Insecticidal composition, application thereof and insecticide

Abstract

The present invention relates to the field of pesticides, and discloses an insecticidal composition and an application 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 a compound 1 represented by formula (I), and the component B is a compound 2 represented by formula (I). And the component B is selected from at least one of cyantraniliprole, chlorantraniliprole, flubendiamide, emamectin benzoate, cyhalothrin, chlorfenapyr and the like. The insecticidal composition and the insecticide provided by the invention can enlarge the insecticidal spectrum, improve the pest control effect and delay the occurrence of pest drug resistance and drug resistance. # imgabs0 #

Description

Technical Field

[0001] 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

[0002] Protecting crops from pests has always been a recurring problem in agriculture. To help solve this problem, researchers in the field of synthetic chemistry have prepared many different pesticides, but long-term continuous high-dose use of a single variety or a single mode of action chemical pesticide will gradually increase pest resistance. Even if the dosage of the agent is increased, the ideal control effect cannot be achieved. Faced with this situation, the advantages of compound pesticides stand out, effectively mitigating the problem of resistance and increasing the insecticide spectrum, reducing the amount of pesticides used, and effectively increasing the utilization rate of pesticides. Summary of the invention

[0003] The object of the present invention is to provide an insecticide composition and an insecticide containing the composition which can expand the insecticide spectrum, improve the pest control effect and delay the occurrence of pest resistance.

[0004] 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 shown in formula (I); the component B is selected from cyantraniliprole shown in formula (II-1), chlorantraniliprole shown in formula (II-2), flubendiamide shown in formula (II-3), emamectin benzoate shown in formula (II-4), chlorflucythrinate shown in formula (II-5), cypermethrin shown in formula (II-6), triazophos shown in formula (II-7), acephate shown in formula (II-8), chlorpyrifos shown in formula (II-9), clothianidin shown in formula (II-10), thiamethoxam shown in formula (II-11), dimethomorph shown in formula (II-12), carbosulfan shown in formula (II-13), and avermectin B shown in formula (II-14). 1a , Avermectin B represented by formula (II-15) 1b, lufenac uron 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), cypermethrin represented by formula (II-29), chlorpyrifos represented by formula (II-30), and chlorpyrifos represented by formula (II-31). 1) hexaflumuron, bromofenac shown in formula (II-32), indoxacarb shown in formula (II-33), fenbumid shown in formula (II-34), fipronil shown in formula (II-35), profenofos shown in formula (II-36), thiacloprid shown in formula (II-37), spirodiclofen shown in formula (II-38), bifenazate shown in formula (II-39), bifenthrin shown in formula (II-40), fenpropathrin shown in formula (II-41), methoxyfenozide shown in formula (II-42), dimethoate shown in formula (II-43), matrine shown in formula (II-44), spinosad A shown in formula (II-45), and spinosad D shown in formula (II-46);

[0005]

[0006]

[0007]

[0008]

[0009]

[0010]

[0011]

[0012] In formula (II-4), R is a methyl group or an ethyl group.

[0013] The second aspect of the present invention provides use of the insecticidal composition described in the first aspect in controlling crop pests.

[0014] The third aspect of the present invention provides an insecticide, which consists of an active ingredient and an auxiliary material, wherein the active ingredient includes the insecticide composition described in the first aspect.

[0015] 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 drug resistance of crop pests.

[0016] In particular, the inventors of the present invention have found that the insecticide composition in the above preferred specific embodiments provided by the present invention has a more excellent pest control effect and can significantly delay the occurrence of pest resistance and drug resistance. In particular, it has a significant control effect on Plutella xylostella and other Plutella xylostella pests, beet armyworm, Spodoptera litura, fall armyworm, cutworm and other Noctuidae pests, rice leaf roller, Chilo suppressalis and other Pyralidae pests, and codling moth and other Codling moth pests. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a graph showing the synergistic effect of compound 1 on the population of codling moth susceptible to cyhalothrin;

[0018] Figure 2 This is a graph showing the synergistic effect of compound 1 on the cyhalothrin-resistant population of codling moth. DETAILED DESCRIPTION

[0019] The endpoints and any values ​​of the ranges disclosed in this article 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 endpoint values ​​of each range, the endpoint values ​​of each range and the 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 as specifically disclosed in this article.

[0020] 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 remaining compounds all represent configurations.

