CN117099787A - Insecticidal composition containing oxazine amide and D-limonene and application thereof - Google Patents

Abstract

The invention discloses a pesticidal composition containing acetamiprid and D-limonene and its application. The pesticidal composition includes active ingredients, and the active ingredients are acetamiprid and D-limonene, and the The mass ratio of D-limonene and the tebuconazole is 1:50 to 50:1. Due to the compounding of D-limonene and tebuconazole, the two can produce a synergistic effect, thereby making the formed insecticidal composition have good insecticidal effect and a large control spectrum, especially for tomato tobacco. It has good control effect on sucking pests such as mealybugs. In addition, D-limonene is a plant-derived compound. The combination of the two will not produce resistance and can also delay the development of resistance to other chemical agents. The insecticidal composition has extremely low side effects and will not affect crop safety and yield. Therefore, it can solve the problem of difficult control of piercing-sucking mouthpart pests such as tomato whitefly and achieve good insecticidal effect.

Description

A kind of insecticidal composition containing acetamiprid and D-limonene and its application

Technical field

The present invention relates to the technical field of pesticides, specifically an insecticidal composition containing acetamiprid and D-limonene and its application.

Background technique

Bemisia tabaci (Gennadius), whose scientific name is Bemisia tabaci (Gennadius), belongs to the order Hemiptera and the family Aleyrodidae. Bemisia tabaci is one of the most harmful invasive species in the world. Bemisia tabaci directly sucks plant sap, causing plant weakness. The nymphs and adults also secrete honeydew, inducing sooty stains on plants. When the density of sooty stains is high, Plant leaves appear black, seriously affecting plant photosynthesis. In addition, Bemisia tabaci can spread more than 70 kinds of viral diseases on more than 30 crops, spreading different viruses to different biotypes and causing different harm symptoms to different plants.

D-limonene (D-limonene), molecular formula: C ₁₀ H ₁₆ , D-limonene is orange oil extracted from orange peels using professional cold-pressing technology. It is a natural plant-derived pesticide and has a unique physical contact mode of action against pests. It has no cross-resistance with commonly used chemical pesticides. The insecticidal mechanism is to dissolve the waxy layer on the surface of the pests, causing the pests to quickly knock down and die in an obvious state of dehydration.

Trimethonazole is a pyrazole amide compound. Its English common name is dimpropyridaz; trade name: 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 N ₅ O; The structural formula is as follows:

Trimethonazole products have excellent performance and good systemic conductivity. Mainly suitable for field crops such as fruit trees and vegetables, soybeans, other leguminous plants, cotton, cereals, potatoes, as well as flowers and ornamental plants. Tribeconazole products are used to control Lepidoptera (Stem borer, Spodoptera exigua, Diamondback moth, Spodoptera frugiperda, etc.), Coleoptera (beetles, corn root leaf beetles, potato leaf beetles, and yellow cabbage flea beetles). etc.), Diptera (flies, mosquitoes, vegetable leafminers, etc.), Hemiptera (aphids, planthoppers, psyllids, whiteflies, etc.), Thysanoptera (thrips, orchid thrips, palm thrips, Nicotiana tabaci, etc.), Isoptera (termites, etc.), cockroaches, ants and other pests, especially effective against aphids, whiteflies, thrips and other sucking mouthparts pests.

Because tomato whitefly and other piercing-sucking mouthparts pests reproduce quickly, are difficult to control, cause serious harm, and are prone to develop resistance. Currently, commonly used control chemicals all have a certain degree of resistance, making them difficult to control. . There has been no in-depth study on the activity of D-limonene and acetamiprid against piercing-sucking mouthpart pests such as tomato Bemisia tabaci, and there has been no report on the combination of D-limonene and acetamiprid for controlling tomato Bemisia tabaci.

Contents of the invention

In view of the above problems, the present invention provides an insecticidal composition containing acetamiprid and D-limonene that overcomes the above problems or at least partially solves the above problems and its application, which can solve the problem of sucking mouthworms such as tomato whitefly. It solves the problem of difficult pest control and achieves good insecticidal effect.

Specifically, the present invention provides a pesticidal composition of acetamiprid and D-limonene. The pesticidal composition includes active ingredients. The active ingredients are acetamiprid and D-limonene, and the D -The mass ratio of limonene and the tebuconazole is 1:50 to 50:1.

Optionally, the mass ratio of the D-limonene and the acetamiprid is 1:20 to 20:1

Optionally, the mass ratio of the D-limonene and the acetamiprid is 2:15.

Optionally, the ratio of the mass of D-limonene to the mass of the insecticidal composition is 1-50%.

