WO2018068772A1 - Bactericidal composition containing benzisothiazolinone and ametoctradin - Google Patents

Abstract

Provided is a bactericide composition. Said composition includes two active ingredients, A and B, active component A being a compound having the structure of formula (I), active component B being ametoctradin, the weight ratio of the two components being 10-1:1-40. Also provided are a preparation method for the composition and a use of the composition. Test results show that the bactericidal composition provided in the present invention has significant synergy and, more importantly, reduced application amounts and decreased usage costs. The present bactericidal composition effectively prevents and treats certain bacteria or fungal diseases of corps. By compounding bactericides having different mechanisms and modes of action, the bactericidal spectrum is expanded, fungi and bacterial resistance are delayed, and the prevention and treatment effect is improved.

Description

Bactericidal composition comprising benzisothiazolinones and azoxystrobin Technical field

The invention belongs to the field of agricultural plant protection, in particular to a germicidal composition with improved properties, in particular to a germicidal composition comprising benzisothiazolinones and azoxystrobin.

Background technique

Benzoisothiazolinones are a new type of broad-spectrum fungicide mainly used for the prevention and treatment of various bacterial and fungal diseases such as cereal crops, vegetables and fruits. The mechanism of bactericidal action mainly includes destroying the nuclear structure of the pathogen, causing it to lose the heart part and failing to death and interfering with the metabolism of the pathogenic cells, causing its physiological disorder and ultimately leading to death. It can effectively protect plants from pathogens in the early stage of disease occurrence. Increasing the dosage after disease occurrence can obviously control the spread of pathogens, thus achieving the dual functions of protection and eradication.

Ametoctradin is a triazole pyrimidine bactericide that belongs to mitochondrial respiratory inhibitors and has a controlling effect on downy mildew and Phytophthora fungi. Azoxystrobin is a highly selective fungicide for the efficient and flexible control of downy mildew and late blight. The product is resistant to rain and can be redistributed in the leaves to protect the healthy growth of the crop and maximize its growth potential.

Practical pesticide experience has shown that repeated and specific application of an active compound to control harmful fungi will in many cases lead to rapid selectivity of fungal strains, and in order to reduce the risk of selectivity of resistant fungal strains, different activities are currently used. A mixture of compounds to control harmful fungi. By combining active compounds having different mechanisms of action, resistance can be delayed, application rates can be reduced, and cost of control can be reduced.

Summary of the invention

The object of the present invention is to solve the resistance of the bactericide in practical application and the problem of soil residue, and to screen out the fungicides with different sterilization principles to obtain a new fungicide composition, so as to improve the control effect of the bactericide and delay the resistance. Sexual production, reducing the amount of application, reducing the cost of prevention.

Another object of the present invention is to provide an application comprising a bactericidal composition of two active ingredients A and B for controlling crop diseases in the agricultural field.

The object of the invention can be achieved by the following measures:

A synergistic fungicidal composition comprising two active components A and B, wherein active component A is a structural compound having formula (I) and active component B is azoxystrobin.

In the formula (I), R is selected from H or a C ₁ - C ₈ alkyl group.

The C ₁ -C ₈ alkyl group in the present invention means a linear or branched alkyl group having 1 to 8 carbon atoms, and includes a C ₁ alkyl group (e.g., methyl group) and a C ₂ alkyl group (e.g., ethyl group). , C ₃ alkyl (such as n-propyl, isopropyl), C ₄ alkyl (such as n-butyl, isobutyl, tert-butyl, sec-butyl), C ₅ alkyl (such as n-pentyl, etc.) , C ₆ alkyl, C ₇ alkyl, C ₈ alkyl. It includes, but is not limited to, C ₁ -C ₆ alkyl, C ₁ -C ₅ alkyl, C ₁ -C ₄ alkyl, and the like.

In a preferred embodiment, R is selected from H or a C ₁ -C ₄ alkyl group.

In a more preferred embodiment, R is selected from the group consisting of H, -CH ₃ or -C ₄ H ₉ .