[0021] As described above, 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, the weight ratio of component A to component B is 1:50-50:1, the component A is compound 1 shown in formula (I); the component B is selected from cyantraniliprole shown in formula (II-1), chlorantraniliprole shown in formula (II-2), flubendiamide shown in formula (II-3), emamectin benzoate shown in formula (II-4), chlorflucythrinate shown in formula (II-5), cypermethrin shown in formula (II-6), triazophos shown in formula (II-7), acephate shown in formula (II-8), chlorpyrifos shown in formula (II-9), clothianidin shown in formula (II-10), thiamethoxam shown in formula (II-11), dimethomorph shown in formula (II-12), carbosulfan shown in formula (II-13), and avermectin B shown in formula (II-14). 1a, Avermectin B represented by formula (II-15) 1b , lufenac uron 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), cypermethrin represented by formula (II-29), chlorpyrifos represented by formula (II-30), and chlorpyrifos represented by formula (II-31). 1) hexaflumuron, bromofenac shown in formula (II-32), indoxacarb shown in formula (II-33), fenbumid shown in formula (II-34), fipronil shown in formula (II-35), profenofos shown in formula (II-36), thiacloprid shown in formula (II-37), spirodiclofen shown in formula (II-38), bifenazate shown in formula (II-39), bifenthrin shown in formula (II-40), fenpropathrin shown in formula (II-41), methoxyfenozide shown in formula (II-42), dimethoate shown in formula (II-43), matrine shown in formula (II-44), spinosad A shown in formula (II-45), and spinosad D shown in formula (II-46);

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028] In formula (II-4), R is a methyl group or an ethyl group.

[0029] 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.

[0030] 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, and the formed insecticidal composition has the highest co-toxicity coefficient and has a more excellent control effect on crop pests of the family Plutella xylostella, Noctuidae, Pyralidae, and family.

[0031] 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.

[0032] Preferably, the crop pests are one or more of the family Plutella xylostella, Noctuidae and Pyralidae.

[0033] More preferably, the crop pests are one or more of the group consisting of Plutella xylostella, Spodoptera exigua, Spodoptera litura, Spodoptera frugiperda, Cutworm, Rice Leaf Roller, Chilo suppressalis, and Codling Moth.

[0034] As mentioned above, the third aspect of the present invention provides an insecticide, which is composed of an active ingredient and an auxiliary material, and the active ingredient includes the insecticide composition described in the first aspect.

[0035] Preferably, based on the total weight of the pesticide, the content of the active ingredient is 5-20%, more preferably 10-15%.

[0036] Preferably, the auxiliary material is at least one of an emulsifier, a dispersant, a wetting agent, a spreader, a stabilizer, a defoamer, a synergist, a penetrant, an adhesive, a safener, a carrier and a filler.

[0037] Preferably, the formulation of the insecticide is selected from at least one of wettable powders, soluble powders, emulsifiable concentrates, aqueous suspensions, dispersible oil suspensions, aqueous emulsions, microemulsions and water-dispersible granules.

[0038] The present invention has no particular restrictions on how to form 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.

[0039] Component B of the present invention may be other active forms of the aforementioned substances, for example, in the form of esters or salts thereof.

[0040] The components in 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 in the pesticide composition forming the active ingredient separately and mixing them in a barrel for immediate use.

[0041] The pesticides of the present invention include, but are not limited to, application to crops and / or pests by methods such as spraying.

[0042] The present invention has no particular limitation on the method for synthesizing component A represented by formula (I). A person 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 a synthesis method in the field of chemistry, and the present invention will not be described in detail here.

[0043] The present invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, the respective raw materials used are commercially available products. The amounts of the raw materials used in the following examples are all by weight unless otherwise specified.

[0044] Cyantraniliprole represented by formula (II-1): purchased from FMC (Shanghai) Agricultural Technology Co., Ltd., product number 736994-63-1;

[0045] Chlorantraniliprole represented by formula (II-2): purchased from Lier Chemical Co., Ltd., product number 500008-45-7;

[0046] Flubendiamide represented by formula (II-3): purchased from Bayer AG, product number 272451-65-7;

[0047] Emamectin benzoate represented by formula (II-4): R = CH2CH3 was purchased from Syngenta Nantong Crop Protection Co., Ltd., product number 137512-74-4;

[0048] Cyfluthrin represented by formula (II-5): purchased from Shandong Weifang Runfeng Chemical Co., Ltd., item number 91465-08-6;

[0049] Chlorfenapyr represented by formula (II-6) was purchased from BASF SE, product number 122453-73-0.

