Bactericidal composition containing oxadiazine acetate and oxadiazine and preparation method thereof

Abstract

The present invention discloses a bactericidal composition containing oxadiazine acetate and mefenamic acid and a preparation method thereof, comprising mefenamic acid and oxadiazine acetate. The present invention has the following beneficial effects: the raw materials of the bactericidal composition of the present invention have an excellent synergistic effect, and the mixed composition significantly improves the bactericidal effect compared with its single agent, thereby reducing the dosage used, while reducing the cost of farmers' medicine use and reducing the degree of environmental impact. The bactericidal composition of the present invention has a wider bactericidal range, and the characteristics of the agents are also strongly complementary. One agent can prevent and treat a variety of crop diseases, providing a convenient and effective means of prevention and control. The application of the bactericidal composition of the present invention can delay the occurrence and development of resistance of a single agent, and the structure and mechanism between varieties are quite different, and there is no cross-resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of pesticide compounding, and particularly relates to a bactericidal composition containing oxadiazine acetate and oxadiazine. Background Art

[0002] Disease resistance is one of the main problems that restrict the long-term and continuous application of pesticides and fungicides. The synthesis of new compounds is characterized by long cycles, high difficulty, and high investment. Long-term continuous use of a single compound can easily cause pathogens to develop resistance. Therefore, compounding existing compounds to obtain high-efficiency and low-toxic compositions can delay the occurrence of resistance in existing fungicide compounds, which can extend the use cycle of fungicides and improve their efficacy, and has good application prospects. Summary of the invention

[0003] The object of the present invention is to provide a bactericidal composition containing oxadiazine acetate and oxadiazine which has high efficacy, a wide bactericidal range and can delay drug resistance.

[0004] In order to achieve the above-mentioned purpose of the present invention, the present invention adopts the following technical solutions:

[0005] A fungicide composition containing oxadiazine acetate and mefenamic acid comprises mefenamic acid and oxadiazine acetate.

[0006] The chemical name of oxadiazine is: 3-hydroxy-5-methylisoxazole, the molecular formula is: C4H5NO2, and the structure is:

[0007]

[0008] Methacin is a highly effective systemic pesticide fungicide and soil disinfectant. It has unique efficacy, is highly effective, low-toxic, and pollution-free, and is a green, environmentally friendly, high-tech product. Methacin can effectively inhibit the normal growth of pathogenic fungal mycelium or directly kill pathogens, and promote plant growth; it also promotes the growth and development of crop roots, rooting and strengthening seedlings, and improves the survival rate of crops. Methacin has a very high penetration rate, and can move to the stem in two hours and move to the whole plant in 20 hours. Methadone is a broad-spectrum fungicide that has a high control effect on plant diseases caused by various pathogenic fungi. It has a good therapeutic effect on flagellates, ascomycetes, basidiomycetes, pythium, seedling rot, fusarium, Rhizoctonia, cortex, rhizoctonia, and snow mold of the subphylum Ascomycetes. It has special effects on wilt, damping-off, verticillium wilt, damping-off, sheath blight, seedling rot, sclerotinia, blight, dry rot, black spot, sclerotium soft rot, seedling blight, stem blight, leaf blight, root rot, and continuous cropping obstacles. It also has the effect of promoting the growth and development of crop roots, rooting and strengthening seedlings, and improving the survival rate.

[0009] Octofenamid acetate is an amino acid polymer fungicide with a novel structure and unique mode of action. The chemical name of Octofenamid is: N,N-dioctyldiethylenetriamine, commonly used in its acetate form, with a molecular formula of: C20H 45 N3, molecular weight is 327.59. The structural formula of octamidine is as follows:

[0010]

[0011] Sintrazone acetate is a highly effective, low-toxic, environmentally friendly amino acid polymer bactericide. Its mechanism of action is that it can produce ionization in aqueous solution, and its hydrophilic group can strongly generate positive electricity, adsorbing various types of bacteria that are usually negatively charged in water, thereby inhibiting their reproduction, coagulating pathogenic bacteria proteins, and denaturing pathogenic enzyme systems. At the same time, the film formed by the polymer can block ion channels, and has systemic, permeable and bidirectional conduction effects.

