An insecticide composition containing methoxazole and D-limonene and its application

Abstract

The invention discloses a kind of insecticidal composition containing methoxazole and D limonene and its application, the insecticidal composition includes active ingredient, the active ingredient is methoxazole and D limonene, and the mass ratio of the D limonene and the methoxazole is 1:50 to 50:1.Due to D limonene and methoxazole are compounded, so that the two can produce synergistic effect, then the insecticidal composition formed has good insecticidal effect, and has a larger prevention and control spectrum, especially for tomato whitefly and other piercing-sucking mouthparts pests have good prevention and control effect.In addition, D limonene is a plant-derived compound, and the combination of the two will not produce resistance while also delaying the development of other chemical resistance, and the insecticidal composition side effect is extremely low, will not affect crop safety and yield, etc., thus can solve the problem that tomato whitefly and other piercing-sucking mouthparts pests are difficult to prevent and control, achieve good insecticidal effect.

Description

Technical Field

[0001] The present invention relates to the technical field of pesticides, and in particular to an insecticidal composition containing methoprene and D-limonene and an application thereof. Background Art

[0002] Bemisia tabaci (Gennadius), a whitefly, belongs to the order Hemiptera, family Aleyrodidae. It is one of the most damaging invasive species worldwide. It directly sucks plant sap, weakening the plants. Both nymphs and adults secrete honeydew, which can cause sooty mold disease. High densities of sooty mold cause leaves to turn black, severely impacting photosynthesis. Furthermore, whiteflies can spread over 70 viral diseases to over 30 crops, with different biotypes transmitting different viruses and causing varying symptoms for different plants.

[0003] D-limonene, molecular formula: C 10 H 16 D-limonene is orange oil extracted from orange peel using professional cold-pressing technology. It is a natural plant-based pesticide that acts on pests through a unique physical contact effect. It has no cross-resistance with commonly used chemical pesticides. Its insecticidal mechanism is to dissolve the wax layer on the surface of the pest, causing the pest to be quickly knocked down and die in an obvious state of dehydration.

[0004] Dimethoprim is a pyrazole amide compound, its English common name is dimpropyridaz; its trade name is Axalion TM IUPAC name: 1-[(1RS)-1,2-dimethylpropyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-1H-pyrazole-4-carboxamide; CAS registration number: 1403615-77-9; molecular formula: C 16 H 23 N5O; the structural formula is as follows:

[0005]

[0006] Methicillin has excellent performance and good systemic conductivity. It is primarily suitable for field crops such as fruit trees and vegetables, soybeans, other legumes, cotton, cereals, potatoes, as well as flowers and ornamental plants. Methicillin is used to control pests such as Lepidoptera (striped stem borer, beet armyworm, diamondback moth, fall armyworm), Coleoptera (beetles, corn root beetle, potato leaf beetle, yellow flea beetle), Diptera (flies, mosquitoes, vegetable leafminer), Hemiptera (aphids, planthoppers, psyllids, whiteflies), Thysanoptera (thrips, orchid thrips, palm thrips, tobacco thrips), Isoptera (termites), cockroaches, and ants. It is particularly effective against piercing-sucking pests such as aphids, whiteflies, and thrips.

[0007] Because piercing-sucking pests like the tomato whitefly reproduce rapidly, are difficult to control, carry significant damage, and are prone to developing pesticide resistance, commonly used pesticides often develop resistance to varying degrees, making them difficult to control. The activity of D-limonene and methoprene against piercing-sucking pests like the tomato whitefly has not been thoroughly studied, and there are currently no reports on the combination of D-limonene and methoprene for control of the tomato whitefly. Summary of the Invention

[0008] In view of the above problems, the present invention provides an insecticidal composition containing methipamide and D-limonene and its application that overcomes the above problems or at least partially solves the above problems, which can solve the problem that piercing-sucking mouthparts pests such as tomato whitefly are difficult to control and achieve good insecticidal effects.

