A bactericidal composition, preparation and its application

Abstract

The present invention relates to the technical field of pesticides, and particularly relates to a bactericidal composition, a preparation and their applications. The bactericidal composition comprises active ingredient A and active ingredient B; the active ingredient A comprises metalaxyl, metalaxyl-M or cymoxanil; the active ingredient B comprises a triazolesulfonamide compound represented by formula (I). The bactericidal composition or preparation provided by the present invention can play a strong synergistic effect through the synergistic compounding of active ingredient A and active ingredient B; can delay the generation and development of drug resistance; improves the safety to crops; reduces the drug use cost and labor cost; and reduces the environmental pollution caused by excessive use of pesticides.

Description

Technical Field

[0001] The present invention relates to the technical field of pesticides, and particularly relates to a bactericidal composition, a preparation and their applications. Background Art

[0002] During the growth process, plants are often invaded by diseases. If not controlled, the resulting reduction in yield and crop failure will have a serious adverse impact on social economy. At present, the use of chemical agents is undoubtedly one of the most effective methods for controlling plant diseases. However, the long-term repeated use of single pesticides and other non-standard use methods have led to the rapid development of resistance of diseases to agents. Subsequently, there are a series of problems such as the continuous increase in the dosage of pesticides, as well as pesticide residues and environmental pollution. The scientific combination of different pesticides can achieve positive application effects such as expanding the control spectrum, improving the efficacy of pesticides, reducing the dosage of pesticides, and delaying the development of drug resistance. Summary of the Invention

[0003] The present invention provides a bactericidal composition, a preparation and their applications to improve the efficacy of pesticides, reduce the dosage of pesticides and delay the development of drug resistance.

[0004] In the first aspect of the present invention, a bactericidal composition is provided, and the bactericidal composition comprises active ingredient A and active ingredient B;

[0005] The active ingredient A comprises metalaxyl, metalaxyl-M or cymoxanil;

[0006] The active ingredient B comprises a triazolesulfonamide compound represented by formula (I):

[0007]

[0008] wherein R represents hydrogen, a halogen, or a substituted or unsubstituted alkyl group.

[0009] As a preferred embodiment, the halogen is preferably fluorine, chlorine or bromine, and more preferably bromine.

[0010] As a preferred embodiment, the substituted or unsubstituted alkyl group is a substituted or unsubstituted C 1 ~C 4 alkyl group, and more preferably a substituted or unsubstituted C 1 ~C 2 alkyl group. When it is a substituted alkyl group, the substituent group is preferably a halogen, and more preferably fluorine. As a specific embodiment, the substituted alkyl group is trifluoromethyl.

[0011] In formula (I), the substitution position of R can be ortho-substitution, meta-substitution or para-substitution.

[0012] As a preferred embodiment, the triazolesulfonamide compound represented by formula (I) is cyflufenamid. The chemical name of cyflufenamid is N3 -Cyclopropyl-N 1 ,N 1 -Dimethyl-N 3 -(3-(Trifluoromethyl)benzyl)-1H-1,2,4-triazole-1,3-disulfonamide.

[0013] As a specific embodiment, the cyproconazole is the compound shown in formula (r);

[0014]

[0015] As a preferred embodiment, the triazolesulfonamide compound shown in formula (I) is bromuconazole. The chemical name of the bromuconazole is N 3 -(3-Bromobenzyl)-N 3 -Cyclopropyl-N 1 ,N 1 -Dimethyl-1H-1,2,4-triazole-1,3-disulfonamide.

[0016] As a specific embodiment, the bromuconazole is the compound shown in formula (m);

[0017]

[0018] The metalaxyl described in the present invention belongs to phenylamide fungicides, and its chemical name is D,L-N-(2,6-dimethylphenyl)-N-(2-methoxyacetyl)alanine methyl ester, English name (±)-metalaxyl, molecular formula C 15 H 21 NO 4 , and the CAS number is 57837-19-1. Metalaxyl is effective against various crop downy mildews caused by downy mildew pathogens, Phytophthora pathogens and Pythium pathogens, Phytophthora blight of fruits, vegetables and melons, and white blight of millet.

[0019] As a specific embodiment, the metalaxyl is the compound shown in formula (x);

[0020]

[0021] The Chinese common name of metalaxyl-M in the present invention: methyl N-(2-methoxyacetyl)-N-(2,6-dimethylphenyl)-D-alaninate; methyl N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-D-alaninate. English common name: (R)-Metalaxyl; English name: N-(2,6-dimethylphenyl)-n-(methoxyacetyl)-alanine methylester; methyl N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-D-alaninate, CAS No. 70630-17-0.

[0022] As a specific embodiment, the metalaxyl-M is the compound shown in formula (n);

[0023]

[0024] The cymoxanil in the present invention is a cyanacetamide fungicide, which has the ability of systemic and short-distance conduction, has a protective effect and a certain therapeutic effect on crops, and can improve the biological activity when mixed with protective fungicides, and has obvious effects on preventing and controlling fungal diseases such as downy mildew and phytophthora blight of crops such as peppers, grapes, cucumbers, etc. Chemical name: (E)-2-(3-ethylureido)-N-methoxy-2-oxoacetimidoyl cyanide, English name: (E)-2-(3-ethylureido)-N-methoxy-2-oxoacetimidoyl cyanide, CAS registration number: 57966-95-7, and the structural formula of cymoxanil is:

[0025]

[0026] In some embodiments, the active ingredients of the fungicidal composition provided by the present invention include active ingredient A and active ingredient B; the active ingredient A is metalaxyl, metalaxyl-M or cymoxanil, and the active ingredient B is a triazolesulfonamide compound shown in general formula (I).

[0027] In some embodiments, the active ingredients of the fungicidal composition provided by the present invention consist of active ingredient A and active ingredient B; the active ingredient A is metalaxyl, metalaxyl-M or cymoxanil, and the active ingredient B is a triazolesulfonamide compound shown in general formula (I).

[0028] In some embodiments, the active ingredients of the bactericidal composition provided by the present invention include active ingredient A and active ingredient B; the active ingredient A is metalaxyl, metalaxyl-M or cymoxanil, and the active ingredient B is cyflufenamid or bromuconazole. Specifically, the active ingredient A is metalaxyl and the active ingredient B is cyflufenamid; or the active ingredient A is metalaxyl and the active ingredient B is bromuconazole; or the active ingredient A is metalaxyl-M and the active ingredient B is cyflufenamid; or the active ingredient A is metalaxyl-M and the active ingredient B is bromuconazole; or the active ingredient A is cymoxanil and the active ingredient B is cyflufenamid; or the active ingredient A is cymoxanil and the active ingredient B is bromuconazole.

[0029] In some embodiments, the active ingredients of the bactericidal composition provided by the present invention consist of active ingredient A and active ingredient B; the active ingredient A is metalaxyl, metalaxyl-M or cymoxanil, and the active ingredient B is cyflufenamid or bromuconazole. Specifically, the active ingredient A is metalaxyl and the active ingredient B is cyflufenamid; or the active ingredient A is metalaxyl and the active ingredient B is bromuconazole; or the active ingredient A is metalaxyl-M and the active ingredient B is cyflufenamid; or the active ingredient A is metalaxyl-M and the active ingredient B is bromuconazole; or the active ingredient A is cymoxanil and the active ingredient B is cyflufenamid; or the active ingredient A is cymoxanil and the active ingredient B is bromuconazole.

[0030] In some other embodiments, the active ingredients of the bactericidal composition provided by the present invention include active ingredient A and active ingredient B; the active ingredient A is propamocarb or oxadixyl, and the active ingredient B is a triazolesulfonamide compound represented by the general formula (I).

[0031] Propamocarb described in the present invention is a low-toxic bactericide with local systemic action and belongs to the carbamate class. It is highly effective against oomycete fungi. It can be widely applied to vegetables such as yellow eggplant, pepper, lettuce, potato, etc., as well as tobacco, strawberry, lawn, and flowers, and has a good control effect on oomycete fungal diseases such as downy mildew, phytophthora blight, damping-off, late blight, black shank disease, etc. The molecular formula is: C 9 H 20 N 2 O 2 ; CAS No. 24579-73-5; the chemical structural formula is:

[0032]

[0033] The oxadixyl described in the present invention is a type of systemic fungicide with protective and therapeutic effects, having a long residual efficacy period, good activity against pathogens of the order Peronosporales, and playing an important role in the control of oomycete diseases. Oxadixyl can be used to control pathogens of the order Peronosporales such as downy mildew, phytophthora blight, etc. of tobacco, cucumber, grape, and vegetables, and can also concurrently control various secondary diseases such as brown spot, black rot, etc. The molecular formula of oxadixyl is: C 14 H 18 N 2 O 4 ; The CAS number is 77732-09-3, and its structural formula is:

[0034]

[0035] In some other embodiments, the active ingredients of the fungicidal composition provided by the present invention are composed of active ingredient A and active ingredient B; the active ingredient A is propamocarb or oxadixyl, and the active ingredient B is a triazolesulfonamide compound represented by the general formula (I).

[0036] In some other embodiments, the active ingredients of the fungicidal composition provided by the present invention include active ingredient A and active ingredient B; the active ingredient A is propamocarb or oxadixyl, and the active ingredient B is cyflufenamid or bromuconazole. Specifically, the active ingredient A is propamocarb and the active ingredient B is cyflufenamid; or, the active ingredient A is propamocarb and the active ingredient B is bromuconazole; or, the active ingredient A is oxadixyl and the active ingredient B is cyflufenamid; or, the active ingredient A is oxadixyl and the active ingredient B is bromuconazole.

[0037] In some other embodiments, the active ingredients of the fungicidal composition provided by the present invention are composed of active ingredient A and active ingredient B; the active ingredient A is propamocarb or oxadixyl, and the active ingredient B is cyflufenamid or bromuconazole. Specifically, the active ingredient A is propamocarb and the active ingredient B is cyflufenamid; or, the active ingredient A is propamocarb and the active ingredient B is bromuconazole; or, the active ingredient A is oxadixyl and the active ingredient B is cyflufenamid; or, the active ingredient A is oxadixyl and the active ingredient B is bromuconazole. The present invention discovers that combining the active ingredient A with the active ingredient B can improve the efficacy of the pesticide, reduce the dosage of the drug, and can delay drug resistance, showing excellent persistence.

[0038] The mass ratio of active ingredient A and active ingredient B in the composition of the present invention can be arbitrary, and the mass ratio of active ingredient A and active ingredient B can vary within a relatively wide range. Specifically, in the composition of the present invention, the optional mass ratios of the active ingredient A and the active ingredient B include 40:1, 30:1, 20:1, 15:1, 10:1, 5:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:5, 1:10, 1:15, 1:20, 1:30 or 1:40.

[0039] As a preferred embodiment, the active ingredient A is metalaxyl; the active ingredient B is cyproconazole. The mass ratio of the metalaxyl to the cyproconazole is (1 - 40):(40 - 1); preferably the mass ratio is (1 - 40):(20 - 1); preferably the mass ratio is (1 - 20):(20 - 1); more preferably the mass ratio is (1 - 15):(15 - 1); more preferably the mass ratio is (1 - 10):(10 - 1); more preferably the mass ratio is (1 - 10):(5 - 1); more preferably the mass ratio is (1 - 5):(5 - 1); more preferably the mass ratio is (1 - 3):(3 - 1); more preferably the mass ratio is (1 - 2):(3 - 1).