Optionally, the ratio of the mass of the tebuconazole to the mass of the insecticidal composition is 1-50%.

Optionally, the ratio of the mass of D-limonene to the mass of the insecticidal composition is 2%; the ratio of the mass of tebuconazole to the mass of the insecticidal composition is 15%.

Optionally, the pesticidal composition also includes the following substances in terms of mass percentage: 12-20.5% solvent, 4-13% emulsifier, and the balance is vegetable oil methyl ester; the vegetable oil methyl ester is vegetable oil methyl ester. It is prepared by methyl esterification modification method.

Optionally, the dosage form of the insecticidal composition is a liquid formulation.

Optionally, the dosage form of the insecticidal composition is a dispersible liquid.

The present disclosure also provides the use of the aforementioned insecticidal composition in the preparation of medicaments for preventing and controlling sucking mouthpart pests.

Optionally, the sucking mouthpart pests include at least tomato whitefly.

The beneficial effects of the present invention are:

In the insecticidal composition containing tebuconazole and D-limonene provided by the present invention, due to the compounding of D-limonene and cebupromide, the two can produce a synergistic effect, thereby forming a pesticide combination. The chemical has good insecticidal effect and has a large control spectrum, especially for tomato whitefly and other piercing-sucking mouthpart pests. In addition, D-limonene is a plant-derived compound. The combination of the two will not produce resistance and can also delay the development of resistance to other chemical agents. The insecticidal composition has extremely low side effects and will not affect crop safety and yield. Therefore, it can solve the problem of difficult control of piercing-sucking mouthpart pests such as tomato whitefly and achieve good insecticidal effect.

Detailed ways

In order to make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described clearly and completely below. If no specific conditions are specified in the examples, the conditions should be carried out according to conventional conditions in the prior art or according to the conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not indicated, they are all conventional products that can be purchased commercially.

The active ingredients in the insecticidal composition provided by the invention are composed of D-limonene and acetamiprid. In the embodiment of the present invention, D-limonene and methylpyridoxamide are specifically selected for compounding. When the insecticidal composition of the present invention is used to prevent and control sucking mouthpart pests, the mass ratio of D-limonene and methylpyridoxamide 1:50, 1:25, 1:20, 1:15, 1:10, 1:5, 2:5, 2:15, 1:1, 2:15, 10:1, 20:1, 50 : 1. The two can produce a synergistic effect, so that the formed insecticidal composition has good insecticidal effect and has a large control spectrum, especially for sucking mouthworms such as tomato whitefly. It has good control effect on organ pests.

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

The emulsifiers are Nongru 500# (calcium dodecyl benzene sulfonate), Nongru 700# (alkyl phenol formaldehyde resin polyoxyethylene ether), Nongru 2201# (agricultural emulsifier 2201), Span-60# ( Span 60), emulsifier T-60, octylphenol polyoxyethylene ether, Nongru 1601# (triphenylethylphenol polyoxypropylene polyoxyethylene block polymer), Nongru 600# (styrylphenol polyoxyethylene block polymer) One or more of oxyethylene ether) and agricultural milk 400# (benzyl dimethylphenol polyoxyethylene ether).

Vegetable oil methyl ester is one or more of palm oil methyl ester, coconut oil methyl ester, soybean oil methyl ester, and oleic acid methyl ester.

It should be noted that the insecticidal composition provided by the present invention is used to prevent and control crop pests, including but not limited to piercing-sucking mouthpart pests such as tomato Bemisia tabaci. The control effect of mouthpart pests is better. In addition, the insecticidal composition will not affect the normal growth of plants.

The insecticidal composition is a liquid preparation, preferably a dispersible liquid preparation. It should be noted that the dispersible liquid preparation is a liquid preparation, which means that the original drug that is insoluble or not easily soluble in water is dissolved in a solvent, supplemented by necessary The additives make the original drug precipitated from the solvent due to watering evenly dispersed in the water in the form of extremely small particles. After being diluted with water, it is similar to the solid-liquid dispersion system of a suspension agent, but it can maintain a single-phase state before being diluted with water, improving the stability of the preparation and reducing processing costs. In addition, due to different considerations of technicians, the dispersible liquid agent may also contain other ingredients, such as film-forming agents, thickeners, lubricants, etc., and these additives may not be dissolved but dispersed in the solvent. Although the embodiments of the present invention only illustrate dispersible liquid preparations, it can be understood that other types of liquid preparations are also within the protection scope of the embodiments of the present invention.

The features and performance of the present invention will be described in further detail below with reference to specific embodiments.

