of 99%. The yield was 87.34%.

[0070] The nuclear magnetic resonance characterization data of compound 1 represented by formula (I) provided by the present invention are as follows: 1 H NMR (600MHz, DMSO-d6) δ10.44(s,1H),8.04(s,1H),7.83(d,J=6.0Hz,2H),7.65(d,J=10.0Hz,2H),7.56(d,J=7.8Hz ,1H),7.52(s,1H),4.49(m,1H),4.40(d,J=18.4Hz,1H),4.34(d,J=18.4Hz,1H),2.42(s,3H),1.41(d,J=6.6Hz,6H).

[0071] Test Example 1

[0072] 1. Biological testing methods

[0073] 1) Cabbage leaf soaking method:

[0074] This study investigated the indoor toxicity of mixed pesticide technicals against Plutella xylostella, Spodoptera litura, Spodoptera litura, Spodoptera exigua, and Cutworms, as well as their synergistic effects. Fresh cabbage leaves, collected from a net room and previously untreated, were rinsed with tap water and blotted dry with paper towels. Leaf discs were then punched using a 6-cm diameter punch and immersed in a prepared solution (10 mg of the mixed technical in 1 ml of dimethyl sulfoxide (DMSO), followed by dilution with an aqueous solution containing 0.1 wt% Triton X-100 to a series of concentrations of 10, 5, 2, 1, 0.5, 0.3, 0.1, 0.05, and 0.025 mg / L) for approximately 15 seconds. The treated leaves were then removed and air-dried for later use. The treated leaves were placed in petri dishes, one leaf disc per dish, and ten second-instar larvae were inoculated and allowed to feed on the leaves. Each dish was replicated, and each concentration was replicated four times. The cells were cultured in a light incubator (temperature 26°C, humidity 60%). The mortality of each treatment was investigated after 24 hours, 48 ​​hours, and 72 hours. The mortality rate was calculated using the Abbott formula. plus The toxicity regression curve was calculated by software.

[0075] 2) Rice leaf immersion method:

[0076] Toxicity to rice leaf folders was determined indoors using the leaf dip method. The test agent was dissolved in a small amount of DMSO and then diluted with a 0.1% Triton X-100 solution to a concentration series of 10, 5, 2, 1, 0.5, 0.3, 0.1, 0.05, and 0.025 mg / L. Rice leaves (5-6 cm long) were immersed in the solution for 15 seconds, removed and air-dried, and then placed in a Petri dish lined with moisturizing filter paper. Ten rice leaves and ten third-instar larvae of the rice leaf folder were placed in each dish. Four replicates were performed for each concentration. A control was used, using a Triton X-100 solution. The dishes were covered with black cloth and tied with a rubber band. Small holes were punctured with a needle to allow air to pass through. The leaves were then incubated in a lighted incubator (26°C, 70% humidity). Mortality was recorded over 72 hours, and toxicity regression curves were calculated using POLOplus software.

[0077] 3) Rice stem immersion method:

[0078] The indoor toxicity test for the Chilo suppressalis was performed using the rice stem immersion method. The test agent was dissolved in a small amount of DMSO and then diluted with a 0.1% Triton X-100 solution to a series of concentrations of 10, 5, 2, 1, 0.5, 0.3, 0.1, 0.05, and 0.025 mg / L. Rice stalks (5-6 cm long) were soaked in the solution for 15 seconds, taken out and naturally dried, and placed in a culture dish with moisturizing filter paper. Fifteen rice stalks were placed in each culture dish, and 10 second-instar larvae of the Chilo suppressalis were inoculated. Four replicates were performed for each concentration, with the Triton X-100 solution as a control. The culture dishes were covered with paper towels and tied with rubber bands, and placed in a light incubator (temperature 27°C, humidity 70%). The mortality of the Chilo suppressalis was recorded after six days, and then the POLO plus The toxicity regression curve was calculated by software.

[0079] 2. Calculation method of synergistic effect:

[0080] Toxicity was assessed using the Sun Yunpei method, with the co-toxicity coefficient calculated and the combined toxicity of the two agents evaluated using the CTC value. A CTC value less than 80 indicates antagonism, greater than 120 indicates synergism, and between 80 and 120 indicates additive effects.