[0040] For example, in the bactericidal composition, the mass ratio of metalaxyl to cyproconazole is 15:1, 10:1, 5:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:5, 1:10, 1:15.

[0041] As a preferred embodiment, the active ingredient A is metalaxyl; the active ingredient B is bromuconazole. The mass ratio of the metalaxyl to the bromuconazole is (1 - 40):(40 - 1); preferably the mass ratio is (1 - 40):(20 - 1); preferably the mass ratio is (1 - 20):(20 - 1); more preferably the mass ratio is (1 - 15):(15 - 1); more preferably the mass ratio is (1 - 10):(10 - 1); more preferably the mass ratio is (1 - 10):(5 - 1); more preferably the mass ratio is (1 - 5):(5 - 1); more preferably the mass ratio is (1 - 3):(3 - 1); more preferably the mass ratio is (1 - 2):(3 - 1).

[0042] For example, in the bactericidal composition, the mass ratio of metalaxyl to bromuconazole is 15:1, 10:1, 5:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:5, 1:10, 1:15.

[0043] As a preferred embodiment, the active ingredient A is metalaxyl-M; the active ingredient B is cyproconazole. The mass ratio of metalaxyl-M to cyproconazole is (1 - 80):(80 - 1); preferably the mass ratio is (1 - 40):(40 - 1); more preferably the mass ratio is (1 - 40):(20 - 1); more preferably the mass ratio is (1 - 20):(20 - 1); even more preferably the mass ratio is (1 - 10):(20 - 1).

[0044] For example, in the bactericidal composition, the mass ratio of metalaxyl-M to cyproconazole is 40:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20, 1:40.

[0045] As a preferred embodiment, the active ingredient A is metalaxyl-M; the active ingredient B is bromuconazole. The mass ratio of metalaxyl-M to bromuconazole is (1 - 80):(80 - 1); preferably the mass ratio is (1 - 40):(40 - 1); more preferably the mass ratio is (1 - 40):(20 - 1); more preferably the mass ratio is (1 - 20):(20 - 1).

[0046] For example, in the bactericidal composition, the mass ratio of metalaxyl-M to bromuconazole is 40:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20, 1:40.

[0047] As a preferred embodiment, the active ingredient A is cymoxanil; the active ingredient B is cyproconazole. The mass ratio of cymoxanil to cyproconazole is (1 - 30):(30 - 1); preferably the mass ratio is (1 - 20):(5 - 1); further preferably the mass ratio is (1 - 5):(5 - 1); more preferably the mass ratio is (1 - 3):(5 - 1).

[0048] For example, in the bactericidal composition, the mass ratio of cymoxanil to cyproconazole is 30:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20, 1:30.

[0049] As a preferred embodiment, the active ingredient A is cymoxanil; the active ingredient B is bromuconazole. The mass ratio of cymoxanil to bromuconazole is (1 - 30):(30 - 1); preferably the mass ratio is (1 - 20):(5 - 1); further preferably the mass ratio is (1 - 5):(5 - 1); more preferably the mass ratio is (1 - 3):(5 - 1).

[0050] For example, in the bactericidal composition, the mass ratio of cymoxanil to bromuconazole is 30:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20, 1:30.

[0051] In the composition of the present invention, based on the total mass percentage of the composition being 100%, the sum of the mass percentages of the active ingredient A and the active ingredient B in the bactericidal composition is 1-95%, preferably 1-90%, preferably 5-90%, preferably 5-80%, preferably 10-80%.

[0052] Specifically, based on the total mass percentage of the composition being 100%, the sum of the mass percentages of the active ingredient A and the active ingredient B in the composition is 10%, 12%, 20%, 21%, 24%, 30%, 36%, 40%, 50%, 60%, 63%, 72%, 77%, 80% or other values within the range of 10-80%.

[0053] The second aspect of the present invention provides a preparation containing the above-mentioned bactericidal composition.

[0054] In the preparation of the present invention, the mass ratio of the active ingredient A to the active ingredient B is arbitrary, and the mass ratio of the active ingredient A to the active ingredient B can vary within a relatively wide range. Specifically, in the preparation of the present invention, the optional mass ratios of the active ingredient A to the active ingredient B include 40:1, 30:1, 20:1, 15:1, 10:1, 5:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:5, 1:10, 1:15, 1:20, 1:30 or 1:40.

[0055] As a preferred embodiment, the active ingredient A is metalaxyl; the active ingredient B is cyflufenamid. The mass ratio of the metalaxyl to the cyflufenamid is (1-40):(40-1); preferably the mass ratio is (1-40):(20-1); preferably the mass ratio is (1-20):(20-1); more preferably the mass ratio is (1-15):(15-1); more preferably the mass ratio is (1-10):(10-1); more preferably the mass ratio is (1-10):(5-1); more preferably the mass ratio is (1-5):(5-1); more preferably the mass ratio is (1-3):(3-1); more preferably the mass ratio is (1-2):(3-1).

[0056] For example, in the preparation, the mass ratio of metalaxyl to cyflufenamid is 15:1, 10:1, 5:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:5, 1:10, 1:15.

[0057] As a preferred embodiment, the active ingredient A is metalaxyl; the active ingredient B is cyproconazole. The mass ratio of metalaxyl to cyproconazole is (1 - 40):(40 - 1); preferably the mass ratio is (1 - 40):(20 - 1); preferably the mass ratio is (1 - 20):(20 - 1); more preferably the mass ratio is (1 - 15):(15 - 1); more preferably the mass ratio is (1 - 10):(10 - 1); more preferably the mass ratio is (1 - 10):(5 - 1); more preferably the mass ratio is (1 - 5):(5 - 1); more preferably the mass ratio is (1 - 3):(3 - 1); more preferably the mass ratio is (1 - 2):(3 - 1).

[0058] For example, in the formulation, the mass ratio of metalaxyl to cyproconazole is 15:1, 10:1, 5:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:5, 1:10, 1:15.

[0059] As a preferred embodiment, the active ingredient A is metalaxyl-M; the active ingredient B is cyproconazole. The mass ratio of metalaxyl-M to cyproconazole is (1 - 80):(80 - 1); preferably the mass ratio is (1 - 40):(40 - 1); more preferably the mass ratio is (1 - 40):(20 - 1); more preferably the mass ratio is (1 - 20):(20 - 1); more preferably the mass ratio is (1 - 10):(20 - 1).

[0060] For example, in the formulation, the mass ratio of metalaxyl-M to cyproconazole is 40:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20, 1:40.

[0061] As a preferred embodiment, the active ingredient A is metalaxyl-M; the active ingredient B is cyproconazole. The mass ratio of metalaxyl-M to cyproconazole is (1 - 80):(80 - 1); preferably the mass ratio is (1 - 40):(40 - 1); more preferably the mass ratio is (1 - 40):(20 - 1); more preferably the mass ratio is (1 - 20):(20 - 1).

[0062] For example, in the formulation, the mass ratio of metalaxyl-M to cyproconazole is 40:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20, 1:40.

[0063] As a preferred embodiment, the active ingredient A is cymoxanil; the active ingredient B is cyproconazole. The mass ratio of cymoxanil to cyproconazole is (1 - 30):(30 - 1); preferably the mass ratio is (1 - 20):(5 - 1); further preferably the mass ratio is (1 - 5):(5 - 1); more preferably the mass ratio is (1 - 3):(5 - 1).

[0064] For example, in the preparation, the mass ratio of cymoxanil to cyproconazole is 30:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20, 1:30.

[0065] As a preferred embodiment, the active ingredient A is cymoxanil; the active ingredient B is bromuconazole. The mass ratio of cymoxanil to bromuconazole is (1 - 30):(30 - 1); preferably the mass ratio is (1 - 20):(5 - 1); more preferably the mass ratio is (1 - 5):(5 - 1); even more preferably the mass ratio is (1 - 3):(5 - 1).

[0066] For example, in the preparation, the mass ratio of cymoxanil to bromuconazole is 30:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20, 1:30.

[0067] In the preparation of the present invention, based on the total mass percentage of the preparation being 100%, the sum of the mass percentages of the active ingredient A and the active ingredient B in the preparation is 1 - 95%, preferably 1 - 90%, preferably 5 - 90%, preferably 5 - 80%, preferably 10 - 80%.

[0068] Specifically, based on the total mass percentage of the preparation being 100%, the sum of the mass percentages of the active ingredient A and the active ingredient B in the preparation is 10%, 12%, 20%, 21%, 24%, 30%, 36%, 40%, 50%, 60%, 63%, 72%, 77%, 80% or other values within the range of 10 - 80%.

[0069] In addition to the above - mentioned bactericidal composition, the preparation provided by the present invention usually may also contain auxiliaries commonly used in pesticides.

[0070] As a specific embodiment, the auxiliaries are selected from at least one of wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreezing agents, defoaming agents, solvents, preservatives, stabilizers, synergists, carriers. It can be appropriately added according to the needs of the preparation, and can vary according to different situations, without special limitation. Auxiliaries are auxiliary substances added during the processing or use of pesticide preparations to improve the physical and chemical properties of the agents. The auxiliaries themselves have basically no biological activity, but can affect the control effect.

[0071] As a specific embodiment, the wetting agent is selected from at least one of alkylphenol polyoxyethylene ethers (such as nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, dodecylphenol ether, dinonylphenol ether, and mixed alkylphenol ethers, etc.), fatty alcohol polyoxyethylene ethers, fatty acid or fatty acid ester sulfates, dioctyl sulfosuccinate, phosphate esters, alkylnaphthalene sulfonates (such as sodium dibutylnaphthalene sulfonate, sodium isopropylnaphthalenesulfonate), alkylbenzene sulfonates (such as sodium dodecylbenzene sulfonate, calcium dodecylbenzene sulfonate), sodium dodecyl sulfate (SDS), succinate ester sulfonates, alkyl sulfates, and lignosulfonates (such as sodium lignosulfonate, calcium lignosulfonate). Suitable wetting agents are selected from OTB (dioctyl sulfosuccinate), EFW (alkylnaphthalene sulfonate), BX (alkylnaphthalene sulfonate), MT 804 (alkylnaphthalene sulfonate), JR-P (phosphate ester), or at least one of them.

[0072] As a specific embodiment, the dispersant is selected from at least one of naphthalene sulfonates, naphthalene sulfonate formaldehyde condensates, lignosulfonates, alkylbenzene sulfonates, alkylphenol polyoxyethylene ether formaldehyde condensate sulfates, high molecular weight polycarboxylates, comb-shaped structure dispersants, non-alkylphenol-based highly efficient dispersants, alkylbenzene polyoxyethylene ethers, ethylene oxide-propylene oxide block polyethers, and organic phosphate esters. For wettable powder formulations, the most common dispersant is sodium lignosulphonate. For suspension concentrates, polyelectrolytes such as sodium naphthalene sulphonate formaldehyde condensate can be used to achieve very good adsorption and stabilization effects, and tristyrylphenol ethoxylate phosphate ester can also be used. Suitable dispersants are selected from 2700 (high molecular weight polycarboxylate), 2500 (comb-shaped structure dispersant), 4894 (non-alkylphenol-based highly efficient dispersant), Ultrazine NA (lignosulfonate), Borresperse NA (lignosulfonate), GY-D06 (high molecular weight polycarboxylate), Antraox B / 848 (EO-PO block copolymer), Morwet D425 (naphthalene sulfonate formaldehyde condensate), and Ethylan NS-500LQ (EO-PO block copolymer), or at least one of them.