[0050] Preparation Example 1

[0051] Preparation method of compound 1 represented by formula (I):

[0052] Carboxylic acid part synthesis:

[0053]

[0054] Amine part synthesis:

[0055]

[0056] Synthesis of compound 1:

[0057]

[0058] (i): Synthesis of Intermediate 2

[0059]

[0060] 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 in sequence, and nitrogen was pumped in three times. Then, n-butyl vinyl ether (30.00 g) and 100 mL of n-butanol were added, and the mixture 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. The pH was adjusted to 2. The organic phases were combined by ethyl acetate extraction, and then washed three times with saturated NaCl water. The mixture was dehydrated with a desiccant, filtered with a funnel, 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. The yield was 89.10%.

[0061] 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).

[0062] (ii): Synthesis of Intermediate 3

[0063]

[0064] Intermediate 2 (10.00 g) and 150 mL of methanol were placed in a three-necked flask, 8 mL of sulfuric acid was slowly added dropwise, the reaction was carried out at 60° C. for 4 h, and the mixture was 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 yellow liquid intermediate 3 with a yield of 95.69%.

[0065] 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).

[0066] (iii): Synthesis of intermediate 4

[0067]

[0068] 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, reacted at 60°C for 8 h, cooled to room temperature, and a white solid was precipitated and filtered to obtain 10.30 g of intermediate 4 as a white solid, with a yield of 75.75%.

[0069] 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).

[0070] (iv): Synthesis of Intermediate 5

[0071]

[0072] 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 in sequence, reacted at 60° C. for 8 h, cooled to room temperature, extracted with ethyl acetate, and the organic phase was washed with saturated NaCl aqueous solution, filtered through a funnel, concentrated, and then column chromatographed (petroleum ether: ethyl acetate = 97:3) to obtain 6.31 g of light yellow liquid intermediate 5, with a yield of 80.55%.

[0073] 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).

[0074] (v): Synthesis of Intermediate 6

[0075]

[0076] Intermediate 5 (6.31 g), 50% hydroxylamine aqueous solution (1.91 g), tetrabutylammonium bromide (0.93 g), and 100 ml of dichloromethane were placed in a three-necked flask in sequence, and 30 mL of sodium hydroxide aqueous solution (2.32 g) was added dropwise at 0°C. The mixture was reacted at room temperature for 12 h, and the pH value was adjusted to 5. The mixture was extracted with dichloromethane. The organic phase was washed with saturated NaCl aqueous solution, filtered through a funnel, concentrated, and then subjected to column chromatography (petroleum ether: ethyl acetate = 97:4) to obtain 5.00 g of intermediate 6 as a yellow solid. The yield was 76.59%.

[0077] 1H 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).

[0078] (vi): Synthesis of Intermediate 7

[0079]

[0080] Intermediate 6 (5.00 g) and 50 mL of methanol were placed in a reaction flask in sequence, 15% aqueous sodium hydroxide solution (1.56 g) was added, and the reaction mixture 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 combined by ethyl acetate extraction, and then washed three times with saturated NaCl water. The mixture was desiccant was used to remove water, and the mixture was filtered through a funnel, concentrated, and purified by column chromatography to obtain 4.45 g of intermediate 7 as a white solid. The yield was 91.90%.

[0081] 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).

[0082] (vii): Synthesis of Intermediate 9

[0083]

[0084] 4-Nitropyrazole (100.00 g), potassium carbonate (146.67 g), and 1000 mL of N,N-dimethylformamide were placed in a reaction bottle in sequence, and 2-bromopropane (130.52 g) was added in batches. The mixture was reacted 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, concentrated, and subjected to column chromatography (petroleum ether: ethyl acetate = 97:3) to obtain 131.85 g of intermediate 9 as a white solid. The yield was 96.09%.

[0085] 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).

[0086] (viii): Synthesis of Intermediate 10

[0087]

[0088] Take intermediate 9 (10.00 g, 64.45) and 100 mL of methanol in a reaction bottle, add palladium carbon (1.00 g) with a mass ratio of 10%, react for 24 hours under H2 atmosphere, filter with diatomaceous earth, rinse the filter cake with ethyl acetate, and spin dry to obtain 7.81 g of red oily intermediate 10, with a yield of 96.80%.

[0089] 1 H 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).