[0009] Specifically, the present invention provides an insecticidal composition of thiamethoxam and D-limonene, which comprises active ingredients, wherein the active ingredients are thiamethoxam and D-limonene, and the mass ratio of the D-limonene to the thiamethoxam is 1:50 to 50:1.

[0010] Optionally, the mass ratio of the D-limonene to the anthracene is 1:20 to 20:1.

[0011] Optionally, the mass ratio of the D-limonene to the anthracene is 2:15.

[0012] Optionally, the ratio of the mass of the D-limonene to the mass of the insecticide composition is 1-50%.

[0013] Optionally, the ratio of the mass of the thiamethoxam to the mass of the insecticidal composition is 1-50%.

[0014] Optionally, the ratio of the mass of the D-limonene to the mass of the insecticidal composition is 2%; the ratio of the mass of the anthracene to the mass of the insecticidal composition is 15%.

[0015] Optionally, the insecticide composition further comprises the following substances by mass percentage: 12-20.5% of a solvent, 4-13% of an emulsifier, and the remainder is vegetable oil methyl ester; the vegetable oil methyl ester is prepared by methylating vegetable oil.

[0016] Optionally, the insecticide composition is in the form of a liquid preparation.

[0017] Optionally, the insecticide composition is in the form of a dispersible liquid.

[0018] The present disclosure also provides use of the aforementioned insecticide composition in the preparation of a medicament for controlling piercing-sucking mouthpart pests.

[0019] Optionally, the piercing-sucking mouthparts pests include at least Bemisia tabaci.

[0020] The beneficial effects of the present invention are:

[0021] The insecticidal composition containing methipridazole and D-limonene provided by the present invention has a synergistic effect due to the compounding of D-limonene and methipridazole, thereby making the two have a good insecticidal effect and a wide control spectrum, especially having a good control effect on piercing-sucking mouthparts pests such as tomato whitefly. In addition, D-limonene is a plant-derived compound, and the combination of the two does not produce resistance while also delaying the development of resistance to other chemical agents. The insecticidal composition has extremely low side effects and does not affect the safety and yield of crops. Therefore, it can solve the problem that piercing-sucking mouthparts pests such as tomato whitefly are difficult to control, and achieve a good insecticidal effect. DETAILED DESCRIPTION

[0022] To make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely below. Where specific conditions are not specified in the embodiments, the experiments were carried out according to conventional conditions in the prior art or according to the conditions recommended by the manufacturer. Where the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0023] The active ingredients in the insecticidal composition provided by the present invention are composed of D-limonene and methoprene. In the embodiment of the present invention, D-limonene and methoprene are specifically selected for compounding. When the insecticidal composition of the present invention is used to control piercing-sucking mouthparts pests, the mass ratio of D-limonene to methoprene is one of 1:50, 1:25, 1:20, 1:15, 1:10, 1:5, 2:5, 2:15, 1:1, 2:15, 10:1, 20:1, and 50:1. The two can produce a synergistic effect, thereby making the formed insecticidal composition have a good insecticidal effect and a large control spectrum, especially having a good control effect on piercing-sucking mouthparts pests such as tomato whitefly.

[0024] The solvent provided in the embodiment of the present invention is one or more of dimethyl phthalate, dibutyl phthalate, ethyl acetate, methyl benzoate, acetone, alkyl pyrrolidone, ethanol, isopropyl alcohol, and isobutyl alcohol.

[0025] The emulsifier is one or more of Nongru 500# (calcium dodecylbenzenesulfonate), Nongru 700# (alkylphenol formaldehyde resin polyoxyethylene ether), Nongru 2201# (agricultural emulsifier 2201), Span-60# (Span 60), emulsifier T-60, octylphenol polyoxyethylene ether, Nongru 1601# (triphenethylphenol polyoxypropylene polyoxyethylene block polymer), Nongru 600# (styrylphenol polyoxyethylene ether), and Nongru 400# (benzyldimethylphenol polyoxyethylene ether).