[0012] The above-mentioned fungicidal composition containing oxadiazine acetate and oxadiazine, as a preferred embodiment, also includes a cosolvent, an emulsifier, an antifreeze agent and water.

[0013] Preferably, the raw materials are included in the following weight percentages: 0.25%-2% of oxamexyl, 2%-8% of oxamexyl acetate, 1%-10% of a solvent, 3%-10% of an emulsifier, 5%-10% of an antifreeze agent, and the balance of water.

[0014] Preferably, the weight ratio of the oxazolidinone to the oxazolidinone acetate is 1:4-1:8.

[0015] In the above-mentioned fungicidal composition containing oxadiazine acetate and oxadiazine, as a preferred embodiment, the co-solvent is at least one of methanol, ethanol and N,N-dimethylformamide.

[0016] The above-mentioned bactericidal composition containing octamidine acetate and oxadiazine is, as a preferred embodiment, the emulsifier is at least one of isomeric decanol polyoxyethylene ether, lauryl alcohol polyoxyethylene polyoxypropylene ether, secondary octanol polyoxyethylene ether and water-soluble azone.

[0017] In the above-mentioned bactericidal composition containing oxadiazine acetate and oxadiazine, as a preferred embodiment, the antifreeze agent is at least one of ethylene glycol, propylene glycol and glycerol.

[0018] The second aspect of the present application provides a method for preparing a fungicidal composition containing oxadiazine acetate and oxadiazine, comprising the following steps: mixing and stirring the raw materials uniformly to obtain the fungicidal composition containing oxadiazine acetate and oxadiazine.

[0019] The application site of the product made from the composition of the present invention is farmland, orchard or warehouse, etc. The composition of the present invention can be used to prevent and control various crop diseases: cereals such as wheat and rice, vegetables such as cucumber and tomato, fruits such as strawberry, apple and citrus, as well as peanuts, flowers, lawns and Chinese medicinal materials.

[0020] The composition of the present invention can be applied by common methods, such as spraying, sprinkling, root irrigation, drip irrigation, soil treatment, etc. The application amount varies with weather conditions and the state of the crop. The application period can be before or after the crop is infected with the disease. The duration of the protective effect is usually related to the content of the individual compounds in the composition and the changes in external environmental conditions.

[0021] The beneficial effects of the present invention are as follows: the various raw materials of the bactericidal composition of the present invention have an excellent synergistic effect, and the mixed composition significantly improves the bactericidal effect compared with its single agent, thereby reducing the dosage used, reducing the cost of farmers' medicine use, and reducing the degree of environmental impact.

[0022] The bactericidal composition of the present invention has a wider bactericidal range, and the characteristics of the agents are also strongly complementary. One agent can prevent and treat a variety of crop diseases, providing a convenient and effective prevention and treatment means.

[0023] The application of the bactericidal composition of the present invention can delay the occurrence and development of resistance of a single agent. The structures and mechanisms of the varieties are quite different, and there is no cross-resistance. DETAILED DESCRIPTION

[0024] To make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described in detail below. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other implementation methods obtained by ordinary technicians in this field without creative work belong to the scope of protection of the present invention.

[0025] Example 1

[0026] The bactericidal composition containing oxadiazine acetate and meconium chloride described in Example 1 comprises the following raw materials in weight percentage: 0.25% meconium chloride, 2% oxadiazine acetate, 5% methanol, 5% ethylene glycol, 5% isomeric decanol polyoxyethylene ether, and water makes up to 100%.

[0027] The method for preparing a fungicide composition containing oxadiazine acetate and oxadiazine described in Example 1 comprises the following steps: mixing and stirring the raw materials uniformly to obtain the fungicide composition containing oxadiazine acetate and oxadiazine.

[0028] Example 2

[0029] The bactericidal composition containing oxadiazine acetate and meconium-methyl described in Example 2 includes the following raw materials in weight percentage: 0.5% meconium-methyl, 4% oxadiazine acetate, 5% methanol, 5% ethylene glycol, 3% isomeric decanol polyoxyethylene ether, and water makes up to 100%.