[0090] (ix): Synthesis of Compound 1:

[0091]

[0092] Take intermediate 7 (100 g) and 500 mL of dichloromethane in a reaction bottle, add oxalyl chloride (58.21 g) and a few drops of N,N-dimethylformamide, react for 5 hours, and spin dry the solvent to obtain the acyl chloride. Take intermediate 10 (31.57 g), 200 mL of dichloromethane, and triethylamine (46.40 g) in turn, add the acyl chloride dropwise at 0°C, react overnight at room temperature, spin dry a large amount of solvent to precipitate a white solid, filter, rinse the filter cake with 100 mL of petroleum ether, slurry the filter cake with 500 mL of water overnight, filter, and dry. The dried filter cake was placed in a 500 mL eggplant-shaped bottle, and 40 mL of tetrahydrofuran was added. At this time, some white solids were not dissolved. After heating under reflux, tetrahydrofuran was slowly added until the system became a yellow transparent solution. The heating was stopped and 250 mL of petroleum ether was dropped. After cooling to room temperature, 108.74 g of white target compound 1 with a purity of 99% was obtained by suction filtration. The yield was 87.34%.

[0093] The nuclear magnetic resonance characterization data of compound 1 represented by formula (I) provided by the present invention are as follows:

[0094] 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).

[0095] Test Example 1

[0096] 1. Biological testing methods

[0097] 1) Cabbage leaf soaking method:

[0098] The indoor toxicity of the mixed pesticide original drug to the diamondback moth, fall armyworm, armyworm, beet armyworm and cutworm and its mixed synergistic effect were carried out by the following method: fresh cabbage leaves collected from the net room without any pesticide application were rinsed with tap water and dried with paper towels, and then made into leaf discs with a 6 cm diameter puncher, and immersed in the prepared solution (10 mg of the mixed original drug was dissolved in 1 ml of dimethyl sulfoxide (DMSO), and then the mother solution was diluted to a series of concentrations of 10, 5, 2, 1, 0.5, 0.3, 0.1, 0.05, 0.025 mg / L with an aqueous solution containing 0.1 wt% of TritonX-100) for about 15 seconds, taken out, and dried naturally for use. The treated leaves were placed in a culture dish, with 1 leaf disc placed in each dish, and 10 2nd instar larvae were placed in each dish to feed on the leaves. Each dish was replicated, and each concentration was replicated 4 times. The cells were placed in a light incubator (temperature 26°C, humidity 60%). The mortality of each treatment was investigated at 24h, 48h, and 72h. The mortality was calculated separately, and the corrected mortality was calculated using the Abbott formula. plus The software calculated the toxicity regression curve.

[0099] 2) Rice leaf immersion method:

[0100] The indoor toxicity test of rice leaf roller adopts the leaf dipping method. The test agent is dissolved with a small amount of DMSO, and then diluted with a solution containing 0.1% TritonX-100 to a series of concentrations of 10, 5, 2, 1, 0.5, 0.3, 0.1, 0.05, and 0.025 mg / L. Rice leaves (5-6 cm long) are soaked in the solution for 15 seconds, taken out and dried naturally, and then placed in a culture dish with moisturizing filter paper. Each culture dish is placed with 10 rice leaves and 10 3rd instar larvae of rice leaf roller. Each concentration is repeated 4 times, and the soaking of TritonX-100 solution is used as a control. The culture dish is covered with black cloth and tied with a rubber band, and a small hole is pierced with a fine needle for ventilation. It is placed in a light incubator (temperature 26°C, humidity 70%), and the 72h mortality rate is recorded. Then, the toxicity regression curve is calculated using POLOplus software.

[0101] 3) Rice stem immersion method:

[0102] The indoor toxicity test of the Chilo suppressalis was carried out by the rice stem immersion method. The test agent was dissolved with a small amount of DMSO and then diluted with a solution containing 0.1% TritonX-100 to a series of concentrations of 10, 5, 2, 1, 0.5, 0.3, 0.1, 0.05, and 0.025 mg / L. The rice stems (5-6 cm long) were soaked in the solution for 15 seconds, taken out and dried naturally, and then placed in a culture dish with moisturizing filter paper. 15 rice stems were placed in each culture dish, and 10 2nd-instar larvae of the Chilo suppressalis were inoculated. Each concentration was repeated 4 times, and the Triton X-100 solution was used as a control. The culture dishes were covered with hand 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 software calculated the toxicity regression curve.

