WO2018157649A1 - Microbicide composition containing emodin derivative and benzisothiazolinone - Google Patents

Abstract

Provided is a microbicide composition containing an emodin derivative and benzisothiazolinone. The composition contains two effective ingredients, i.e. A and B. Active component A is one of physcion or aloe-emodin, active component B is a structural compound of formula (I), and the weight ratio of the two components is 10 - 1 : 1 - 50. Also provided are a preparation method for the composition and the use thereof. Test results show that the above microbicide composition provided by the present invention has a significant synergistic effect, and more importantly, the application amount thereof is reduced and the cost of use thereof is lowered. The microbicide composition can effectively control certain specific bacterial or fungal diseases of crops. By compounding microbicides with different action mechanisms and action modes, the composition has good effects with regard to expanding the bactericidal spectrum, delaying the resistance of bacteria, and improving control effects, etc. In formula (I), R is selected from H or a C1-C8 alkyl.

Description

A bactericidal composition comprising an emodin derivative and a benzisothiazolinone 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 a emodin derivative and benzisothiazolinone.

Background technique

Both Physcion and Aloeemodin belong to terpenoids. In the field of medicine, these compounds are widely used, such as immunoregulation, scavenging oxygen free radicals, antibacterial, anti-inflammatory, antiviral effects, diuretic effects, protective effects on cerebral ischemic injury, cardiovascular pharmacological effects, and anti-tumor effects. In recent years, these terpenoids are gradually being used in agriculture for the control of fungal or bacterial diseases. This kind of compound is a kind of high-activity plant-derived fungicide extracted from the roots and stems of Chinese herbal plant rhubarb. It is a terpenoid compound, powdery mildew, downy mildew, gray mold, anthrax on vegetables, fruits, grains, etc. Diseases and other diseases have good control effects. At the same time, they are low-toxic to humans and animals, environmentally friendly, and have no cross-resistance with other chemical agents. They have good systemic conduction and strong persistence. Its bactericidal mechanism is to interfere with the biosynthesis of chitin in the cell wall of pathogenic fungi, inhibit the germination of pathogenic spores, the growth of hyphae, the formation of aspirator, thereby blocking the spread of the disease, and also induce the crop to produce an anti-retroviral reaction. The effect of disease prevention.

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.

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 a process for the preparation of a bactericidal composition comprising two active ingredients A and B and to combat crop diseases in the agricultural sector.

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

A bactericidal composition, the composition comprising two active components A and B, wherein the active component A is one of emodin derivatives selected from the group consisting of emodin methyl ether and aloe emodin, wherein the active component A Component B is a structural compound having the formula (I), and the weight ratio between the two components is from 10 to 1:1 to 50.

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.

In a preferred embodiment, the weight ratio of the active component A to the active component B is from 1:1 to 40, and the weight ratio may be more preferably from 1:1 to 30 in order to make the effect more remarkable. Still more preferably, the weight ratio of emodin methyl ether to 1,2-benzisothiazolin-3-one is 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, 1:41, 1:42, 1:43, 1:44, 1:45, 1:46, 1:47, 1:48, 1:49, 1:50, it is also possible to select within the range of any two of the above ratios, which can be understood as a weight ratio or 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 comprises from 1 to 85% by weight of the active ingredient and from 99 to 15% by weight of the pesticide adjuvant or adjuvant to form a pesticide-acceptable dosage form.

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 dosage forms acceptable for pesticides, including but not limited to emulsifiable concentrates, suspending agents, wettable powders, water-dispersible granules, powders, granules, aqueous preparations, aqueous emulsions, microemulsions, micro In a preferred embodiment, the dosage form of the present invention is a suspending agent, a liquid, a wettable powder or an aqueous emulsion. 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.

In the preparation of the liquid dosage form, the active component B may be first dissolved in a basic substance to form a benzisothiazolin metal salt. Suitable basic substances include: alkali metal carbonates, alkali metal hydroxides (such as hydroxides). Sodium, potassium hydroxide), alkali metal alkoxy carbonate, alkali metal alkoxide or magnesium methoxide.

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, alkyl aryl polyglycol ether, tributyl benzene polyglycol ether, three Stearyl phenyl polyglycol ether, alkyl aryl polyether alcohol, ethoxylated castor oil, polyoxyethylene alkyl ether, ethylene oxide condensate, ethoxylated polyoxypropylene, lauric acid poly Glycol ether acetal, sorbitol ester, lignin sulfite waste liquor and methyl cellulose.