[0030] The method for preparing a fungicide composition containing oxadiazine acetate and oxadiazine described in Example 2 comprises the following steps: mixing and stirring the raw materials evenly to obtain the fungicide composition containing oxadiazine acetate and oxadiazine.

[0031] Example 3

[0032] The bactericidal composition containing oxadiazine acetate and meconium chloride described in Example 3 includes the following raw materials in weight percentage: 2% meconium chloride, 8% oxadiazine acetate, 10% methanol, 5% ethylene glycol, 3% isomeric decanol polyoxyethylene ether, and water makes up to 100%.

[0033] The method for preparing a fungicide composition containing oxadiazine acetate and oxadiazine described in Example 3 comprises the following steps: mixing and stirring the raw materials evenly to obtain the fungicide composition containing oxadiazine acetate and oxadiazine.

[0034] Comparative Example 1

[0035] The difference between the fungicidal composition containing oxadiazine acetate and oxadiazine described in Comparative Example 1 and the fungicidal composition described in Example 1 is that:

[0036] The bactericidal composition described in Comparative Example 1 comprises the following raw materials in percentage by weight: 1% of oxadipate, 1% of octamidine acetate, 5% of methanol, 5% of ethylene glycol, 5% of isomeric decanol polyoxyethylene ether, and water makes up to 100%.

[0037] Comparative Example 2

[0038] The difference between the fungicidal composition containing oxadiazine acetate and oxadiazine described in Comparative Example 2 and the fungicidal composition described in Example 1 is that:

[0039] The bactericidal composition described in Comparative Example 2 comprises the following raw materials in percentage by weight: 3% of oxadipate, 4% of octamidine acetate, 5% of methanol, 5% of ethylene glycol, 5% of isomeric decanol polyoxyethylene ether, and water makes up to 100%.

[0040] Comparative Example 3

[0041] The difference between the fungicidal composition containing oxadiazine acetate and oxadiazine described in Comparative Example 3 and the fungicidal composition described in Example 1 is that:

[0042] The bactericidal composition described in Comparative Example 3 comprises the following raw materials in percentage by weight: 2% of oxadipate, 4% of octamidine acetate, 5% of methanol, 5% of ethylene glycol, 5% of isomeric decanol polyoxyethylene ether, and water makes up to 100%.

[0043] Comparative Example 4

[0044] The difference between the fungicidal composition containing oxadiazine acetate and oxadiazine described in Comparative Example 4 and the fungicidal composition described in Example 1 is that:

[0045] The bactericidal composition described in Comparative Example 4 comprises the following raw materials in percentage by weight: 1.8% of oxadipate, 3% of octamidine acetate, 5% of methanol, 5% of ethylene glycol, 5% of isomeric decanol polyoxyethylene ether, and water makes up to 100%.

[0046] 1. The technical indicators of a fungicide composition containing oxadiazine acetate and oxadiazine described in Example 1 of the present application are studied. The results are shown in Table 1:

[0047] Table 1

[0048] project pH 5.0-8.0 Water insoluble matter (%) ≤0.5 Dilution stability qualified Low temperature stability qualified Thermal storage stability qualified

[0049] Note: Determination method of pH value of pesticides GB / T 1601-1993

[0050] Determination of thermal storage stability of pesticides GB / T 19136

[0051] Determination of low temperature stability of pesticides GB / T 19137

[0052] The technical indicators of the fungicidal composition containing oxadiazine acetate and oxadiazine described in Comparative Examples 1 to 4 are studied, and the results are shown in Table 2:

[0053] Table 2

[0054] name Problems Comparative Example 1 Unqualified appearance, turbid Comparative Example 2 Low temperature stability is unqualified, oil separation Comparative Example 3 qualified Comparative Example 4 qualified

[0055] As can be seen from Table 2, the dosage of 1% of the fungicide composition succinimidyl acetate in Comparative Example 1 is lower than the dosage of succinimidyl acetate (2%-8%) in the fungicide composition described in the present application, and the appearance of the obtained product is unqualified and turbid;

[0056] The dosage of 3% of oxadipate in Comparative Example 2 is higher than the dosage of oxadipate (0.25%-2%) in the fungicide composition described in the present application. The low-temperature stability of the obtained product is unqualified and oil separation occurs.