[0103] 2. Calculation method of synergistic effect:

[0104] The toxicity was evaluated by Sun Yunpei method, the co-toxicity coefficient was calculated, and the CTC value was used to evaluate the combined toxicity of the two agents. A CTC value less than 80 indicates antagonism, greater than 120 indicates synergism, and between 80 and 120 indicates additive effect.

[0105] Compound 1 was used as the standard agent, and its toxicity index (TIA) = 100;

[0106] Toxicity index (TIB) of the test agent = LC of the standard agent 50 / LC of the test agent 50 ×100;

[0107] Actual Toxicity Index (ATI) of the mixture = LC of the standard agent 50 / LC of mixture 50 ×100;

[0108] 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;

[0109] Co-toxicity coefficient CTC = ATI / TTI×100.

[0110] 3. Test results

[0111] In the present invention, 95% FL refers to 95% confidence limit.

[0112] 1) The control effect of compound 1 and cyantraniliprole on crop pests is shown in Table 1:

[0113] Table 1

[0114]

[0115]

[0116] As can be seen from Table 1, the co-toxicity coefficient of compound 1 and cyantraniliprole for controlling Plutella xylostella was greater than 120 when the weight ratio was 1:9-9:1, showing a synergistic effect; at a weight ratio of 8:2, the co-toxicity coefficient was 379, and the synergistic effect was most obvious.

[0117] The co-toxicity coefficient of compound 1 and cyantraniliprole for controlling fall armyworm 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.

[0118] The co-toxicity coefficient of compound 1 combined with cyantraniliprole for controlling Spodoptera litura was less than 120 at a weight ratio of 2:8, 4:6, and 5:5, showing an additive effect; at a weight ratio of 9:1, the co-toxicity coefficient was 357, and the synergistic effect was most obvious.

[0119] 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 most obvious.

[0120] When compound 1 and cyantraniliprole were combined for controlling Chilo suppressalis at a weight ratio of 9:1, the co-toxicity coefficient was 641, and the synergistic effect was most obvious.

[0121] The co-toxicity coefficient of compound 1 and cyantraniliprole for controlling rice leaf folder 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.

[0122] 2) The control effect of compound 1 and chlorantraniliprole on crop pests is shown in Table 2:

[0123] Table 2

[0124]

[0125]

[0126] As can be seen from Table 2, the combination of compound 1 and chlorantraniliprole for controlling Plutella xylostella has an additive or synergistic effect when the weight ratio is 1:9-9:1; at a weight ratio of 8:2, the co-toxicity coefficient is 393, and the synergistic effect is most obvious.

[0127] The combination of compound 1 and chlorantraniliprole for controlling fall armyworm had 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.

[0128] When compound 1 and chlorantraniliprole are used together to control beet armyworm in a weight ratio of 1:9, the co-toxicity coefficient is between 80-120, showing an additive effect; the rest are synergistic effects; especially when the weight ratio is 9:1, the co-toxicity coefficient is 512, and the synergistic effect is most obvious.

[0129] When compound 1 and chlorantraniliprole were combined for controlling Chilo suppressalis at a weight ratio of 7:3, the co-toxicity coefficient was 292, and the synergistic effect was the most obvious.

[0130] When compound 1 and chlorantraniliprole were combined in a weight ratio of 2:8 to control rice leaf folder, the co-toxicity coefficient was between 80-120, showing an additive effect; the rest were synergistic effects; especially when the weight ratio was 8:2, the co-toxicity coefficient was 532, and the synergistic effect was most obvious.

[0131] 3) The control effect of compound 1 and flubendiamide on crop pests is shown in Table 3:

[0132] Table 3

[0133]

[0134]

[0135] As can be seen from Table 3, when the weight ratio of compound 1 and flubendiamide for controlling Plutella xylostella is 5:5, the co-toxicity coefficient is greater than 120, which is 249, and the synergistic effect is most obvious; when the weight ratio is 1:9 and 4:6, the co-toxicity coefficient is between 80-120, showing an additive effect.

[0136] 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.

[0137] The co-toxicity coefficient of compound 1 and flubendiamide for controlling Spodoptera litura was greater than 120 when the weight ratio was 1:9-9:1, both showing a synergistic effect; at a weight ratio of 9:1, the co-toxicity coefficient was 633, and the synergistic effect was most obvious.

[0138] 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.

[0139] When compound 1 and flubendiamide were combined for controlling Chilo suppressalis at a weight ratio of 8:2, the co-toxicity coefficient was 504, and the synergistic effect was most obvious.