[0026] The vegetable oil methyl ester is one or more of palm oil methyl ester, coconut oil methyl ester, soybean oil methyl ester and methyl oleate.

[0027] It should be noted that the insecticide composition provided by the present invention is used to control crop pests including, but not limited to, piercing-sucking pests such as the tomato whitefly. However, the insecticide composition is more effective against piercing-sucking pests such as the tomato whitefly. Furthermore, the insecticide composition does not affect the normal growth of the plants.

[0028] The insecticide composition is a liquid preparation, preferably a dispersible liquid. It should be noted that a dispersible liquid is a liquid preparation, which refers to a raw medicine that is insoluble or not easily soluble in water and is dissolved in a solvent. It is supplemented with necessary auxiliary agents so that the raw medicine separated out from the solvent due to water is uniformly dispersed in water in the form of very small particles. It is similar to the solid-liquid dispersion system of a suspension after dilution with water, but can maintain a single-phase state before dilution, thereby improving the stability of the preparation and reducing processing costs. In addition, for different considerations of technical personnel, other ingredients such as film-forming agents, thickeners, lubricants, etc. may also be contained in the dispersible liquid, and these additives may not dissolve but be dispersed in the solvent. Although the embodiments of the present invention only list dispersible liquids, it is understandable that other types of liquid preparations are also within the scope of protection of the embodiments of the present invention.

[0029] The features and performance of the present invention are further described in detail below with reference to specific embodiments.

[0030] Example 1

[0031] An embodiment of the present invention provides an insecticidal composition, wherein the active ingredients of the insecticidal composition are D-limonene and methoprene, and the mass ratio of D-limonene to methoprene is 1:5.

[0032] Specifically, the insecticide composition has the following components by mass percentage:

[0033] Table 1 Dosage ratio of each component in the insecticide composition

[0034] Ingredient name content(%) D-limonene 1 Mefenamic acid 5 Alkyl pyrrolidone 3 acetone 9 Agricultural milk 700# 2 Agricultural milk 2201# 2 Coconut oil methyl ester 78

[0035] Example 2

[0036] An embodiment of the present invention provides an insecticidal composition, wherein the active ingredients of the insecticidal composition are D-limonene and methoprenaline, and the mass ratio of D-limonene to methoprenaline is 2:5.

[0037] Specifically, the insecticide composition has the following components by mass percentage:

[0038] Table 2 Dosage ratio of each component in the insecticide composition

[0039]

[0040]

[0041] Example 3

[0042] An embodiment of the present invention provides an insecticidal composition, wherein the active ingredients of the insecticidal composition are D-limonene and methoprene, and the mass ratio of D-limonene to methoprene is 1:10.

[0043] Specifically, the insecticide composition has the following components by mass percentage:

[0044] Table 3 Dosage ratio of each component in the insecticide composition

[0045] Ingredient name content(%) D-limonene 1 Mefenamic acid 10 Alkyl pyrrolidone 4 acetone 12 Agricultural milk 700# 6 Agricultural milk 2201# 5 Coconut oil methyl ester 62

[0046] Example 4

[0047] An embodiment of the present invention provides an insecticidal composition, wherein the active ingredients of the insecticidal composition are D-limonene and methoprene, and the mass ratio of D-limonene to methoprene is 1:15.

[0048] Specifically, the insecticide composition has the following components by mass percentage:

[0049] Table 4 Dosage ratio of each component in the insecticide composition

[0050]

[0051]

[0052] Example 5

[0053] An embodiment of the present invention provides an insecticidal composition, wherein the active ingredients of the insecticidal composition are D-limonene and thiamethoxam, and the mass ratio of D-limonene to thiamethoxam is 2:15.

[0054] Specifically, the insecticide composition has the following components by mass percentage:

[0055] Table 5 Dosage ratio of each component in the insecticide composition

[0056] Ingredient name content(%) D-limonene 2 Mefenamic acid 15 Alkyl pyrrolidone 5.5 acetone 15 Agricultural milk 700# 8 Agricultural milk 2201# 5 Coconut oil methyl ester 49.5

[0057] Example 6

[0058] An embodiment of the present invention provides an insecticidal composition, wherein the active ingredients of the insecticidal composition are D-limonene and methoprene, and the mass ratio of D-limonene to methoprene is 1:20.

