CN1261026C - Bactericidal composition containing enoxastrobin and triazoles - Google Patents

Abstract

The present invention discloses a germicide composition containing alkene oxime amine and triazole. The part by weight ratio of the alkene oxime amine to the triazole is from (1:100) to (100:1). The composition contains at least two kinds of carriers, and at leat one kind of the two kinds of carriers is a surface active agent. The composition can be prepared into agents, such as an emulsifiable solution, a suspension agent, a water emulsion, wettable powder, a water dispersion granule, etc., and is used for preventing and controlling plant diseases caused by pathogen fungi.

Description

Bactericidal composition containing enoxastrobin and triazoles

technical field

The invention belongs to the field of agricultural fungicides.

Background technique

Enoxastrobin is an excellent fungicide for the control of various plant diseases such as grains, rice, fruits, vegetables and economic crops. It has a wide bactericidal spectrum, high activity, preventive and therapeutic effects, and has good compatibility with environmental organisms It has a good control effect on various plant diseases caused by flagellate fungi, combined fungi, ascomycetes, basidiomycetes and deuteromycetes, especially for powdery mildew and rust of crops such as grains and vegetables. This compound has been disclosed in CN1309897A. Enoxastrobin is a new type of methoxyacrylate fungicide. This type of fungicide has high activity and low dosage. It has therapeutic and protective effects and is widely used to prevent and control crop diseases. However, because the action site of this type of fungicide is very single, the bacteria will produce adaptive variation of the agent, which will reduce the control effect of the agent or even make it ineffective, resulting in drug resistance. Resistance to enoxastrobin has not yet been found in the field, but there have been reports of resistance in similar varieties in Europe.

Contents of the invention

In order to avoid problems such as the occurrence of resistance and the decline in drug efficacy that may be caused by the use of a single agent of enoxastrobin, the present invention proposes a fungicidal composition containing enoxastrobin and triazoles, the preparation and application of the composition.

Enoxastrobin chemical name: N-methyl-2-[2-((((1-methyl-3-(2',6'-dichlorophenyl)-2-propenyl)amino)oxy ) methyl) phenyl] -2-methoxyiminoacetamide, structural formula is as follows:

Chinese name: Enoxastrobin Molecular formula: C ₂₁ H ₂₁ CI ₂ N ₃ O ₃ Molecular weight: 434

In the bactericidal composition of the present invention, the triazole bactericide is selected from:

(1).1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butanone (triazolone):

Molecular formula: C ₁₄ H ₁₆ ClN ₃ O ₂ Molecular weight: 293.8

(2). Cis, trans-3-chloro-4-[4-methyl-2-(1H-1,2,4-triazol-1-ylmethyl)-1,3-dioxolane- 2-yl]phenyl-4-chlorophenyl ether (oxafeconazole):

分子式：C₁₉H₁₇Cl₂N₃O₃分子量：406.3

Molecular formula: C ₁₉ H ₁₇ Cl ₂ N ₃ O ₃ Molecular weight: 406.3

(3).β-[(2,4-dichlorophenyl)-methylidene]-α-(1,1-dimethylethyl)-1H-1,2,4-triazoleethanol (enazole alcohol):

Molecular formula: C ₁₅ H ₁₇ Cl ₂ N ₃ O Molecular weight: 326.2

(4). 2-(4-Chlorophenyl)-2-(1H-1,2,4-triazole-1-methyl)capronitrile (myclobutanil):

Molecular formula: C ₁₅ H ₁₇ ClN ₄ Molecular weight: 286.8

(5).1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolane-2-methyl]-1-hydrogen-1,2,4- Triazole (propiconazole):

Molecular formula: C ₁₅ H ₁₇ Cl ₂ N ₃ O ₂ Molecular weight: 342.2

(6).(1RS, 2RS; 1RS, 2SR)-1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazole-1-butane Base) -2-ol (triadimenol):