[0081] Compound 1 was used as the standard agent, and its toxicity index (TIA) = 100;

[0082] Toxicity index (TIB) of the test agent = LC of the standard agent 50 / LC of the test agent 50 ×100;

[0083] Actual Toxicity Index (ATI) of mixture = LC of standard agent 50 LC of mixture 50 ×100;

[0084] Theoretical toxicity index (TTI) of mixture = toxicity index of standard agent × percentage of standard agent in the mixture + toxicity index of test agent × percentage of test agent in the mixture;

[0085] Co-toxicity coefficient CTC = ATI / TTI × 100.

[0086] 3. Test results

[0087] In the present invention, 95% FL refers to 95% confidence limit.

[0088] 1) The control effect of compound 1 and cyantraniliprole on crop pests is shown in Table 1:

[0089] Table 1

[0090] As can be seen from Table 1, the co-toxicity coefficients of compound 1 and cyantraniliprole for controlling Plutella xylostella were greater than 120 at a weight ratio of 1:9 to 9:1, showing a synergistic effect; at a weight ratio of 8:2, the co-toxicity coefficient was 379, and the synergistic effect was most obvious.

[0091] When compound 1 and cyantraniliprole were combined to control fall armyworm, the co-toxicity coefficient was less than 120 at a weight ratio of 1:9, showing an additive effect; at a weight ratio of 8:2, the co-toxicity coefficient was 297, and the synergistic effect was most obvious.

[0092] The co-toxicity coefficient of compound 1 combined with cyantraniliprole for the control of Spodoptera litura was less than 120 at the weight ratios of 2:8, 4:6, and 5:5, showing an additive effect; at the weight ratio of 9:1, the co-toxicity coefficient was 357, and the synergistic effect was most obvious.

[0093] When compound 1 and cyantraniliprole were combined to control beet armyworm at a weight ratio of 9:1, the co-toxicity coefficient was 161, and the synergistic effect was the most obvious.

[0094] When compound 1 and cyantraniliprole were combined to control the chilo suppressalis at a weight ratio of 9:1, the co-toxicity coefficient was 641, and the synergistic effect was the most obvious.

[0095] The co-toxicity coefficient of compound 1 and cyantraniliprole for controlling rice leaf roller was less than 120 at a weight ratio of 4:6, showing an additive effect; at a weight ratio of 9:1, the co-toxicity coefficient was 312, and the synergistic effect was most obvious.

[0096] 2) The control effect of compound 1 and chlorantraniliprole on crop pests is shown in Table 2:

[0097] Table 2

[0098] As can be seen from Table 2, the combination of compound 1 and chlorantraniliprole has an additive or synergistic effect on the control of diamondback moth at a weight ratio of 1:9 to 9:1; at a weight ratio of 8:2, the co-toxicity coefficient is 393, and the synergistic effect is most obvious.

[0099] The combination of compound 1 and chlorantraniliprole for the control of fall armyworm showed a synergistic effect at a weight ratio of 1:9 to 9:1; at a weight ratio of 5:5, the co-toxicity coefficient was 314, and the synergistic effect was most obvious.

[0100] When compound 1 and chlorantraniliprole were combined to control beet armyworm at a weight ratio of 1:9, the co-toxicity coefficient was between 80-120, showing an additive effect; the rest were synergistic effects; especially at a weight ratio of 9:1, the co-toxicity coefficient was 512, and the synergistic effect was most obvious.

[0101] When compound 1 and chlorantraniliprole were combined in a weight ratio of 7:3 for controlling the chilo suppressalis, the co-toxicity coefficient was 292, and the synergistic effect was the most obvious.

[0102] When compound 1 and chlorantraniliprole were combined in a weight ratio of 2:8 to control rice leaf roller, the co-toxicity coefficient was between 80-120, showing an additive effect; the rest were synergistic; especially at a weight ratio of 8:2, the co-toxicity coefficient was 532, and the synergistic effect was most obvious.

[0103] 3) The control effect of compound 1 and flubendiamide on crop pests is shown in Table 3:

[0104] Table 3

[0105] As can be seen from Table 3, the co-toxicity coefficient of compound 1 and flubendiamide for controlling Plutella xylostella was greater than 120 at a weight ratio of 5:5, which was 249, and the synergistic effect was most obvious; at the weight ratios of 1:9 and 4:6, the co-toxicity coefficient was between 80-120, showing an additive effect.