[0059] Specifically, the insecticide composition has the following components by mass percentage:

[0060] Table 6 Dosage ratio of each component in the insecticide composition

[0061] Ingredient name content(%) D-limonene 1 Mefenamic acid 20 Alkyl pyrrolidone 6 acetone 14 Agricultural milk 700# 6 Agricultural milk 2201# 6 Coconut oil methyl ester 47

[0062] The insecticide compositions provided in the above examples were used in the following experimental examples to verify the thermal storage decomposition rate, dispersion stability, biological activity and efficacy of the insecticide compositions.

[0063] Experimental Example 1 Dispersion Stability and Thermal Storage Decomposition Rate Test

[0064] The insecticide compositions provided in the above examples were prepared into dispersible liquids, and experiments were carried out according to the following method.

[0065] The dispersion stability test method is as follows: prepare a dispersion according to the specified concentration, place it in two scaled emulsification tubes respectively, let it stand upright for a period of time, then turn the emulsification tube upside down several times, and observe the dispersibility of the dispersion at the beginning, after a certain period of time and after re-dispersion. The test results are qualified if they meet the requirements in Table 7.

[0066] Table 7 Dispersion stability standards

[0067]

[0068] The thermal storage decomposition rate test is based on the "GB / T19136-2021 Pesticide Thermal Storage Stability Determination Method." Specifically, the sample is sealed in a glass bottle and stored in a constant temperature oven at 54°C ± 2°C for 14 days. The sample is then removed, placed in a desiccator, and cooled to room temperature. Determination of the active ingredient mass fraction and other required parameters is completed within 24 hours. The decomposition rate must be less than 5%, and the dispersion rate in water must be rapid. Both dilution stability and dispersion stability must meet the test.

[0069] The results of the dispersion stability and thermal storage decomposition rate tests are shown in Table 8:

[0070] Table 8 Dispersion stability and thermal storage decomposition rate of D-limonene and anthracene in different proportions of solvent and additive systems

[0071] Source of medicine Dispersion stability Heat storage decomposition rate Example 1 qualified 3.12％ Example 2 qualified 4.11％ Example 3 qualified 2.54％ Example 4 qualified 3.51％ Example 5 qualified 2.84％ Example 6 qualified 4.32％

[0072] It can be seen from the data in Table 8 that the dispersible liquids prepared by the formulations of Examples 1 to 6 meet the requirements of the quality standards; in addition, the solvents and emulsifiers used are cheap, readily available, safe and environmentally friendly.

[0073] Experimental Example 2 Biological Activity Test

[0074] According to the guidelines for indoor pesticide bioassays (NY / T1154.16-2013 and NY / T1154.7-2006), the effects of D-limonene, methipram and their mixtures at different mass ratios on Bemisia tabaci were determined to screen the optimal mixing ratio of the two insecticides.

[0075] A. Tomato whitefly Bemisia tabaci (Gennadius) was provided by the College of Plant Medicine, Qingdao Agricultural University.

[0076] B. The test agents were 93% D-limonene (purchased from Qingdao Rishengyuan Crop Nutrition Co., Ltd.) and 90% anthracenesulfonamide technical (provided by Shanghai Hulian Biopharmaceutical (Xiayi) Co., Ltd.).

