Acyloxy or amide pesticide synergist and pesticide composition applying same

Abstract

The molecular structure of the acyloxy or amide pesticide synergist contains medium and long hydrophobic chains C5-C9 to improve hydrophobicity so as to assist in penetrating a barrier, active ingredients can be promoted to penetrate a plant wax coat and an outer protective layer of pests and fungi, and the overall spatial configuration and electron distribution of the synergist molecule are changed through different group structures, so that the synergistic effect of the synergist is improved. According to the synergistic pesticide synergist, the penetration resistance is reduced, permeation is assisted, the binding capacity of the synergist and a target spot is enhanced, amide or acyloxy bonds in the structure have good biocompatibility, adsorption and transmembrane transport of pesticide in the target spot are enhanced, and the synergistic effect of the pesticide synergist is improved through synergism of amide, acyloxy bonds and amide or acyloxy bonds. The pesticide composition prepared from the synergist greatly improves the pesticide effect of the pesticide, can reduce the pesticide dosage, and is beneficial to the environment.

Description

Technical Field

[0001] This invention relates to the field of pesticide synergists, and in particular to an acyloxy or amide pesticide synergist and a pesticide composition using the same. Background Technology

[0002] In pesticide formulations, the efficacy of the active ingredient can often be enhanced by adding appropriate adjuvants. These adjuvants generally achieve synergistic effects through mechanisms such as improving pesticide dispersibility and stability, enhancing pesticide penetration, and improving crop absorption and translocation. For example, US 20050170965(A1) (Rhodia) (WO 03 / 063589 A2, EP1469731A2, US2003 / 0158042, US2004 / 0224846, EP2025230) discloses a surfactant containing betaine and at least one containing tallow amine ethoxylate, which, when combined with active ingredients such as glyphosate, enhances herbicidal activity. However, tallow amine ethoxylate is toxic to aquatic organisms and causes eye irritation. While using commonly used alkyl polyglucosides (APG) to replace tallow amine ethoxylate in glyphosate is environmentally friendly and safe, practical experience has shown that it is actually less effective in enhancing the glyphosate effect.

[0003] Furthermore, the compatibility of added adjuvants with the active ingredients of pesticides needs to be considered. For example, the main application of synergistic amines in the pesticide field is to enhance the efficacy of insecticides, especially when used in combination with pyrethroid insecticides, which can significantly improve the control effect on pests such as cockroaches and body lice. However, its synergistic mechanism mainly lies in inhibiting metabolic enzymes, so its effect as a synergist for glyphosate herbicides is not significant. This invention aims to study a synergist with good synergistic ability, low degradation and irritation, and good compatibility. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides an acyloxy or amide pesticide synergist that can be used in pesticide compositions for weeding, insecticidal, etc., to enhance the efficacy of the active pesticide ingredient.

[0005] The technical solution of this invention is as follows: An acyloxy or amide pesticide synergist, the structural formula of which is as follows: (Equation 1) in: R3 is a C5-C9 alkyl carbon chain; R2 is either N or O; R1 is a group of formula 2 or formula 3. (Equation 2) (Equation 3) In Equation 1, n1 is 1-3, and in Equation 2, n2 is 2-5.

[0006] The pesticide synergist of the present invention enhances the control effect of pesticides through the synergistic effect of R1, R2, and R3 in its molecular structure.