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 agricultural field for controlling crop diseases, and the crop diseases referred to herein are grape powdery mildew, cucumber powdery mildew, cucumber downy mildew, bitter gourd powdery mildew, tomato gray mold disease, wheat powdery mildew. Rice blast disease. However, in addition to the above-mentioned diseases, the composition of the present invention can prevent and cure specific diseases including but not limited to wheat diseases (such as wheat scab, wheat powdery mildew, wheat rust, etc.), rice diseases (such as rice stalks). Disease, rice smut, rice bacterial streaks, etc.), corn diseases (such as: corn smut, corn big spot, corn small spot disease), cucumber diseases (such as: cucumber powdery mildew, cucumber anthracnose, cucumber Botrytis, cucumber bacterial leaf spot, etc., tomato diseases (eg tomato powdery mildew, tomato anthracnose, tomato virus disease, tomato bacterial angular spot disease, etc.), grape diseases (eg grape downy mildew, grapes) Gray mold), apple diseases (such as: apple ring disease, apple anthracnose, etc.), citrus diseases (such as: citrus scab, citrus anthracnose), tobacco diseases (such as: tobacco wildfire, tobacco brown spot disease), rape Diseases (such as: Sclerotinia sclerotiorum), cotton diseases (such as: cotton verticillium wilt, cotton blight).

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 very different, the mechanism of action is completely Different, there is no cross-resistance, which can delay the resistance problem caused by the two single agents used alone; 3. The composition of the invention is safe and effective against 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 agents

The active ingredient active group A and the active ingredient B are mixed with the components such as the surfactant and water in a ratio of the formulation to obtain a finished product.

(1) Active ingredient A (emodin methyl ether) and active ingredient B (BIT) preparation of water agent

Example 1: 2.2% emodin methyl ether BIT water (10:1)

Emodin methyl ether 2%, BIT 0.2%, polyoxyethylene octyl phenyl ether 6.28%, ethoxylated castor oil 7.53%, water to 100%.

Example 2: 5.25% emodin methyl ether BIT water (1:20)

Emodin methyl ether 0.25%, BIT 5%, tributyl phenyl polyglycol ether 8.63%, water to 100%.

(2) Active ingredient A (emodin methyl ether) and active component B (MBIT))

Example 3: 2.2% emodin methyl ether·MBIT water agent

Emodin methyl ether 2%, MBIT 0.2%, and the remaining components were prepared according to the method of Example 1.

Example 4: 5.25% emodin methyl ether·MBIT water agent

The emodin methyl ether was 0.25%, MBIT was 5%, and the remaining components were prepared in accordance with the method of Example 2.

(3) Aqueous preparation of active ingredient A (emodin methyl ether) and active component B (BBIT)

Example 5: 2.2% emodin methyl ether · BBIT water agent

The emodin methyl ether 2%, BBIT 0.2%, and the remaining components were prepared in accordance with the method of Example 1.

Example 6: 5.25% emodin methyl ether · BBIT water agent

The emodin methyl ether was 0.25%, BBIT was 5%, and the remaining components were prepared in accordance with the method of Example 2.

(4) Active ingredient A (aloe emodin) and active ingredient B (BIT) preparation of water

Example 7: 2.2% aloe emodin·BIT water

Aloe-emodin 2%, BIT 0.2%, and the remaining components were prepared in accordance with the method of Example 1.

Example 8: 5.25% aloe-emodin·BIT water agent

Aloe-emodin 0.25%, BIT 5%, and the remaining components were prepared according to the method of Example 2.

(5) Active ingredient A (aloe emodin) and active ingredient B (MBIT) preparation of water agent

Example 9: 2.2% aloe-emodin·MBIT water agent

Aloe-emodin 2%, MBIT 0.2%, and the remaining components were prepared according to the method of Example 1.

Example 10: 5.25% aloe-emodin·MBIT water agent

Aloe-emodin 0.25%, MBIT 5%, and the remaining components were prepared according to the method of Example 2.

(6) Active ingredient A (aloe emodin) and active ingredient B (BBIT) preparation of water agent

Example 11: 2.2% aloe-emodin BBIT liquid

Aloe-emodin 2%, BBIT 0.2%, and the remaining components were prepared in accordance with the method of Example 1.

Example 12: 5.25% aloe-emodin BBIT liquid

Aloe-emodin 0.25%, BBIT 5%, and the remaining components were prepared according to the method of Example 2.