[0073] As a specific embodiment, the emulsifier is selected from at least one of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, alkylphenol polyoxyethylene polyoxypropylene ether, fatty amine, ethylene oxide adduct of fatty amide, fatty acid polyoxyethylene ester, ethylene oxide adduct of castor oil and its derivatives, ethylene oxide adduct of rosin acid and analogues, polyol fatty acid and its ethylene oxide adduct, and polyoxyethylene polyoxypropylene block copolymer. Suitable emulsifiers are selected from at least one of agricultural emulsifier 500#, agricultural emulsifier 601#, agricultural emulsifier 602#, agricultural emulsifier 700#, agricultural emulsifier 1601#, agricultural emulsifier 1602#, and Ethylan 992.

[0074] As a specific embodiment, the thickener is selected from at least one of silica white, kaolin, bentonite, xanthan gum, arabic gum, polyacrylic acid, and sodium carboxymethyl cellulose.

[0075] As a specific embodiment, the disintegrant is selected from at least one of urea, modified starch, bentonite, aluminum chloride, ammonium sulfate, succinic acid, sodium bicarbonate, and sodium chloride.

[0076] As a specific embodiment, the antifreeze is selected from at least one of glycerol, ethylene glycol, and propylene glycol.

[0077] As a specific embodiment, the defoamer is selected from at least one of silicone defoamers, C 8-10 fatty alcohol defoamers, polyureas, and polyethylene glycol fatty acid esters.

[0078] As a specific embodiment, the solvent is selected from at least one of toluene, xylene, cyclohexanone, aromatic solvent, methanol, ethyl acetate, soybean oil, epoxy soybean oil, castor oil, methyl oleate, rapeseed oil, and N-octylpyrrolidone.

[0079] As a specific embodiment, the preservative is selected from at least one of sodium benzoate, benzoic acid, potassium sorbate, and Kathon.

[0080] As a specific embodiment, the stabilizer is selected from at least one of phosphoric acid, pyrophosphoric acid, phthalic acid, benzoic acid, triphenyl phosphite, acetic anhydride, epichlorohydrin, resorcinol, and sodium citrate.

[0081] As a specific embodiment, the synergist is selected from synergistic phosphorus and / or synergistic ether. The synergist itself has no biological activity, but can inhibit the detoxifying enzymes in organisms. When mixed with certain pesticides, it can greatly improve the toxicity and efficacy of pesticides.

[0082] As a specific embodiment, the carrier is selected from at least one of kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, silica, alumina, silicate, resin, wax, solid fertilizer, water, alcohol (especially butanol), organic solvent, mineral oil, and vegetable oil and their derivatives. The silicate is selected from natural and / or artificial silicates.

[0083] The preparation provided by the present invention may further include other components, such as at least one of protective colloid, binder, adhesive, thixotropic substance, penetrant, chelating agent, complexing agent, and dye. Usually, the active ingredient can be combined with any solid or liquid additive commonly used for preparation purposes.

[0084] The bactericidal composition provided by the present invention can be used as it is or in its preparation form or the use form prepared therefrom according to its various physical properties and / or chemical properties, such as aerosol, capsule suspension, cold atomization concentrate, hot atomization concentrate, granule encapsulated in a capsule, fine granule, flowable concentrate for seed treatment, ready-to-use solution, dustable powder, emulsifiable concentrate, oil-in-water emulsion, water-in-oil emulsion, large granule, microgranule, oil-dispersible powder, oil-soluble flowable concentrate, oil-soluble liquid, foam, paste, insecticide-coated seed, suspension concentrate, suspoemulsion concentrate, soluble concentrate, suspension, wettable powder, soluble powder, powder and granule, water-soluble granule or tablet, water-soluble powder for seed treatment, wettable powder impregnated with the active compound, microcapsules in natural products and synthetic substances as well as polymeric substances and coating materials for seeds, and ULV cold atomization and hot atomization preparations.

[0085] As a preferred embodiment, the preparation is dustable powder, wettable powder, microcapsule, water-dispersible granule, granule, aqueous solution, suspension, oil suspension, emulsifiable concentrate, microemulsion, water-in-oil emulsion, suspoemulsion, ultra-low volume spray, seed coating agent, or smoke agent.

[0086] Dustable powder (DP) is a powdery substance obtained by adding a certain amount of inert powder, such as clay, kaolin, talcum powder, etc., to the active substance and mechanically processing it into a powder, and the powder particle diameter is below 100 microns.

[0087] Wettable powder (WP) refers to a mixture of the composition in a certain proportion with a suitable surfactant and an inert substance (kaolin powder). Wettable powder is a preparation that can be uniformly dispersed in water. In addition to the active ingredient and the inert substance (kaolin powder), it also contains a certain amount of anionic or non-ionic surfactants (dispersant, wetting agent).

[0088] Microcapsule agent (MC) is a preparation method in which the active ingredient is first encapsulated in adhesives, film-forming agents, etc. to form tiny capsule-like preparations, and then processed into the required dosage forms. It is divided into capsule suspensions (CS), encapsulated granules (CG), capsulated dry flowables (CDF), etc.

[0089] Water dispersible granule (WDG) refers to a mixture composed of a composition in a certain proportion, suitable surfactants and inert substances (kaolin powder). After air-flow pulverization to make the particle fineness meet the requirements, and using a double-screw mixer and a plowshare mixer for multiple times to make the product evenly mixed, and then made by conventional methods such as fluidized bed granulation, spray granulation, and pan granulation.

[0090] Granule (GR) refers to a mixture composed of a composition in a certain proportion, suitable surfactants, diluents and inert substances (kaolin powder). Granulation is carried out by a granulator, such as the fluidized bed granulation method, which is a granulation method that keeps the powder in a flowing state and sprays a binder solution to make it agglomerate. This method enables processes such as mixing, kneading, granulation, drying, and classification to be completed in a single device in a short time under a closed state.

[0091] Aqueous solution (AS) is a liquid directly prepared by water, taking advantage of the property that some technical materials can dissolve in water without decomposition.

[0092] Suspension concentrate (SC) refers to a preparation made by mixing a composition in a certain proportion with suitable surfactants, water or organic solvents, uniformly grinding it through a colloid mill, and then grinding it to a certain fineness through a sand mill.

[0093] Oil suspension concentrate (OD / OF) refers to a preparation in which the composition is dispersed in a non-aqueous medium (mineral oil, vegetable oil and its derivatives, etc.) in the form of tiny particles. With the help of suitable surfactants (such as emulsifiers, dispersants, etc.), through sand mill grinding, the technical material is evenly dispersed in the oil phase.

[0094] Emulsifiable concentrate (EC) refers to a preparation made by dissolving a composition in an organic solvent such as benzene, toluene, xylene, cyclohexanone in a certain proportion and adding a certain amount of anionic or non-ionic surfactants (emulsifiers) to the mixture.

[0095] Microemulsion (ME) generally consists of liquid pesticides, surfactants (emulsifiers), water, stabilizers, etc.; its characteristic is that water is used as the medium and contains little or no organic solvents. The droplet size in the microemulsion is generally several nanometers to dozens of nanometers, less than one-fourth of the visible light wavelength.

[0096] An emulsion in water (EW) is a pesticide formulation in which the technical material, which is insoluble in water, or a solution of the technical material in an organic solvent insoluble in water is dispersed in water.

[0097] An ultra-low volume spray is a special formulation for ultra-low volume spraying, in which the liquid medicine sprayed onto the target crop is ejected in extremely fine droplets and in extremely low amounts.

[0098] A suspension emulsion (SE) is a highly suspended dispersion system in which the active ingredients of a solid technical material insoluble in water and an oil-phase technical material form uniformly stable suspensions and emulsions of solid particles and fine oil droplets in water with the aid of auxiliaries such as dispersants and emulsifiers.

[0099] A seed coating (SD) is prepared by grinding and mixing the active ingredient and auxiliaries, and can be directly or after dilution coated on the surface of seeds to form a protective film with a certain strength and permeability.

[0100] A fumigant (FU), also known as a smoke agent, is a medicament in which the active ingredient is mixed with a combustible substance, etc., and after combustion, the pesticide is vaporized and condensed into smoke particles or directly dispersed into smoke particles.

[0101] As a preferred embodiment of the present invention, the preparation is a wettable powder. In the wettable powder, the mass percentage of the bactericidal composition is 1-95%, preferably 40-80%. Among them, the bactericidal composition contains metalaxyl-M and cyflufenamid in a mass ratio of (40-1):(1-40), and the mass ratio of metalaxyl-M and cyflufenamid can specifically be 40:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20 or 1:40; or, the bactericidal composition contains metalaxyl-M and bromuconazole in a mass ratio of (40-1):(1-40), and the mass ratio of metalaxyl-M and bromuconazole can specifically be 40:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20 or 1:40.

[0102] As a preferred embodiment of the present invention, the preparation is a water dispersible granule. In the water dispersible granule, the mass percentage of the bactericidal composition is 1-95%, preferably 20-80%. Among them, the bactericidal composition contains metalaxyl-M and cyproconazole in a mass ratio of (40-1):(1-40), and the mass ratio of metalaxyl-M to cyproconazole can specifically be 40:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20 or 1:40. Or, the bactericidal composition contains metalaxyl-M and bromuconazole in a mass ratio of (40-1):(1-40), and the mass ratio of metalaxyl-M to bromuconazole can specifically be 40:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20 or 1:40.

[0103] As a preferred embodiment of the present invention, the preparation is a suspension concentrate. In the suspension concentrate, the mass percentage of the bactericidal composition is 1-95%, preferably 10-30%. Among them, the bactericidal composition contains metalaxyl-M and cyproconazole in a mass ratio of (40-1):(1-40), and the mass ratio of metalaxyl-M to cyproconazole can specifically be 40:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20 or 1:40. Or, the bactericidal composition contains metalaxyl-M and bromuconazole in a mass ratio of (40-1):(1-40), and the mass ratio of metalaxyl-M to bromuconazole can specifically be 40:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20 or 1:40.

[0104] As a preferred embodiment of the present invention, the preparation is an emulsion in water. In the emulsion in water, the mass percentage of the bactericidal composition is 1-95%, preferably 10-60%, more preferably 30-60%, even more preferably 30-50%. Among them, the bactericidal composition contains cymoxanil and bromuconazole in a mass ratio of (30-1):(1-30), and the mass ratio of cymoxanil to bromuconazole can specifically be 30:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20 or 1:30; or, the bactericidal composition contains cymoxanil and cyproconazole in a mass ratio of (30-1):(1-30), and the mass ratio of cymoxanil to cyproconazole can specifically be 30:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20 or 1:30.

[0105] As a preferred embodiment of the present invention, the preparation is a suspending agent. In the suspending agent, the mass percentage of the bactericidal composition is 1 to 95%, preferably 10 to 60%, more preferably 40 to 60%. Among them, the bactericidal composition contains cymoxanil and epoxiconazole with a mass ratio of (30 to 1):(1 to 30), and the mass ratio of cymoxanil to epoxiconazole can specifically be 30:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20 or 1:30; or, the bactericidal composition contains cymoxanil and cyproconazole with a mass ratio of (30 to 1):(1 to 30), and the mass ratio of cymoxanil to cyproconazole can specifically be 30:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20 or 1:30.