In the formula (I), when R is H, A is 1,2-benzisothiazolin-3-one (abbreviated as BIT in the specification).

In the formula (I), when R is CH ₃ , A is 2-methyl-1,2-benzisothiazolin-3-one (abbreviated as MBIT in the specification).

In the formula (I), when R is C ₄ H ₉ , A is 2-butyl-1,2-benzisothiazolin-3-one, and the "butyl group" in the formula is preferably n-butyl (instruction Referred to as BBIT).

The inventors have found through experiments that the composition of the present invention is used for controlling bacterial or fungal diseases of crops, and the control effect is obvious, and more importantly, the application amount is reduced, and the use cost is lowered. The compounds containing component A and component B have different structural types and different mechanisms of action. The combination of the two can expand the bactericidal spectrum, and can delay the generation and development of pathogen resistance to a certain extent, and component A and group There is no cross-resistance between points B.

The weight ratio between the two components in the bactericide composition of the present invention is from 10 to 1:1 to 40. In order to make the synergistic effect between the two components more significant, the weight ratio between the two components of the components A and B can be further optimized to 1:1 to 30.

In a preferred embodiment, the weight ratio between the two components of A and B can be arbitrarily adjusted within the range of the following ratios: 10:1, 9:1, 8:1, 7:1, 6:1 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1: 9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, 1:26, 1:27, 1:28, 1:29, 1:30, 1:31, 1:32, 1:33, 1: 34, 1:35, 1:36, 1:37, 1:38, 1:39, 1:40, can also be selected within the range of any two ratios above, these ratios can be understood as the weight ratio It can also include a molar ratio.

The composition of the present invention can be made into a pesticide-acceptable dosage form from the active ingredient and agrochemical adjuvant or adjuvant. Further, the composition is made into a pesticide-acceptable dosage form from 2 to 80% by weight of the active ingredient and 98 to 20% by weight of the pesticide adjuvant or adjuvant.

The present invention provides the use of a bactericidal composition comprising component A and component B for controlling crop diseases in the agricultural sector, in particular for controlling fungal or bacterial diseases of certain crops.

The above composition may specifically comprise an agrochemical adjuvant or an auxiliary such as one or more of a carrier, a solvent, a dispersing agent, a wetting agent, an adhesive, a thickener, a binder, a surfactant or a fertilizer. Common auxiliaries can be mixed during the application.

Suitable auxiliaries or auxiliaries may be solid or liquid, they are usually materials commonly used in the processing of dosage forms, such as natural or regenerated minerals, solvents, dispersants, wetting agents, adhesives, thickeners, binders. .

The method of application of the compositions of the invention comprises the use of the compositions of the invention for aerial parts of plants, in particular leaves or foliage. You can choose to soak or apply to the surface of the control object. The frequency of administration and the amount administered will depend on the biological and climatic conditions of the pathogen. The plant growth site, such as rice fields, may be wetted with a liquid formulation of the composition, or the composition may be applied to the soil in solid form, such as in the form of granules (soil application), the composition may be passed from the soil to the plant through the roots of the plant. In vivo (systemic action).

The composition of the present invention can be prepared into various pesticide-acceptable dosage forms including, but not limited to, emulsifiable concentrates, suspending agents, wettable powders, water-dispersible granules, powders, granules, aqueous preparations, aqueous emulsions, microemulsions, poison baits. A mother liquor, a mother powder or the like. In a preferred embodiment, the dosage form of the invention employs a wettable powder, a suspending agent, a water-dispersible granule, an aqueous emulsion or a microemulsion. Depending on the nature of the compositions and the intended purpose and environmental conditions to which the compositions are to be applied, the compositions may be applied by spraying, misting, dusting, spreading or pouring, and the like.

The composition of the present invention can be prepared into various dosage forms by a known method, and the active ingredient and the auxiliary agent, such as a solvent, a solid carrier, and, if necessary, can be uniformly mixed and ground together with the surfactant to prepare a desired preparation. Dosage form.