[0057] 2.2.1 Biological Activity Test of the Bactericidal Composition Described in the Application

[0058] The example of the present invention is to use the growth rate method to carry out indoor toxicity determination to determine the toxicity coefficients of oxadipamide, sinopyridin acetate and a control agent.

[0059] After the effective inhibition concentration range of each agent was determined by preliminary test, 5 gradient doses were set according to the active ingredient content, namely R, 1 / 2R, 1 / 4R, 1 / 8R, 1 / 16R, where R is the recommended dose, the recommended dose of 20% cypermethrin acetate stock drug is 1777 times liquid, and the active ingredient content of the culture medium is 112.5mg / L. The recommended dose of 98% oxadiazine soluble powder is 2000 times liquid, and the active ingredient content of the culture medium is 495mg / L. Set up a blank control. According to the "Guidelines for Indoor Bioassay Tests of Pesticides and Fungicides", the inhibitory effect of the agents on Fusarium oxysporum was determined. Fusarium oxysporum was pre-cultured on PDA culture medium at 26°C for 5 days. A 7-mm diameter puncher was used to punch out bacterial cakes on the same circumference near the edge of the colony. The cakes were inoculated on PDA culture medium containing different concentrations of the agent, one piece per culture dish. The cakes were placed in a 26°C light incubator for 4 days. The mycelium growth rate method was used to determine the toxicity of the agents to crop pathogens, and the cross method was used to determine the colony diameter. The net growth of each treatment and the mycelium growth inhibition rate were calculated.

[0060] Net growth = measured colony diameter - 0.7

[0061] Mycelial growth inhibition rate (%) = (net growth of control group - net growth of treatment group) / net growth of control group × 100

[0062] The mycelium growth inhibition rate was converted into a probability value (y), and the drug concentration (μg / ml) was converted into a logarithmic value (x). The toxicity regression equation (y=a+bx) was obtained by the least squares method, and the EC50 value of each drug was calculated from it.

[0063] The present invention uses the co-toxicity coefficient method to calculate the combined effect of the bactericidal composition. First, the independent regression lines of agent A, agent B and A+B mixture are determined according to the growth rate method, and the inhibition concentration EC50 value of each agent is calculated. Then, the toxicity index (TI) is calculated according to the following formula, and finally the co-toxicity coefficient (CTC) is calculated to represent the result of the mixture.

[0064] Toxicity index (TI) = EC50 of standard fungicide / EC50 of test agent × 100%;

[0065] The toxicity index (ATI) of the measured mixture = EC50 of agent A alone / EC50 of the mixture × 100%;

[0066] Theoretical toxicity index of mixture (TTI) = toxicity index of A × content of A in mixture (%) + toxicity index of B × content of B in mixture (%);

[0067] Co-toxicity coefficient (CTC) of the mixture = (measured toxicity index (ATI) of the mixture) / (theoretical toxicity index (TTI) of the mixture) × 100%;

[0068] If the co-toxicity coefficient is much greater than 100, it indicates a synergistic effect. If the co-toxicity coefficient is significantly lower than 100 (below 80), it indicates an antagonistic effect. If the co-toxicity coefficient is close to 100, it indicates an additive effect.

[0069] Table 3

[0070]

[0071] Note: EC50 is the concentration of the preparation required to inhibit bacterial growth by 50%;

[0072] After calculation:

[0073] The measured toxicity index of the bactericidal composition described in Example 1 is TI=409.9, the theoretical toxicity index is TTI=92.1, the co-toxicity coefficient CTC=445.3, and the co-toxicity coefficient is much greater than 100, which has a significant synergistic effect and is higher than the co-toxicity coefficient of the two preparations alone.

[0074] The measured toxicity index of the bactericidal composition in Comparative Example 3 is TI=90.5, the theoretical toxicity index is TTI=76.4, the co-toxicity coefficient CTC=118.3, and the co-toxicity coefficient is close to 100, which is mainly an additive effect.