[0106] As a preferred embodiment of the present invention, the preparation is a microemulsion. In the microemulsion, the mass percentage of the bactericidal composition is 1 to 95%, preferably 10 to 60%, more preferably 10 to 30%. Among them, the bactericidal composition contains cymoxanil and epoxiconazole with a mass ratio of (30 to 1):(1 to 30), and the mass ratio of cymoxanil to epoxiconazole can specifically be 30:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20 or 1:30; or, the bactericidal composition contains cymoxanil and cyproconazole with a mass ratio of (30 to 1):(1 to 30), and the mass ratio of cymoxanil to cyproconazole can specifically be 30:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20 or 1:30.

[0107] As a preferred embodiment of the present invention, the preparation is an emulsifiable concentrate. In the emulsifiable concentrate, the mass percentage of the bactericidal composition is 1 to 95%, preferably 10 to 60%, more preferably 40 to 60%. Among them, the bactericidal composition contains cymoxanil and epoxiconazole with a mass ratio of (30 to 1):(1 to 30), and the mass ratio of cymoxanil to epoxiconazole can specifically be 30:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20 or 1:30; or, the bactericidal composition contains cymoxanil and cyproconazole with a mass ratio of (30 to 1):(1 to 30), and the mass ratio of cymoxanil to cyproconazole can specifically be 30:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20 or 1:30.

[0108] As a preferred embodiment of the present invention, the preparation is a water dispersible granule. In the water dispersible granule, the mass percentage of the bactericidal composition is 1-95%, preferably 20-90%, more preferably 70-90%. Among them, the bactericidal composition contains cymoxanil and bromuconazole with a mass ratio of (30-1):(1-30), and the mass ratio of cymoxanil to bromuconazole can specifically be 30:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20 or 1:30; or, the bactericidal composition contains cymoxanil and cyflufenamid with a mass ratio of (30-1):(1-30), and the mass ratio of cymoxanil to cyflufenamid can specifically be 30:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20 or 1:30.

[0109] As a preferred embodiment of the present invention, the preparation is a wettable powder. In the wettable powder, the mass percentage of the bactericidal composition is 1-95%, preferably 20-90%, more preferably 50-70%. Among them, the bactericidal composition contains cymoxanil and bromuconazole with a mass ratio of (30-1):(1-30), and the mass ratio of cymoxanil to bromuconazole can specifically be 30:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20 or 1:30; or, the bactericidal composition contains cymoxanil and cyflufenamid with a mass ratio of (30-1):(1-30), and the mass ratio of cymoxanil to cyflufenamid can specifically be 30:1, 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, 1:20 or 1:30.

[0110] Regarding the meanings of various adjuvants and various preparations, due to differences in expression, there will be differences in understanding. It should be understood that all kinds of adjuvants and preparations disclosed in the art fall within the scope covered by the present invention, such as those described in "Pesticide Formulation Processing Technology", Luo Yanping, Song Weiwei, Chemical Industry Press, 2015; "Pesticide Formulation Science", Wang Kaiyun, China Agriculture Press, 2009; "Modern Pesticide Formulation Processing Technology Series", Liu Guangwen, Chemical Industry Press, 2018; "Pesticide Formulations and Their Application Methods", Tu Yuqin, Jindun Press, 2008; "China Pesticides", China Pesticide Industry Association; and so on. The preparation methods of various preparations include but are not limited to those described in the present invention.

[0111] The above-mentioned preparations can be prepared in a manner known per se, for example, by mixing the active compound or the active compound combination with at least one additive. Suitable additives are all conventional formulation adjuvants, such as organic solvents, fillers, solvents or diluents, solid carriers and fillers, surfactants (such as adjuvants, emulsifiers, dispersants, protective colloids, wetting agents and thickeners), dispersants and / or binders or fixatives, preservatives, dyes and pigments, defoamers, inorganic and organic thickeners, water repellents, and if appropriate, drying agents and UV stabilizers, gibberellins, as well as water and other processing aids. In each case, depending on the type of preparation to be prepared, other processing steps may be required, such as wet grinding, dry grinding or granulation.

[0112] The bactericidal composition of the present invention not only includes a ready-to-use bactericidal composition (which can be applied to plants or seeds using a suitable device), but also includes a commercially available concentrate (which must be diluted before use).

[0113] The third aspect of the present invention provides the use of the above-mentioned bactericidal composition or the above-mentioned preparation in the prevention and control of plant diseases.

[0114] The bactericidal composition or preparation of the present invention can treat all plants and plant parts. Plants refer to all plants and plant populations, such as desired and undesired wild plants, cultivated species and plant varieties (whether protected by plant variety rights or plant breeder rights). Cultivated species and plant varieties can be plants obtained by conventional propagation and breeding methods (assisted or supplemented by one or more biotechnological methods, such as by using doubled haploids, protoplast fusion, random mutagenesis and directed mutagenesis, molecular markers or genetic markers), or by methods of bioengineering and genetic engineering. Plant parts refer to all above-ground and underground parts and organs of plants, which include, for example, buds, leaves, flowers and roots, such as leaves, needles, stems, branches, flowers, fruiting bodies, fruits and seeds, as well as roots, bulbs and rhizomes. Crops and asexual and sexual propagation materials, such as cuttings, bulbs, rhizomes, tillers and seeds, also belong to plant parts.

[0115] The treatment of the whole plant and / or plant parts with the bactericidal composition and its preparation provided by the present invention can be carried out directly using conventional treatment methods or acting on its surrounding environment, habitat or storage place, such as by dipping, spraying, atomizing, irrigation, evaporation, dusting, misting, broadcasting, foaming, smearing, coating, watering (irrigation), dripping, and in the case of propagation materials, especially in the case of seeds, it can also be used to powder-treat dry seeds, treat seeds with a solution, treat slurries with a water-soluble powder by incrusting, coating with one or more coatings, etc. The composition or preparation can also be injected into the soil.

[0116] As a more specific embodiment, the bactericidal composition or preparation is sprayed on the stems and / or leaves of plants.

[0117] Furthermore, the present invention provides a method for controlling plant diseases, which is to simultaneously apply, separately apply, or successively apply the active ingredients metalaxyl, metalaxyl-M, or cymoxanil and the active ingredient bromuconazole or cyflufenamid to the plant or plant part to be treated.

[0118] The simultaneous application can directly apply the active ingredients metalaxyl, metalaxyl-M, or cymoxanil and the active ingredient bromuconazole or cyflufenamid after mixing them evenly, or can prepare them into a preparation after mixing them evenly and then apply the preparation.

[0119] The separate application can separately apply the active ingredients metalaxyl, metalaxyl-M, or cymoxanil and the active ingredient bromuconazole or cyflufenamid, or can separately apply the active ingredients metalaxyl, metalaxyl-M, or cymoxanil and the active ingredient bromuconazole or cyflufenamid after each is prepared into a preparation.

[0120] The successive application can successively apply the active ingredients metalaxyl, metalaxyl-M, or cymoxanil and the active ingredient bromuconazole or cyflufenamid, or can successively apply the active ingredients metalaxyl, metalaxyl-M, or cymoxanil and the active ingredient bromuconazole or cyflufenamid after each is prepared into a preparation. When applying successively, bromuconazole or cyflufenamid (active ingredient or preparation) can be applied first and then metalaxyl, metalaxyl-M, or cymoxanil (active ingredient or preparation), or metalaxyl, metalaxyl-M, or cymoxanil (active ingredient or preparation) can be applied first and then bromuconazole or cyflufenamid (active ingredient or preparation).

[0121] As a specific embodiment, the plant diseases include downy mildew, Phytophthora blight, late blight, rot, white rust, cotton blight.

[0122] Among the plants that can be protected by the method of the present invention, mainly include crops, preferably include cereal, fruit and / or vegetable crops, such as cucumber, tomato, corn, soybean, cotton, rape, rice, wheat, beet, sugarcane, oat, rye, barley, millet, triticale, flax, vine plants, and various fruits and vegetables from various plant taxa, horticultural and forest crops; ornamental plants; and genetically modified homologues of these crops.

[0123] The present invention also includes a method for treating seeds with the bactericidal composition or preparation of the present invention. The bactericidal composition of the present invention can be directly applied, that is, it does not include other components and is not diluted. Generally, it is preferred to apply the bactericidal composition of the present invention in a suitable preparation form to the seeds. Suitable preparations and methods for treating seeds are conventional in the art. The bactericidal composition of the present invention can be converted into conventional seed dressing preparations, such as solutions, emulsions, suspensions, powders, foams, pastes or other coating materials for seeds, as well as ULV preparations.

[0124] Depending on the plant species or plant cultivar, their location and growth conditions (soil, climate, vegetative period, nutrition), the treatment of the present invention can also bring about supra-additive ("synergistic") effects. For example, the following effects exceeding the actual expectations can be brought about: reduction in the application rate of the bactericidal composition and its preparation provided by the present invention and / or broadening of the activity spectrum and / or increase in activity, better plant growth, improvement in tolerance to high or low temperatures, improvement in tolerance to drought or water or soil salinity, improvement in flowering quality, easier harvesting, acceleration of ripening, higher harvesting yield, larger fruits, higher plant height, greener leaf color, earlier flowering, higher quality and / or higher nutritional value of the harvested product, higher sugar concentration in the fruits, better storage stability and / or processability of the harvested product.

[0125] The bactericidal composition or preparation provided by the present invention is a synergistic compound of active ingredient A and active ingredient B, and has the following beneficial effects: (1) it plays a strong synergistic effect; (2) it can delay the generation and development of drug resistance; (3) it improves the safety to crops; (4) it reduces the drug use cost and labor cost; and (5) it reduces the environmental pollution caused by excessive use of pesticides. Detailed implementation mode

[0126] The present invention will be further described below through examples. It should be understood that the examples of the present invention are only for illustrating the present invention, rather than limiting the present invention. Any simple improvement of the present invention under the premise of the concept of the present invention belongs to the scope protected by the present invention. In the following examples, the bromocyclazole technical and the cyflufenamid technical are self-made. The cyflufenamid is prepared according to the preparation method of Example 12 in PCT / CN2019 / 108170; the bromocyclazole is prepared according to the preparation method of Example 8 in PCT / CN2018 / 081979; metalaxyl-M is purchased from Wuhu Beida Trading Co., Ltd., and cymoxanil is purchased from Limin Chemical Co., Ltd. For those not specifying specific conditions in the examples, they are carried out according to conventional conditions or conditions recommended by the manufacturer. For those reagents or instruments not indicating the manufacturer, they are all conventional products that can be prepared by the methods described in the prior art records or obtained through commercial purchase.

[0127] Synthesis and characterization of cyflufenamid:

[0128]

[0129] Take N 3 -(3-(trifluoromethyl)benzyl)-N 1 ,N 1-Dimethyl-1H-1,2,4-triazole-1,3-disulfonamide (0.41 g, 1.0 mmol), potassium carbonate (0.28 g, 2.0 mmol) and N,N-dimethylformamide (10 mL) were added to a 100 mL three-necked flask, and then bromocyclopropane (0.24 g, 2.0 mmol) was slowly added to the reaction system. The reaction was carried out at room temperature for 8 hours; the reaction was quenched by adding water (20 mL), and the mixture was extracted with ethyl acetate (15 mL×3). The organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure using a rotary evaporator. The residue was purified by column chromatography (ethyl acetate / petroleum ether (v / v) = 1 / 3) to obtain 0.24 g of a white solid, yield: 53%.