The above solvent may be selected from aromatic hydrocarbons, preferably containing from 8 to 12 carbon atoms, such as a mixture of xylenes or substituted benzenes, phthalates such as dibutyl phthalate or dicaprylic acid, aliphatic hydrocarbons such as rings. Alkenes or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl; ketones, such as cyclohexanone, highly polar solvents such as N-methyl-2 Pyrrolidone, dimethyl sulfoxide or dimethylformamide, and vegetable or vegetable oils such as soybean oil.

The above solid carriers, such as those used in powders and dispersibles, are typically natural mineral fillers such as talc, kaolin, montmorillonite or activated clay. In order to manage the physical properties of the composition, it is also possible to add a highly dispersible silicic acid or a highly dispersible adsorbent polymer carrier, such as a particulate adsorbent carrier or a non-adsorbing carrier, and a suitable particulate adsorbent carrier is porous, such as pumice, bentonite or Bentonite; a suitable non-adsorbing carrier such as calcite or sand. In addition, a large amount of pre-granulated materials of inorganic or organic nature can be used as a carrier, in particular dolomite.

Suitable surfactants according to the chemical nature of the active ingredient in the composition of the present invention are lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, alkaline earth metal or amine salts, alkylarylsulfonates, alkyl groups Sulfates, alkyl sulfonates, fatty alcohol sulphates, fatty acids and sulfated fatty alcohol glycol ethers, as well as condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, naphthalene or naphthalene sulfonic acid with phenol and formaldehyde Condensate, polyoxyethylene octyl phenyl ether, ethoxylated isooctyl phenol, octyl phenol, nonyl phenol, alkane Aromatic polyglycol ether, tributyl benzene polyglycol ether, tristearyl phenyl polyglycol ether, alkyl aryl polyether alcohol, ethoxylated castor oil, polyoxyethylene hydride Ethyl ether, ethylene oxide condensate, ethoxylated polyoxypropylene, lauric acid polyglycol ether acetal, sorbitol ester, lignin sulfite waste liquid and methyl cellulose.

In the preparation of a liquid or solid dosage form, the active ingredient A can be first dissolved in certain specific basic substances to form a benzisothiazolin metal salt. Suitable basic substances include: alkali metal carbonates, alkali metal hydrogens Oxide (such as sodium hydroxide, potassium hydroxide), alkali metal alkoxy carbonate, alkali metal alkoxide or magnesium methoxide.

The two active ingredients in the compositions of the present invention exhibit synergistic effects, the activity of which is more pronounced than the expected sum of activity using a single compound, and the individual activity of a single compound. The synergistic effect is manifested by allowing for a reduced application rate, a broader fungicidal control profile, quicker effect, longer lasting control effect, better control of plant harmful fungi by only one or a few applications, and broadening of possible application. Intervals. These properties are particularly desirable in the practice of plant fungi control.

The fungicide composition of the invention can be applied to the field of agricultural diseases for controlling crop diseases, and the specific diseases targeted include, but not limited to, wheat diseases (such as wheat scab, wheat powdery mildew, wheat rust, etc.) and rice diseases (such as: Rice sheath blight, rice blast disease, rice blast, rice bacterial streaks, etc., corn diseases (such as: corn smut, corn big spot, corn spot), cucumber diseases (such as: cucumber frost Mold disease, cucumber powdery mildew, cucumber anthracnose, cucumber bacterial angular spot disease, etc., tomato diseases (such as: tomato anthracnose, tomato gray mold, tomato bacterial angular spot disease, etc.), grape diseases (such as: grape frost Mildew, grape gray mold, grape powdery mildew), apple disease (such as apple ring disease, apple anthracnose, etc.), citrus disease (citrus canker disease, citrus canker, citrus anthracnose), tobacco disease (tobacco wildfire disease) )Wait.