Example 1

The embodiment of the present invention provides an insecticidal composition. The active ingredients of the insecticidal composition are D-limonene and methylpyridamid, and the mass ratio of D-limonene and methylpyridamid is 1:5.

Specifically, the ingredients of the insecticidal composition are as shown in Table 1 in terms of mass percentage:

Table 1 The dosage ratio of each component in the insecticidal composition

Ingredient name content(%) D-limonene 1 Acetamiprid 5 Alkyl pyrrolidone 3 acetone 9 Farm milk 700# 2 Nongru 2201# 2 coconut oil methyl ester 78

Example 2

The embodiment of the present invention provides an insecticidal composition. The active ingredients of the insecticidal composition are D-limonene and methylpyridamid, and the mass ratio of D-limonene and methylpyridamid is 2:5.

Specifically, the ingredients of the insecticidal composition are as shown in Table 2 in terms of mass percentage:

Table 2 The dosage ratio of each component in the insecticidal composition

Example 3

The embodiment of the present invention provides an insecticidal composition. The active ingredients of the insecticidal composition are D-limonene and acetamiprid, and the mass ratio of D-limonene and acetamiprid is 1:10.

Specifically, the ingredients of the insecticidal composition are as shown in Table 3 in terms of mass percentage:

Table 3 The dosage ratio of each component in the insecticidal composition

Ingredient name content(%) D-limonene 1 Acetamiprid 10 Alkyl pyrrolidone 4 acetone 12 Farm milk 700# 6 Nongru 2201# 5 coconut oil methyl ester 62

Example 4

The embodiment of the present invention provides an insecticidal composition. The active ingredients of the insecticidal composition are D-limonene and acetamiprid, and the mass ratio of D-limonene to acetamiprid is 1:15.

Specifically, the ingredients of the insecticidal composition are as shown in Table 4 in terms of mass percentage:

Table 4 The dosage ratio of each component in the insecticidal composition

Example 5

The embodiment of the present invention provides an insecticidal composition. The active ingredients of the insecticidal composition are D-limonene and acetamiprid, and the mass ratio of D-limonene and acetamiprid is 2:15.

Specifically, the ingredients of the insecticidal composition are as shown in Table 5 in terms of mass percentage:

Table 5 The dosage ratio of each component in the insecticidal composition

Ingredient name content(%) D-limonene 2 Acetamiprid 15 Alkyl pyrrolidone 5.5 acetone 15 Farm milk 700# 8 Nongru 2201# 5 coconut oil methyl ester 49.5

Example 6

Embodiments of the present invention provide a pesticidal composition. The active ingredients of the pesticidal composition are D-limonene and methylpyridamid, and the mass ratio of D-limonene and methylpyridamid is 1:20.

Specifically, the ingredients of the insecticidal composition are as shown in Table 6 in terms of mass percentage:

Table 6 The dosage ratio of each component in the insecticidal composition

Ingredient name content(%) D-limonene 1 Acetamiprid 20 Alkyl pyrrolidone 6 acetone 14 Farm milk 700# 6 Nongru 2201# 6 coconut oil methyl ester 47

The insecticidal composition provided in the above examples was used in the following experimental examples to verify the thermal storage decomposition rate, dispersion stability, biological activity and efficacy of the insecticidal composition.

Experimental Example 1 Dispersion Stability and Heat Storage Decomposition Rate Test

The insecticidal composition provided in the above examples was prepared into a dispersible liquid formulation, and the experiment was conducted according to the following method.

The dispersion stability test method is: prepare the dispersion according to the specified concentration, place it in two-scale emulsification tubes, let it stand upright for a period of time, then invert the emulsification tube several times, and observe the dispersion of the dispersion initially, after being left for a certain period of time and after redispersion. If the test result meets the requirements in Table 7, it is qualified.

Table 7 Dispersion stability standards

The thermal storage decomposition rate test is based on "GB/T19136-2021 Determination Method for Pesticide Thermal Storage Stability". The specific steps are: place the sample in a glass bottle and seal it, store it in a thermostat at 54°C ± 2°C for 14 days, take it out, and put it in In a desiccator, cool to room temperature. The determination of the mass fraction of active ingredients and other specified items is completed within 24 hours, the decomposition rate is less than 5%, and the dispersion speed into water is fast; the dilution stability and dispersion stability are both qualified.

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

Table 8 Dispersion stability and thermal storage decomposition rate of D-limonene and stribuproyl in different proportions of solvent and additive systems

Potion source 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%

It can be seen from the data in Table 8 that the dispersible liquid preparations prepared from the formulas of Examples 1 to 6 meet the requirements of the quality standards; in addition, the solvents and emulsifiers used are cheap, easy to obtain, safe and environmentally friendly.

