A composition containing a mitochondrial electron transport inhibitor class of insecticide and use thereof

Abstract

The present application relates to a composition containing a biologically effective amount of compound I and a mitochondrial electron transport inhibitor class insecticide, and their methods for controlling pests in agronomic and non-agronomic environments. The compound I has a synergistic effect with the mitochondrial electron transport inhibitor class insecticide, which can improve the pest control effect, reduce the application amount, reduce the use frequency, and reduce the use cost.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of pesticide combination, and specifically relates to a composition containing compound I and a mitochondrial electron transport inhibitor type insecticide, and a method thereof for preventing and treating pests in agronomic and non-agronomic environments. BACKGROUND

[0002] In recent years, the occurrence of various crop pests shows a trend of increasing year by year, and the occurrence area increases year by year, which brings great harm to crops, thereby causing problems such as crop yield reduction and agricultural production cost increase. In order to improve the prevention and treatment effect on pests, farmers increase the amount of pesticide or randomly mix pesticides. Such unscientific use of pesticides not only fails to achieve the effect of increasing efficiency, but also leads to problems such as waste of pesticides, excessive pesticide residues, pollution of the environment, and resistance of pests to pesticides. Therefore, it is urgent to develop a synergistic composition for pests, which can achieve the effects of expanding the range of prevention and treatment objects, reducing the amount of pesticide, and delaying the generation of resistance.

[0003] In the actual process of agricultural production, long-term continuous use of the same pesticide will quickly lead to pesticide resistance of pests, resulting in reduced prevention and treatment effect and increased use of pesticides, which aggravates the damage to the ecological environment and the residues of agricultural products. Through combination with insecticides of completely different mechanisms, the resistance of pests to pesticides can be delayed, the insecticidal spectrum can be expanded, the service life can be prolonged, and the use amount of pesticides can be reduced. However, how to combine the pesticides to produce synergistic effect rather than antagonistic effect is a big difficulty.

[0004] Patent document CN 111909143 A discloses compound I, which has broad-spectrum insecticidal activity, especially good control effect on pests such as Lepidoptera, Hemiptera, Coleoptera, Thysanoptera, Diptera, and mites. However, how to combine it with other pesticides to achieve the purpose of synergism is not disclosed.

[0005] The structural formula of compound I is as follows,

[0006] SUMMARY

[0007] In order to improve the deficiencies of the prior art, the present application provides a composition containing compound I and compound II, wherein the compound II is a mitochondrial electron transport inhibitor type insecticide, and the mitochondrial electron transport inhibitor type insecticide is at least one selected from the group consisting of pyridaben, halofenprox, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ANM-138 (CAS: 875775-74-9), NNI-0711 (CAS: 926914-55-8).

[0008] The compound I has the following structural formula,

[0009]

[0010] According to an embodiment of the present application, the compound I is prepared by referring to the method of Example 1 in the patent document CN 111909143 A, which is incorporated herein by reference in its entirety.

[0011] According to an embodiment of the present application, the compound ANM-138 is 2-ethyl-3,7-dimethyl-6-[4-(trifluoromethoxy)phenoxy]quinolin-4-yl methyl carbonate.

[0012] According to an embodiment of the present application, the compound NNI-0711 is 3'-isobutyl-N-isobutyryl-1,3,5-trimethyl-4'-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]pyrazole-4-carboxanilide.

[0013] According to an embodiment of the present application, the mass ratio of the compound I and the mitochondrial electron transport inhibitor class of insecticide is 80-1:1-80.

[0014] According to an embodiment of the present application, the mass ratio of the compound I and the mitochondrial electron transport inhibitor class of insecticide is 50-1:1-50, for example 50:1, 40:1, 30:1, 20:1, 10:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:10, 1:20, 1:30, 1:40 or 1:50.

[0015] According to a preferred embodiment of the present application, the mass ratio of the compound I and the mitochondrial electron transport inhibitor class of insecticide is 10-1:1-10.

[0016] According to an embodiment of the present application, the sum of the mass of the compound I and the mitochondrial electron transport inhibitor class of insecticide in the composition is 1-80%, preferably 2-70%, or 5-65%; 10-60%, for example 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50%, based on the total weight of the composition being 100%.

[0017] According to an embodiment of the present application, the composition can be prepared into a liquid preparation or a solid preparation.

[0018] According to the embodiments of the present application, the content of the effective active ingredient in the formulation varies according to different formulation types. Generally, the content of the effective active ingredient in the liquid formulation is 1% to 60% by weight, preferably 5% to 50% by weight; the content of the effective active ingredient in the solid formulation is 5% to 80% by weight, preferably 10% to 70% by weight.

[0019] According to the embodiments of the present application, the composition further comprises at least one of deionized water, organic solvent, emulsifier, dispersant, wetting agent, thickening agent, antifoaming agent, stabilizer, binder, disintegrant, anti-freezing agent, anti-caking agent, suspending agent, film-forming agent, preservative, colorant, high molecular capsule wall material, pH adjustor, or filler.

[0020] According to the embodiments of the present application, the composition can be diluted by the user before use or used directly. The preparation thereof can be prepared by mixing the effective active ingredient with one or more of deionized water, organic solvent, emulsifier, dispersant, wetting agent, thickening agent, antifoaming agent, stabilizer, binder, disintegrant, anti-freezing agent, anti-caking agent, suspending agent, film-forming agent, preservative, colorant, high molecular capsule wall material, pH adjustor, or filler, and the like.

[0021] According to the embodiments of the present application, the composition can be prepared into various dosage forms. Preferably, the dosage forms include wettable powder, water dispersible granule, suspension concentrate, emulsion, suspension seed coating, microcapsule suspension, microcapsule suspension-suspension, emulsifiable concentrate, microemulsion, dispersible liquid, granule.

[0022] According to the embodiments of the present application, when the composition is prepared into wettable powder, the composition comprises the following components and contents: compound I 1% to 80%, mitochondrial electron transport inhibitor class insecticide 1% to 80%, dispersant 0% to 10%, wetting agent 0% to 8%, and the balance is filler.