The other characteristics exhibited by the bactericidal composition of the present invention are mainly as follows: 1. The compounding of the composition of the present invention has obvious synergistic effect; 2. Since the chemical composition of the two single agents of the present composition is greatly different, the effect The mechanism is completely different, there is no cross-resistance, and the problem of resistance caused by the separate use of the two single agents can be delayed; 3. The composition of the present invention is safe and safe for crops. It has been proved by experiments that the bactericidal composition of the invention has stable chemical properties, remarkable synergistic effect, and exhibits obvious synergistic effect and complementary effect on the control object.

detailed description

In order to make the objects, technical solutions and advantages of the present invention more comprehensible, the present invention will be further described in detail below with reference to the embodiments. It is understood that the specific embodiments described herein are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention. Within the scope of protection of the present invention.

The percentages in all formulations in the following examples are percentages by weight. The processing techniques of the various formulations of the compositions of the present invention are all prior art and may vary depending on the circumstances.

First, the dosage form preparation example

(1) Processing and examples of water-dispersible granules

The active ingredient active group A and the active component B, and the auxiliary agent and the filler are uniformly mixed according to the formula, and are pulverized into a wettable powder by a jet stream, and then added with a certain amount of water to be mixed and extruded, granulated, and dried and sieved. A water dispersible granule product.

(1) Preparation of water-dispersible granules by active component A (BIT) and azoxystrobin

Example 1: 10% BIT · Azoxystrobin water dispersible granules (1:1)

BIT 5%, oxacillin 5%, gelatin 3%, polyacrylamide 3%, sodium bicarbonate 5%, white carbon black to 100%

Example 2: 21% BIT · Azoxystrobin water dispersible granules (1:20)

BIT 1%, azoxystrobin 20%, bentonite 8%, pull open powder BX 6%, aluminum chloride 5%, light calcium carbonate to 100%

(2) Preparation of water-dispersible granules by active component A (MBIT) and azoxystrobin

Example 3: 10% MBIT·oxacillin water dispersible granules

MBIT was 5%, oxacillin was 5%, and the remaining components were prepared in accordance with the procedure of Example 1.

Example 4: 21% MBIT·oxacillin water dispersible granules

MBIT 1%, azoxystrobin 20%, and the remaining components were prepared in the same manner as in Example 2.

(3) Preparation of water-dispersible granules by active ingredient A (BBIT) and azoxystrobin

Example 5: 10% BBIT·oxacillin water dispersible granules

BBIT 5%, azocilin 5%, and the remaining components were prepared in accordance with the procedure of Example 1.

Example 6: 21% BBIT · Azoxystrobin water dispersible granules

BBIT 1%, azoxystrobin 20%, and the remaining components were prepared in accordance with the procedure of Example 2.

(2) Processing and examples of suspending agents

The active ingredient active group A and the active component B, and the components such as a dispersing agent, a wetting agent, a thickener and water are uniformly mixed according to the formula, and after being sanded and/or sheared at a high speed, a semi-finished product is obtained. After the analysis, the water is mixed and evenly filtered to obtain the finished product.

(1) Preparation of suspending agent from active ingredient A (BIT) and azoxystrobin

Example 7: 16.5% BIT - Azoxystrobin Suspension (10:1)

BIT 15%, azoxystrobin 1.5%, methylpentanol 5%, sodium alginate 4%, polyethylene glycol 4%, silicone oil 0.02%, water to 100%.

Example 8: 31% BIT · Azoxyprost Suspension (1:30)

BIT 1%, azoxystrobin 30%, fatty acid polyethylene glycol ester 10%, xanthan gum 8%, propylene glycol 8%, silicone oil 0.05%, The water is made up to 100%.

(2) Preparation of suspending agent from active ingredient A (MBIT) and azoxystrobin

Example 9: 16.5% MBIT · Azoxystrobin suspension

MBIT 15%, azoxystrobin 1.5%, and the remaining components were prepared in accordance with the procedure of Example 7.

Example 10: 31% MBIT · Azoxystrobin Suspension

MBIT 1%, azoxystrobin 30%, and the remaining components were prepared in accordance with the procedure of Example 8.