[0007] Generally, as the length of the alkyl carbon chain increases, the hydrophobicity and lipophilicity of the molecule increase. However, if the carbon chain is too short, the hydrophobic effect is weak and the penetration is poor, while if the carbon chain is too long, it is prone to forming hydrophobic bonds and aggregation, reducing dispersibility, both of which affect the penetration effect. Therefore, appropriate hydrophobicity and lipophilicity are crucial for synergists to exert their synergistic effect. In this synergist structure, R3 is a C5-C9 alkyl carbon chain, which allows the synergist to more easily penetrate hydrophobic barriers such as the epidermal wax layer of pests and the cell walls of pathogens, creating conditions for subsequent pesticides to enter the target area. This allows it to better reach the target site with the pesticide, increasing the pesticide concentration at the target site and enhancing the control effect. R2 is N or O, which determines whether the synergist molecule is an amide (R2 is N) or an acyloxy (R2 is O). R2 (N or O) has a lone pair of electrons, which can participate in the formation of hydrogen bonds and other interactions. This interaction can further adjust the behavior of the synergist molecule within the barrier, thus working in conjunction with the effects of R3 and R1 to jointly promote the penetration of the synergist and pesticide molecules. Moreover, when interacting with pesticide molecules or target biomolecules, R2 can bind to the polar groups of other molecules through hydrogen bonds, affecting the recognition and binding ability between molecules, thereby regulating the synergist's enhancing effect on pesticide activity and its effect on target organisms. R1 has formula 2 or formula 3. Two different group structures, and n2 in Formula 2 is 2-5. The different group structures and the change in the value of n2 will change the spatial configuration and electronic distribution of the entire synergist molecule. This change helps the synergist molecule to better adapt to the structural characteristics of the barrier when penetrating the hydrophobic barrier, and to interact with the molecules in the barrier at a more suitable angle and in a more appropriate manner. This enhances the binding ability of the synergist to the target site, thereby reducing the penetration resistance. It can specifically bind to different parts of the target site. This binding can change the structure or function of the target site, making it more sensitive to pesticide molecules, thereby improving the biological activity of the pesticide.

[0008] The alkyl carbon chain of the present invention is preferably derived from vegetable oils. Vegetable oil carbon chains are green and renewable raw materials, and have certain chemical stability and biocompatibility.

[0009] The pesticide composition formulated with the synergist of the present invention can effectively improve the efficacy of herbicides, fungicides, or insecticides.

[0010] In a preferred embodiment, the prepared pesticide composition includes the pesticide active ingredient and the synergist. When the content of the synergist is 0.1 to 20 parts by weight, it has a good synergistic effect compared with the efficacy of a single pesticide active ingredient.

[0011] In a preferred embodiment, the formulated herbicidal composition comprises, by weight, 30 parts glyphosate isopropylamine salt and 3 to 5 parts of the synergist.

[0012] In a preferred embodiment, the formulated insecticidal composition comprises, by weight, 10 parts imidacloprid and 3-5 parts of the synergist. The synergist of the present invention is prepared by oxidative reaction of acyl chloride with hydroxyl group or by amidation reaction of acyl chloride with amino group.

[0013] Compared with the prior art, the present invention has at least the following advantages: 1. The pesticide synergist of the present invention preferably has a long hydrophobic chain C5-C9 in R3 to improve hydrophobicity and facilitate penetration of the barrier, which can promote the penetration of active ingredients into the plant wax layer, the outer protective layer of pests and fungi. At the same time, the R1 structure changes the overall spatial configuration and electronic distribution of the synergist molecule, which synergistically enables the synergist molecule to better adapt to the structural characteristics of the barrier when penetrating the hydrophobic barrier, and specifically bind to different parts of the target, reducing penetration resistance, assisting penetration and enhancing the binding ability of the synergist to the target. The amide or acyl oxygen bond in the structure has good biocompatibility, which enhances the adsorption and transmembrane transport of pesticides within the target. The three factors work synergistically to improve the synergistic effect of the pesticide synergist.

[0014] 2. The pesticide synergist of the present invention has excellent degradation ability and is environmentally friendly.

[0015] 3. The pesticide compositions formulated with the pesticide synergists of the present invention greatly improve the efficacy of pesticides. For example, the 30wt% glyphosate isopropylamine salt herbicidal composition has a maximum fresh weight inhibition rate of up to 97.1% against 3-leaf stage foxtail grass, and the 10% imidacloprid insecticidal composition has a maximum mortality rate of 98% for cotton aphids after 48 hours. Therefore, the use of pesticide synergists of the present invention can reduce the amount of pesticides used, which is beneficial to the environment. Detailed Implementation

[0016] To facilitate understanding of the present invention, the present invention will be described below with reference to relevant embodiments.

[0017] It should be noted that the various component raw materials used in the embodiments and comparative examples in this application are all existing commercially available products. The content in this application refers to the weight parts, and the yield mentioned in this application is determined by high performance liquid chromatography.

[0018] It should be noted that the synergist of this application can be prepared in a variety of ways. In the implementation of this application, it is prepared by oxidation or amidation of acyl chloride with hydroxyl or amino acyl groups.

