Acaricidal active ingredient compositions and uses thereof

Abstract

The present application relates to a miticidal active ingredient combination composition containing a compound of formula (I) and at least one active ingredient combination of compounds of formulae (II) to (IV). The miticidal active ingredient combination composition of the present application can be used to control troublesome mites on important crops such as fruit trees, cotton, stone fruits, tea trees, vegetables, etc., and can produce a good mite control effect on various mites even when used at a low concentration.

Description

Technical Field

[0001] This application relates to a combination of active ingredients for the control of animal pests, particularly suitable for the control of mites and ticks. The combination of active ingredients comprises known alkylphenyl sulfide derivatives and other known insecticidal active ingredients. Background Technology

[0002] Mites that parasitize agricultural and horticultural crops have short life cycles and occur frequently throughout the year. The effectiveness of commonly used agricultural and horticultural insecticides decreases after years of use due to reduced sensitivity. For example, mites that are major pests of fruit trees such as apples, pears, and citrus, especially the two-spotted spider mite and / or the apple psyllid, have developed significant resistance, shortening the lifespan of existing acaricide active ingredient combinations.

[0003] However, developing new acaricide active ingredients requires enormous costs and time, and is extremely difficult. Given this situation, it is necessary to extend the lifespan of existing acaricide active ingredients and reduce the dosage and frequency of application to prevent decreased sensitivity, restore sensitivity, and maintain, restore, or enhance the acaricidal effect.

[0004] An alkylphenyl sulfide derivative represented by formula (I) is described in patent document WO2013157229A1, which records its excellent efficacy against various pests, particularly spider mites such as the two-spotted spider mite, the Japanese spider mite, and the citrus spider mite. This substance exhibits good activity, but sometimes falls short at low application rates.

[0005] Summary of the Invention

[0006] It has been found that combinations of alkylphenyl sulfide derivatives of formula (I) and active ingredients derived from at least one of etoxazole, etoxazole-methyl, and cyprodinil are highly effective in controlling animal pests, particularly mites and ticks in annual or perennial crops. Particularly unexpectedly, the acaricidal activity of the combination of active ingredients is significantly higher than the sum of the activities of the individual active ingredients.

[0007] Particularly preferred are active ingredients comprising an alkylphenyl sulfide derivative of general formula (I) and at least one of the following compounds:

[0008]

[0009] (1) Etoxazole of formula (II) derived from diphenyloxazoline derivatives

[0010]

[0011] (2) Cyetpyrafen, a product of formula (III) from acrylonitrile.

[0012] or

[0013] (3) Cyenopyrafen, a product of acrylonitrile of formula (IV),

[0014]

[0015] In this application, it is necessary to use the alkylphenyl sulfide derivative of formula (I) in combination with at least one of etoxazole, etoxazole-methyl, or cyprodinil. Significant mite control effects are achieved in this application by using the alkylphenyl sulfide derivative of formula (I) in combination with at least one of etoxazole, etoxazole-methyl, or cyprodinil.

[0016] When the active ingredients in the active ingredient combination of this application are present in a specific weight ratio, they exhibit a particularly significant improvement effect. The weight ratio of the active ingredients in the active ingredient combination can vary in the range of 1:250-100:1. Typically, the active ingredient combination of this application comprises a mixture of the active ingredient of formula (I) and the preferred and particularly preferred mixing ratios given in the table below.

[0017] Mixed pairings Preferred mixing ratio A more optimized mixing ratio The preferred mixing ratio Ethoxydazole (II) 1:250 to 100:1 1:80 to 5:1 1:40 to 4:1 Ethoxamyl (III) 1:250 to 100:1 1:250 to 1:1 Cyclopyralid (IV) 1:250 to 100:1 10:1 to 1:40 4:1 to 1:40

[0018] *The mixing ratio is based on a weight ratio, which is understood as formula (I) active ingredient: mixed pair.

[0019] The acaricidal active ingredient composition of this application is effective against harmful mites even at low doses. Examples of harmful mites include plant parasites such as the two-spotted spider mite (Tetranychus urticae), the carmine spider mite (Tetranychus cinnatarinus (Boisduval)), the citrus red spider mite (Panonychus citri McGregor), the kassa spider mite (Tetranychus kanzawai kishida), the apple red spider mite (Panonychus ulmiKoch), the tea tarsonemite (Polyphagotarsonemus latus Banks), the citrus rust gall mite (Phyllocoptruta oleivora (Ashmead)), and the root spiny plant mite (Rhizoglyphus echinopus).

[0020] The acaricide active ingredient composition of this application can be used to control thorny mites on important crops such as fruit trees (e.g., citrus, apples and pears), cotton, stone fruits, tea trees, and vegetables (Chinese cabbage, potatoes, green beans, cucumbers, eggplants, etc.).