(3) Preparation of suspending agent from active ingredient A (BBIT) and azoxystrobin

Example 11: 16.5% BBIT · Azoxystrobin suspension

BBIT 15%, azoxystrobin 1.5%, and the remaining components were prepared in accordance with the procedure of Example 7.

Example 12: 31% BBIT · Azoxystrobin Suspension

BBIT 1%, azoxystrobin 30%, and the remaining components were prepared in accordance with the procedure of Example 8.

(3) Processing and examples of wettable powders

The active ingredient A and the B active ingredient are sufficiently mixed with various auxiliary agents and fillers, and are pulverized by an ultrafine pulverizer to obtain a wettable powder.

(1) Preparation of wettable powder by active ingredient A (BIT) and azoxystrobin

Example 13: 33% BIT-oxacillin wettable powder (1:10)

BIT 3%, azoxystrobin 30%, saponin powder 10%, sodium lauryl sulfate 8%, silica gel 6%, kaolin supplement to 100%.

Example 14: 61.5% BIT-lazostrobin wettable powder (1:40)

BIT 1.5%, azoxystrobin 60%, sodium alkylbenzene sulfonate 15%, sodium lignin sulfonate 8%, ammonium sulfate 6%, white carbon black to 100%.

(2) Preparation of wettable powder by active ingredient A (MBIT) and azoxystrobin

Example 15: 33% MBIT·13% azoxystrobin wettable powder

MBIT 3%, azoxystrobin 30%, and the remaining components were prepared in accordance with the procedure of Example 13.

Example 16: 61.5% MBIT·razinamide wettable powder

MBIT 1.5%, azoxystrobin 60%, and the remaining components were prepared in accordance with the procedure of Example 14.

(3) Preparation of wettable powder by active ingredient A (BBIT) and azoxystrobin

Example 17: 33% BBIT·razinamide wettable powder

BBIT 3%, azoxystrobin 30%, and the remaining components were prepared in accordance with the procedure of Example 13.

Example 18: 61.5% BBIT·razinamide wettable powder

BBIT 1.5%, azoxystrobin 60%, and the remaining components were prepared in accordance with the procedure of Example 14.

Second, the efficacy test

(1) Bioassay examples

According to the test grading standards, the incidence of the whole plant leaves was investigated, and the disease index and control effect were calculated.

The control effect is converted into the probability value (y), the concentration of the drug solution (μg/ml) is converted into the logarithm value (x), the virulence equation is calculated by the least squares method and the concentration EC50 is suppressed, and the virulence index of the drug is calculated according to the method of Sun Yunpei. And the co-toxicity coefficient (CTC).

Measured virulence index (ATI) = (standard drug EC50 / test drug EC50) * 100

Theoretical virulence index (TTI) = A virulence index * Percentage of A in the mixture + B virulence index * Percentage of B in the mixture

Co-toxicity coefficient (CTC) = [mixture measured virulence index (ATI) / mixed theory virulence index (TTI)] * 100

CTC ≤ 80, the composition showed antagonism, 80 < CTC < 120, the composition showed an additive effect, CTC ≥ 120, and the composition showed synergistic effect.

1, BIT and azoxystrobin combined with capsicum virus test

Table 1. Analysis of the results of BIT and azocilin paired with capsicum virus

The results (Table 1) showed that the effect of BIT and azoxystrobin on the control of capsicum blight was significantly improved, indicating that there was a significant synergistic effect between the two on the control of capsicum blight.

2, MBIT and azoxystrobin complex pairing pumpkin plaque virus test

Table 2. Analysis of the results of the determination of pumpkin keratosis virus by MBIT and azoxystrobin

The results (Table 2) showed that the effect of MBIT and azoxystrobin on pumpkin keratosis was significantly improved, indicating that the combination of the two had a significant synergistic effect on the prevention and treatment of pumpkin keratosis.

3, BBIT and azoxystrobin on the determination of garlic rust virus

Table 3. Analysis of the results of the determination of garlic rust virus by BBIT and azoxystrobin

The results (Table 3) showed that the effect of BBIT and azoxystrobin on the control of garlic rust was significantly improved, indicating that the two had a significant synergistic effect on the control of garlic rust.