(2) 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 component A (emodin methyl ether) and active component B (BIT)

Example 13: 6% emodin methyl ether·BIT wettable powder (1:1)

Emodin methyl ether 3%, BIT 3%, xanthan gum 1.27%, naphthalene sulfonate sodium salt 5.24%, saponin powder 4.62%, ammonium sulfate 4.79%, kaolin clay to 100%.

Example 14: 15.5% emodin methyl ether·BIT wettable powder (1:30)

Emodin methyl ether 0.5%, BIT 15%, magnesium silicate aluminum 4.11%, sodium lauryl sulfate 6.52%, alkylphenol ethoxylate 5.15%, sodium bicarbonate 3.54%, white carbon black to 100 %.

(2) Preparation of wettable powder by active component A (emodin methyl ether) and active component B (MBIT)

Example 15: 6% emodin methyl ether·MBIT wettable powder

The emodin methyl ether was 3%, MBIT was 3%, and the remaining components were prepared in accordance with the procedure of Example 13.

Example 16: 15.5% emodin methyl ether·MBIT wettable powder

The emodin methyl ether was 0.5%, the MBIT was 15%, and the remaining components were prepared in the same manner as in Example 14.

(3) Preparation of wettable powder by active component A (emodin methyl ether) and active component B (BBIT)

Example 17: 6% emodin methyl ether · BBIT wettable powder

The emodin methyl ether was 3%, BBIT was 3%, and the remaining components were prepared in accordance with the procedure of Example 13.

Example 18: 15.5% emodin methyl ether · BBIT wettable powder

Emodin methyl ether 0.5%, BBIT 15%, and the remaining components were prepared in accordance with the procedure of Example 14.

(4) Preparation of wettable powder by active ingredient A (aloe emodin) and active ingredient B (BIT)

Example 19: 6% aloe-emodin·BIT wettable powder

Aloe-emodin 3%, BIT 3%, and the remaining components were prepared in accordance with the procedure of Example 13.

Example 20: 15.5% aloe-emodin·BIT wettable powder

Aloe-emodin 0.5%, BIT 15%, and the remaining components were prepared in accordance with the procedure of Example 14.

(5) Preparation of wettable powder by active ingredient A (aloe emodin) and active ingredient B (MBIT)

Example 21: 6% aloe-emodin·MBIT wettable powder

Aloe-emodin 3%, MBIT 3%, and the remaining components were prepared in accordance with the procedure of Example 13.

Example 22: 15.5% aloe-emodin·MBIT wettable powder

Aloe-emodin 0.5%, MBIT 15%, and the remaining components were prepared in accordance with the procedure of Example 14.

(6) Preparation of wettable powder by active ingredient A (aloe emodin) and active ingredient B (BBIT)

Example 23: 6% aloe-emodin BBIT wettable powder

Aloe-emodin 3%, BBIT 3%, and the remaining components were prepared in accordance with the procedure of Example 13.

Example 24: 15.5% aloe-emodin BBIT wettable powder

Aloe-emodin 0.5%, BBIT 15%, and the remaining components were prepared in accordance with the procedure of Example 14.

(III) Processing and examples of water emulsion

The active ingredient A and the B active ingredient are mixed well with a solvent, an emulsifier, a dispersing agent, an antifreezing agent, etc., and the water emulsion is prepared by adding water and then uniformly mixing.

(1) Preparation of water emulsion by active component A (emodin methyl ether) and active component B (BIT)

Example 25: 2.75% emodin methyl ether BIT water emulsion (1:10)

Emodin methyl ether 0.25%, BIT 2.5%, concentrated milk 600 6.32%, toluene 10%, calcium dodecylbenzenesulfonate 5.25%, ammonium sulfate 5%, water to 100%.

Example 26: 10.25% emodin methyl ether BIT water emulsion (1:40)

Emodin methyl ether 0.25%, BIT 10%, alkylphenol polyoxyethylene ether formaldehyde condensate 5.43%, xylene 15.0%, saponin powder 8.62%, glycerol 10%, water to 100%.

Example 27: 5.1% emodin methyl ether BIT water emulsion (1:50)

Emodin methyl ether 0.1%, BIT 5%, Tween-80 5.87%, xylene 8.0%, sodium lauryl sulfate 4.65%, propylene glycol 6%, water to 100%.