[0021] The combination of acaricidal active ingredients in this application produces excellent mite control effects against various mites even when used at low concentrations.

[0022] The combination of acaricidal active ingredients in this application has a significant mite control effect not only on chemically sensitive mites, but also on most chemically insensitive mites.

[0023] The combination of acaricidal active ingredients in this application demonstrates excellent mite control effects over a long period of 14-40 days.

[0024] In addition, the combination of acaricidal active ingredients in this application also has excellent mite control effects on mites that have developed resistance to conventional acaricidal active ingredient combinations.

[0025] The term "mite control effect" used in this article refers to acaricidal activity at any stage of the mite life cycle (egg, larva, and adult).

[0026] The active ingredient combination for killing mites in this application also contains carriers such as solid carriers, liquid carriers, and gaseous carriers (propellants), as well as surfactants and other adjuvants including fixatives, dispersants, and stabilizers, as needed.

[0027] Solid carriers include, for example, fine powders or granules of clays (kaolin, diatomaceous earth, bentonite, acid clay, etc.), talc and its derivatives, ceramics, other inorganic minerals (calcium ironite, quartz, activated carbon, calcium carbonate, hydrated silica, etc.), and chemical fertilizers (ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride, etc.).

[0028] Liquid carriers include, for example, water; esters such as ethyl acetate and butyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; dimethyl sulfoxide; and vegetable oils such as soybean oil and cottonseed oil.

[0029] Gas carriers include, for example, butane, liquid petroleum gas, dimethyl ether, carbon dioxide, etc.

[0030] Surfactants include, for example, polyethylene glycol ethers, polyol esters, sugar alcohol derivatives, alkyl aryl sulfonates, alkyl sulfate esters, alkyl sulfonates, alkyl aryl ethers and their polyoxyethylene adducts.

[0031] The acaricide active ingredient combination of this application can be used directly or diluted with, for example, water. This acaricide active ingredient combination can also be used as a mixture with other insecticides, nematicides, acaricide active ingredient combinations, fungicides, herbicides, plant growth regulators, synergists, soil conditioners, animal feed, etc.

[0032] The total amount of the active ingredient, the compound of formula (I) and at least one of etoxazole, etoxazole-methyl, and cyprodinil, generally accounts for 0.01-95% by weight of the formulation, preferably 0.1-50% by weight.

[0033] The combination of acaricidal active ingredients containing the above-mentioned components of this application can be prepared into solutions, emulsions, suspensions, powders, pastes, granules, microcapsules, etc., according to known preparation methods.

[0034] A method for repelling spider mites involves spraying the acaricide composition described in this application onto crops infested by spider mites to repel them.

[0035] The dosage and concentration of the acaricidal active ingredient combination in this application are not limited to the range of the examples above, and may be appropriately increased or decreased according to the type of formulation, application time, application location, application method, pest species, degree of damage, etc.

[0036] The acaricide active ingredient combination of this application contains a compound of formula (I) and at least one of etoxazole, etoxazole-methyl, and cyprodinil. Alternatively, a combination of one or two individual compounds of formula (I) or etoxazole, etoxazole-methyl, and cyprodinil can be prepared first, and then these compositions can be used sequentially or simultaneously during mite control, preferably simultaneously. In this case, the compound of formula (I) and at least one of etoxazole, etoxazole-methyl, and cyprodinil can be used in the proportions described above. Detailed Implementation

[0037] To facilitate understanding of this application, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of this application.

[0038] When the active ingredients in the combination of active ingredients in this application are present in a specific weight ratio, they exhibit a particularly significant improvement effect. The weight ratio of active ingredients in the active ingredient combination can vary within the range of 1:250-100:1, for example, 1:250, 1:200, 1:150, 1:120, 1:100, 1:95, 1:90, 1:85, 1:80, 1:75, 1:60, 1:55, 1:50, 1:45, 1:40, 1:35, 1:30, 1:25, 1:20, 1:15, 1:10, 1:5, 1:1, 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, 85:1, 90:1, 95:1, or 100:1.

[0039] The acaricide active ingredient composition of this application contains a compound of formula (I) and etoxazole, wherein the weight ratio of the compound of formula (I) to etoxazole is 1:80 to 5:1, for example 1:80, 1:75, 1:60, 1:55, 1:50, 1:45, 1:40, 1:35, 1:30, 1:25, 1:20, 1:15, 1:10, 1:5, 1:1, 5:1, preferably 1:40 to 4:1.

[0040] The acaricide active ingredient composition of this application contains a compound of formula (I) and etoxazole, wherein the weight ratio of the compound of formula (I) to etoxazole is 1:250 to 1:1, for example 1:250, 1:200, 1:150, 1:120, 1:100, 1:95, 1:90, 1:85, 1:80, 1:75, 1:60, 1:55, 1:50, 1:45, 1:40, 1:35, 1:30, 1:25, 1:20, 1:15, 1:10, 1:5, 1:1.