(2) Field efficacy test

Test method: In the early stage of the disease, the first spray was immediately performed, and after 7 days, the second application was carried out, each treatment of 4 cells, 20 square meters per cell. The incidence of the disease was investigated before the drug and 11 days after the second drug. Each plot was randomly sampled at 5 points, and 5 crops were investigated at each point. The percentage of the lesion area per leaf on the whole plant was counted and graded. Disease index and control effect.

Expected control effect (%) = X + Y-XY / 100 (where X, Y is a single dose control)

Grading standards:

Level 0: no lesions;

Grade 1: less than 5 leaf lesions, less than 1 cm in length;

Grade 3: 6-10 leaf lesions, some lesions are longer than 1 cm;

Grade 5: 11-25 leaf lesions, some lesions are connected into pieces, and the lesion area accounts for 10-25% of the leaf area;

Grade 7: more than 26 leaf lesions, the lesions are connected into pieces, and the lesion area accounts for 26-50% of the leaf area;

Grade 9: The lesions are connected into pieces, and the area of the lesions accounts for more than 50% of the leaf area or the whole leaves are dead.

1. Field efficacy test of BIT and azoxystrobin

Table 4 BIT combined with azoxystrobin to control early potato blight

The results of the determination (Table 4) showed that the compounding effect of BIT and azoxystrobin on potato early blight was significantly improved, indicating that the two had a significant synergistic effect on potato early blight.

2, MBIT and azoxystrobin compound field efficacy experiment

Table 5 MBIT and azoxystrobin mixed with grape downy mildew control effect

The results of the determination (Table 5) showed that the control effect of MBIT and azoxystrobin on grape downy mildew was significantly improved, indicating that the two had a significant synergistic effect on grape downy mildew.

3, BBIT and azoxystrobin compound field efficacy experiment

Table 6 Effect of BBIT and azoxystrobin on the control of white rust in Chinese cabbage

The results of the determination (Table 6) showed that the control effect of BBIT and azoxystrobin on cabbage white rust was significantly improved, indicating that the two had a significant synergistic effect on white cabbage rust.

Claims (9)

A bactericidal composition, characterized in that the composition comprises two active components A and B, wherein the active component A is a structural compound having the formula (I), and the active component B is azoxystrobin. The weight ratio between the two components is 10 to 1:1 to 40

In the formula (I), R is selected from H or a C ₁ - C ₈ alkyl group. The bactericidal composition according to claim 1, wherein in the formula (I), R is selected from H or a C ₁ - C ₄ alkyl group. The bactericidal composition according to claim 1, wherein in the formula (I), R is preferably selected from H, -CH ₃ or -C ₄ H ₉ , and the corresponding active component A is 1,2-benzene. Isothiazolin-3-one, 2-methyl-1,2-benzisothiazolin-3-one or 2-butyl-1,2-benzisothiazolin-3-one. The bactericide composition according to claim 1, wherein the weight ratio of the active component A to the active component B is from 1:1 to 30. The bactericidal composition according to any one of claims 1 to 4, wherein the composition is made into a pesticide-acceptable dosage form from an active ingredient and an agrochemical adjuvant or an auxiliary. The bactericide composition according to claim 5, wherein the composition is made into a pesticide-acceptable dosage form from 2 to 80% by weight of the active ingredient and 98 to 20% by weight of the pesticide adjuvant or adjuvant. The bactericidal composition according to claim 5 or 6, wherein the dosage form is a wettable powder, a suspending agent, a water-dispersible granule, an aqueous emulsion or a microemulsion. The bactericidal composition according to claim 5 or 6, wherein the pesticide adjuvant or adjuvant is selected from the group consisting of a carrier, a solvent, a dispersing agent, a wetting agent, an adhesive, a thickener, a binder, and a surfactant. Or one or more of the fertilizers. Use of the bactericide composition according to any one of claims 1 to 8 for controlling crop diseases in the agricultural field.