[0106] When compound 1 and flubendiamide were combined to control fall armyworm at a weight ratio of 3:7, the co-toxicity coefficient was 89.6, showing an additive effect. When the weight ratio was 9:1, the co-toxicity coefficient was 512, and the synergistic effect was the most obvious.

[0107] The co-toxicity coefficient of compound 1 and flubendiamide for controlling Spodoptera litura was greater than 120 at a weight ratio of 1:9 to 9:1, showing a synergistic effect; at a weight ratio of 9:1, the co-toxicity coefficient was 633, and the synergistic effect was most obvious.

[0108] The co-toxicity coefficient of compound 1 and flubendiamide for controlling beet armyworm was greater than 120 at a weight ratio of 1:9 to 9:1, showing a synergistic effect; at a weight ratio of 9:1, the co-toxicity coefficient was 873, and the synergistic effect was most obvious.

[0109] When compound 1 and flubendiamide were combined to control the Chilo suppressalis at a weight ratio of 8:2, the co-toxicity coefficient was 504, and the synergistic effect was the most obvious.

[0110] When compound 1 and flubendiamide were combined to control rice leaf roller at a weight ratio of 7:3, the co-toxicity coefficient was 229, and the synergistic effect was the most obvious.

[0111] 4) The control effect of compound 1 and emamectin benzoate on crop pests is shown in Table 4:

[0112] Table 4

[0113] As can be seen from Table 4, when the weight ratio of compound 1 and emamectin benzoate was 2:8, the co-toxicity coefficient was between 80-120 for the control of diamondback moth, showing an additive effect; the rest showed synergistic effects; especially when the weight ratio was 3:7, the co-toxicity coefficient was 521, and the synergistic effect was the most obvious.

[0114] When compound 1 and emamectin benzoate were combined to control Spodoptera litura at a weight ratio of 3:7, the co-toxicity coefficient was 192, and the synergistic effect was the most obvious.

[0115] 5) The control effect of compound 1 and cyhalothrin on crop pests is shown in Table 5:

[0116] Table 5

[0117] As can be seen from Table 5, when compound 1 and cyhalothrin were combined to control Plutella xylostella at a weight ratio of 6:4, the co-toxicity coefficient was 520, and the synergistic effect was significant.

[0118] The co-toxicity coefficient of compound 1 and chlorfenapyr for controlling fall armyworm was greater than 120 at a weight ratio of 1:9 to 9:1, showing a synergistic effect; at a weight ratio of 8:2, the co-toxicity coefficient was 499, and the synergistic effect was most obvious.

[0119] When compound 1 and chlorfenapyr were combined to control Spodoptera litura at a weight ratio of 1:9 and 2:8, the co-toxicity coefficient was between 80-120, showing an additive effect; at a weight ratio of 6:4, the co-toxicity coefficient was 288, and the synergistic effect was most obvious.

[0120] When compound 1 and chlorfenapyr were combined to control beet armyworm at a weight ratio of 9:1, the co-toxicity coefficient was 441, and the synergistic effect was the most obvious.

[0121] When compound 1 was combined with chlorflucythrinate to control cutworms at a weight ratio of 8:2, the co-toxicity coefficient was 319, and the synergistic effect was the most obvious.

[0122] 6) The control effect of compound 1 and chlorfenapyr on crop pests is shown in Table 6:

[0123] Table 6

[0124] As can be seen from Table 6, the co-toxicity coefficients of compound 1 and chlorfenapyr for controlling Plutella xylostella were between 80-120 at weight ratios of 3:7 and 9:1, showing an additive effect; the rest showed synergistic effects; especially at a weight ratio of 4:6, the co-toxicity coefficient was 189, and the synergistic effect was the most obvious.

[0125] The co-toxicity coefficient of compound 1 and chlorfenapyr for controlling fall armyworm was greater than 120 at a weight ratio of 1:9 to 9:1, showing a synergistic effect; at a weight ratio of 8:2, the co-toxicity coefficient was 254, and the synergistic effect was most obvious.

[0126] The combination of compound 1 and chlorfenapyr for controlling Spodoptera litura has an additive or synergistic effect at a weight ratio of 1:9 to 9:1; at a weight ratio of 5:5, the co-toxicity coefficient is 222, and the synergistic effect is most obvious.

[0127] The co-toxicity coefficient of compound 1 and chlorfenapyr for controlling beet armyworm was greater than 120 at a weight ratio of 1:9 to 9:1, showing a synergistic effect; at a weight ratio of 7:3, the co-toxicity coefficient was 662, and the synergistic effect was most obvious.