[0140] When compound 1 and flubendiamide were combined in a weight ratio of 7:3 for controlling rice leaf folder, the co-toxicity coefficient was 229, and the synergistic effect was the most obvious.

[0141] 4) The control effect of compound 1 and emamectin benzoate on crop pests is shown in Table 4:

[0142] Table 4

[0143]

[0144] As can be seen from Table 4, when the weight ratio of compound 1 and emamectin benzoate for controlling Plutella xylostella was 2:8, the co-toxicity coefficient was between 80-120, 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 most obvious.

[0145] 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.

[0146] 5) The control effect of compound 1 and cyhalothrin on crop pests is shown in Table 5:

[0147] Table 5

[0148]

[0149]

[0150] 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.

[0151] 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.

[0152] 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 and 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.

[0153] When compound 1 was combined with cyhalothrin for controlling beet armyworm at a weight ratio of 9:1, the co-toxicity coefficient was 441, and the synergistic effect was most obvious.

[0154] When compound 1 was combined with cyfluthrin for controlling cutworms at a weight ratio of 8:2, the co-toxicity coefficient was 319, and the synergistic effect was most obvious.

[0155] 6) The control effect of compound 1 and chlorfenapyr on crop pests is shown in Table 6:

[0156] Table 6

[0157]

[0158]

[0159] As can be seen from Table 6, the co-toxicity coefficient of compound 1 and chlorfenapyr for controlling Plutella xylostella was between 80-120 when the weight ratio was 3:7 and 9:1, showing an additive effect; the rest showed a synergistic effect; especially when the weight ratio was 4:6, the co-toxicity coefficient was 189, and the synergistic effect was the most obvious.

[0160] 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.

[0161] The combination of compound 1 and chlorfenapyr for controlling Spodoptera litura has an additive or synergistic effect when the weight ratio is 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.

[0162] 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.

[0163] Test Example 2

[0164] Toxicity of compound 1 to codling moth and its synergistic effect on cyhalothrin

[0165] 1. Test methods

[0166] The third instar larvae of cyfluthrin-sensitive population (SS) and cyfluthrin-resistant population (LCR) of codling moth were selected and the toxicity was determined by the drop method.

[0167] Compound 1 was dissolved in DMSO to prepare a 10 mg / mL stock solution, which was then diluted into five concentration gradients (400, 200, 100, 50 and 20 ng / μL).

[0168] Drop 1 μL of the drug solution on the pronotum of each third-instar larva of the codling moth, and transfer the test insects to artificial diet after the droplet has basically penetrated the insect body. Take an equal amount of DMSO as a negative control and λ-cyhalothrin as a positive control. Each concentration includes 15 larvae, and a total of 3 replicates are set. The mortality rate is counted every 24 hours after treatment, and the death of insects in each group at different times after treatment is recorded. Touch the insect body lightly with a small brush, and it is considered dead if there is no reaction.

[0169] 2. Results and Analysis

[0170] 1) The results of the toxicity test of compound 1 on the cyhalothrin-sensitive population of codling moth are shown in Table 7:

[0171] Table 7

[0172]

[0173] Among them, 95% FL refers to the 95% confidence limit of the lethal dose, slope±SD represents the slope of the toxicity regression curve and its standard error, and χ 2 It represents the chi-square value.

[0174] As can be seen from Table 7, the LD 50 The value is 226.34 ng / μL, and the LD for 72 hours 50 The value was 195.46 ng / μL, and the LD for 96 h 50 The value was 137.77 ng / μL, which was higher than the LD of the positive control λ-cyhalothrin under the same treatment time. 50 The value indicated that compound 1 was weaker than cyhalothrin in the toxicity to the susceptible population of codling moth.

[0175] 2) The results of the toxicity test of compound 1 on the cyhalothrin-resistant population of codling moth are shown in Table 8;

[0176] In the early stage, our laboratory used cyfluthrin to select codling moth larvae for multiple generations indoors, and obtained the cyfluthrin-resistant population LCR of codling moth (LCR is the English abbreviation of this population). This population was used as the test object to determine the toxicity of compound 1 against it.

[0177] Table 8

[0178]

[0179] Among them, 95% FL refers to the 95% confidence limit of the lethal dose, slope±SD represents the slope of the toxicity regression curve and its standard error, and χ 2 It represents the chi-square value.