分子式：C₁₄H₁₈ClN₃O₂分子量：295.8

Molecular formula: C ₁₄ H ₁₈ ClN ₃ O ₂ Molecular weight: 295.8

(7).(RS)-1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)penta-3- Alcohol (tebuconazole):

分子式：C₁₆H₂₂ClN₃O分子量：307.8

Molecular formula: C ₁₆ H ₂₂ ClN ₃ O Molecular weight: 307.8

(8).(RS)-2-(2,4-dichlorophenyl)-1-(1H-1,2,4-triazol-1-yl)-hexan-2-ol (hexaconazole) :

Molecular formula: C ₁₄ H ₁₇ Cl ₂ N ₃ O Molecular weight: 314.2

(9).(2RS, 3SR)-1-[3-(2-chlorophenyl)-2,3-epoxy-2-(4-fluorophenyl)propyl]-1-hydrogen-1,2 , 4-triazole (epoxyconazole):

分子式：C₁₇H₁₃ClFN₃O分子量：329.8

Molecular formula: C ₁₇ H ₁₃ ClFN ₃ O Molecular weight: 329.8

In the fungicidal composition of the present invention, the active component contains enoxistrobin and one or any two or more triazole fungicides. When the active components are enoxastrobin and a triazole fungicide, the weight-number ratio of the two active components is 1:100 to 100:1. A more suitable ratio is 1:20 to 20:1.

In the fungicidal composition of the present invention, the active component is 0.5% to 95% of the total weight. The amount of active components contained in the fungicidal composition of the present invention depends on the application rate of each component when used alone, and also depends on the ratio of one component to another component and the degree of synergistic effect.

The bactericidal composition of the present invention contains at least two kinds of carriers, which can be solid or liquid, and the carriers usually used for preparing bactericidal compositions can be used. At least one carrier in the composition of the present invention is a surfactant, which can be selected from emulsifiers, dispersants or wetting agents. The surfactants selected for the germicidal compositions of the present invention are well known to those skilled in the art.

The fungicidal composition of the present invention can be formulated into emulsifiable concentrates, suspension concentrates, (water) emulsions, wettable powders, (water dispersible) granules, etc., and these formulations can be prepared by common methods.

The fungicidal composition of the present invention can be provided in the form of a finished preparation, that is, each substance in the composition has been mixed; but the components of the composition can also be provided in the form of a separate preparation, which is directly mixed in a barrel (tank) before use. The concentrates of the present invention are generally mixed with water to obtain the desired concentration of active substance.

The fungicidal composition of the present invention can be used to prevent and treat plant diseases caused by pathogenic fungi, such as diseases caused by Ascomycetes, Basidiomycetes and Deuteromycetes, such as cereals, wheat, rice, grapes, strawberries, cucumbers, zucchini, Pepper, sweet pepper, eggplant, tomato, kidney bean, cowpea, leek, lettuce, cabbage, sunflower, lychee, tobacco, rubber and some flowers, Chinese medicinal materials, lawn, etc. The application site of the fungicidal composition of the present invention is farmland, orchard or warehouse.

The fungicidal composition of the present invention can also be mixed with other compounds with herbicidal, insecticidal or fungicidal properties, especially protective fungicides, and can also be mixed with nematicides, protective agents, growth regulators, plant nutrients or soil conditioners use.

The present invention also includes a method for killing fungi on the spot, applying the composition of the present invention to the crops and the place where the crops are grown or stored before or after the crops are susceptible to disease. It can be applied by ordinary methods, such as pouring, spraying, spraying and the like. The application rates of the present invention vary with weather conditions or crop conditions. The duration of the protective effect is usually related to the content of the individual compounds in the composition, but also to external factors, such as climate, which can be mitigated by using appropriate formulations.