[0128] Test Example 2

[0129] Toxicity of compound 1 to codling moth and its synergistic effect on cyhalothrin

[0130] 1. Test method

[0131] The third instar larvae of the cyhalothrin-sensitive population (SS) and the cyhalothrin-resistant population (LCR) of the codling moth (Cyperidinus pomonella) were selected and the toxicity was determined by the drop method.

[0132] Compound 1 was dissolved in DMSO to prepare a 10 mg / mL stock solution, which was then diluted to form five concentration gradients (400, 200, 100, 50, and 20 ng / μL).

[0133] 1 μL of the drug solution was applied to the pronotum of each third-instar codling moth larva. Once the solution had largely penetrated the insect, the insect was transferred to an artificial diet. An equal amount of DMSO served as a negative control, and λ-cyhalothrin served as a positive control. Fifteen larvae were included for each concentration, with three replicates. Mortality was recorded every 24 hours after treatment, with mortality recorded for each group at different times after treatment. Insects were considered dead if no reaction was observed by gently touching them with a small brush.

[0134] 2. Results and Analysis

[0135] 1) The results of the toxicity test of compound 1 on the cyhalothrin-sensitive population of codling moth are shown in Table 7:

[0136] Table 7

[0137] Among them, 95% FL refers to the 95% confidence limit of the median lethal dose, slope±SD represents the slope of the virulence regression curve and its standard error, and χ2 represents the chi-square value.

[0138] As can be seen from Table 7, the LD50 value at 48 h was 226.34 ng / μL, the LD50 value at 72 h was 195.46 ng / μL, and the LD50 value at 96 h was 137.77 ng / μL, all of which were higher than the LD50 value of the positive control λ-cyhalothrin under the same treatment time, indicating that the toxicity of compound 1 to the sensitive population of codling moth was weaker than that of chlorfenapyr.

[0139] 2) The results of the toxicity test of compound 1 against the cyhalothrin-resistant population of codling moth are shown in Table 8;

[0140] In the early stage, our laboratory used cyhalothrin to select codling moth larvae for multiple generations indoors, obtaining a cyhalothrin-resistant population (LCR) of codling moth. This population was used as the test object to determine the toxicity of compound 1 against it.

[0141] Table 8

[0142] Among them, 95% FL refers to the 95% confidence limit of the median lethal dose, slope±SD represents the slope of the virulence regression curve and its standard error, and χ2 represents the chi-square value.

[0143] As shown in Table 8, while the LD50 value derived from regression fitting of compound 1 against cyfluthrin-resistant codling moth populations was slightly higher than that obtained for susceptible populations, there was no significant difference (confidence intervals overlapped). This is consistent with the previous bioassay results for fourth-instar larvae. This suggests that compound 1 may have a different mechanism of action from cyfluthrin, but it exhibits a significant toxicity against cyfluthrin-resistant populations and is expected to play an important role in managing codling moth resistance.

[0144] Test Example 3

[0145] Determination of the synergistic ability of compound 1

[0146] 1. Test method

[0147] To determine whether compound 1 has a synergistic effect with cyhalothrin, third-instar larvae of codling moth (Cydonia pomonella) from SS and LCR populations were co-treated with varying doses of compound 1 and the 48-hour LD50 of cyhalothrin. The experimental groups included cyhalothrin at the LD50 and compound 1 at doses of 1 / 4, 1 / 2, 1, 2, or 4 times the LD50 (LCR-LD50 + 1 / 4 Compound 1-LD50, LCR-LD50 + 1 / 2 Compound 1-LD50, LCR-LD50 + Compound 1-LD50, LCR-LD50 + 2 Compound 1-LD50, and LCR-LD50 + 4 Compound 1-LD50, respectively). The LD50 of cyhalothrin was first applied to the pronotum of each third-instar larva, followed by titration with varying doses of compound 1. After complete solvent evaporation, the larvae were transferred to 24-well plates containing artificial diet. Mortality was recorded every 24 hours. Each group of larvae contained 15 larvae, and there were 3 groups in total. The control groups were LD50 dose of cyhalothrin (LCR-LD50) + DMSO and LD50 dose of compound 1 (Compound 1-LD50) + Acetone.