(2) Preparation of water emulsion by active component A (emodin methyl ether) and active component B (MBIT)

Example 28: 2.75% emodin methyl ether·MBIT water emulsion

The emodin methyl ether was 0.25%, the MBIT was 2.5%, and the remaining components were prepared in accordance with the procedure of Example 25.

Example 29: 10.25% emodin methyl ether·MBIT water emulsion

The emodin methyl ether was 0.25%, the MBIT was 10%, and the remaining components were prepared in the same manner as in Example 26.

Example 30: 5.1% emodin methyl ether·MBIT water emulsion

Emodin methyl ether 0.1%, MBIT 5%, and the remaining components were prepared in accordance with the procedure of Example 27.

(3) Preparation of water emulsion by active component A (emodin methyl ether) and active component B (BBIT)

Example 31: 2.75% emodin methyl ether BBIT water emulsion

The emodin methyl ether was 0.25%, BBIT was 2.5%, and the remaining components were prepared in accordance with the procedure of Example 25.

Example 32: 10.25% emodin methyl ether BBIT water emulsion

Emodin methyl ether 0.25%, BBIT 10%, and the remaining components were prepared according to the method of Example 26.

Example 33: 5.1% emodin methyl ether BBIT water emulsion

Emodin methyl ether 0.1%, BBIT 5%, and the remaining components were prepared in accordance with the procedure of Example 27.

(4) Preparation of water emulsion by active component A (aloe emodin) and active component B (BIT)

Example 34: 2.75% aloe-emodin·BIT water emulsion

Aloe-emodin 0.25%, BIT 2.5%, and the remaining components were prepared in accordance with the procedure of Example 25.

Example 35: 10.25% aloe-emodin BIT water emulsion

Aloe-emodin 0.25%, BIT 10%, and the remaining components were prepared according to the method of Example 26.

Example 36: 5.1% aloe emodin·BIT water emulsion

Aloe-emodin 0.1%, BIT 5%, and the remaining components were prepared in accordance with the procedure of Example 27.

(5) Preparation of water emulsion by active component A (aloe emodin) and active component B (MBIT)

Example 37: 2.75% aloe-emodin·MBIT water emulsion

Aloe-emodin 0.25%, MBIT 2.5%, and the remaining components were prepared according to the method of Example 25.

Example 38: 10.25% aloe-emodin·MBIT water emulsion

Aloe-emodin 0.25%, MBIT 10%, and the remaining components were prepared according to the method of Example 26.

Example 39: 5.1% aloe-emodin·MBIT water emulsion

Aloe-emodin 0.1%, MBIT 5%, and the remaining components were prepared in accordance with the procedure of Example 27.

(6) Preparation of water emulsion by active component A (aloe emodin) and active component B (BBIT)

Example 40: 2.75% aloe-emodin BBIT water emulsion

Aloe-emodin 0.25%, BBIT 2.5%, and the remaining components were prepared in accordance with the procedure of Example 25.

Example 41:10.25% Aloe-emodin·BBIT Water Emulsion

Aloe-emodin 0.25%, BBIT 10%, and the remaining components were prepared according to the method of Example 26.

Example 42: 5.1% aloe-emodin BBIT water emulsion

Aloe-emodin 0.1%, BBIT 5%, and the remaining components were prepared in accordance with the procedure of Example 27.

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, emodin methyl ether and BIT complex pairing pepper leaf spot virus test

Table 1. Analysis of the results of the determination of emodin methyl ether and BIT complex pepper leaf spot virus

The results (Table 1) showed that in the range of emodin methyl ether: BIT=10～1:1～50, the control effect of emodin methyl ether and BIT on pepper leaf spot was significantly improved, indicating that the two were paired with chili. Leaf spot disease prevention and treatment has a significant synergistic effect.

2, emodin methyl ether and MBIT complex pairing tomato leaf mold virus test

Table 2. Analysis of the results of the determination of phytohormone methyl ether and MBIT complex against tomato leaf mold virus

Pharmacy name	EC50 (ug/mL)	ATI	TTI	CTC
Emodin methyl ether	2.75	100.00	\	\
MBIT	4.89	56.24	\	\
Emodin methyl ether: MBIT=20:1	2.09	131.85	97.92	134.66
Emodin methyl ether: MBIT=10:1	1.42	193.54	96.02	201.56
Emodin methyl ether: MBIT = 1:1	1.56	175.74	78.12	224.96
Emodin methyl ether: MBIT=1:10	1.86	147.55	60.22	245.02
Emodin methyl ether: MBIT=1:20	1.78	154.65	58.32	265.16
Emodin methyl ether: MBIT=1:30	1.98	138.76	57.65	240.68
Emodin methyl ether: MBIT=1:40	2.18	125.93	57.31	219.75
Emodin methyl ether: MBIT=1:50	2.37	116.13	57.10	203.39
Emodin methyl ether: MBIT=1:60	3.72	73.89	56.96	129.72

The results (Table 2) showed that the control effect of emodin methyl ether and MBIT on tomato leaf mold was significantly improved, indicating that the two had a significant synergistic effect on tomato leaf mold control.