[0180] It can be seen from Table 8 that although the LD 50 The value was higher than that of the sensitive population, but there was no significant difference (confidence intervals overlapped). This is consistent with the previous results of the 4th instar larvae bioassay. This shows that the mechanism of action of compound 1 and cyfluthrin may be different, but it has a better toxic effect on cyfluthrin-resistant populations and is expected to play an important role in the resistance management of codling moth.

[0181] Test Example 3

[0182] Determination of the synergistic ability of compound 1

[0183] 1. Test methods

[0184] To determine whether compound 1 has a synergistic effect on cyhalothrin, different doses of compound 1 and 48h LD 50 The third instar larvae of codling moth of SS and LCR populations were treated with cyhalothrin of different doses. The experimental groups were: LD 50 The dose of cyhalothrin was 1 / 4, 1 / 2, 1, 2, and 4 times the LD 50 dose of compound 1 (LCR-LD 50 +1 / 4 Compound 1-LD 50 、LCR-LD 50 +1 / 2 Compound 1-LD 50 、LCR-LD 50 +Compound 1-LD 50 、LCR-LD 50 +2 Compound 1-LD 50 、LCR-LD 50 +4 Compound 1-LD 50 ) combined treatment. First, drop LD on the pronotum of each 3rd instar larva 50 The larvae were then titrated with different doses of cyhalothrin and compound 1. After the solvent was fully evaporated, the larvae were transferred to a 24-well plate with artificial diet. The mortality rate was recorded every 24 hours. There were 15 larvae in each group, and there were 3 groups in total. The LD 50 Dose of cyhalothrin (LCR-LD 50 )+DMSO、LD 50 Dose of Compound 1 (Compound 1-LD 50 )+Acetone was the control group.

[0185] 2. Results and Analysis

[0186] 1) The synergistic effect of compound 1 on the population of Cyfluthrin-sensitive codling moth is shown in Figure 1 As shown;

[0187] Among them, in the figure, from Figure 1 As can be seen from the figure, compared with the control group (LCR-LD 50 +DMSO) compared with LCR-LD 50 +1 / 4 Compound 1-LD 50 There was no significant difference in mortality between the treatment groups within 96 h, indicating that the mortality rate was less than or equal to 1 / 4 LD 50 Compound 1 at these doses had no synergistic effect on the population of codling moth susceptible to cyhalothrin.

[0188] Equal to or higher than 2 times LD 50Compound 1 at the dose of 2 times LD 50 The synergistic ratios of compound 1 at different doses on cyhalothrin were 1.44 times (24h), 1.44 times (48h), 1.36 times (72h), and 1.42 times (96h), respectively; 4 times LD 50 The synergistic ratios of compound 1 at different doses on cyhalothrin were 1.44 times (24h), 1.48 times (48h), 1.44 times (72h), and 1.46 times (96h).

[0189] 2) The synergistic effect of compound 1 on the cyhalothrin-resistant population of codling moth is shown in Figure 2 As shown;

[0190] from Figure 2 As can be seen from the figure, compared with the control group (LCR-LD 50 +DMSO) compared with LCR-LD 50 +1 / 4 Compound 1-LD 50 There was no significant difference in mortality between the treatment groups within 96 h, indicating that the mortality rate was less than or equal to 1 / 4 LD 50 The dose of compound 1 had no synergistic effect on cyhalothrin against resistant populations.

[0191] 1 times and above 1 times LD 50 Compound 1 at a dose of 1:1 had a significant synergistic effect on cyhalothrin-resistant populations: 1 times LD 50 The synergistic ratios of compound 1 at different doses on cyhalothrin were 1.42 times (24h), 1.38 times (48h), 1.27 times (72h), and 1.25 times (96h), respectively; 2 times LD 50 The synergistic ratios of compound 1 at different doses on cyhalothrin were 1.47 times (24h), 1.38 times (48h), 1.31 times (72h), and 1.39 times (96h), respectively; 4 times LD 50 The synergistic ratios of compound 1 at different doses on chlorfenapyr were 1.42 times (24h), 1.57 times (48h), 1.42 times (72h), and 1.43 times (96h), respectively.

[0192] The results also showed that higher than or equal to 2 times LD 50 96 hours after the treatment with the mixed compound 1 of the dose and cyhalothrin, the mortality rate of the third-instar larvae of the LCR population exceeded 80%.

[0193] The above results show that compound 1 can significantly improve the biological activity of cyfluthrin against the third instar larvae of cyfluthrin-sensitive populations and cyfluthrin-resistant populations of codling moth after mixing with cyfluthrin. Therefore, by using it in combination with compound 1, while reducing the amount of cyfluthrin used, it can effectively control codling moth, delay its resistance development, and achieve resistance management of codling moth.