[0130] 1 H NMR(400MHz,CDCl 3 ): δ(ppm) 8.76 (s, 1H), 7.49 - 7.16 (m, 4H), 3.82 (s, 2H), 2.67 (s, 6H), 1.36 - 1.32 (m, 1H), 0.71 - 0.68 (m, 2H), 0.22 - 0.19 (m, 2H).

[0131] LC-MS: (M + 1) m / z = 454.0.

[0132] Synthesis and characterization of bromocyclazole:

[0133]

[0134] Potassium carbonate (0.276 g, 2.0 mmol), N 3 -Cyclopropyl-N 1 ,N 1 -Dimethyl-1H-1,2,4-triazole-1,3-disulfonamide (0.40 g, 1.36 mmol), 1-bromo-3-(bromomethyl)benzene (0.48 g, 2.0 mmol) and N,N-dimethylformamide (15 ml) were added to a 50 mL three-necked flask, and the mixture was stirred at room temperature for 12 hours. Water (30 mL) was added, and the mixture was extracted with ethyl acetate (20 mL×3). The organic phase was washed with saturated brine (10 ml), dried over magnesium sulfate, filtered, and the solvent was removed under reduced pressure using a rotary evaporator. The residue was purified by column chromatography (ethyl acetate / petroleum ether (v / v) = 1 / 5) to obtain 0.287 g of a white solid, yield 45%.

[0135] 1 H NMR(400MHz,CDCl 3)δ(ppm): 8.63 (s, 1H), 7.52 (s, 1H), 7.44 (d, J = 7.9 Hz, 1H), 7.33 (d, J = 7.7 Hz, 1H), 7.21 (t, J = 7.8 Hz, 1H), 4.54 (s, 2H), 3.08 (s, 6H), 2.58 - 2.53 (m, 1H), 0.87 - 0.83 (m, 2H), 0.77 - 0.73 (m, 2H).

[0136] LC-MS: (M+1) m / z = 464.0.

[0137] Indoor bioassay 1

[0138] Using the potting method indoors, the inhibitory effects of different bactericidal compositions on the growth of the cucumber downy mildew pathogen (Pseudoperonospora cubensis (Berk. et Curt.) Rostov, collected from the Zengcheng Experimental Base of South China Agricultural University and preserved in the living generation) were determined, and the EC 50 value of each agent against the pathogen was calculated.

[0139] Drug application: Select potted cucumber seedlings with consistent growth at the two-leaf stage for the experiment. The single agent or each composition (see Tables 1 and 2) was dissolved in solvent DMSO and then diluted with 0.1 wt% Tween 80 water to an appropriate concentration gradient (bromuconazole / epoxiconazole: 5 mg / L, 2.5 mg / L, 1.25 mg / L, 0.625 mg / L, 0.3125 mg / L, 0.15625 mg / L; metalaxyl-M: 20 mg / L, 10 mg / L, 5 mg / L, 2.5 mg / L, 1.25 mg / L, 0.625 mg / L; bactericidal composition: 12.5 mg / L, 6.25 mg / L, 3.125 mg / L, 1.562 mg / L, 0.781 mg / L, 0.391 mg / L). After foliar spray treatment, the test materials were air-dried for 24 h. The control group was sprayed with the same amount of solvent.

[0140] Inoculation: Use a 0.1 wt% Tween 80 aqueous solution to wash the fresh sporangia on the cucumber diseased leaves, filter with 4 layers of gauze, and prepare a sporangia suspension with a concentration of 6×10 5 CFU / mL, and then evenly spray it on the cucumber seedlings with an inoculation sprayer (pressure 0.1 MPa) until the surface is wet. After spray inoculation, transfer it to an artificial climate chamber with a relative humidity > 90%, a temperature of 22 °C, and a light intensity greater than 2000 lx, and conduct a disease investigation after 7 d.

[0141] Grading standard:

[0142] Grade 0: No disease spots;

[0143] Level 1: The lesion area accounts for less than 5% of the whole leaf area;

[0144] Level 3: The lesion area accounts for 6% - 10% of the whole leaf area;

[0145] Level 5: The lesion area accounts for 11% - 25% of the whole leaf area;

[0146] Level 7: The lesion area accounts for 26% - 50% of the whole leaf area;

[0147] Level 9: The lesion area accounts for more than 50% of the whole leaf area.

[0148] Calculation of drug efficacy:

[0149]

[0150]

[0151] Based on the concentrations of each single agent and the bactericidal composition and the corresponding control effects, perform corresponding regression analysis to obtain the EC 50 value and 95% confidence interval of each bactericidal composition.

[0152] Adopt the co-toxicity coefficient calculation method introduced by Sun Yunpei to calculate the co-toxicity coefficient (CTC) of the mixture and determine the synergistic effect of the mixture.

[0153] Taking a certain single agent in the mixture as the standard agent (usually choose the one with a lower EC 50 value) for calculation:

[0154] Single-agent toxicity index = EC of the standard agent 50 / EC of a certain single agent 50 × 100;

[0155] Theoretical toxicity index (TTI) = Toxicity index of single agent A × Proportion of single agent A in the mixture + Toxicity index of single agent B × Proportion of single agent B in the mixture;

[0156] Actual toxicity index (ATI) = EC of the standard agent 50 value / EC of the mixture 50 value × 100;

[0157] Co-toxicity coefficient (CTC) = Actual toxicity index / Theoretical toxicity index × 100.

[0158] When CTC is greater than 120, the mixture has a synergistic effect; when CTC is less than 80, it is antagonistic; when CTC is between 80 - 120, it is an additive effect.

[0159] Table 1: Determination results of the co-toxicity coefficient of the ratio of metalaxyl-M and cyflufenamid against cucumber downy mildew

[0160]

[0161]

[0162] Note: F represents cyproconazole; C represents metalaxyl-M.

[0163] From the results in Table 1, it can be seen that when the mass ratio of metalaxyl-M to cyproconazole is (1 - 20):(20 - 1) in the compounding, it has an obvious synergistic effect on cucumber downy mildew. Thus, the composition of metalaxyl-M and cyproconazole is an ideal agent for controlling cucumber downy mildew.

[0164] Table 2: Determination results of the co-toxicity coefficient of the ratio of metalaxyl-M to difenoconazole against cucumber downy mildew

[0165]

[0166] Note: D represents difenoconazole; C represents metalaxyl-M.

[0167] From the results in Table 2, it can be seen that when the mass ratio of metalaxyl-M to difenoconazole is (1 - 20):(20 - 1) in the compounding, it has an obvious synergistic effect on cucumber downy mildew. Thus, the composition of metalaxyl-M and difenoconazole is an ideal agent for controlling cucumber downy mildew.

[0168] Indoor bioassay two

[0169] Using the pot method indoors, the inhibitory effect of different bactericidal compositions on the growth of cucumber downy mildew pathogen (Pseudoperonospora cubensis (Berk. et Curt.) Rostov, collected from the Zengcheng experimental base of South China Agricultural University and preserved in the living generation) was determined, and the EC 50 value of each agent against the pathogen was calculated.

[0170] Drug application: Select potted cucumber seedlings with consistent growth at the two-leaf stage for the experiment. The single agent or each composition (see Tables 3 and 4) was dissolved in solvent DMSO and then diluted with 0.1 wt% Tween 80 water to appropriate concentration gradients (difenoconazole / cyproconazole: 5 mg / L, 2.5 mg / L, 1.25 mg / L, 0.625 mg / L, 0.3125 mg / L, 0.15625 mg / L; cymoxanil: 200 mg / L, 100 mg / L, 50 mg / L, 25 mg / L, 12.5 mg / L, 6.25 mg / L; bactericidal composition: 50 mg / L, 25 mg / L, 12.5 mg / L, 6.25 mg / L, 3.125 mg / L, 1.562 mg / L). After foliar spray treatment, the test materials were air-dried for 24 h. The control group was treated with the same amount of solvent by spraying.

[0171] Inoculation: Fresh sporangia on cucumber diseased leaves were washed with an aqueous solution of Tween 80 at a concentration of 0.1 wt%, filtered through four layers of gauze, and a sporangia suspension with a concentration of 6×10 5 CFU / mL was prepared. Then, it was evenly sprayed onto cucumber seedlings with an inoculation sprayer (pressure 0.1 MPa) until the surface was wet. After spray inoculation, the seedlings were transferred to an artificial climate chamber with a relative humidity > 90%, a temperature of 22°C, and a light intensity greater than 2000 lx. The disease condition was investigated after 7 days.

[0172] Grading standard:

[0173] Grade 0: Disease-free;

[0174] Grade 1: The diseased area accounts for less than 5% of the entire leaf area;

[0175] Grade 3: The diseased area accounts for 6% - 10% of the entire leaf area;

[0176] Grade 5: The diseased area accounts for 11% - 25% of the entire leaf area;

[0177] Grade 7: The diseased area accounts for 26% - 50% of the entire leaf area;

[0178] Grade 9: The diseased area accounts for more than 50% of the entire leaf area.

[0179] Calculation of drug efficacy:

[0180]

[0181]

[0182] According to the concentration of each single agent and the bactericidal composition and the corresponding control efficacy, a corresponding regression analysis was performed to obtain the EC 50 value and 95% confidence interval of each bactericidal composition.

[0183] Using the co-toxicity coefficient calculation method introduced by Sun Yunpei, the co-toxicity coefficient (CTC) of the mixture was calculated to determine the synergistic effect of the mixture.

[0184] Taking a single agent in the mixture as the standard agent (usually choosing the one with a lower EC 50 ), the calculation was carried out as follows:

[0185] Single agent virulence index = EC of the standard agent 50 / EC of a certain single agent 50 ×100;

[0186] Theoretical virulence index (TTI) = virulence index of single agent A × proportion of single agent A in the mixture + virulence index of single agent B × proportion of single agent B in the mixture;

[0187] Actual virulence index (ATI) = EC of the standard agent50 EC of the value / mixed agent 50 Value × 100;

[0188] Coefficient of co-toxicity (CTC) = measured toxicity index / theoretical toxicity index × 100.

[0189] When CTC is greater than 120, the mixed agent has a synergistic effect; when CTC is less than 80, it is antagonistic; when CTC is between 80 and 120, it is additive.

[0190] Table 3: Determination results of the coefficient of co-toxicity of the ratio of cymoxanil and bromuconazole against Pseudoperonospora cubensis

[0191]

[0192] Note: D represents bromuconazole; G represents cymoxanil.

[0193] It can be seen from the results in Table 3 that when the mass ratio of bromuconazole and cymoxanil is (1 - 5):(20 - 1) in the compounding, it has an obvious synergistic effect against Pseudoperonospora cubensis. It can be seen that the composition of cymoxanil and bromuconazole is an ideal agent for controlling Pseudoperonospora cubensis.

[0194] Table 4: Determination results of the coefficient of co-toxicity of the ratio of cymoxanil and cyflufenamid against Pseudoperonospora cubensis

[0195]

[0196]

[0197] Note: F represents cyflufenamid; G represents cymoxanil.

[0198] It can be seen from the results in Table 4 that when the mass ratio of cyflufenamid and cymoxanil is (1 - 5):(20 - 1) in the compounding, it has an obvious synergistic effect against Pseudoperonospora cubensis. It can be seen that the composition of cymoxanil and cyflufenamid is an ideal agent for controlling Pseudoperonospora cubensis.