[0023] Preferably, the content of compound I in the composition is 2% to 70%, 5% to 65%, 10% to 60%, 15% to 50%, and the like;

[0024] The content of the mitochondrial electron transport inhibitor class insecticide is 2% to 70%, 5% to 65%, 10% to 60%, 15% to 50%, and the like;

[0025] The content of the dispersant is 1% to 8%, 2% to 7%, 3-6%, or 4% to 5%;

[0026] The content of the wetting agent is 1% to 8%, 2% to 7%, 3-6%, or 4% to 5%.

[0027] According to embodiments of the present application, the composition, when formulated as a water dispersible granule, comprises the following components and amounts: Compound I 1-80%, a mitochondrial electron transport inhibitor class of insecticide 1-80%, a dispersing agent 0-10%, a wetting agent 0-16%, a disintegrant 0-20%, and the balance being a filler.

[0028] Preferably, Compound I in the composition is 2-70%, 5-65%, 10-60%, 15-50%, etc.

[0029] The mitochondrial electron transport inhibitor class of insecticide is 2-70%, 5-65%, 10-60%, 15-50%, etc.

[0030] The dispersing agent is 1-8%, 2-7%, 3-6%, or 4-5%.

[0031] The wetting agent is 1-8%, 2-7%, 3-6%, or 4-5%.

[0032] The disintegrant is 1-18%, 2-16%, 3-15%, 4-12%, 5-10%, or 6-8%.

[0033] According to embodiments of the present application, the composition, when formulated as a suspension concentrate, comprises the following components and amounts: Compound I 1-50%, a mitochondrial electron transport inhibitor class of insecticide 1-50%, a dispersing agent 0-5%, a wetting agent 0-8%, a thickening agent 0-0.3%, an anti-freeze agent 0-5%, and the balance being deionized water.

[0034] Preferably, Compound I in the composition is 2-45%, 5-40%, 10-35%, 15-30%, 20-25%, etc.

[0035] The mitochondrial electron transport inhibitor class of insecticide is 2-45%, 5-40%, 10-35%, 15-30%, 20-25%, etc.

[0036] The dispersing agent is 1-4% or 2-3%.

[0037] The wetting agent is 1-8%, 2-7%, 3-6%, or 4-5%.

[0038] The thickening agent is 0.1-0.25%.

[0039] The anti-freeze agent is 1-4% or 2-3%.

[0040] According to an embodiment of the present application, the composition, when made into a water emulsion, comprises the following components and contents: Compound I 1% to 50%, a mitochondrial electron transport inhibitor class of insecticide 1% to 50%, an organic solvent 0% to 95%, an emulsifier 0% to 10%, an anti-freezing agent 0% to 5%, an antifoaming agent 0% to 0.2%, a thickening agent 0% to 0.5%, and the balance being deionized water.

[0041] Preferably, Compound I in the composition is 2% to 45%, 5% to 40%, 10% to 35%, 15% to 30%, 20% to 25%, etc.

[0042] The mitochondrial electron transport inhibitor class of insecticide is 2% to 45%, 5% to 40%, 10% to 35%, 15% to 30%; 20% to 25%, etc.

[0043] The organic solvent is 1% to 90%, 2% to 80%, 5% to 70%, 10% to 60%, 15% to 50%; 20% to 50%, 30% to 40%, etc.

[0044] The emulsifier is 1% to 8%, 2% to 7%, 3-6%, or 4% to 5%;

[0045] The anti-freezing agent is 1% to 4% or 2% to 3%;

[0046] The antifoaming agent is 0.05% to 0.1%, or

[0047] The thickening agent is 0.1% to 0.4%, 0.2% to 0.3%.

[0048] According to an embodiment of the present application, the composition, when made into a water emulsion, comprises the following components and contents: Compound I 1% to 50%, a mitochondrial electron transport inhibitor class of insecticide 1% to 50%, an organic solvent 0% to 95%, an emulsifier 0% to 10%, an anti-freezing agent 0% to 5%, an antifoaming agent 0% to 0.2%, a thickening agent 0% to 0.5%, and the balance being deionized water.

[0049] Preferably, Compound I in the composition is 2% to 45%, 5% to 40%, 10% to 35%, 15% to 30%, 20% to 25%, etc.

[0050] The mitochondrial electron transport inhibitor class of insecticide is 2% to 45%, 5% to 40%, 10% to 35%, 15% to 30%; 20% to 25%, etc.

[0051] The dispersing agent is 2% to 10%, 3% to 8%, 4% to 7%, or 5% to 6%;

[0052] The wetting agent is 1-8%, 2-7%, 3-6%, or 4-5%;

[0053] The anti-freezing agent is 1-8%, 2-7%, 3-6%, or 4-5%;

[0054] The anti-caking agent is 0.5-9%, 1-8%, 2-7%, 3-6%, or 4-5%;

[0055] The suspending agent is 0.2-4%, 0.5-3.5%, 1-3%, 1.5-2.5%, or 1.8-2%;

[0056] The film-forming agent is 2-9%, 3-8%, 4-7%, or 5-6%;

[0057] The preservative is 0.2-4%, 0.5-3.5%, 1-3%, 1.5-2.5%, or 1.8-2%;

[0058] The coloring agent is 2-25%, 3-20%, 5-15%, 8-12%, or 9-10%;

[0059] The pH regulator is 0.1-5%, 0.2-4%, 0.5-3.5%, 1-3%, 1.5-2.5%, or 1.8-2%;

[0060] The thickening agent is 0.5-7, 1-6%, 2-5%, or 3-4%.

[0061] According to an embodiment of the present application, when the composition is made into a microcapsule suspension agent, it comprises the following components and contents: Compound I 1-50%, a mitochondrial electron transport inhibitor class of insecticide 1-50%, a high molecular capsule wall material 1-30%, a dispersing agent 2-10%, an organic solvent 1-50%, an emulsifying agent 1-7%, a pH regulator 0.1-5%, an antifoaming agent 0.01-2%, a thickening agent 0.1-8%, an anti-freezing agent 0.1-8%, and the balance is deionized water.

[0062] Preferably, Compound I in the composition is 2-45%, 5-40%, 10-35%, 15-30%, 20-25%, etc.

[0063] The mitochondrial electron transport inhibitor class of insecticide is 2-45%, 5-40%, 10-35%, 15-30%, 20-25%, etc.