[0148] 2. Results and Analysis

[0149] 1) The synergistic effect of compound 1 on the cyhalothrin-sensitive population of codling moth is shown in Figure 1;

[0150] Among them, it can be seen from Figure 1 that compared with the control group (LCR-LD50+DMSO), there was no significant difference in the mortality rate within 96 hours in the LCR-LD50+1 / 4 compound 1-LD50 treatment group, indicating that compound 1 at a dose lower than or equal to 1 / 4 LD50 had no synergistic effect on the chlorfenapyr sensitive population of codling moth.

[0151] Compound 1 at a dose equal to or higher than 2 times the LD50 had a significant synergistic effect on the chlorflucythrin-sensitive population of codling moth, among which: the synergistic ratios of compound 1 at a dose of 2 times the LD50 on chlorflucythrin were 1.44 times (24h), 1.44 times (48h), 1.36 times (72h), and 1.42 times (96h), respectively; the synergistic ratios of compound 1 at a dose of 4 times the LD50 on chlorflucythrin were 1.44 times (24h), 1.48 times (48h), 1.44 times (72h), and 1.46 times (96h).

[0152] 2) The synergistic effect of compound 1 on the cyhalothrin-resistant population of codling moth is shown in Figure 2;

[0153] As can be seen from Figure 2, compared with the control group (LCR-LD50+DMSO), there was no significant difference in the mortality rate within 96 hours in the LCR-LD50+1 / 4 compound 1-LD50 treatment group, indicating that compound 1 at a dose less than or equal to 1 / 4 LD50 had no synergistic effect on chlorfenapyr resistant populations.

[0154] Compound 1 at a dose of 1 times or higher than 1 times the LD50 had a significant synergistic effect on chlorfenvinphos against resistant populations: the synergistic ratios of compound 1 at a dose of 1 times the LD50 were 1.42 times (24h), 1.38 times (48h), 1.27 times (72h), and 1.25 times (96h), respectively; the synergistic ratios of compound 1 at a dose of 2 times the LD50 were 1.47 times (24h), 1.38 times (48h), 1.31 times (72h), and 1.39 times (96h), respectively; the synergistic ratios of compound 1 at a dose of 4 times the LD50 were 1.42 times (24h), 1.57 times (48h), 1.42 times (72h), and 1.43 times (96h), respectively.

[0155] The results also showed that the mortality rate of the third-instar larvae of the LCR population exceeded 80% 96 hours after treatment with a dose of compound 1 greater than or equal to 2 times the LD50 and mixed with chlorfenapyr.

[0156] These results demonstrate that compound 1, when mixed with cyhalothrin, significantly enhances the bioactivity of cyhalothrin against third-instar larvae of both cyhalothrin-susceptible and cyhalothrin-resistant populations of codling moth. Therefore, by combining compound 1 with the compound, while reducing the amount of cyhalothrin used, it effectively controls codling moth and delays the development of resistance, ultimately achieving resistance management in codling moth.

[0157] Test Example 4

[0158] The activity was determined using the same cabbage leaf immersion method as in Test Example 1, and the synergistic effect calculation method was also the same as in Test Example 1.

[0159] The results are shown in Tables 9, 10 and 11.

[0160] Table 9

[0161] In Table 9, avermectin is a mixture of avermectin B1a and avermectin B1b, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., with the brand name A109741-500mg and the CAS number 71751-41-2.

[0162] As can be seen from Table 9, the co-toxicity coefficient of compound 1 and avermectin for controlling Plutella xylostella at a weight ratio of 3:7 was 135.8, which was greater than 120, showing a synergistic effect, and the synergistic effect was the most obvious.

[0163] Table 10

[0164] As can be seen from Table 10, the co-toxicity coefficients of compound 1 and fipronil for controlling Plutella xylostella were greater than 120 at weight ratios of 5:5, 8:2, and 9:1, showing a synergistic effect. At weight ratios of 1:9, 2:8, 3:7, 4:6, and 7:3, the co-toxicity coefficients were between 80 and 120, showing an additive effect. In particular, at a weight ratio of 9:1, the co-toxicity coefficient was 160.6, showing the most obvious synergistic effect.

[0165] Table 11

[0166] As can be seen from Table 11, the co-toxicity coefficients of compound 1 and emamectin benzoate for controlling cotton bollworm were greater than 120 at a weight ratio of 1:9 to 6:4, showing a synergistic effect; at a weight ratio of 5:5, the co-toxicity coefficient was 357.4, and the synergistic effect was most obvious.