[0199] Example 1: 77% metalaxyl - M·cyflufenamid (10:1) wettable powder

[0200] Mix 70% metalaxyl - M, 7% cyflufenamid, 5% lignosulfonate (trade name: Ultrazine NA, Borregaard Industries), 4% EOPO block copolymer (trade name: Antraox B / 848, Solvay) and 2% sodium dodecyl sulfate (Aladdin reagent) and kaolin (Hangzhou Zuotu New Materials Co., Ltd.) to make up to 100% pre - pulverize and mix evenly, and then pulverize with an air - jet mill (Kunshan Younaike Machinery Co., Ltd.) to obtain a wettable powder of metalaxyl - M·cyflufenamid with an active ingredient mass content of 77%.

[0201] Example 2: 40% Metalaxyl-M · Cyproconazole (3:1) Wettable Powder

[0202] Mix 30% Metalaxyl-M, 10% Cyproconazole, 7% polycarboxylate (trade name: KMA, Beijing Guangyuan Yinnong Chemical Co., Ltd.), 3% sodium dodecyl sulfate (Aladdin reagent), 5% silica white (Aladdin reagent) and bentonite (Hangzhou Zuotu New Materials Co., Ltd.) to make up to 100% and pre-crush and mix them evenly, then crush them with a jet mill (Kunshan Younaike Machinery Co., Ltd.) to obtain a wettable powder of Metalaxyl-M · Cyproconazole with an active ingredient mass content of 40%.

[0203] Example 3: 40% Metalaxyl-M · Bromuconazole (3:1) Wettable Powder

[0204] Mix 30% Metalaxyl-M, 10% Bromuconazole, 9% alkylnaphthalenesulfonate formaldehyde condensate (trade name: Morwet D425, AkzoNobel), 2% sodium dodecyl sulfate (Aladdin reagent) and kaolin (Hangzhou Zuotu New Materials Co., Ltd.) to make up to 100% and pre-crush and mix them evenly, then crush them with a jet mill (Kunshan Younaike Machinery Co., Ltd.) to obtain a wettable powder of Metalaxyl-M · Bromuconazole with an active ingredient mass content of 40%.

[0205] Example 4: 63% Metalaxyl-M · Bromuconazole (20:1) Wettable Powder

[0206] Mix 60% Metalaxyl-M, 3% Bromuconazole, 8% polycarboxylate (trade name: GY-D06, Beijing Guangyuan Yinnong Chemical Co., Ltd.), 4% sodium dodecyl sulfate (Aladdin reagent), 5% silica white (Aladdin reagent) and bentonite (Hangzhou Zuotu New Materials Co., Ltd.) to make up to 100% and pre-crush and mix them evenly, then crush them with a jet mill (Kunshan Younaike Machinery Co., Ltd.) to obtain a wettable powder of Metalaxyl-M · Bromuconazole with an active ingredient mass content of 63%.

[0207] Example 5: 63% Metalaxyl-M · Cyproconazole (1:20) Water Dispersible Granule

[0208] Mix 3% Metalaxyl-M, 60% Cyproconazole, polycarboxylate (trade name: 2700, Huntsman), 7%, sulfonate wetting agent (trade name: Morwet EFW, AkzoNobel), 2%, ammonium sulfate (Aladdin reagent), 5%, silica white (Aladdin reagent) and bentonite (Hangzhou Zuotu New Materials Co., Ltd.) to make up to 100% and pre-crush and mix them evenly, then crush them with a jet mill (Kunshan Younaike Machinery Co., Ltd.), then granulate with a rotary granulator, dry and screen to obtain a water dispersible granule of Metalaxyl-M · Cyproconazole with an active ingredient mass content of 63%.

[0209] Example 6: 30% Metalaxyl-M · Epoxiconazole (5:1) Water Dispersible Granules

[0210] Take 25% Metalaxyl-M, 5% Epoxiconazole, 4% alkylnaphthalenesulfonate formaldehyde condensate (trade name: Morwet D425, AkzoNobel), 4% polycarboxylate (trade name: 2700, Huntsman), 2% sodium dodecyl sulfate (Aladdin reagent), 5% ammonium sulfate (Aladdin reagent) and kaolin (Hangzhou Zuotu New Materials Co., Ltd.) to make up to 100%, pre-crush and mix evenly, then crush with a jet mill (Kunshan Younaike Machinery Co., Ltd.), then granulate with a rotary granulator, dry, and screen to obtain Metalaxyl-M · Epoxiconazole water dispersible granules with an active ingredient mass content of 30%.

[0211] Example 7: 72% Metalaxyl-M · Bromuconazole (5:1) Water Dispersible Granules

[0212] Take 60% Metalaxyl-M, 12% Bromuconazole, 7% alkylnaphthalenesulfonate formaldehyde condensate (trade name: Morwet D425, AkzoNobel), 2% sodium dodecyl sulfate (Aladdin reagent), 5% ammonium sulfate (Aladdin reagent) and kaolin (Hangzhou Zuotu New Materials Co., Ltd.) to make up to 100%, pre-crush and mix evenly, then crush with a jet mill (Kunshan Younaike Machinery Co., Ltd.), then granulate with a rotary granulator, dry, and screen to obtain Metalaxyl-M · Bromuconazole water dispersible granules with an active ingredient mass content of 72%.

[0213] Example 8: 24% Metalaxyl-M · Bromuconazole (1:5) Water Dispersible Granules

[0214] Take 4% Metalaxyl-M, 20% Bromuconazole, 8% lignosulfonate (trade name: Borresperse NA, Borregaard Industries), 3% sodium dodecyl sulfate (Aladdin reagent), 5% ammonium sulfate (Aladdin reagent) and kaolin (Hangzhou Zuotu New Materials Co., Ltd.) to make up to 100%, pre-crush and mix evenly, then crush with a jet mill (Kunshan Younaike Machinery Co., Ltd.), then granulate with a rotary granulator, dry, and screen to obtain Metalaxyl-M · Bromuconazole water dispersible granules with an active ingredient mass content of 24%.

[0215] Example 9: 20% Metalaxyl-M · Epoxiconazole (1:1) Suspension Concentrate

[0216] (i) Preparation of the grinding slurry

[0217] Take 10% Metalaxyl-M, 10% Epoxiconazole, 3% alkylnaphthalenesulfonate formaldehyde condensate (trade name: Morwet D425, AkzoNobel), 4% polycarboxylate (trade name: 2500, Huntsman Corporation) 3% and silicone defoamer (trade name: ETXP-40, Hangzhou Zuotu New Materials Co., Ltd.) 0.4% were fully dispersed in water up to 80%, and glass beads were used for wet grinding with a sand mill (Shenyang Research Institute of Chemical Industry) to obtain 80% of the ground slurry.

[0218] (ii) Preparation of suspending agent

[0219] To 80% of the ground slurry, 0.2% of xanthan gum (Aladdin reagent), 1.0% of magnesium aluminum silicate (Hangzhou Zuotu New Materials Co., Ltd.), 3% of ethylene glycol (Aladdin reagent), and 0.5% of sodium benzoate (Aladdin reagent) were added and mixed evenly. Water was added to make up to 100%, and it was sheared at high speed to obtain a 20% metalaxyl-M · cyproconazole suspending agent with the mass content of the active ingredient.

[0220] Example 10: 12% metalaxyl-M · cyproconazole (1:5) suspending agent

[0221] (i) Preparation of ground slurry

[0222] 2% of metalaxyl-M, 10% of cyproconazole, 4% of lignosulfonate (trade name: Ultrazine NA, Borregaard Industries AS), 2% of JR-P (AkzoNobel), 2% of sulfonate wetting agent (trade name: Morwet EFW, AkzoNobel) and 0.4% of silicone defoamer (trade name: ETXP-40, Hangzhou Zuotu New Materials Co., Ltd.) were fully dispersed in water up to 80%, and glass beads were used for wet grinding with a sand mill (Shenyang Research Institute of Chemical Industry) to obtain 80% of the ground slurry.

[0223] (ii) Preparation of suspending agent

[0224] To 80% of the ground slurry, 0.2% of xanthan gum (Aladdin reagent), 0.4% of organobentonite (Hangzhou Zuotu New Materials Co., Ltd.), 3% of ethylene glycol (Aladdin reagent), and 0.5% of sodium benzoate (Aladdin reagent) were added and mixed evenly. Water was added to make up to 100%, and it was sheared at high speed to obtain a 12% metalaxyl-M · cyproconazole suspending agent with the mass content of the active ingredient.

[0225] Example 11: 21% metalaxyl-M · bromuconazole (1:20) suspending agent

[0226] (i) Preparation of ground slurry

[0227] Mix 1% metalaxyl-M, 20% difenoconazole, 3% alkylnaphthalenesulfonate formaldehyde condensate (trade name: Morwet D425, AkzoNobel), 2% EO-PO block copolymer (trade name: Ethylan NS-500LQ, AkzoNobel) and 0.4% silicone defoamer (trade name: ETXP-40, Hangzhou Zuotu New Materials Co., Ltd.) thoroughly in water up to 80%, and use glass beads, and wet grind with a sand mill (Shenyang Research Institute of Chemical Industry) to obtain 80% of the ground slurry.

[0228] (ii) Preparation of the suspending agent

[0229] Add 0.2% xanthan gum (Aladdin reagent), 1.0% magnesium aluminum silicate (Hangzhou Zuotu New Materials Co., Ltd.), 3% ethylene glycol (Aladdin reagent) and 0.5% sodium benzoate (Aladdin reagent) to 80% of the ground slurry and mix evenly. Add water to make up to 100%, and uniformly prepare a metalaxyl-M·difenoconazole suspending agent with an active ingredient mass content of 21% by high-speed shearing.

[0230] Example 12: 10% metalaxyl-M·difenoconazole (1:1) suspending agent

[0231] (i) Preparation of the ground slurry

[0232] Mix 5% metalaxyl-M, 5% difenoconazole, 4% polycarboxylate (trade name: 2500, Huntsman), 2% sulfonate wetting agent (trade name: Morwet EFW, AkzoNobel) and 0.4% silicone defoamer (trade name: ETXP-40, Hangzhou Zuotu New Materials Co., Ltd.) thoroughly in water up to 80%, and use glass beads, and wet grind with a sand mill (Shenyang Research Institute of Chemical Industry) to obtain 80% of the ground slurry.

[0233] (ii) Preparation of the suspending agent

[0234] Add 0.2% xanthan gum (Aladdin reagent), 0.4% organobentonite (Hangzhou Zuotu New Materials Co., Ltd.), 3% ethylene glycol (Aladdin reagent) and 0.5% sodium benzoate (Aladdin reagent) to 80% of the ground slurry and mix evenly. Add water to make up to 100%, and uniformly prepare a metalaxyl-M·difenoconazole suspending agent with an active ingredient mass content of 10% by high-speed shearing.

[0235] Example 13: 50% cymoxanil·cyflufenamid (1:1) emulsion in water

[0236] 1. Preparation of the oil phase

[0237] Add 25% of cymoxanil technical and 25% of cyflufenamid technical to a mixed solvent consisting of 7% cyclohexanone (Aladdin reagent) and 3% xylene (Aladdin reagent). After mixing evenly by ultrasound, then add 1.5% of an emulsifier (trade name: TERMUL 200, Huntsman) and 1.5% of castor oil polyoxyethylene ether (trade name: EL360, Xingtai Yancheng Chemical Auxiliary Co., Ltd.) and stir slowly until completely dissolved.