It has been found that the mixed use of enoxastrobin and triazole fungicides has a very obvious synergistic effect within a certain ratio range, which significantly improves the control effect on crop diseases, reduces the cost of pesticides for farmers, and reduces the cost of pesticides. degree of impact on the environment. The composition of the present invention expands the bactericidal spectrum, and one medicament can prevent and treat various crop diseases at the same time, and is effective against powdery mildew, rust, glume blight, leaf spot, etc. Downy mildew, blight, etc. have a good control effect. The bactericidal composition proposed by the present invention can delay the occurrence and development of drug resistance of pathogens to a greater extent, thereby achieving the purpose of the present invention.

Detailed ways

The present invention is described in detail with the following specific examples to make the advantages of the present invention more obvious, but the present invention is by no means limited to these examples. The percentages in the proportions of all preparations are percentages by weight; the treatment doses of biologically active parts are effective content.

Preparation of Compositions and Examples of Biological Activity

1. Preparation of EC

According to the requirements of the formula, add the solvent, the original drug, and the emulsifier respectively, mix evenly, heat and dissolve with a hot water bath if necessary, and obtain a transparent emulsifiable oil. Such as example 1～4 formula.

Example 1 (10% EC)

Enoxastrobin 5%, myclobutanil 5%, Nongru 500 ^# 7.5%, Nongru 600-2 ^# 4.5%, methanol 8%, xylene to 100%.

Example 2 (25% EC)

Enoxastrobin 15%, Difenoconazole 10%, Nongru 507 ^# 10%, Nongru OX-6533%, Methanol 10%, Xylene supplemented to 100%.

Example 3 (30% EC)

Enoxastrobin 20%, Hexaconazole 10%, Nongru 500 ^# 10%, Nongru OX-6355%, Methanol 10%, Xylene supplemented to 100%.

Example 4 (50% EC)

Enoxastrobin 47.5%, Epocloconazole 2.5%, Nongru 500 ^# 18%, Nongru OX-6358%, Methanol 12%, Xylene supplemented to 100%.

2. Preparation of wettable powder

According to the requirements of the formula, the original drug, various additives and fillers are fully mixed, and the processed product is obtained after being pulverized by an ultra-fine pulverizer. Such as example 5～10 formula

Example 5 (20% wettable powder)

Enoxastrobin 4%, diniconazole 16%, sodium lauryl sulfate 1.5%, carboxymethyl cellulose 1%, sodium lignosulfonate 10%, light calcium carbonate supplemented to 100%.

Example 6 (30% wettable powder)

Enoxastrobin 1.5%, triadimefon 28.5%, sodium dodecylbenzene sulfonate 1%, white carbon black 10%, sodium lignosulfonate 10%, and light calcium carbonate make up to 100%.

Example 7 (40% wettable powder)

15% of enoxastrobin, 25% of triadimenol, 1% of sodium dodecylbenzene sulfonate, 10% of white carbon black, 10% of sodium lignosulfonate, and 100% of light calcium carbonate.

Example 8 (45% wettable powder)

Enoxastrobin 25%, propiconazole 20%, alkylamido taurate 2%, alkylnaphthalene formaldehyde condensation 5%, alkylphenol polyoxyethylene phosphate 5%, light calcium carbonate topped up to 100% .

Example 9 (50% wettable powder)

Enoxastrobin 15%, Difeconazole 35%, Sodium Dodecylbenzene Sulfonate 1%, White Carbon Black 10%, Naphthol Sulfonic Acid Formaldehyde Condensate Sodium Salt 10%, Light Calcium Carbonate to 100% .

Example 10 (60% wettable powder)

Enoxastrobin 55%, Tebuconazole 5%, Sodium Dodecyl Benzene Sulfonate 1.5%, White Carbon Black 10%, Naphthol Sulfonic Acid Formaldehyde Condensate Sodium Salt 13%, Light Calcium Carbonate to 100% .