Experimental Example 2 Biological Activity Test

According to the pesticide indoor bioassay test guidelines NY/T1154.16-2013 and NY/T1154.7-2006, the effects of D-limonene, acetamiprid and their different mass ratios on tomato Bemisia tabaci were screened. The optimal mixture mass ratio of pesticides.

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

B. The test chemicals are 93% D-limonene (purchased from Qingdao Rishengyuan Crop Nutrition Co., Ltd.) and 90% acetamiprid active drug (provided by Shanghai Hulian Biopharmaceutical (Xiayi) Co., Ltd.).

The mixing ratio of C, D-limonene: tebuconazole is: 1:5, 2:5, 1:10, 1:15, 2:15, 1:20 (corresponding to Examples 1 to 6 respectively ) The preparation concentration is shown in Table 9:

Table 9 The dosage ratio of each substance in the insecticidal composition

D. Toxicity test method

Prepare 15g/L agar with distilled water. Use a pipette to transfer 2 ml of liquid agar into a flat-bottomed test tube with a diameter of 2 cm and a length of 8 cm. Use a hole punch to make fresh tomato leaves into leaf discs. Soak in the agent to be tested for 10 seconds, take it out, and lay it flat in a test tube covered with agar. Insert 20 3-year-old Bemisia tabaci nymphs into each test tube, and set the test tube to 25±1°C and a humidity of 60%-80%. , reared under the conditions of photoperiod 14h:8h, with 4 repetitions for each treatment. After 48 hours, the number of deaths of whiteflies was counted, and the mortality rate or calibrated mortality rate was calculated. The average mortality rate of the four replicates was converted into a probability value, and the agent concentration was converted into a logarithmic value. Then the toxicity index of each agent and the co-toxicity coefficient of the mixture were calculated according to Sun Yunpei's method.

If the mortality rate of the control agent is <5%, no correction is required. If the mortality rate is between 5% and 20%, correction shall be made according to Equation 2. If the mortality rate is >20%, the test will be repeated.

Use DPS statistical software to conduct regression analysis on the logarithmic value of the treatment concentration and the corresponding inhibition rate probability value of each single agent and different mixture combinations, calculate the toxicity regression curve, LC ₅₀ value, and correlation coefficient, and calculate the mixture according to Sun Yunpei's method co-toxicity coefficient (CTC value).

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

In the formula: ATI—the measured toxicity index of the mixture;

S—LC ₅₀ of standard pesticide, in milligrams per liter (mg/L);

M—LC ₅₀ of the mixture, in milligrams per liter (mg/L).

TTI＝A×P _A +B×P _A (4)

In the formula: TTI—theoretical toxicity index of the mixture;

A-A agent toxicity index;

P _A —The percentage content of agent A in the mixture, the unit is percentage (%);

B—B agent toxicity index;

P _B —The percentage content of B agent in the mixture, the unit is percentage (%).

In the formula: CTC - co-toxicity coefficient; ATI - measured toxicity index of the mixture; TTI - theoretical toxicity index of the mixture.

The co-toxicity coefficient (CTC) of the compound combination ≥120 indicates synergistic effect; CTC≤80 indicates antagonism; 80＜CTC＜120 indicates additive effect.

E. The test results are shown in Table 10:

Table 10D-Results of combined toxicity test of limonene and acetamiprid against tomato Bemisia tabaci

It can be seen from Table 10 that when the six mixing ratios of D-limonene:acetamiprid = 1:5, 2:5, 1:10, 1:15, 2:15, and 1:20, the total The toxicity coefficients (CTC) are 144.99, 151.21, 119.15, 125.50, 154.17, and 112.33 respectively. It can be seen that the ratios of D-limonene and acetamiprid are 1:5, 2:5, 1:15, and 2:15. It shows a synergistic effect and shows an additive effect when the ratio is 1:10 or 1:20. Among them, the synergistic effect is the best when the ratio of D-limonene and tebuconazole corresponding to Example 5 is 2:15.

Experimental Example 3 Field Efficacy Test

Field efficacy test 1: Apply the insecticidal composition provided in Example 5 for field control of tomato whitefly. The test chemicals are shown in Table 11 below:

Table 11 Dosage table for each pharmaceutical test

1Test method

Guojiazhuang Village, Jimo District, Qingdao City (36.467832 north latitude, 120.4412 east longitude), the experimental field covers an area of 2 acres, the soil pH value is 6.4, and the organic matter content is 1.8%. The test crops are tomatoes, base powder king, seedlings were raised on June 10, 2022, and manually transplanted on July 6, 2022, with about 3,000 plants per mu, plant spacing 30cm, and row spacing 50cm; land preparation was carried out on July 5, 2022, and each mu was used 30kg of compound fertilizer (15-15-15) is used as base fertilizer.