[0041] The acaricide active ingredient composition of this application contains a compound of formula (I) and cyproterone, wherein the weight ratio of the compound of formula (I) to cyproterone is 10:1 to 1:40, for example 1:40, 1:35, 1:30, 1:25, 1:20, 1:15, 1:10, 1:4, 1:5, 1:1, 5:1, 10:1, preferably 4:1 to 1:40.

[0042] The total amount of the active ingredient, the compound of formula (I), and at least one of etoxazole, etoxazole-methyl, or cyprodinil, is generally 0.01-95% by weight of the formulation, for example 0.01% by weight, 0.1% by weight, 0.5% by weight, 1% by weight, 5% by weight, 8% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, or 95% by weight, preferably 0.1-50% by weight.

[0043] Biological test cases

[0044] Experiment Example 1: Acaricide Test against Tetranychus cinnabarinus

[0045] The compound of formula (I) and etoxazole technical grade were dissolved in solvents to prepare a single-agent stock solution, which was then diluted with an aqueous solution containing 0.1% Tween-80 to the required concentration.

[0046] Healthy, active female adult mites of uniform size were selected for testing. Healthy, intact, and uniformly sized cotton leaves were used. The cotton leaves were punched into leaf discs with a diameter of 2 cm using a perforator. A moist sponge block was placed in the petri dish, followed by filter paper, and then leaf butterflies. Adult *Tetranychus carmineus* mites were inoculated. Twenty female adult mites were inoculated onto each leaf disc.

[0047] The POTTER spray tower was used for treatment. The spray volume for each treatment was 2 mL. After treatment, the cotton leaves were placed in a constant temperature chamber with a temperature of (25±1)℃, relative humidity of (70±10)%, and a light ratio of L:D of 16:8. Each treatment was repeated three times. Adult mite mortality was observed after 2 days. The legs and mouthparts of the spider mites were touched with the tip of a small paintbrush; those without a reaction were considered dead. A blank control was treated with purified water.

[0048] The spider mite reduction rate and control effect of each treatment were calculated using the following formula:

[0049] Mite reduction rate (%) = (Number of live mites before application - Number of live mites after application) / Number of live mites before application * 100

[0050] Control efficacy (%) = (Reduction rate of live mites in the treated area - Reduction rate of live mites in the control area) / (100 - Reduction rate of live mites in the control area) * 100

[0051] In addition, the theoretical control effect (%) can be calculated using the Colby formula. When the actual control effect (%) is higher than the theoretical control effect (%), the composition of this application has a synergistic effect.

[0052] Table 1

[0053]

[0054]

[0055] As shown in Table 1, the efficacy of compound (I) at 1 ppm is 36.8%, while that of etoxazole at 5 ppm is 0. When compound (I) and etoxazole are used in combination at a ratio of 1 ppm: 5 ppm, the actual efficacy can reach 53.6%, which is significantly higher than the theoretical efficacy of 36.8%. Similarly, when compound (I) is used in combination with etoxazole at 2.5 ppm, 5 ppm, 10 ppm and 20 ppm respectively, the actual efficacy is higher than the theoretical efficacy.

[0056] Experiment Example 2: Acaricide Test against Two-spotted Tetranychus spp.

[0057] The compound of formula (I) and the technical grade of etoxazole were dissolved in solvents to prepare a single-agent stock solution, which was then diluted with an aqueous solution containing 0.1% Tween-80 to the required concentration.

[0058] Healthy, active female adult mites of uniform size were selected for testing. Healthy, intact, and uniformly sized cotton leaves were used. The cotton leaves were punched into leaf discs with a diameter of 2 cm using a perforator. A moist sponge block was placed in the petri dish, followed by filter paper, and then leaf butterflies. Adult two-spotted spider mites were inoculated. Twenty female adult mites were inoculated onto each leaf disc.

[0059] The POTTER spray tower was used for treatment. The spray volume for each treatment was 2 mL. After treatment, the cotton leaves were placed in a constant temperature chamber with a temperature of (25±1)℃, relative humidity of (70±10)%, and a light ratio of L:D of 16:8. Each treatment was repeated three times. Adult mite mortality was observed after 2 days. The legs and mouthparts of the spider mites were touched with the tip of a small paintbrush; those without a reaction were considered dead. A blank control was treated with purified water.

[0060] The spider mite reduction rate and control effect of each treatment were calculated using the following formula:

[0061] Mite reduction rate (%) = (Number of live mites before application - Number of live mites after application) / Number of live mites before application * 100

[0062] Control efficacy (%) = (Reduction rate of live mites in the treated area - Reduction rate of live mites in the control area) / (100 - Reduction rate of live mites in the control area) * 100

[0063] In addition, the theoretical control effect (%) can be calculated using the Colby formula. When the actual control effect (%) is higher than the theoretical control effect (%), the composition of this application has a synergistic effect.