[0075] The measured toxicity index of the bactericidal composition described in Comparative Example 4 is TI=101.8, the theoretical toxicity index is TTI=55.3, the co-toxicity coefficient CTC=183.9, and the co-toxicity coefficient is greater than 120, which shows a certain synergistic effect.

[0076] 2.2 Biological activity test of the fungicidal composition of copper nonyl acetate microemulsion and oxadiazine

[0077] Test method (refer to test method in 2.1), test results are shown in Table 4:

[0078] Table 4

[0079]

[0080] Note: The auxiliary agent is the same as that in Example 1: containing methanol, ethylene glycol and isomeric decanol polyoxyethylene ether in the same weight ratio, and water makes up 100%.

[0081] After calculation: the actual toxicity index of the fungicide composition composed of 30% copper nonanthracene microemulsion + 98% chlorothalonil soluble powder is TI=98.7, the theoretical toxicity index is TTI=88.1, the co-toxicity coefficient CTC=111.9, and the co-toxicity coefficient is close to 100, indicating that there is no synergistic effect in the combination of copper nonanthracene and chlorothalonil fungicides, but a simple additive effect. Therefore, there is no general synergistic effect in the combination of chlorothalonil and fungicides.

[0082] 2.3.1. Test on the biological activity of the fungicidal composition of 8% cephalosporin acetate aqueous solution + 50% chlorobromoisocyanuric acid soluble powder

[0083] Test method, (refer to the test method in 2.1) The results are shown in Table 5:

[0084] Table 5

[0085]

[0086] From Table 5, it can be seen that after the mixture of 1.8% cintamidine acetate aqueous solution and 50% chlorobromoisocyanuric acid soluble powder, the EC50 is close to 10 times that of 1.8% cintamidine acetate aqueous solution alone. At each dose set in the EC50 test (R, 1 / 2R, 1 / 4R, 1 / 8R, 1 / 16R), the inhibition rate of the two fungicides after the mixture is lower than the inhibition rate of 1.8% cintamidine acetate aqueous solution alone, and there is a certain antagonistic effect. Therefore, there is no universal synergistic effect between cintamidine acetate and fungicides.

[0087] The above description is only the preferred embodiment of the present application and is not intended to limit the present application. For those skilled in the art, the present application may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A fungicidal composition containing oxadiazine acetate and oxadiazine, characterized in that: The active ingredients of the bactericidal composition are composed of oxadixyl and oxadixyl acetate, and the weight ratio of the oxadixyl to the oxadixyl acetate is 1:4-1:

8.

2. A fungicidal composition containing oxadiazine acetate and oxadiazine according to claim 1, characterized in that: It also includes cosolvents, emulsifiers, antifreeze and water.

3. A fungicidal composition containing oxadiazine acetate and oxadiazine according to claim 2, characterized in that: The invention comprises the following raw materials in percentage by weight: 0.25%-2% of oxadipate, 2%-8% of oxadipamide acetate, 1%-10% of a solvent aid, 3%-10% of an emulsifier, 5%-10% of an antifreeze agent, and the balance of water.

4. A fungicidal composition containing oxadiazine acetate and oxadiazine according to claim 3, characterized in that: The co-solvent is at least one of methanol, ethanol and N,N-dimethylformamide.

5. A fungicidal composition containing oxadiazine acetate and oxadiazine according to claim 3, characterized in that: The emulsifier is at least one of isomeric decanol polyoxyethylene ether, lauryl alcohol polyoxyethylene polyoxypropylene ether, secondary octanol polyoxyethylene ether and water-soluble azone.

6. A fungicidal composition containing oxadiazine acetate and oxadiazine according to claim 3, characterized in that: The antifreeze agent is at least one of ethylene glycol, propylene glycol and glycerol.

7. A method for preparing a fungicidal composition containing oxadiazine acetate and oxadiazine according to any one of claims 1 to 6, characterized in that: The following steps are involved: The raw materials are mixed and stirred uniformly to obtain the bactericidal composition containing oxadiazine acetate and oxadiazine.

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