[0238] 2. Preparation of aqueous phase

[0239] Add 4% of ethylene glycol (Aladdin reagent), 0.4% of magnesium aluminum silicate (Aladdin reagent), 0.1% of high-efficiency silicone defoamer (trade name: ETXP-40, Hangzhou Zuotu New Materials Co., Ltd.), and add water to 32.5% and stir evenly.

[0240] 3. Preparation of aqueous emulsion of pesticide composition

[0241] Slowly add the aqueous phase to the oil phase and keep stirring until completely added. Then, under high shear (4000 rpm) of a high-speed disperser (trade name: TG25, IKA, Germany) for 30 minutes, a cymoxanil·cyflufenamid aqueous emulsion with an active ingredient mass content of 50% is prepared.

[0242] Example 14: 20% cymoxanil·cyflufenamid (1:3) microemulsion

[0243] Weigh 5% of cymoxanil technical, 15% of cyflufenamid technical, 10% of solvent xylene (Aladdin reagent), 5% of solvent cyclohexanone (Aladdin reagent), 9% of emulsifier phenyl ethyl phenol polyoxyethylene ether (trade name: Nongru 601#, Xingtai Yancheng Chemical Auxiliary Co., Ltd.), 5% of emulsifier dodecyl benzene sulfonate (trade name: Nongru 500#, Xingtai Yancheng Chemical Auxiliary Co., Ltd.), and 5% of antifreeze propylene glycol (Aladdin reagent). After fully dissolving cyflufenamid and cymoxanil with the solvent, add the emulsifier and antifreeze and mix evenly. Finally, add 46% of deionized water and stir evenly to obtain a cymoxanil·cyflufenamid microemulsion with an active ingredient mass content of 20%.

[0244] Example 15: 80% cymoxanil·cyflufenamid (3:1) water dispersible granule

[0245] 60% cymoxanil, 20% prothioconazole technical, 4.0% polycarboxylate dispersant (trade name: GY-D180, Beijing Guangyuan Yinuo Chemical Co., Ltd.), 4.0% high-purity modified sodium lignosulfonate dispersant (trade name: Ultrazine 3A, AkzoNobel), 5.0% ammonium sulfate (Aladdin reagent), 0.5% organic bentonite (Hangzhou Zuotu New Materials Co., Ltd.), 1000-mesh kaolin (Hangzhou Zuotu New Materials Co., Ltd.) are added to 100%. First, pre-crush and mix evenly, then crush to the required particle size (10 - 15 microns) by an air jet mill (model: SJM-100, Kunshan Younaike Machinery Co., Ltd.), and then granulate by a rotary granulator (model: ZLB1-80, Zhuoying Dry Engineering Technology Co., Ltd.) to obtain a cymoxanil·prothioconazole water dispersible granule with an active ingredient mass content of 80%.

[0246] Example 16: 50% Cymoxanil·Bromuconazole (1:1) Suspension Concentrate

[0247] 1. Preparation of the pulverized slurry

[0248] Disperse 2% non-alkylphenol-based highly efficient dispersant (trade name: 500LQ, Nouryon), 2% comb-shaped polymer compound dispersant (trade name: GY-800, Beijing Guangyuan Yinuo Chemical Co., Ltd.), 2% wetting agent (trade name: GY-WS10, Beijing Guangyuan Yinuo Chemical Co., Ltd.) and 0.4% highly efficient organosilicon defoamer (trade name: ETXP-40, Hangzhou Zuotu New Materials Co., Ltd.) in 23.6% water. Disperse 25% cymoxanil technical and 25% bromuconazole technical in it. Use 0.6 - 0.8 mmφ glass beads and conduct wet grinding for 1.5 h with a sand mill (Shenyang New Micro Motor Factory) to obtain 80% of the pulverized slurry.

[0249] 2. Preparation of the dispersion medium

[0250] Disperse 0.3% xanthan gum (Aladdin reagent), 0.4% magnesium aluminum silicate (Aladdin reagent), 5% ethylene glycol (Aladdin reagent) and 0.5% sodium benzoate (Aladdin reagent) in 13.8% water to obtain 20% of the dispersion medium.

[0251] 3. Preparation of the aqueous suspension pesticide composition

[0252] Mix 80% of the above pulverized slurry and 20% of the dispersion medium to obtain 100% of the aqueous suspension pesticide composition, and carry out high-shear (5000 revolutions per minute) for 30 minutes with a high-speed disperser (trade name: TG25, IKA, Germany). A cymoxanil·bromuconazole suspension concentrate with an active ingredient mass content of 50% is prepared.

[0253] Example 17: 20% Cymoxanil·Bromuconazole (1:3) Emulsifiable Concentrate

[0254] Add 5% of cyclohexanone (Aladdin reagent) and 15% of emulsifier (trade name: YUS-EC2011CX, Nippon Yushi Co., Ltd.) to 60% of quinamide solvent (trade name: FMPC, Nanjing Jierun). After stirring evenly, add 5% of cymoxanil technical and 15% of bromuconazole technical. Stir continuously in a 40°C constant temperature water bath until the technicals are fully dissolved, obtaining cymoxanil·bromuconazole EC with an active ingredient mass content of 20%.

[0255] Example 18: 80% Cymoxanil·Bromuconazole (3:1) Water Dispersible Granules

[0256] Add 60% of cymoxanil, 20% of bromuconazole technical, 4.0% of polycarboxylate dispersant (trade name: ULT, Solvay), 4.0% of high-purity modified sodium lignosulfonate dispersant (trade name: Ultrazine NA, AkzoNobel), 5.0% of ammonium sulfate (Aladdin reagent), and bentonite (Hangzhou Zuotu New Materials Co., Ltd.) to 100%. First, pre-crush and mix evenly, then crush to the required particle size (10 - 15 microns) by an air flow crusher (model: SJM-100, Kunshan Younaike Machinery Co., Ltd.), and then granulate with a rotary granulator (model: ZLB1-80, Zhuoying Drying Engineering Technology Co., Ltd.) to obtain cymoxanil·bromuconazole water dispersible granules with an active ingredient mass content of 80%.

[0257] Example 19: 60% Cymoxanil·Bromuconazole (1:5) Wettable Powder

[0258] Add 10% of cymoxanil, 50% of bromuconazole technical, 5.0% of naphthalene sulfonate condensate (trade name: BB4, Croda), 3.0% of lignin C (Hangzhou Zuotu New Materials Co., Ltd.), 5.0% of ammonium sulfate (Aladdin reagent), 0.7% of xanthan gum (Aladdin reagent), and kaolin (Hangzhou Zuotu New Materials Co., Ltd.) to 100%. First, pre-crush and mix evenly, then crush to the required particle size (10 - 15 microns) by air flow crushing (model: SJM-100, Kunshan Younaike Machinery Co., Ltd.) to obtain cymoxanil·bromuconazole wettable powder with an active ingredient mass content of 60%.

[0259] Example 20: 36% Cymoxanil·Cyflufenamid (1:5) Emulsion in Water

[0260] 1. Preparation of Oil Phase

[0261] Add 6% of cymoxanil technical and 30% of cyflufenamid technical to a mixed solvent consisting of 7% of cyclohexanone (Aladdin reagent) and 3% of xylene (Aladdin reagent). After ultrasonic mixing until uniform, then add 1.5% of an emulsifier (trade name: TERMUL 5036, Huntsman) and 1.5% of castor oil polyoxyethylene ether (trade name: EMULPON CO-360, AkzoNobel), and slowly stir until completely dissolved.

[0262] 2. Preparation of aqueous phase

[0263] Add 4% of ethylene glycol (Aladdin reagent), 0.4% of magnesium aluminum silicate (Aladdin reagent), 0.1% of high-efficiency organosilicon defoamer (trade name: ETXP-40, Hangzhou Zuotu New Materials Co., Ltd.), and add water to 46.5%, and stir evenly.

[0264] 3. Preparation of aqueous emulsion of pesticide composition

[0265] Slowly add the aqueous phase to the oil phase, and continuously stir until completely added, and then use a high-speed disperser (trade name: TG25, IKA, Germany) at high shear (4000 rpm) for 30 minutes to obtain a cymoxanil·cyflufenamid aqueous emulsion with an active ingredient mass content of 36%.

[0266] Control Example 1: 20% metalaxyl-M suspension concentrate

[0267] (i) Preparation of pulverized slurry

[0268] Disperse 20% of metalaxyl-M, 4% of lignosulfonate (trade name: YUS-WG4, Takemoto Oil & Fat), 2% of sulfonate wetting agent (trade name: Morwet EFW, AkzoNobel) and 0.5% of organosilicon defoamer (trade name: ETXP-40, Hangzhou Zuotu New Materials Co., Ltd.) in water supplemented to 80%, and use Glass beads, and perform wet grinding with a sand mill (Shenyang Research Institute of Chemical Industry) to obtain 80% of pulverized slurry.

[0269] (ii) Preparation of suspension concentrate

[0270] Add 0.2% of xanthan gum (Aladdin reagent), 1.0% of magnesium aluminum silicate (Hangzhou Zuotu New Materials Co., Ltd.), 4% of ethylene glycol (Aladdin reagent), and 0.5% of sodium benzoate (Aladdin reagent) to 80% of the pulverized slurry and mix evenly, and supplement water to 100%, and shear evenly at high speed to obtain a metalaxyl-M suspension concentrate with an active ingredient mass content of 20%.

[0271] Control Example 2: 20% cyflufenamid suspension concentrate

[0272] (i) Preparation of pulverized slurry

[0273] Fluopyram 20%, lignosulfonate (trade name: YUS-RXB, Takemoto Oil & Fat Co., Ltd.) 5%, sulfonate wetting agent (trade name: Morwet EFW, AkzoNobel) 2% and silicone defoamer (trade name: ETXP-40, Hangzhou Zuotu New Materials Co., Ltd.) 0.5% were fully dispersed in water supplemented to 80%, and glass beads were used and wet grinding was carried out with a sand mill (Shenyang Research Institute of Chemical Industry) to obtain 80% of the ground slurry.

[0274] (ii) Preparation of the suspending agent

[0275] To 80% of the ground slurry was added 0.2% of xanthan gum (Aladdin reagent), 1.0% of magnesium aluminum silicate (Hangzhou Zuotu New Materials Co., Ltd.), 4% of ethylene glycol (Aladdin reagent), and 0.5% of sodium benzoate (Aladdin reagent), and they were mixed evenly. Water was supplemented to 100%, and a suspending agent of fluopyram with an active ingredient mass content of 20% was prepared by high-speed shearing and homogenization.

[0276] Control Example 3: 20% bromuconazole suspending agent

[0277] (i) Preparation of the ground slurry

[0278] 20% of bromuconazole, 6% of lignosulfonate (trade name: 24, Xingfei Chemical Industry (Shanghai) Co., Ltd.), 2% of sulfonate wetting agent (trade name: Morwet EFW, AkzoNobel) and 0.5% of silicone defoamer (trade name: ETXP-40, Hangzhou Zuotu New Materials Co., Ltd.) were fully dispersed in water supplemented to 80%, and glass beads were used and wet grinding was carried out with a sand mill (Shenyang Research Institute of Chemical Industry) to obtain 80% of the ground slurry.