[0064] The high molecular capsule wall material is 2-25%, 5-20%, 6-18%, or 10-15%, etc.

[0065] The dispersant is 3% to 8%, 4% to 7%, or 5% to 6%;

[0066] The organic solvent is 2% to 45%, 5% to 40%, 10% to 35%, 15% to 30%; or 20% to 25%, etc.

[0067] The emulsifier is 2% to 6% or 4% to 5%;

[0068] The pH regulator is 0.2% to 4%, 0.5% to 3.5%, 1% to 3%, 1.5% to 2.5%, or 1.8% to 2%;

[0069] The antifoaming agent is 0.05% to 1.8%, 0.1% to 1.5%, 0.5% to 1.3%, 0.8% to 1.0%;

[0070] The thickening agent is 0.2% to 7, 0.5% to 6%, 1% to 5%, 1.5% to 4%, or 2% to 3%;

[0071] The antifreeze agent is 0.5% to 7%, 1% to 6%, 2% to 5%, or 3% to 4%.

[0072] According to an embodiment of the present application, when the composition is made into a microcapsule suspension-suspension agent, it comprises the following components and contents: Compound I 1% to 50%, a mitochondrial electron transport inhibitor class of insecticide 1% to 50%, a high molecular capsule wall material 1% to 12%, a dispersant 1% to 12%, a wetting agent 1% to 8%, an organic solvent 1% to 50%, an emulsifier 1% to 8%, an antifoaming agent 0.01% to 2%, a thickening agent 0.1% to 8%, a pH regulator 0.1% to 5%, an antifreeze agent 0.1% to 8%, and the balance is deionized water.

[0073] According to an embodiment of the present application, when the composition is made into an emulsifiable concentrate, it comprises the following components and contents: Compound I 1% to 50%, a mitochondrial electron transport inhibitor class of insecticide 1% to 50%, an emulsifier 0% to 10%, an antifreeze agent 0% to 5%, a stabilizer 0% to 0.5%, and the balance is an organic solvent.

[0074] Alternatively, Compound I 1% to 50%, a mitochondrial electron transport inhibitor class of insecticide 1% to 50%, an emulsifier 0% to 12%, a stabilizer 0% to 0.5%, and the balance is an organic solvent.

[0075] According to an embodiment of the present application, when the composition is made into a microemulsion, it comprises the following components and contents: Compound I 1% to 50%, a mitochondrial electron transport inhibitor class of insecticide 1% to 50%, an organic solvent 1% to 50%, an emulsifier 1% to 30%, an antifreeze agent 1% to 10%, a stabilizer 0.1% to 5%, and the balance is deionized water.

[0076] According to the embodiment of the present application, the composition, when made into a dispersible liquid, comprises the following components and contents: Compound I 1% to 50%, a mitochondrial electron transport inhibitor class of insecticide 1% to 50%, an emulsifier 1 to 30%, an anti-freezing agent 1% to 10%, a stabilizer 0.1% to 5%, and the rest is an organic solvent.

[0077] According to the embodiment of the present application, the composition, when made into a granule, comprises the following components and contents: Compound I 0.1% to 10%, a mitochondrial electron transport inhibitor class of insecticide 0.1% to 10%, a dispersant 0% to 5%, a wetting agent 0% to 5%, a binder 0% to 3%, and the rest is a filler.

[0078] According to the embodiment of the present application, the emulsifier can be selected from at least one of the following: sodium lignosulfonate, agricultural emulsifier, phenyl phenol polyoxyethyl ether phosphate, triphenyl styryl phenol polyoxyethylene ether phosphate triethanolamine salt, benzyl dimethyl phenol polyoxyethyl ether, sorbitan fatty acid ester polyoxyethylene ether, sorbitan oleate (Span-80), fatty alcohol polyoxyethylene ether, sodium alkyl naphthalene sulfonate, isooctanol succinate sodium sulfonate, nonyl phenol polyoxyethylene ether phosphate, castor oil polyoxyethylene ether phosphate.

[0079] According to the embodiment of the present application, the dispersant can be selected from at least one of the following: glycerol fatty acid polyoxyethylene ether, polyoxyethylene alkyl aryl ether, sodium lignosulfonate, naphthalene sulfonate formaldehyde condensate, fatty alcohol polyoxyethylene ether sulfate, naphthalene sulfonate formaldehyde condensate, naphthalene sulfonate formaldehyde condensate sodium salt, nonyl phenol polyoxyethylene ether, polyoxyethylene lanolin alcohol, alkyl phenol polyoxyethylene ether formaldehyde condensate, fatty alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ether phosphate, polyoxyethylene sorbitan fatty acid ester, phosphate ester.

[0080] According to the embodiment of the present application, the wetting agent can be selected from at least one of the following: trisiloxane polyoxyethylene ether, sodium N-lauroyl glutamate, sodium dodecyl sulfate, sodium lauroyl sarcosinate, sodium methyl naphthalene sulfonate formaldehyde condensate, castor oil polyoxyethylene ether, triphenyl ethyl phenol polyoxyethylene ether, sodium dodecyl benzene sulfonate, sodium alkyl naphthalene sulfonate, isooctanol succinate sodium sulfonate, polyoxyethylene alkyl aryl ether, fatty alcohol polyether glycerol fatty acid polyoxyethylene ether, fatty alcohol polyoxyethylene ether.

[0081] According to the embodiment of the present application, the binder can be selected from at least one of the following: xanthan gum, starch, urea-formaldehyde resin, gelatin, gum arabic, carboxymethyl cellulose, carboxyethyl cellulose, polyvinyl alcohol.

[0082] According to the embodiment of the present application, the disintegrant can be selected from at least one of the following: sodium bicarbonate, ammonium sulfate, sodium sulfate, calcium sulfate, magnesium chloride.

[0083] According to an embodiment of the present application, the thickening agent can be selected from at least one of magnesium aluminum silicate, polyvinyl acetate, xanthan gum, gelatin, gum arabic, and polyvinyl alcohol.

[0084] According to an embodiment of the present application, the antifoaming agent can be selected from at least one of silicone oil, n-octanol, silicone, butyl phosphate, isobutyl phosphate, and the like.