[0064] Table 2

[0065]

[0066] Experiment Example 3: Acaricide Test for Citrus Paronychia

[0067] The compound of formula (I) and the technical grade of cypermethrin were dissolved in a solvent to prepare a stock solution for a single agent, and then diluted with an aqueous solution containing 0.1% Tween-80 to the required concentration.

[0068] Healthy, active female adult mites of uniform size were selected for testing. The test leaves were healthy, intact, and uniformly sized citrus leaves. The citrus leaves were perforated to form leaf discs with a diameter of 2 cm using a perforator. A moist sponge block was placed in the petri dish, followed by filter paper, and then leaf butterflies. Adult *Pachycerium citrinum* mites were inoculated. Twenty female adult mites were inoculated onto each leaf disc.

[0069] The POTTER spray tower was used for treatment. The spray volume for each treatment was 2 mL. After treatment, the citrus leaves were placed in a constant temperature chamber with a temperature of (25±1)℃, relative humidity of (70±10)%, and a light ratio of L:D of 16:8. Each treatment was repeated three times. Adult mite mortality was observed after 2 days. The legs and mouthparts of the spider mites were touched with the tip of a small paintbrush; those without a reaction were considered dead. A blank control was treated with purified water.

[0070] The spider mite reduction rate and control effect of each treatment were calculated using the following formula:

[0071] Mite reduction rate (%) = (Number of live mites before application - Number of live mites after application) / Number of live mites before application * 100

[0072] Control efficacy (%) = (Reduction rate of live mites in the treated area - Reduction rate of live mites in the control area) / (100 - Reduction rate of live mites in the control area) * 100

[0073] In addition, the theoretical control effect (%) can be calculated using the Colby formula. When the actual control effect (%) is higher than the theoretical control effect (%), the composition of this application has a synergistic effect.

[0074] Table 3

[0075]

[0076] As can be clearly seen from Tables 1-3, the combination of compound (I) with etoxazole, etoxazole-methyl, or cyprodinil significantly enhances the mite control effect, exceeding the predictions of those skilled in the art.

Claims

1. A composition of acaricidal active ingredients, characterized in that, The active ingredient composition consists of a compound of active ingredient formula (I) and etoxazole, wherein the weight ratio of the compound of formula (I) to etoxazole is 4:1 to 1:

10. Alternatively, the active ingredient composition consists of an active ingredient compound of formula (I) and etoxazole, wherein the weight ratio of the compound of formula (I) to etoxazole is 1:31.25 to 1:1; Alternatively, the active ingredient composition consists of an active ingredient compound of formula (I) and cypermethrin, wherein the weight ratio of the compound of formula (I) to cypermethrin is 4:1 to 1:

20. Equation (I) (1) Ethoxydazole of formula (II) derived from diphenyloxazoline derivatives, Formula (II); (2) Ethoxadiazonium of formula (III) from acrylonitrile, Formula (III); or (3) Acrylonitrile of formula (IV) derived from acrylonitrile, Formula (IV).

2. The acaricidal active ingredient composition according to claim 1, characterized in that, The active ingredient composition consists of an active ingredient compound of formula (I) and etoxazole, wherein the weight ratio of the compound of formula (I) to etoxazole is 1:1 to 1:

10.

3. The acaricidal active ingredient composition according to claim 1, characterized in that, The active ingredient composition consists of an active ingredient compound of formula (I) and cypermethrin, wherein the weight ratio of the compound of formula (I) to cypermethrin is 1:4 to 1:

20.

4. The use of the acaricidal active ingredient composition according to claim 1 for the control of mites and ticks, characterized in that, The active ingredient composition is a combination of the compound of formula (I) and etoxazole, and the animal pest controlled by ticks is Tetranychus carmineus. Alternatively, the active ingredient composition is a combination of a compound of formula (I) and etoxazole, and the animal pest controlled by ticks is the two-spotted spider mite; Alternatively, the active ingredient composition may be a combination of a compound of formula (I) and cypermethrin, wherein the animal pest controlled by mites is the citrus paris mite.

5. A method for controlling mites, characterized in that, The method uses the acaricidal active ingredient composition of claim 1, wherein the active ingredient composition is a combination of a compound of formula (I) and etoxazole, and the mite is Tetranychus cinnabarinus; Alternatively, the active ingredient composition is a combination of a compound of formula (I) and etoxazole, wherein the mite is a two-spotted spider mite; Alternatively, the active ingredient composition may be a combination of a compound of formula (I) and cyproterone, wherein the mite is *Pachycerium citrinum*.

6. The method according to claim 5, characterized in that, The acaricidal active ingredient composition is sprayed onto crops infested by spider mites to repel them.

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