3. Preparation of water emulsion

Add the original drug, solvent, emulsifier and co-emulsifier together to dissolve into a homogeneous oil phase. Mix water, antifreeze, etc. together to form a homogeneous water phase. Under high-speed stirring, add the water phase to the oil phase or add the oil phase to the water phase to form a water emulsion with good dispersibility. Such as example 11～13 formula.

Example 11 (10% water emulsion)

Enoxastrobin 5%, Tebuconazole 5%, Polyvinyl Alcohol 0.8%, Tristyrylphenol + Ethylene Oxide, Phosphorylated, Triethanolamine Neutralized 8.5%, Alkyl-Diethylene Glycol Ether-Sulphonic Acid Sodium 2.5%, Nongru 2201 13%, DMF 8%, Ethylene Glycol 5%, water to make up to 100%.

Example 12 (15% water emulsion)

Enoxastrobin 10%, Difenoconazole 5%, Polyvinyl Alcohol 0.9%, Alkylaryl Polyoxyethylene Polyoxypropylene Ether 8.5%, Nongru 2201 15%, Dimethylformamide 12%, Ethylene Glycol 5%, water to make up to 100%.

Example 13 (30% water emulsion)

Enoxastrobin 15%, propiconazole 15%, polyvinyl alcohol 1.5%, alkylaryl polyoxyethylene polyoxypropylene ether 10%, Nongru 2201 15%, dimethylformamide 15%, ethylene glycol 5%, water to make up to 100%.

4. Preparation of water dispersible granules

Mix and pulverize the original drug, powdery carrier, wetting and spreading agent, binder, etc., add water and knead, then add to a granulator equipped with a certain size screen for granulation. Then dry and sieve (according to the range of the sieve) to obtain granular products. Such as example 14～15 formula.

Example 14 (50% water dispersible granules)

Enoxastrobin 15%, myclobutanil 35%, sodium methylnaphthalenesulfonate formaldehyde condensate 12%, epoxy polyether 5%, soluble starch 15%, and gypsum supplemented to 100%.

Example 15 (60% water dispersible granules)

Enoxastrobin 35%, oxafeconazole 25%, sodium methylene naphthalene sulfonate 5%, epoxy polyether 5%, sodium sulfate 15%, gypsum supplemented to 100%.

5. Preparation of suspending agent

According to the requirements of the formula, with water as the medium, add the original drug, dispersant, suspending agent and antifreeze into the sand mill, and grind to make a suspension. Such as example 16～18 formula.

Example 16 (10% suspending agent)

Enoxastrobin 2%, myclobutanil 8%, sodium methylnaphthalenesulfonate formaldehyde condensate 5.5%, white carbon black 0.2%, magnesium aluminum silicate 0.18%, ethylene glycol 4%, a little silicone, water to make up to 100%.

Example 17 (25% suspending agent)

Enoxastrobin 15%, propiconazole 10%, calcium lignosulfonate 5%, white carbon black 0.3%, ethylene glycol 4%, silicone a little, water to make up to 100%.

Example 18 (35% suspending agent)

Enoxastrobin 10%, Diniconazole 15%, Epoconazole 10%, Sodium Naphthalene Sulfonate Formaldehyde Condensate 2.5%, Bentonite 1.0%, Nongru 1601 3%, Glycerol 4%, Silicone A little, water to make up to 100%.

6. In vitro biological activity

The in vitro biological activity measurement adopts the method of toxic medium, that is, adding quantitative amount of the test agent (the test dose is calculated according to the active ingredient) in the PDA medium, inoculating the test pathogenic bacteria after cooling, and culturing in the dark at 25°C. When the diameter of the blank control colony grows to 40-50 mm, measure the growth diameter of the colony of different treatments, and calculate the bacteriostatic rate and EC ₅₀ value of each treatment. Test results: the in vitro biological activity of the mixture is significantly higher than that of the two control single agents, and has obvious synergistic effect, see examples 19-21 for details.