[0085] According to an embodiment of the present application, the antifreezing agent can be selected from at least one of propylene glycol, ethylene glycol, glycerol, and the like.

[0086] According to an embodiment of the present application, the stabilizer can be selected from at least one of triethanolamine, epichlorohydrin, butyl glycidyl ether, triphenyl phosphite, N-soybean oil-based triethylene diamine, and dialkyl succinate acid sulfonate.

[0087] According to an embodiment of the present application, the filler includes a solid filler and a liquid filler, wherein the solid filler can be selected from at least one of kaolin, attapulgite, diatomite, white carbon, bentonite, montmorillonite, calcium carbonate, and talc powder. The liquid filler can be selected from at least one of soybean oil, castor oil, and mineral oil.

[0088] According to an embodiment of the present application, the organic solvent can be selected from at least one of ethyl acetate, acetone, isopropyl alcohol, 2,2,2-trifluoroethanol, propylene carbonate, benzene, toluene, xylene, dimethylformamide, dimethyl sulfoxide, dichloromethane, cyclohexane, cyclohexanone, N-methyl pyrrolidone, and solvent oil (e.g., 150# solvent oil).

[0089] The present application also provides a use of the above composition for controlling pests in agriculture and non-agriculture.

[0090] According to an embodiment of the present application, the pests are selected from Lepidoptera, Hemiptera, Coleoptera, Thysanoptera, Diptera, mites, and the like.

[0091] As an embodiment, the pests are selected from the group consisting of Tetranychus urticae, Tetranychus cinnabarinus, Panonychus citri.

[0092] The present application also provides a method for controlling pests in agriculture or non-agriculture, which comprises applying the above composition to plants where the pests exist.

[0093] The composition of the present application can be provided in the form of finished preparation, or in the form of single agent, which is mixed directly before use, then mixed with water to the required concentration, and can be applied to the crop in any way, such as spraying, irrigation at the root of the plant, smearing, etc. In specific application, it can also be mixed with other agents, such as growth regulator, soil conditioner, herbicide, nematicide, etc.

[0094] The present application also provides a composition for controlling invertebrate pests, which comprises a biologically effective amount of compound I, a mitochondrial electron transport inhibitor class of insecticide and at least one other component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said composition optionally further containing an effective amount of at least one other biologically active compound or active agent, said mitochondrial electron transport inhibitor class of insecticide being selected from at least one of the following: pyridaben, halofenprox, ethyl acecarbotoxate, tolfenpyrad, fenoxycarb, bifenazate, clofentezine, ANM-138 (CAS: 875775-74-9), NNI-0711 (CAS: 926914-55-8).

[0095] The present application also provides a method for controlling invertebrate pests, which comprises contacting said invertebrate pests or their environment with a biologically effective amount of the composition of the present application as described above.

[0096] The present application also provides a spray composition, which comprises the composition of the present application as described above and a propellant.

[0097] The present application also provides a bait composition, which comprises the composition of the present application as described above; one or more food materials; optionally an attractant; and optionally a wetting agent.

[0098] Advantages of the present application:

[0099] The synergistic composition of the present application has the following advantages:

[0100] 1) synergistic effect, which can improve the effect of pest control; 2) expand the insecticidal spectrum, mixed occurrence of field pests, stronger effect on pests; 3) different action mechanisms of the two effective components, mixed use can delay the development of pest resistance; 4) reduce the amount of application, reduce the use frequency, and reduce the use cost. DETAILED DESCRIPTION

[0101] The present application will be further described in detail below with reference to specific examples. It should be understood that the following examples are only illustrative and explanatory of the present application, and should not be interpreted as limiting the scope of protection of the present application. Any technology realized based on the above description of the present application is covered within the scope of protection intended by the present application.

[0102] The experimental methods used in the following examples are conventional methods unless otherwise specified; the reagents, materials, etc. used in the following examples are commercially available unless otherwise specified.

[0103] The insecticidal effect of the composition is tested by indoor bioassay and field test. It should be noted that any modification, equivalent replacement and improvement within the spirit and principles of the present application shall be included in the protection scope of the present application.

[0104] The compound I used in the following examples is prepared according to the method of Example 1 in the patent document CN 111909143 A.

[0105] The % of each component in the preparation of the following preparation examples and examples refers to the mass percentage if not specifically stated.

[0106] I. Preparation Example of Formulation

[0107] Preparation Example 1: Wettable powder

[0108]

[0109] The above materials are coarsely crushed in proportion and then mixed uniformly in a mixer, and then the finished product is prepared after air flow crushing.

[0110] Preparation Example 2: Water dispersible granule

[0111]

[0112] The effective active ingredient and various adjuvants are mixed uniformly in proportion to the formula, and then powder is obtained after air flow crushing, and then a certain amount of water is mixed and extruded to form granules, and then the finished product is obtained after drying and screening.

[0113] Preparation Example 3: Suspension concentrate

[0114]

[0115] The effective active ingredient and various adjuvants are mixed uniformly in proportion to the formula, and then the finished product is obtained after high-speed shearing and sand milling.

[0116] Preparation Example 4: Emulsifiable concentrate

[0117]

[0118] The above raw materials are mixed in proportion to make them dissolve into a uniform oil phase; after passing the inspection, the finished product is obtained by metering and packaging.

[0119] Preparation Example 5: Emulsion in water

[0120]

[0121] The above raw materials are added into a batching kettle according to the requirements of the formula, mixed uniformly by a high-speed shearing machine to prepare a water emulsion, and after inspection, the product is obtained by metering and packaging.

[0122] Preparation Example 6: emulsifiable concentrate

[0123]

[0124] The above raw materials are mixed in proportion to dissolve into a uniform oil phase; after inspection, the product is obtained by metering and packaging.

[0125] Preparation Example 7: granules

[0126]

[0127] The components are mixed according to the formula, crushed, wetted with water, and then stirred uniformly. The product is obtained by granulating with a screw extrusion granulator, drying, and sieving.

[0128] The mitochondrial electron transport inhibitor insecticide is selected from one of the following: pyridaben, cyflumetofen, ethyl acecarbotoxate, tolfenpyrad, fenpyroximate, bifenazate, clofentezine, ANM-138 (CAS: 875775-74-9), NNI-0711 (CAS: 926914-55-8).