[0194] Test Example 4

[0195] The activity was determined by 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.

[0196] The results are shown in Tables 9, 10 and 11.

[0197] Table 9

[0198]

[0199] In Table 9, avermectin is avermectin B 1a and avermectin B 1b The mixture was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. with the brand name A109741-500mg and the CAS number 71751-41-2.

[0200] As can be seen from Table 9, the co-toxicity coefficient of compound 1 and avermectin for controlling Plutella xylostella was 135.8 at a weight ratio of 3:7, which was greater than 120, showing a synergistic effect, and the synergistic effect was the most obvious.

[0201] Table 10

[0202]

[0203] As can be seen from Table 10, when the weight ratio of compound 1 and fipronil for controlling Plutella xylostella is 5:5, 8:2, and 9:1, the co-toxicity coefficient is greater than 120, which shows a synergistic effect; when the weight ratio is 1:9, 2:8, 3:7, 4:6, and 7:3, the co-toxicity coefficient is between 80 and 120, which shows an additive effect; especially when the weight ratio is 9:1, the co-toxicity coefficient is 160.6, and the synergistic effect is most obvious.

[0204] Table 11

[0205]

[0206] 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 when the weight ratio was 1:9-6:4, 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.

[0207] The above results show that the insecticide composition provided by the present invention can expand the insecticide spectrum and improve the pest control effect and delay the occurrence of drug resistance and drug resistance of crop pests.

[0208] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. An insecticidal composition, characterized in that: The composition contains an insecticidal effective amount of component A and an insecticidal 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); The component B is selected from cyantraniliprole shown in formula (II-1), chlorantraniliprole shown in formula (II-2), flubendiamide shown in formula (II-3), emamectin benzoate shown in formula (II-4), cyhalothrin shown in formula (II-5), chlorfenapyr shown in formula (II-6), triazophos shown in formula (II-7), acephate shown in formula (II-8), chlorpyrifos shown in formula (II-9), clothianidin shown in formula (II-10), thiamethoxam shown in formula (II-11), dinotefuran shown in formula (II-12), carbosulfan shown in formula (II-13), and avermectin B shown in formula (II-14). 1a , Avermectin B represented by formula (II-15) 1b , lufenac uron 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), cypermethrin represented by formula (II-29), chlorpyrifos represented by formula (II-30), and chlorpyrifos represented by formula (II-31). 1) hexaflumuron, bromofenac shown in formula (II-32), indoxacarb shown in formula (II-33), fenbumid shown in formula (II-34), fipronil shown in formula (II-35), profenofos shown in formula (II-36), thiacloprid shown in formula (II-37), spirodiclofen shown in formula (II-38), bifenazate shown in formula (II-39), bifenthrin shown in formula (II-40), fenpropathrin shown in formula (II-41), methoxyfenozide shown in formula (II-42), dimethoate shown in formula (II-43), matrine shown in formula (II-44), spinosad A shown in formula (II-45), and spinosad D shown in formula (II-46); In formula (II-4), R is a methyl group or an ethyl group.

2. The insecticidal composition according to claim 1, characterized in that 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.

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

4. The use according to claim 3, characterized in that: The crop pests are one or more than two of the family Plutella xylostella, Noctuidae, Pyralidae and Cichoridae.

5. The use according to claim 3 or 4, characterized in that: The crop pests are one or more of the group consisting of diamondback moth, beet armyworm, fall armyworm, fall armyworm, cutworm, rice leaf roller, striped stem borer and codling moth.

6. An insecticide, characterized in that: The insecticide consists of active ingredients and auxiliary materials, and the active ingredients include the insecticide composition described in claim 1 or 2.

7. The insecticide 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 material is at least one of an emulsifier, a dispersant, a wetting agent, a spreader, a stabilizer, a defoamer, a synergist, a penetrant, an adhesive, a safener, a carrier and a filler.

9. The insecticide according to any one of claims 6 to 8, characterized in that The dosage form of the insecticide is selected from at least one of wettable powder, soluble powder, emulsifiable concentrate, water suspension, dispersible oil suspension, water emulsion, microemulsion and water dispersible granule.

10. The insecticide according to any one of claims 6 to 9, wherein The insecticide is prepared by storing the components of the pesticide composition forming the active ingredient separately and mixing them in a tank mix before use.

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