3, emodin methyl ether and BBIT complex pairing test for Aspergillus fumigatus virus

Table 3. Analysis of the results of the determination of emodin methyl ether and BBIT complex against Aspergillus fumigatus virus

The results (Table 3) showed that the control effect of emodin methyl ether and BBIT on the control of zucchini aspergillosis was significantly improved, indicating that the combination of the two had a significant synergistic effect on the control of aspergillus fumigatus.

4, aloe emodin and BIT complex pairing watermelon bacterial fruit spot virus test

Table 4. Analysis of the results of determination of bacterial fruit spot virus in watermelons with aloe-emodin and BIT

Pharmacy name	EC50 (ug/mL)	ATI	TTI	CTC
Aloe-emodin	2.84	100.00	\	\
BIT	3.71	76.55	\	\
Aloe-emodin: BIT=20:1	2.29	124.27	98.88	125.67
Aloe-emodin: BIT=10:1	2.12	134.23	97.87	137.15
Aloe-emodin: BIT=1:1	2.12	134.23	88.28	152.06
Aloe-emodin: BIT=1:10	2.19	129.81	78.68	164.98
Aloe-emodin: BIT=1:20	2.05	138.67	77.67	178.54
Aloe-emodin: BIT=1:30	2.32	122.42	77.31	158.36
Aloe-emodin: BIT=1:40	2.60	109.18	77.12	141.57
Aloe-emodin: BIT=1:50	2.84	99.84	77.01	129.65
Aloe-emodin: BIT=1:60	3.20	88.76	76.93	115.37

The results (Table 4) showed that the control effect of aloe-emodin and BIT on watermelon bacterial fruit spot disease was significantly improved, indicating that the two had a significant synergistic effect on the prevention and control of watermelon bacterial fruit spot disease.

5, aloe emodin and MBIT complex pairing melon virus test

Table 5. Analysis of the results of the determination of aloe emodin and MBIT complex melon virus

Pharmacy name	EC50 (ug/mL)	ATI	TTI	CTC
Aloe-emodin	3.68	100.00	\	\
MBIT	5.42	67.90	\	\
Aloe-emodin: MBIT=20:1	3.00	122.70	98.47	124.60
Aloe-emodin: MBIT=10:1	2.48	148.65	97.08	153.12
Aloe-emodin: MBIT=1:1	2.60	141.30	83.95	168.31
Aloe-emodin: MBIT=1:10	2.88	127.68	70.82	180.29
Aloe-emodin: MBIT=1:20	2.73	134.94	69.43	194.36

Aloe-emodin: MBIT=1:30	2.95	124.95	68.94	181.25
Aloe-emodin: MBIT=1:40	3.16	116.49	68.68	169.60
Aloe-emodin: MBIT=1:50	3.46	106.51	68.53	155.42
Aloe-emodin: MBIT=1:60	4.30	85.57	68.43	125.06

The results (Table 5) showed that the co-toxicity coefficient of aloe-emodin and MBIT compound melon blight was above 153.12 in the range of aloe-emodin: MBIT=10～1:1～50, indicating that the two were paired. Melon blight control has a significant synergistic effect.