[0129] II. Indoor toxicity determination example

[0130] (1) Test insect: Tetranychus urticae Koch, Tetranychus cinnabarinus, Panonychus citri McGregor.

[0131] (2) Determination method:

[0132] Pest toxicity determination method

[0133] The toxicity of the pests is determined by using Tetranychus urticae, Tetranychus cinnabarinus, Panonychus citri and other pests as test materials, and determining the toxicity of compound I, compound II and their mixed formulations.

[0134] According to the Pesticide Indoor Biological Determination Test Guidelines of the People's Republic of China Agricultural Industry Standard NY / T 1154.12-2008, Insecticides Part 12: Leaf Mite Glass Dip Method, the test agent (including compound I and compound II) is prepared into 5 concentration gradients (according to the LC50 of the compound on different pests) with a suitable solvent (the types of solvent are acetone, methanol, N,N dimethylformamide and dimethyl sulfoxide, etc., and are selected according to their solubility on the sample).50 The concentration gradient is set according to the geometric or arithmetic progression, and the compound I and the compound II for mixing are respectively set according to the LC 50 The concentration gradient is set according to the geometric or arithmetic progression, and the compound I and the compound II for mixing are respectively set according to the LC

[0135] Cut the double-sided tape into 2 cm long, and stick it on one end of the glass slide. Then select healthy female adult mites, and stick their backs on the double-sided tape (note that do not stick the mite feet, antennae and mouthparts), 30 per piece, put into the container with wet sponge, cover the lid, and place in the (25±1) ℃ condition. After 2 h, examine under the microscope, remove the dead and injured individuals, and make up 30 per piece. After the glass slide is immersed in the drug solution and gently shaken for 5 s, remove the excess drug solution with a water-absorbing paper, and place in the white porcelain dish with wet sponge, cover with a good light transmission plastic film. Each treatment is repeated 4 times, and a treatment without drug (containing organic solvent and emulsifier) is set as a blank control.

[0136] According to the method of Sun Yunpei, the co-toxicity coefficients (CTC values) of different proportions of the two drugs are calculated. The co-toxicity coefficient (CTC) of the mixed agent is ≥120, which shows synergistic effect, ≤80, which shows antagonistic effect, and 80<CTC<120, which shows additive effect. The co-toxicity coefficient (CTC) of the mixed agent is calculated according to formula (1), formula (2) and formula (3):

[0137]

[0138] In the formula:

[0139] ATI——the measured toxicity index of the mixed agent;

[0140] S——the LC 50 of the standard insecticide, unit: milligrams per liter (mg / L);

[0141] M——the LC 50 of the mixed agent, unit: milligrams per liter (mg / L)

[0142] TTI=TI A ×P A +TI B ×P B (2)

[0143] In the formula:

[0144] TTI——the theoretical co-toxicity index of the mixed agent;

[0145] TI A ——the toxicity index of the drug A;

[0146] P A ——the percentage content of the drug A in the mixed agent, unit: percentage (%)

[0147] TI B Toxicity index of B agent;

[0148] P B Percentage content of B agent in the mixture, in percentage (%).

[0149]

[0150] In the formula:

[0151] CTC - Co-toxicity coefficient

[0152] ATI - Actual toxicity index of the mixture

[0153] TTI - Theoretical toxicity index of the mixture

[0154] When different pesticides are mixed, they usually exhibit three types of action, namely, additive action, synergistic action and antagonistic action, but it is impossible to predict which type of action will occur. The composition described in the present application uses compound I and compound II as effective active ingredients, and is illustrated by means of biological determination examples.

[0155] Insecticide activity determination test of compound on T. urticae

[0156] In this test, the glass slide immersion method was used to determine the indoor activity of the compound on T. urticae, in order to determine the activity of the insecticidal composition of Examples 1-3 on T. urticae.

[0157] Example 1: In order to verify the effect of different proportions of compound I and cyflumetofen on T. urticae, indoor toxicity determination of different proportions of compound I and cyflumetofen on T. urticae was carried out, and the corresponding concentrations were prepared according to the weight ratio in the table, and indoor insecticidal test was carried out, and the test results are as follows:

[0158] Table 1 Toxicity determination results of compound I and cyflumetofen single agent and their mixture on T. urticae

[0159]

[0160]

[0161] From the results in Table 1, it can be seen that the activity of different proportions of compound I and cyflumetofen on T. urticae has obvious synergistic effect.

[0162] Example 2: In order to verify the effect of different proportions of compound I and cyflumetofen on T. urticae, indoor toxicity determination of different proportions of compound I and cyflumetofen on T. urticae was carried out, and the corresponding concentrations were prepared according to the weight ratio in the table, and indoor insecticidal test was carried out, and the test results are as follows:

[0163] Table 2 Toxicity test results of compound I and acetoprole single agent and their mixture on T. urticae

[0164] Active ingredient Ratio Regression equation LC 50 ]] Co-toxicity factor Evaluation Compound I — y = 3.8749 + 2.0618x 3.5131 — — flufenoxuron — y = 4.4079 + 1.7814x 2.1496 — — Compound I: flufenoxuron 50：1 y = 4.4817 + 1.7248x 1.9976 173.7065 Synergism Compound I: flufenoxuron 10：1 y = 4.8044 + 1.6652x 1.3106 253.4399 Synergism Compound I: flufenoxuron 1：1 y = 5.0266 + 1.7269x 0.9652 276.3359 Synergism Compound I: flufenoxuron 1：10 y = 4.9774 + 1.6058x 1.0330 215.7029 Synergism Compound I: flufenoxuron 1：50 y = 4.8679 + 1.9537x 1.1685 185.3725 Synergism

[0165] From the results in Table 2, it can be seen that the activity of compound I and acetoprole mixed in different proportions on T. urticae has obvious synergistic effect.