Example 19 Corn spot disease (Bipolaris mayghi)

Example 20 rape sclerotinia (Sclerotinia sclerotiorm)

Example 21 Cucumber scab (Cladosporium cucumerinum)

7. Bioactivity of greenhouse potted plants

The test adopts the seedling pot test method, and the test crops are potted in the greenhouse until the 2-3 leaf stage. Foliar spray treatment was carried out on the crop sprayer according to the designed dose, and the test pathogenic bacteria were inoculated 24 hours after the chemical treatment. After the inoculation, the test materials were kept moist and cultivated in the artificial climate chamber, and the results were investigated when the blank control without spraying was fully infected. , The disease classification and control effect calculation methods all refer to the national standard of the People's Republic of China "Guidelines for Field Efficacy Tests of Pesticides". The test results showed that the fungicidal composition of enoxastrobin and triazoles had a very excellent control effect on the tested targets, and the pot plant biological activity of the mixture was significantly higher than that of the control single agent, all of which had obvious synergistic effects. See the example for the results 22-28.

Example 22 Cucumber powdery mildew (Erysiphe cucurbitacearum)

Example 23 Wheat powdery mildew (Blumeria graminis)

Example 24 wheat leaf rust (Puccinia recondita)

Embodiment 25 rice blast (Pyricularia grisea)

Example 26 Beet Brown Spot (Cercospora beticoda Sacc.)

8. Control effect of field plots

The experiment was carried out under field conditions, and the cultivation and management of the experimental crops were carried out according to conventional agricultural production. In the field drug efficacy determination, 4 doses of the test agents were set, and a blank control with no application of the drug was set, and 4 repetitions were made. In the experiment, pesticides were applied in the field without disease or at the early stage of disease, and the pesticide application equipment was a knapsack manual sprayer. Natural onset, the result investigation was carried out when the blank control without drug application fully developed the onset. Disease grading and control efficacy calculation methods are in accordance with the national standard of the People's Republic of China, "Guidelines for Field Efficacy Tests of Pesticides". The test results showed that the fungicidal composition of enoxastrobin and triazoles has a very good control effect on disease control. The field control effect of the mixed agent is significantly higher than that of the control single agent, and both have obvious synergistic effects. The results are detailed in Example 27 ~36.

Example 27 Peanut Brown Spot Cercospora arachidicola)

Example 28 Cucumber powdery mildew (Erysiphe cucurbitacearum)

Example 29 wheat powdery mildew (Blumeria gaminis)

Example 30 wheat stripe rust (Puccinia striiformis)

Example 31 Pear scab (Fusicladium virescens)

Example 32 grape white rot (Conithyrium diplodiella)

Example 33 Banana Leaf Spot (Cordana johnstonii)

Example 34 tomato early blight (Alternaria solani)

Example 35 Beet Brown Spot (Cercospora beticoda Sacc.)

Example 36 Apple spotted leaf disease (Alternaria alternata f.sp.mali)

Claims (5)

1. A bactericidal composition, containing two active components of enoxastrobin and a triazole fungicide, the ratio of the two active components by weight is 1:20 to 20:1; the triazole The fungicide is selected from the group consisting of triadimefon, oxaconazole, diniconazole, myclobutanil, triaconazole, tebuconazole, hexaconazole, propiconazole or cycloconazole; the active ingredient weight in the composition The percentage content is 10-60%. 2. The fungicidal composition according to claim 1, characterized in that the composition contains at least two carriers, at least one of which is a surfactant. 3. The fungicidal composition according to claim 1, characterized in that: the composition can be formulated into emulsifiable concentrate, suspension concentrate, water emulsion, wettable powder or water dispersible granule. 4. Use of the fungicidal composition according to claim 1 for preventing and controlling plant diseases caused by pathogenic fungi. 5. A method for killing fungi on site, comprising applying the fungicidal composition according to claim 1 or 2 to crops and the places where they are grown or stored before or after crops are susceptible to disease.