[0077] The mixing ratios of C, D-limonene and anthracene are 1:5, 2:5, 1:10, 1:15, 2:15 and 1:20 (corresponding to Examples 1 to 6, respectively). The prepared concentrations are shown in Table 9:

[0078] Table 9 The dosage ratio of each substance in the insecticide composition

[0079]

[0080] D. Toxicity test method

[0081] Prepare 15 g / L agar with distilled water. Use a pipette to transfer 2 ml of liquid agar to a 2 cm diameter, 8 cm long flat-bottomed test tube. Use a hole punch to create leaf discs from fresh tomato leaves. Soak the discs in various concentrations of the test agent for 10 seconds, remove the discs, and spread them flat on the agar-lined test tubes. Inoculate each tube with 20 third-instar whiteflies (Bemisia tabaci) nymphs. The tubes are maintained at 25 ± 1°C, 60%-80% humidity, and a 14:8 h photoperiod. Four replicates are set for each treatment. After 48 hours, count the number of whiteflies that have died, and calculate the mortality rate or adjusted mortality rate. The average mortality rate of the four replicates is converted to a probability value, and the agent concentration is converted to a logarithm. The toxicity index of each agent and the co-toxicity coefficient of the mixture are then calculated using the Sun Yunpei method.

[0082]

[0083]

[0084] If the mortality rate of the control drug is <5%, no correction is required. If the mortality rate is between 5% and 20%, correction is performed according to Formula 2. If the mortality rate is >20%, the test is repeated.

[0085] DPS statistical software was used to perform regression analysis on the logarithmic values of treatment concentrations of each single agent and different ratios of mixed combinations and the corresponding inhibition rate probability values, and the toxicity regression curve and LC were calculated. 50 The co-toxicity coefficient (CTC value) of the mixture was calculated according to the Sun Yunpei method.

[0086] The co-toxicity coefficient (CTC value) of the mixture is calculated according to formula (3), formula (4), and formula (5):

[0087]

[0088] Where: ATI—measured toxicity index of mixture;

[0089] S—LC of standard pesticide 50 , the unit is milligrams per liter (mg / L);

[0090] M—LC of the mixture 50 , the unit is milligrams per liter (mg / L).

[0091] TTI=A×P A +B×P A (4)

[0092] Where: TTI—theoretical toxicity index of mixture;

[0093] A—Agent toxicity index;

[0094] P A —The percentage of agent A in the mixture, expressed as percentage (%);

[0095] B—B agent toxicity index;

[0096] P B —The percentage of agent B in the mixture, in percentage (%).

[0097]

[0098] Where: CTC—co-toxicity coefficient; ATI—measured toxicity index of mixture; TTI—theoretical toxicity index of mixture.

[0099] A co-toxicity coefficient (CTC) of the combination ≥120 indicates a synergistic effect; CTC ≤80 indicates an antagonistic effect; and 80 < CTC <120 indicates an additive effect.

[0100] E. The test results are shown in Table 10:

[0101] Table 10 Results of the combined toxicity test of D-limonene and anthracene to Bemisia tabaci

[0102]

[0103] As can be seen from Table 10, in the 6 kinds of ratios of D-limonene: thiamethoxam = 1:5, 2:5, 1:10, 1:15, 2:15, 1:20, the co-toxicity coefficient (CTC) was 144.99, 151.21, 119.15, 125.50, 154.17, 112.33, respectively. It can be seen that D-limonene and thiamethoxam showed a synergistic effect when the ratio was 1:5, 2:5, 1:15, 2:15, and an additive effect was shown when the ratio was 1:10 and 1:20. Among them, the synergistic effect of D-limonene and thiamethoxam corresponding to Example 5 was the best when the ratio was 2:15.

[0104] Experimental Example 3 Field efficacy test

[0105] Field efficacy test 1: The insecticide composition provided in Example 5 was used to control tomato whiteflies in the field. The test agents are shown in Table 11 below:

[0106] Table 11 Dosage of each drug tested

[0107]

[0108] 1 Test method

[0109] The experimental field, covering 2 mu (approximately 1.2 acres), was located in Guojiazhuang Village, Jimo District, Qingdao City (36.467832°N, 120.4412°E). The soil pH was 6.4 and the organic matter content was 1.8%. Tomatoes, a cultivar of the Base Fenwang variety, were used. Seedlings were raised on June 10, 2022, and transplanted manually on July 6, 2022. Approximately 3,000 plants were planted per mu (approximately 1.2 acres) with a plant spacing of 30 cm and a row spacing of 50 cm. Land preparation was completed on July 5, 2022, and 30 kg of compound fertilizer (15-15-15) was used per mu (approximately 1.2 acres) as base fertilizer.