[0279] (ii) Preparation of the suspending agent

[0280] To 80% of the ground slurry was added 0.2% of xanthan gum (Aladdin reagent), 1.0% of magnesium aluminum silicate (Hangzhou Zuotu New Materials Co., Ltd.), 4% of ethylene glycol (Aladdin reagent), and 0.5% of sodium benzoate (Aladdin reagent), and they were mixed evenly. Water was supplemented to 100%, and a suspending agent of bromuconazole with an active ingredient mass content of 20% was prepared by high-speed shearing and homogenization.

[0281] Control Example 4: 40% bromuconazole suspending agent

[0282] (i) Preparation of the ground slurry

[0283] 40% of difenoconazole, 3% of lignosulfonate (trade name: BCA, Borregaard Industries Ltd.), 2% of sulfonate wetting agent (trade name: Morwet EFW, AkzoNobel), and 0.5% of silicone defoamer (trade name: ETXP-40, Hangzhou Zuotu New Materials Co., Ltd.) were fully dispersed in water to make up 80%, and then glass beads were used and wet grinding was carried out with a sand mill (Shenyang Research Institute of Chemical Industry) to obtain 80% of the ground slurry.

[0284] (ii) Preparation of the suspending agent

[0285] To 80% of the ground slurry was added 0.2% of xanthan gum (Aladdin reagent), 1.0% of magnesium aluminum silicate (Hangzhou Zuotu New Materials Co., Ltd.), 4% of ethylene glycol (Aladdin reagent), and 0.5% of sodium benzoate (Aladdin reagent), and they were mixed evenly. Water was added to make up to 100%, and it was sheared at high speed and evenly to prepare a difenoconazole suspending agent with an active ingredient mass content of 40%.

[0286] Control Example 5: 40% cyflufenamid emulsion in water

[0287] 1. Preparation of the oil phase

[0288] 40% of the cyflufenamid technical was added to a mixed solvent of 7% of cyclohexanone (Aladdin reagent) and 3% of xylene (Aladdin reagent). After ultrasonic mixing evenly, then 2% of phenethylphenol polyoxyethylene ether (trade name: 602#, Xingtai Yancheng Chemical Auxiliary Co., Ltd.) and 3% of castor oil polyoxyethylene ether (trade name: EL360, Xingtai Yancheng Chemical Auxiliary Co., Ltd.) were added and slowly stirred until completely dissolved.

[0289] 2. Preparation of the water phase

[0290] 4% of ethylene glycol (Aladdin reagent), 0.4% of magnesium aluminum silicate (Aladdin reagent), 0.1% of high-efficiency silicone defoamer (trade name: ETXP-40, Hangzhou Zuotu New Materials Co., Ltd.), and water were added to make up 40.5% and stirred evenly.

[0291] 3. Preparation of the emulsion in water of the pesticide composition

[0292] The water phase was slowly added to the oil phase, and continuously stirred until completely added, and then it was sheared at high speed (4000 revolutions per minute) for 30 minutes with a high-speed disperser (trade name: TG25, IKA, Germany) to prepare a cyflufenamid emulsion in water with an active ingredient mass content of 40%. Control Example 6: 50% cymoxanil wettable powder

[0293] 50% of cymoxanil, 5.0% of naphthalenesulfonate polycondensate (trade name: 19, Croda, UK), 3.0% of lignin sulfonate (trade name: Borresperse NA, Borrego Industries Co., Ltd.), 5.0% of ammonium sulfate (Aladdin reagent), 0.7% of xanthan gum (Aladdin reagent), and kaolin (Hangzhou Zuotu New Materials Co., Ltd.) were added to 100%, pre-crushed and mixed, and then air flow crushed (model: SJM-100, Kunshan Unak Machinery Co., Ltd.) to the required particle size (10-15 microns) to prepare a cymoxanil wettable powder with an active ingredient mass content of 50%.

[0294] Comparative Example 7:

[0295] Blank water control.

[0296] Field efficacy test 1

[0297] Plot setting: Each treatment was repeated 4 times, and the area of ​​each plot was 30m 2 , randomized block arrangement.

[0298] Time and method of application: Apply the agent at the early stage of cucumber downy mildew, spray on the leaves, and spray the amount of liquid mainly to prevent dripping; apply the agent twice, investigate the disease base before the first application, apply the agent once every 7 days, investigate the disease index 7 days after each application, and calculate the prevention effect.

[0299] Survey method: Four random survey points were selected in each plot, 2 plants were surveyed at each point, all leaves of each plant were surveyed, and the total number of leaves and the number of diseased leaves at various levels were recorded.

[0300] The grading standards are as follows:

[0301] Level 0: no lesions;

[0302] Level 1: The lesion area accounts for less than 5% of the entire leaf area;

[0303] Level 3: The lesion area accounts for 6% to 10% of the entire leaf area;

[0304] Level 5: The lesion area accounts for 11% to 25% of the entire leaf area;

[0305] Level 7: The lesion area accounts for 26% to 50% of the entire leaf area;

[0306] Level 9: The lesion area accounts for more than 50% of the entire leaf area.

[0307] Calculation of drug efficacy:

[0308]

[0309]

[0310] Where: CK0 —— Disease index before treatment in the blank control area; CK 1 —— Disease index after treatment in the blank control area; PT 0 —— Disease index before treatment in the medicament treatment area; PT 1 —— Disease index after treatment in the medicament treatment area.

[0311] The test results are shown in Table 5 for details.

[0312] Table 5: Control efficacy of different medicaments against cucumber downy mildew

[0313]

[0314] As can be seen from the results in Table 5, the compound preparations of metalaxyl-M and cyflufenamid, and metalaxyl-M and bromuconazole have excellent control efficacy against cucumber downy mildew, and also have excellent quick-acting and long-lasting properties. In addition, during the entire indoor and outdoor bioassay experiments, no phytotoxicity to cucumbers was found for the compound medicaments. Therefore, the bactericidal composition and preparation provided by the present invention are safe and efficient, can reduce the environmental pollution caused by pesticides, and lower the cost of plant disease control, having good application value.

[0315] Field efficacy test 2

[0316] Plot setting: Each treatment of the test was repeated 4 times, and the area of each plot was 30 m 2 , arranged in a randomized block design.

[0317] Application time and method: The medicament was applied at the initial stage of cucumber downy mildew occurrence, by foliar spray treatment, with the liquid spraying amount mainly ensuring no dripping water; applied 2 times, the disease base number was investigated before the first application, applied once every 7 days, and the disease index was investigated 7 days after each application to calculate the control efficacy.

[0318] Investigation method: Four points were randomly selected for investigation in each plot, 2 plants were investigated at each point, and all leaves of each plant were investigated to record the total number of leaves and the number of diseased leaves at each level.

[0319] Grading standard:

[0320] Grade 0: No disease spots;

[0321] Grade 1: The disease spot area accounts for less than 5% of the whole leaf area;

[0322] Grade 3: The disease spot area accounts for 6% - 10% of the whole leaf area;

[0323] Grade 5: The disease spot area accounts for 11% - 25% of the whole leaf area;

[0324] Grade 7: The disease spot area accounts for 26% - 50% of the whole leaf area;

[0325] Grade 9: The disease spot area accounts for more than 50% of the whole leaf area.

[0326] Pharmacodynamic calculation:

[0327]

[0328]

[0329] In the formula: CK 0 —— Disease index before treatment in the blank control area; CK 1 —— Disease index after treatment in the blank control area; PT 0 —— Disease index before treatment in the medicament treatment area; PT 1 —— Disease index after treatment in the medicament treatment area.

[0330] See Table 6 for the test results.

[0331] Table 6: Control effects of different medicaments on cucumber downy mildew

[0332]

[0333]

[0334] As can be seen from the results in Table 6, the compound preparations of cymoxanil and cyflufenamid, and cymoxanil and bromuconazole have excellent control effects on cucumber downy mildew, and also have excellent quick-acting and long-lasting properties. In addition, during the entire indoor and outdoor bioassay tests, no phytotoxicity to cucumbers was found for the compound medicaments. Therefore, the bactericidal composition and preparation provided by the present invention are safe and efficient, can reduce the pollution of pesticides to the environment, and reduce the cost of plant disease control, and have good application value.

[0335] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0336] In addition, it should be noted that, among the various specific technical features described in the above specific embodiments, without conflict, they can be combined in any appropriate manner. To avoid unnecessary repetition, the present invention will not separately describe various possible combination methods.

[0337] Furthermore, any combination can be made among various different embodiments of the present invention, as long as it does not violate the idea of the present invention, and it should also be regarded as the content disclosed by the present invention.

Claims

1. A bactericidal composition, characterized in that, the bactericidal composition comprises active ingredient A and active ingredient B; the active ingredient A comprises metalaxyl-M or cymoxanil; the active ingredient B comprises a triazolesulfonamide compound; the triazolesulfonamide compound is selected from bromuconazole or cyflufenamid; wherein, when the active ingredient A is metalaxyl-M and the active ingredient B is bromuconazole or cyflufenamid, the mass ratio of the active ingredient A to the active ingredient B is (1-20):(20-1); or wherein, when the active ingredient A is cymoxanil and the active ingredient B is bromuconazole or cyflufenamid, the mass ratio of the active ingredient A to the active ingredient B is (1-20):(5-1); The structure of bromuconazole is ， The structure of cyflufenamid is 。 2. The bactericidal composition according to claim 1, characterized in that, when the active ingredient A is metalaxyl-M and the active ingredient B is cyflufenamid, the mass ratio of metalaxyl-M to cyflufenamid is (1-10):(20-1).

3. The bactericidal composition according to claim 1, characterized in that, when the active ingredient A is cymoxanil and the active ingredient B is bromuconazole or cyflufenamid, the mass ratio of the active ingredient A to the active ingredient B is (1-5):(5-1).

4. The bactericidal composition according to claim 3, characterized in that, when the active ingredient A is cymoxanil and the active ingredient B is bromuconazole or cyflufenamid, the mass ratio of the active ingredient A to the active ingredient B is (1-3):(5-1).

5. The bactericidal composition according to any one of claims 1-4, characterized in that, the sum of the mass percentage contents of the active ingredient A and the active ingredient B in the bactericidal composition is 1-95%.

6. The bactericidal composition according to claim 5, characterized in that, the sum of the mass percentage contents of the active ingredient A and the active ingredient B in the bactericidal composition is 5-90%.

7. The bactericidal composition according to claim 6, characterized in that, the sum of the mass percentage contents of the active ingredient A and the active ingredient B in the bactericidal composition is 5-80%.

8. The bactericidal composition according to claim 7, characterized in that, the sum of the mass percentage contents of the active ingredient A and the active ingredient B in the bactericidal composition is 10-80%.

9. A preparation, characterized in that, the preparation contains the bactericidal composition according to any one of claims 1-8.

10. The preparation according to claim 9, characterized in that, the dosage form of the preparation is powder, wettable powder, microcapsule, water dispersible granule, granule, aqueous solution, suspension, oil suspension, emulsifiable concentrate, microemulsion, suspo-emulsion, water emulsion, ultra-low volume spray, seed coating agent or smoke agent.

11. The preparation according to claim 10, characterized in that, the dosage form of the preparation is wettable powder, water dispersible granule and / or suspension.

12. Use of the bactericidal composition according to any one of claims 1-8 or the preparation according to any one of claims 9-11 in the prevention and control of plant diseases.

13. According to the use described in claim 12, It is characterized in that the plant disease is at least one of downy mildew, Phytophthora blight, late blight, rot, white rust, and cotton Phytophthora blight.

14. The application according to claim 12 or 13, It is characterized in that the plants include cereal, fruit, and / or vegetable crops.

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