[0166] Example 3: In order to verify the effect of compound I and ANM-138 mixed in different proportions on T. urticae, indoor toxicity test of compound I and ANM-138 mixed in different proportions on T. urticae was carried out, and indoor insecticidal test was carried out according to the corresponding concentration prepared according to the weight ratio in the table, and the test results were as follows:

[0167] Table 3 Toxicity test results of compound I and ANM-138 single agent and their mixture on T. urticae

[0168] Active ingredient Ratio Regression equation LC 50 ]] Co-toxicity factor Evaluation Compound I — y = 3.8749 + 2.0618x 3.5131 — — ANM-138 — y = 3.5386 + 1.7326x 6.9736 — — Compound I: ANM-138 50：1 y = 4.389 + 1.6611x 2.3327 152.0815 Synergism Compound I: ANM-138 10：1 y = 4.7365 + 1.8526x 1.3876 265.1378 Synergism Compound I: ANM-138 1：1 y = 4.5753 + 1.674x 1.7935 260.5177 Synergism Compound I: ANM-138 1：10 y = 4.309 + 1.6755x 2.5847 247.6305 Synergism Compound I: ANM-138 1：50 y = 3.7885 + 1.969x 4.1237 165.9072 Synergism

[0169] From the results in Table 3, it can be seen that the activity of compound I and ANM-138 mixed in different proportions on T. urticae has obvious synergistic effect.

[0170] Indoor pesticide activity determination test of Tetranychus cinnabarinus

[0171] In this test, the indoor activity determination test of compound on Tetranychus cinnabarinus was carried out by mite glass immersion method, in order to determine the activity of the insecticidal composition of examples 4-6 on Tetranychus cinnabarinus.

[0172] Example 4: In order to verify the effect of compound I and ethyl azocyclotin mixed in different proportions on Tetranychus cinnabarinus, indoor toxicity test of compound I and ethyl azocyclotin mixed in different proportions on Tetranychus cinnabarinus was carried out, and indoor insecticidal test was carried out according to the corresponding concentration prepared according to the weight ratio in the table, and the test results were as follows:

[0173] Table 4 Toxicity test results of compound I and ethyl azocyclotin single agent and their mixture on Tetranychus cinnabarinus

[0174] Active ingredient Ratio Regression equation LC 50 ]]> Co-toxicity factor Evaluation Compound I — y = 5.1436 + 1.7814x 0.8306 — — ethoxyfen — y = 6.1221 + 1.9653x 0.2686 — — Compound I: ethoxyfen 50：1 y = 5.4291 + 1.4933x 0.5160 154.6278 Synergism Compound I: ethoxyfen 10：1 y = 6.0197 + 1.6742x 0.2460 283.6870 Synergism Compound I: ethoxyfen 5：1 y = 6.0599 + 1.7285x 0.2437 252.6920 Synergism Compound I: ethoxyfen 3：1 y = 6.3918 + 2.1064x 0.2184 249.6984 Synergism Compound I: ethoxyfen 1：1 y = 6.3900 + 1.8123x 0.1710 237.3860 Synergism Compound I: ethoxyfen 1：3 y = 6.3563 + 1.7176x 0.1623 199.1899 Synergism Compound I: ethoxyfen 1：5 y = 6.4545 + 1.7088x 0.1409 214.8670 Synergism Compound I: ethoxyfen 1：10 y = 6.7873 + 1.8298x 0.1055 271.2823 Synergism Compound I: ethoxyfen 1：50 y = 6.3259 + 1.5996x 0.1483 183.5536 Synergism

[0175] From the results in Table 4, it can be seen that the activity of compound I and ethyl azocyclotin mixed in different proportions on Tetranychus cinnabarinus has obvious synergistic effect.

[0176] Example 5: In order to verify the effect of compound I and azocyclotin mixed in different proportions on Tetranychus cinnabarinus, indoor toxicity test of compound I and azocyclotin mixed in different proportions on Tetranychus cinnabarinus was carried out, and indoor insecticidal test was carried out according to the corresponding concentration prepared according to the weight ratio in the table, and the test results were as follows:

[0177] Table 5 Toxicity test results of compound I and azocyclotin single agent and their mixture on Tetranychus cinnabarinus

[0178] Active ingredient Ratio Regression equation LC 50 ]]> Co-toxicity factor Evaluation Compound I — y = 5.1436 + 1.7814x 0.8306 — — amidoflumet — y = 4.9005 + 1.5547x 1.1587 — — Compound I: amidoflumet 50：1 y = 5.5643 + 1.6641x 0.4580 182.3658 Synergism Compound I: amidoflumet 10：1 y = 5.8811 + 1.7716x 0.3182 267.9271 Synergism Compound I: amidoflumet 1：1 y = 5.5925 + 1.6994x 0.4480 215.9805 Synergism Compound I: amidoflumet 1：10 y = 5.6108 + 1.9032x 0.4776 234.1995 Synergism Compound I: amidoflumet 1：50 y = 5.3538 + 1.7048x 0.6201 185.4214 Synergism

[0179] From the results of Table 5, it can be seen that the activity of compound I and tolfenpyrad in different proportions has obvious synergistic effect on T. cinnabarinus.

[0180] Example 6: In order to verify the effect of compound I and NNI-0711 in different proportions on T. cinnabarinus, indoor toxicity determination of compound I and NNI-0711 in different proportions on T. cinnabarinus was carried out, and the corresponding concentration was prepared according to the weight ratio in the table, and indoor insecticidal test was carried out. The test results are as follows:

[0181] Table 6 Toxicity determination results of compound I and NNI-0711 single agent and their mixtures on T. cinnabarinus

[0182]

[0183]

[0184] From the results of Table 6, it can be seen that the activity of compound I and NNI-0711 in different proportions has obvious synergistic effect on T. cinnabarinus.

[0185] Laboratory activity determination test of citrus panonychus

[0186] In this test, the indoor activity determination test of compound on citrus panonychus was carried out by mite glass immersion method, in order to determine the activity of the insecticidal composition of examples 7-9 on citrus panonychus.