[0019] Synergist 1: CH3CH2CH2CH2CH2COOCH2CH2N(CH3)2 The main preparation steps include: dissolving 1 mol hexanoyl chloride (CAS No.: 142-61-0) in tetrahydrofuran, cooling to 0℃ in an ice bath, adding a mixture of 1.05 mol hydroxyethyl dimethylamine and 1.1 mol liquid alkali dropwise, reacting at room temperature for 6 hours after addition, washing with water and drying, with a yield of 98.5%. Synergist 2: CH3CH2CH2CH2CH2CONH2CH2CH2N(CH3)2 The main preparation steps include: dissolving 1 mol hexanoyl chloride in tetrahydrofuran, cooling to 0℃ in an ice bath, adding a mixture of 1.05 mol 2-dimethylaminoethylamine (CAS No.: 108-00-9) and 1.1 mol liquid alkali dropwise, reacting at room temperature for 6 hours after addition, washing with water and drying, with a yield of 97.4%.

[0020] Synergist 3: C9H 19 COOCH2CH2ON(CH3)2 The main preparation steps include: dissolving 1 mol of decanoyl chloride in tetrahydrofuran, cooling to 0°C in an ice bath, adding a mixture of 1.2 mol of 2-dimethylaminoethanol and 1.1 mol of liquid alkali dropwise, reacting at room temperature for 6 hours after addition, washing with water and drying, with a yield of 98.2%.

[0021] The above-mentioned synergists 1-3 were tested with tallow amine polyoxyethylene ether (CAS No.: 61791-26-2) and alkyl glycoside APG10 (CAS No.: 54549-25-6) as follows: 1) Solubility test: The degradation rate after 28 days was determined according to GB / T 15818-2018 "Test Method for Biodegradability of Surfactants"; 2) Prepare 0.5 g / mL aqueous solutions for each synergist. Using the Heterotropic Embryo-Compartmental (HET-CAM) test, apply 0.3 mL of the solution directly to the CAM, covering at least 50% of the area. After 3 minutes, rinse the CAM surface with pure water and observe for 3 minutes. Perform bleeding, coagulation, and vascularization tests and scoring. Bleeding: Blood flows from the blood vessel, scored from 0-3 points (no bleeding to severe bleeding) according to severity. Coagulation: Protein denaturation inside or outside the blood vessel, manifested as thrombus or turbidity, scored from 0-3 points according to severity. Vascularization: Blood vessels disappear or rupture, scored from 0-2 points (no dissolution to severe dissolution) according to severity. Then calculate the Stimulus Score (ES): ES = Bleeding Score × 1.67 + Coagulation Score × 2.33 + Vascularization Score × 3. Classify irritation based on ES: No irritation: ES ≤ 4.9, Mild irritation: 5.0 ≤ ES ≤ 9.9, Moderate irritation: 10.0 ≤ ES ≤14.9, strong irritant / corrosive: ES ≥ 15.0.

[0022] Table 1 Degradation rate of different pesticide synergists Synergist Synergist 1 Synergist 2 Synergist 3 Tallow amine polyoxyethylene ether Alkyl glycoside APG10 28. Degradation rate (%) 90 91 88 73 96 ES 7.12 6.79 6.64 14.78 1.33 As can be seen from Table 1, compared with tallow amine polyoxyethylene ether, the amide or acyloxy pesticide synergists of Examples 1-3 have excellent degradation ability, are environmentally friendly, and have low irritation.

[0023] During the experiment, the inventors formulated herbicides, insecticides, and fungicides using the synergist of this invention, and tested their efficacy, all of which verified that the synergist of this invention has a good synergistic effect. For example, a 30wt% glyphosate isopropylamine salt herbicidal composition was prepared using synergist 1: Example 1: The formulation components are as follows, by weight: 30 parts of glyphosate isopropylamine salt Synergist 1 3 parts 65 parts water Using 3-leaf stage foxtail grass (with visually consistent growth and no significant differences among plants) as the target, the synergistic effect of synergist 1 was verified by measuring its inhibition rate. Specifically, the plants were randomly divided into treatment and control groups. The prepared herbicidal composition was diluted 100 times and sprayed evenly on the foxtail grass in the treatment group until the leaves dripped water. The control group was sprayed with water. The foxtail grass in both groups was placed in a greenhouse (25℃) for cultivation, and the soil was kept moist. After 7 days, 5 foxtail grass plants were randomly selected from each group, and the whole plant was cut off from the base with scissors, taking care not to miss the roots or leaves. The fresh weight was measured, and the inhibition rate was calculated as (fresh weight of control group - fresh weight of treatment group) × 100%. This was repeated 3 times.