Cultivation and management conditions are in line with local agricultural production practices. The test target is tomato whitefly. The pesticide application method is the conventional spray method. The pesticide is applied once in the early stage of occurrence of whitefly on tomato. In this experiment, the pesticide was used once.

Use a commonly used pressure storage manual sprayer (commercially available) to spray the liquid. The adjustable cone-shaped nozzle has a pressure of 0.3MPa, a spray speed of 0.6L/min, and a dosage of 600L of liquid per hectare.

1.1 Investigation time and frequency

The first survey: Pre-medication survey of insect population base;

Second investigation: investigate the safety and number of remaining insects 3 days after treatment;

The third investigation: 7 days after treatment, investigate the safety and the number of remaining live insects;

The fourth investigation: 10 days after treatment, investigate the safety and the number of remaining live insects.

A total of 4 investigations were conducted.

1.2 Survey methods

Investigation of control effect: Randomly calibrate 10 tomato plants in each plot, and investigate the number of live adults of Bemisia tabaci on each plant in the morning when the adults are not active.

1.3 Calculation method of drug efficacy

2 test results

The control effects of different pesticide treatments on tomato whitefly are shown in Table 12 below.

Table 12 Control effects of different pesticide treatments on tomato Bemisia tabaci

According to the above table, it can be seen that the control effect investigation results show that the insecticidal composition preparation provided according to Example 5 has the best control effect when the dosage is 30 mL/acre, and the control effect 10 days after treatment is 92.05%, which is extremely superior. The control effect of a single dose of control agent. After field observation, the above-mentioned test chemicals and control chemicals were safe for the test crop tomatoes, and no symptoms of phytotoxicity (such as dwarfing, chlorosis, deformity, etc.) were found.

By now, those skilled in the art will appreciate that, although a number of exemplary embodiments of the present invention have been shown and described in detail herein, the disclosed embodiments may still be practiced in accordance with the present invention without departing from the spirit and scope of the present invention. The content directly identifies or leads to many other variations or modifications consistent with the principles of the invention. Accordingly, the scope of the present invention should be understood and deemed to cover all such other variations or modifications.

Claims (10)

1. A kind of insecticidal composition containing acetamiprid and D-limonene, it is characterized in that, the insecticidal composition comprises an active ingredient, and the active ingredient is atrimethonazole and D-limonene, and the D -The mass ratio of limonene and the tebuconazole is 1:50 to 50:1. 2. The insecticidal composition containing acetamiprid and D-limonene according to claim 1, characterized in that the mass ratio of the D-limonene and the acetamipram is 1:20 to 20: 1. 3. The insecticidal composition containing acetamiprid and D-limonene according to claim 1, characterized in that the mass ratio of the D-limonene and the acetamipram is 2:15. 4. The insecticidal composition containing acetamiprid and D-limonene according to claim 1, characterized in that the ratio of the mass of the D-limonene to the mass of the insecticidal composition is 1-50 %. 5. The insecticidal composition containing acetamiprid and D-limonene according to claim 1, characterized in that the ratio of the mass of the acetamiprid to the mass of the insecticidal composition is 1- 50%. 6. The insecticidal composition containing acetamiprid and D-limonene according to claim 1, characterized in that 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 tebuconazole to the mass of the insecticidal composition is 15%. 7. The insecticidal composition containing acetamiprid and D-limonene according to claim 1, characterized in that the insecticidal composition further includes the following substances in terms of mass percentage: 12-20.5% solvent , 4-13% emulsifier, and the balance is vegetable oil methyl ester; the vegetable oil methyl ester is prepared from vegetable oil through a methyl esterification modification method. 8. The insecticidal composition containing acetamiprid and D-limonene according to any one of claims 1 to 7, characterized in that the dosage form of the insecticidal composition is a liquid preparation; the liquid preparation is at least Includes dispersible liquid formulations. 9. Application of the insecticidal composition containing oxamid and D-limonene according to any one of claims 1 to 7 in the preparation of medicines for preventing and treating sucking mouthpart pests. 10. The application of the insecticidal composition containing acetamiprid and D-limonene according to claim 9, characterized in that the sucking mouthpart pests at least include tomato whitefly.