[0187] Example 7: In order to verify the effect of compound I and pyridaben in different proportions on citrus panonychus, indoor toxicity determination of compound I and pyridaben in different proportions on citrus panonychus was carried out, and the corresponding concentration was prepared according to the weight ratio in the table, and indoor insecticidal test was carried out. The test results are as follows:

[0188] Table 7 Toxicity determination results of compound I and pyridaben single agent and their mixtures on citrus panonychus

[0189] Active ingredient Ratio Regression equation LC 50 ]] Co-toxicity factor Evaluation Compound I — y = 4.7185 + 1.9799x 1.3873 — — pyridaben — y = 3.1236 + 1.6946x 12.801 — — Compound I: pyridaben 50：1 y = 5.0987 + 1.6736x 0.8730 161.7383 Synergism Compound I: pyridaben 10：1 y = 5.2937 + 1.3931x 0.6154 245.3129 Synergism Compound I: Pyridaben 5：1 y = 5.1868 + 1.3978x 0.7351 221.6704 synergism Compound I: Pyridaben 3：1 y = 5.1672 + 1.8996x 0.8166 218.6189 synergism Compound I: Pyridaben 1：1 y = 5.0372 + 2.1557x 0.9611 260.4626 synergism Compound I: Pyridaben 1：3 y = 4.4268 + 1.8382x 2.0505 204.2276 synergism Compound I: Pyridaben 1：5 y = 4.2521 + 2.0141x 2.3516 229.5407 synergism Compound I: Pyridaben 1：10 y = 4.1582 + 1.6251x 3.2959 222.2099 synergism Compound I: Pyridaben 1：50 y = 3.5439 + 1.9332x 5.6650 194.5882 synergism

[0190] From the results of Table 7, it can be seen that the activity of compound I and pyridaben in different proportions has obvious synergistic effect on citrus panonychus.

[0191] Example 8: In order to verify the effect of compound I and fenpyroximate in different proportions on citrus panonychus, indoor toxicity determination of compound I and fenpyroximate in different proportions on citrus panonychus was carried out, and the corresponding concentration was prepared according to the weight ratio in the table, and indoor insecticidal test was carried out. The test results are as follows:

[0192] Table 8 Toxicity test results of compound I and azocyclotin single agent and their mixture on Panonychus citri

[0193]

[0194]

[0195] From the results in Table 8, it can be seen that the activity of compound I and azocyclotin mixed in different proportions and amounts has obvious synergistic effect on Panonychus citri.

[0196] Example 9: To verify the effect of compound I and bifenoxid in different proportions and amounts on Panonychus citri, indoor toxicity test of compound I and bifenoxid in different proportions on Panonychus citri was carried out, and indoor insecticidal test was carried out according to the weight ratio of the corresponding concentration, and the test results were as follows:

[0197] Table 9 Toxicity test results of compound I and bifenoxid single agent and their mixture on Panonychus citri

[0198] active ingredient ratio regression equation LC 50 ]]> co-toxicity coefficient evaluation Compound I — y = 4.7185 + 1.9799x 1.3873 — — bifenazate — y = 1.5701 + 1.7463x 92.0544 — — Compound I: Bifenazate 50：1 y = 5.0764 + 1.7211x 0.9028 156.6912 synergism Compound I: Bifenazate 10：1 y = 5.4697 + 1.9196x 0.5692 267.6948 synergism Compound I: Bifenazate 1：1 y = 4.8954 + 2.0184x 1.1267 242.6029 synergism Compound I: Bifenazate 1：10 y = 3.4914 + 1.946x 5.9594 222.5533 synergism Compound I: Bifenazate 1：50 y = 2.3854 + 1.8927x 24.0649 167.7038 synergism

[0199] From the results in Table 9, it can be seen that the activity of compound I and bifenoxid mixed in different proportions and amounts has obvious synergistic effect on Panonychus citri.

[0200] Three, field efficacy examples

[0201] In order to clarify the effect of compound I and mitochondrial electron transport inhibitor insecticides single agent and mixture on Tetranychus urticae Koch, Tetranychus cinnabarinus and Panonychus citri, multiple efficacy tests were carried out in different regions of China. The preparations used were processed according to Preparation Examples 1-7, and the preparation in Table 10 was taken as an example (other test preparations refer to the same preparation example), and the specific preparation method was as follows:

[0202] Table 10 Preparation of compound I · pyridaben suspension concentrate in different proportions

[0203]

[0204]

[0205] Field efficacy test of Panonychus citri

[0206] Test method: According to the application method specified in “People's Republic of China National Standard GB / T 17980.11-2000”, usually when there are 2 live mites per leaf on average, the pesticide is applied.

[0207] Investigation method: According to the investigation method stipulated in the "People's Republic of China National Standard GB / T 17980.11-2000", mark the tender shoots in the east, west, south, north and middle of each plot, and investigate the number of active mites on 25 leaves. Observe the leaf surface directly with a hand magnifying glass, and count the number of mites. If the damage is slight, the number of investigation leaves can be increased. Carry out the investigation on the eve of treatment, and investigate once every 1 day, 3 days, 10 days, 15 days, 20 days and 30 days after treatment, and record the number of active mites. The calculation formula of the control effect is:

[0208]

[0209]

[0210] Field efficacy test of Tetranychus cinnabarinus

[0211] According to the application method stipulated in the "Guidelines for Pesticide Field Efficacy Test (GB / T 17980.17-2000)", spray the stems and leaves of peppers.

[0212] Investigation method: According to the investigation method stipulated in the "Guidelines for Pesticide Field Efficacy Test (GB / T 17980.17-2000)", take 20 leaves in each plot to count the number of active mites. Investigate 1 day, 3 days, 7 days and 14 days after treatment. The calculation formula of the control effect is:

[0213]

[0214]

[0215] Field efficacy test of Tetranychus urticae

[0216] According to the application method stipulated in the "Guidelines for Pesticide Field Efficacy Test (GB / T 17980.17-2000)", spray the stems and leaves of peppers.

[0217] Investigation method: According to the investigation method stipulated in the "Guidelines for Pesticide Field Efficacy Test (GB / T 17980.17-2000)", take 20 leaves in each plot to count the number of active mites. Investigate 1 day, 3 days, 7 days and 14 days after treatment. The calculation formula of the control effect is:

[0218]

[0219]

[0220] Table 11 Field efficacy test of compound I and pyridaben on Panonychus citri

[0221]

[0222] Note: The same column data after different letters represent significant difference at the level of P <0.05 by Duncan's new multiple range test, the same below.

[0223] The 30% compound I·pyridaben suspension agent (1:4) in the above table was prepared according to the preparation example 3, wherein 30% refers to the total mass percentage of active substances (compound I and pyridaben), and 1:4 refers to the mass ratio of the two active ingredients compound I and pyridaben.