6, aloe emodin and BBIT complex pairing loofah vine virus test

Table 6. Analysis of the results of the determination of aloe emodin and BBIT complex

Pharmacy name	EC50 (ug/mL)	ATI	TTI	CTC
Aloe-emodin	5.84	100.00	\	\
BBIT	8.25	70.79	\	\
Aloe-emodin: BBIT=20:1	4.15	140.58	98.61	142.56
Aloe-emodin: BBIT=10:1	2.98	196.30	97.34	201.65
Aloe-emodin: BBIT=1:1	3.05	191.55	85.40	224.31
Aloe-emodin: BBIT=1:10	3.18	183.88	73.45	250.36
Aloe-emodin: BBIT=1:20	2.94	198.79	72.18	275.41
Aloe-emodin: BBIT=1:30	3.21	181.78	71.73	253.41
Aloe-emodin: BBIT=1:40	3.58	162.98	71.50	227.94
Aloe-emodin: BBIT=1:50	4.12	141.74	71.36	198.62
Aloe-emodin: BBIT=1:60	5.92	98.64	71.27	138.41

The results (Table 6) showed that the co-toxicity coefficient of aloe-emodin and BBIT complexed with loofah blight was above 198.62 in the range of aloe-emodin: BBIT=10～1:1～50, indicating that the two were paired. There is a significant synergistic effect on the control of loofah blight.

(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 emodin methyl ether and BIT compounding

Table 7. Effect of emodin methyl ether and BIT mixed with grape downy mildew

The results of the determination (Table 7) showed that the complex effect of emodin methyl ether and BIT on grape downy mildew was significantly improved, indicating that the two had a significant synergistic effect on grape downy mildew.

2, emodin methyl ether and MBIT compound field efficacy experiment

Table 8 Effect of emodin methyl ether and MBIT on the control of kiwi canker

The results (Table 8) showed that the control effect of emodin methyl ether and MBIT on kiwifruit ulcer disease was significantly improved, indicating that the two had a significant synergistic effect on kiwifruit ulcer disease.

3, emodin methyl ether and BBIT compound field efficacy experiment

Table 9 Effect of emodin methyl ether and BBIT on the control of potato late blight

The results of the determination (Table 9) showed that the control effect of emodin methyl ether and BBIT on potato late blight was significantly improved, indicating that the two had a significant synergistic effect on potato late blight.

4, aloe emodin and BIT compound field efficacy experiment

Table 10 Aloe-emodin combined with BIT to control the effect of wheat scab

The results of the assay (Table 10) showed that the control effect of aloe-emodin combined with BIT on wheat scab was significantly improved, indicating that the two had a significant synergistic effect on wheat scab.

5, aloe emodin and MBIT compound field efficacy experiment

Table 11 Aloe-emodin combined with MBIT to control the effects of tobacco black shank

The results (Table 11) showed that the control effect of aloe-emodin combined with MBIT on tobacco black shank was significantly improved, indicating that the two had a significant synergistic effect on tobacco black shank.

6. Field efficacy experiment of aloe-emodin and BBIT compounding

Table 12 Aloe-emodin and BBIT mixed with citrus anthracnose control effect

The results (Table 12) showed that the control effect of aloe-emodin combined with BBIT on citrus anthracnose was significantly improved, indicating that the two had a significant synergistic effect on citrus anthracnose.

Claims (10)

1. A bactericidal composition, characterized in that the composition comprises two active components A and B, and the active component A is one of emodin derivatives selected from the group consisting of emodin methyl ether and aloe emodin. The active component B is a structural compound having the formula (I), wherein the weight ratio between the two components is from 10 to 1:1 to 50.

   

   In the formula (I), R is selected from H or a C ₁ - C ₈ alkyl group.
2. 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.
3. The bactericide composition according to claim 1, wherein in the formula (I), R is selected from H, -CH ₃ or -C ₄ H ₉ , and the corresponding active component A is 1,2-benzox. Isothiazolin-3-one, 2-methyl-1,2-benzisothiazolin-3-one or 2-butyl-1,2-benzisothiazolin-3-one.
4. The bactericidal composition according to claim 1, wherein the weight ratio of the active component A to the active component B is from 1:1 to 40.
5. The bactericidal composition according to claim 4, wherein the weight ratio of the active component A to the active component B is from 1:1 to 30.
6. The bactericide composition according to claim 1, wherein the weight ratio of emodin methyl ether to 1,2-benzisothiazolin-3-one is from 1:1 to 30.
7. The bactericidal composition according to any one of claims 1 to 6, wherein the composition comprises from 1 to 85% by weight of the active component and from 99 to 15% by weight of the pesticide adjuvant or auxiliary compound. Allowed dosage form.
8. The bactericidal composition according to claim 7, wherein the dosage form is a liquid, a wettable powder, or an aqueous emulsion.
9. The bactericidal composition according to claim 7, 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, a surfactant, and a fertilizer. One or several of them.
10. Use of the bactericide composition according to any one of claims 1 to 9 for controlling crop diseases in the agricultural field.