[0167] The above results show that the insecticide composition provided by the present invention can expand the insecticide spectrum, improve the pest control effect, and delay the occurrence of drug resistance and tolerance of crop pests.

[0168] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. An insecticidal composition, characterized in that, The composition contains a pesticidally effective amount of component A and a pesticidally effective amount of component B, and the weight ratio of component A to component B is 1:50 - 50:

1. Component A is compound 1 represented by formula (I); Component B is selected from the group consisting of: cyantraniliprole represented by formula (II-1), chlorantraniliprole represented by formula (II-2), flubendiamide represented by formula (II-3), emamectin benzoate represented by formula (II-4), lambda-cyhalothrin represented by formula (II-5), chlorfenapyr represented by formula (II-6), triazophos represented by formula (II-7), acephate represented by formula (II-8), monosultap represented by formula (II-9), clothianidin represented by formula (II-10), thiamethoxam represented by formula (II-11), dinotefuran represented by formula (II-12), carbosulfan represented by formula (II-13), avermectin B1a represented by formula (II-14) 1a , avermectin B1b represented by formula (II-15) 1b , lufenuron represented by formula (II-16), spirotetramat represented by formula (II-17), pymetrozine represented by formula (II-18), flonicamid represented by formula (II-19), sulfoxaflor represented by formula (II-20), tolfenpyrad represented by formula (II-21), diafenthiuron represented by formula (II-22), nitenpyram represented by formula (II-23), pyriproxyfen represented by formula (II-24), spinetoram I represented by formula (II-25), spinetoram II represented by formula (II-26), acetamiprid represented by formula (II-27), cyfluthrin represented by formula (II-28), deltamethrin represented by formula (II-29), chlorfluazuron represented by formula (II-30), hexaflumuron represented by formula (II-31), broflanilide represented by formula (II-32), indoxacarb represented by formula (II-33), tebufenozide represented by formula (II-34), fipronil represented by formula (II-35), profenofos represented by formula (II-36), thiacloprid represented by formula (II-37), spirodiclofen represented by formula (II-38), bifenazate represented by formula (II-39), bifenthrin represented by formula (II-40), propargite represented by formula (II-41), methoxyfenozide represented by formula (II-42), bisultap represented by formula (II-43), matrine represented by formula (II-44), spinosyn A represented by formula (II-45), spinosyn D represented by formula (II-46); at least one of them Among them, in formula (II - 4), R is methyl or ethyl.

2. The pesticidal composition according to claim 1, characterized in that, The weight ratio of component A to component B is 1:30 - 30:1, more preferably 1:20 - 20:1, and particularly preferably 1:9 - 9:

1.

3. Use of the pesticidal composition according to claim 1 or 2 in controlling crop pests.

4. The application according to claim 3, characterized in that The crop pests are one or more of the families Plutellidae, Noctuidae, Pyralidae, and Tortricidae.

5. The application according to claim 3 or 4, characterized in that, The crop pests are one or more of Plutella xylostella, Spodoptera exigua, Spodoptera litura, Spodoptera frugiperda, Agrotis ypsilon, Cnaphalocrocis medinalis, Chilo suppressalis, and Cydia pomonella.

6. An insecticide, characterized in that, The insecticide consists of an active ingredient and auxiliary materials, and the active ingredient includes the pesticidal composition described in claim 1 or 2.

7. The pesticide according to claim 6, characterized in that, Based on the total weight of the insecticide, the content of the active ingredient is 5 - 20%, preferably 10 - 15%.

8. The insecticide according to claim 6 or 7, characterized in that, The auxiliary materials are at least one of emulsifiers, dispersants, wetting agents, spreading agents, stabilizers, defoaming agents, synergists, penetrants, adhesives, safeners, carriers, and fillers.

9. The insecticide according to any one of claims 6-8, characterized in that, The dosage form of the insecticide is selected from at least one of wettable powders, soluble powders, emulsifiable concentrates, aqueous suspension concentrates, dispersible oil suspension concentrates, emulsifiable oil-in-water concentrates, microemulsions, and water-dispersible granules.

10. The insecticide according to any one of claims 6-9, wherein, The insecticide is such that the components in the pesticide composition forming the active ingredient are stored separately and are mixed and used immediately in a tank-mix form.

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