[0224] The 30% compound I·pyridaben suspension agent (1:3) in example 11 was prepared according to the preparation example 3, wherein 30% refers to the total mass percentage of active substances (compound I and pyridaben), and 1:3 refers to the mass ratio of the two active ingredients compound I and pyridaben.

[0225] The 30% compound I suspension agent in comparative example 1 was also prepared according to the preparation example 3, wherein 30% refers to the mass percentage of active substance compound I.

[0226] The following other examples and comparative examples are also prepared in this way, which will not be described in detail here.

[0227] As can be seen from the determination results in table 11, when preventing and treating citrus full mite, the 1 day, 3 day, 10 day, 15 day, 20 day and 30 day control effects of compound I and pyridaben complex on citrus full mite are obviously higher than those of single agent at the same effective ingredient dosage (comparative examples 1 and 2 correspond to examples 10-16). Among them, the 30 day control effect can still reach more than 94.43%, and the effective period is longer.

[0228] Table 12 Field efficacy test of compound I and pyridaben complex on two-spotted spider mite

[0229]

[0230] As can be seen from the determination results in table 12, when preventing and treating two-spotted spider mite, the 1 day, 3 day, 7 day and 14 day control effects of compound I and pyridaben complex on two-spotted spider mite are obviously higher than those of single agent at the same effective ingredient dosage (comparative examples 3 and 4 correspond to examples 17-23). Among them, the 14 day control effect can still reach more than 92.01%, and the effective period is longer.

[0231] Table 13 Field efficacy test of compound I and pyridaben complex on two-spotted spider mite

[0232]

[0233]

[0234] From the results in Table 13, it can be seen that, in the prevention and treatment of Panonychus citri, the 1-day, 3-day, 10-day, 15-day, 20-day and 30-day control effects of compound I and cyflumetofen on Panonychus citri were significantly higher than those of single agent at the same active ingredient dosage (comparative examples 5 and 6 corresponding to examples 24-30). The 30-day control effect can still reach more than 96.54%, and the duration is longer.

[0235] Table 14 Field efficacy test of compound I and cyflumetofen on Tetranychus urticae

[0236]

[0237] From the results in Table 14, it can be seen that, in the prevention and treatment of Tetranychus urticae, the 1-day, 3-day, 7-day and 14-day control effects of compound I and cyflumetofen on Tetranychus urticae were significantly higher than those of single agent at the same active ingredient dosage (comparative examples 7 and 8 corresponding to examples 31-37). The 14-day control effect can still reach more than 92.16%, and the duration is longer.

[0238] Table 15 Field efficacy test of compound I and ethyl acetate on Tetranychus cinnabarinus

[0239]

[0240]

[0241] From the results in Table 15, it can be seen that, in the prevention and treatment of Tetranychus cinnabarinus, the 1-day, 3-day, 7-day and 14-day control effects of compound I and ethyl acetate on Tetranychus cinnabarinus were significantly higher than those of single agent at the same active ingredient dosage (comparative examples 9 and 10 corresponding to examples 38-44). The 14-day control effect can still reach more than 91.77%, and the duration is longer.

[0242] Table 16 Field efficacy test of compound I and ethyl acetate on Tetranychus urticae

[0243]

[0244] From the results in Table 16, it can be seen that, in the prevention and treatment of Tetranychus urticae, the 1-day, 3-day, 7-day and 14-day control effects of compound I and ethyl acetate on Tetranychus urticae were significantly higher than those of single agent at the same active ingredient dosage (comparative examples 11 and 12 corresponding to examples 45-51). The 14-day control effect can still reach more than 94.13%, and the duration is longer.

[0245] The above describes the embodiments of the present application. However, the present application is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement, and the like made within the spirit and principle of the present application should be included in the scope of protection of the present application.

Claims

1. A composition comprising compound I and a mitochondrial electron transport inhibitor, characterized in that, The mitochondrial electron transport inhibitor insecticide is selected from one of the following: pyridaben, azoxystrobin, and azoxystrobin; The structure of compound I is shown below. I The mass ratio of compound I to the mitochondrial electron transport inhibitor insecticide is 50~1:1~50.

2. The composition according to claim 1, characterized in that, The mass ratio of compound I to the mitochondrial electron transport inhibitor insecticide is 10~1:1~10.

3. The composition according to claim 1 or 2, characterized in that, The composition further includes at least one of the following: deionized water, organic solvent, emulsifier, dispersant, wetting agent, thickener, defoamer, stabilizer, binder, disintegrant, antifreeze, anticaking agent, suspending agent, film-forming agent, preservative, colorant, polymeric capsule wall material, pH adjuster, or filler.

4. The composition according to claim 1, characterized in that, The composition is prepared into a pesticide formulation, which includes wettable powder, water-dispersible granules, suspension concentrate, water-in-oil emulsion, suspension seed coating agent, microcapsule suspension, microcapsule suspension-suspension agent, emulsifiable concentrate, microemulsion, dispersible liquid, or granules.

5. Use of the composition according to any one of claims 1-4 for the prevention and control of pests in agriculture or non-agriculture.

6. The use according to claim 5, characterized in that, The pests mentioned are selected from Lepidoptera, Hemiptera, Coleoptera, Thysanoptera, Diptera, and Mite pests.

7. A method for controlling pests in agricultural or non-agricultural fields, characterized in that, This includes applying the composition of any one of claims 1-4 to plants infested with pests.

8. A composition for controlling invertebrate pests, characterized in that, It contains a biologically effective amount of compound I, a mitochondrial electron transport inhibitor insecticide, and at least one other component selected from surfactants, solid diluents, and liquid diluents, wherein the mitochondrial electron transport inhibitor insecticide is selected from one of the following: pyridaben, azoxystrobin, and azoxystrobin; The structure of compound I is shown below. I The mass ratio of compound I to the mitochondrial electron transport inhibitor insecticide is 50~1:1~50.

9. A method for controlling invertebrate pests, characterized in that, This includes contacting invertebrate pests or their environment with a biologically effective amount of the composition according to any one of claims 1-4.

10. A spray composition comprising the composition according to any one of claims 1-4 and a propellant.

11. A bait composition comprising the composition according to any one of claims 1-4 and one or more food materials.

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