[0110] Cultivation and management conditions were consistent with local agricultural practices. The test target was the tomato whitefly (Bemisia tabaci). The pesticide was applied using a conventional spray method, applied once during the initial infestation phase. This trial used the pesticide once in total.

[0111] A commonly used pressure storage manual sprayer (commercially available) was used for spraying the liquid medicine, with an adjustable conical nozzle, a pressure of 0.3 MPa, a spraying speed of 0.6 L / min, and a liquid medicine usage of 600 L per hectare.

[0112] 1.1 Survey duration and frequency

[0113] First survey: survey insect population base before applying pesticides;

[0114] Second survey: 3 days after the drug was administered to investigate safety and the number of remaining live worms;

[0115] The third survey: 7 days after the drug was administered to investigate safety and the number of remaining live worms;

[0116] Fourth survey: Safety and number of remaining live worms were investigated 10 days after administration.

[0117] A total of 4 surveys were conducted.

[0118] 1.2 Survey Methods

[0119] Investigation of control effectiveness: Ten tomato plants were randomly selected in each plot, and the number of live whitefly adults on each plant was investigated in the morning when the adults were inactive.

[0120] 1.3 Calculation method of drug efficacy

[0121]

[0122]

[0123] 2 Test results

[0124] The control effects of different pesticides on tomato whiteflies are shown in Table 12 below.

[0125] Table 12 Control effects of different pesticides on tomato whiteflies

[0126]

[0127] As shown in the table above, the insecticide composition provided in Example 5 achieved the best control efficacy at a dosage of 30 mL / mu, achieving a control efficacy of 92.05% 10 days after application, significantly superior to the control alone. Field observations showed that both the test and control formulations were safe for the test tomato crop, with no signs of phytotoxicity (such as stunting, chlorosis, and deformities) observed.

[0128] At this point, those skilled in the art will recognize that, although a number of exemplary embodiments of the present invention have been shown and described in detail herein, many other variations or modifications consistent with the principles of the present invention may be directly determined or derived from the disclosure of the present invention without departing from the spirit and scope of the present invention. Therefore, the scope of the present invention should be understood and deemed to cover all such other variations or modifications.

Claims

1. An insecticidal composition containing methipamide and D-limonene, characterized in that: The insecticide composition comprises active ingredients, wherein the active ingredients are thiamethoxam and D-limonene, and the mass ratios of the D-limonene to the thiamethoxam are 2:5-2:15 and 1:

15.

2. The insecticidal composition containing methoprene and D-limonene according to claim 1, characterized in that The mass ratio of the D-limonene to the anthracene is 2:

15.

3. The insecticidal composition containing methoprene and D-limonene according to claim 1, wherein The ratio of the mass of the D-limonene to the mass of the insecticidal composition is 2%; the ratio of the mass of the thiamethoxam to the mass of the insecticidal composition is 15%.

4. The insecticidal composition containing methoprene and D-limonene according to claim 1, wherein The insecticide composition further comprises the following substances by mass percentage: 12-20.5% of a solvent, 4-13% of an emulsifier, and the balance being vegetable oil methyl ester; the vegetable oil methyl ester is prepared by modifying vegetable oil through methyl esterification.

5. The insecticidal composition containing methoprene and D-limonene according to any one of claims 1 to 4, characterized in that The formulation of the insecticide composition is a liquid preparation; the liquid preparation at least includes a dispersible liquid.

6. Use of the insecticidal composition containing methoprene and D-limonene according to any one of claims 1 to 4 in the preparation of a medicament for controlling piercing-sucking mouthparts pests, characterized in that: The piercing-sucking mouthparts pest is tomato whitefly.

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