[0024] Example 2: Replace synergist 1 in Example 1 with synergist 2.

[0025] Example 3: Replace synergist 1 in Example 1 with synergist 3.

[0026] Comparative Example 1: The synergist in Example 1 was changed from 1 part by weight to 0.

[0027] Comparative Example 2: Synergist 1 in Example 1 was replaced with tallow amine polyoxyethylene ether (CAS No.: 61791-26-2). Comparative Example 3: The synergist 1 in Example 1 was replaced with alkyl glycoside APG10 (CAS No.: 54549-25-6).

[0028] Table 2. Results of inhibition rate determination in each sample. Sample Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Inhibition rate (first time) 96.5 94.2 95.1 68.2 88.4 74.4 Inhibition rate (second time) 97.1 96.3 92.8 66.3 85.2 75.9 Inhibition rate (3rd time) 95.9 93.1 94.6 70.4 87.6 76.3 As shown in Table 2, Examples 1-3 and Comparative Example 2 showed a superior synergistic effect of 30% glyphosate isopropylamine salt on the inhibition of foxtail grass at the 3-leaf stage compared to glyphosate isopropylamine salt alone, while Comparative Example 3 showed a relatively weaker enhancement effect.

[0029] For example, a 10% imidacloprid insecticide composition can be prepared using synergist 2.

[0030] The formulation of the 10% imidacloprid insecticidal composition consists of: 10 parts imidacloprid, 15 parts emulsifier, and 2 parts synergists prepared in proportions of 0, 0.05, 0.1, 1, 3, 5, 8, 10, and 15 parts respectively, with the remainder being water. The insecticidal compositions prepared above were used to control cotton aphids. The mortality rate was determined after 48 hours. Specifically, test insects were placed in small gauze cages, immersed in the insecticide solution for 10 seconds, removed, and excess solution was absorbed with absorbent paper. The insects were then transferred to clean petri dishes and kept at 25±1℃ and 70%-80% relative humidity. This process was repeated for 5 groups of 20 insects per group. The mortality rate was checked after 48 hours.

[0031] Table 3. Mortality rates compared to different synergist concentrations. content 0 0.05 0.1 1 3 5 10 15 20 25 mortality rate(%) 70 71 84 90 98 93 89 85 78 63 As shown in Table 3, the 10% imidacloprid insecticide composition prepared with amide compounds using synergist 2 has little synergistic effect at low concentrations (0.05%). The synergistic effect is more obvious at concentrations of 0.1-20%, and reaches its peak at a concentration of 3% (mortality rate reaches 98%). Excessively high concentrations may lead to rapid loss of the pesticide due to osmotic overload, such as seepage from the insect's body surface, shortening the duration of effect, affecting insect inactivation, and thus reducing the synergistic effect.

[0032] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A pesticide synergist based on acyloxy or amide, characterized in that, The structural formula of the synergist is as follows: (Equation 1) in: R3 is a C5-C9 alkyl carbon chain; R2 is either N or O; R1 is a group of formula 2 or formula 3. (Equation 2) (Equation 3) In Equation 1, n1 is 1-3, and in Equation 2, n2 is 2-5.

2. A pesticide composition, characterized in that, Includes the synergist as described in claim 1.

3. The pesticide composition according to claim 2, characterized in that, Pesticide compositions are used for weed control, fungicide or insecticide.

4. The pesticide composition according to claim 3, characterized in that, It includes the active ingredient of pesticide and the synergist, wherein the content of the synergist is 0.1 to 20 parts by weight.

5. The pesticide composition according to claim 4, characterized in that, It comprises, by weight, 30 parts glyphosate isopropylamine salt and 3 to 5 parts the synergist described above.

6. The pesticide composition according to claim 4, characterized in that, It comprises, by weight, 10 parts imidacloprid and 3-5 parts of the aforementioned synergist.

7. The synergist according to claim 1, characterized in that, It is prepared by the oxidation reaction of acyl chloride with hydroxyacyl or the amidation reaction of acyl chloride with amino group.

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