WO2022089447A1 - 一种含喹诺酮类化合物的增效杀菌组合物及其应用 - Google Patents

一种含喹诺酮类化合物的增效杀菌组合物及其应用 Download PDF

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WO2022089447A1
WO2022089447A1 PCT/CN2021/126496 CN2021126496W WO2022089447A1 WO 2022089447 A1 WO2022089447 A1 WO 2022089447A1 CN 2021126496 W CN2021126496 W CN 2021126496W WO 2022089447 A1 WO2022089447 A1 WO 2022089447A1
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compound
bacterial
bactericidal composition
spot
agent
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PCT/CN2021/126496
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English (en)
French (fr)
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迟会伟
赵宝修
吴建挺
牛纪胜
李文涛
邵莒南
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山东省联合农药工业有限公司
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Publication of WO2022089447A1 publication Critical patent/WO2022089447A1/zh

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/34—Nitriles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides

Definitions

  • the invention belongs to the technical field of pesticide compounding, in particular to a synergistic bactericidal composition containing a quinolone compound and its application.
  • quinolones 7-chloro-1-cyclopropyl-6-fluoro-4-oxo-1,4-dihydroquinoline-3-carboxylic acid-2-methoxyethyl ester, which It has broad-spectrum bactericidal activity, especially higher activity against bacteria, and exhibits excellent activity against Gram-positive bacteria and Gram-negative bacteria.
  • crop bacterial diseases such as soft rot of Chinese cabbage and other crops, black rot of Chinese cabbage, cucumber bacterial angular spot, sesame angular spot, western/melon fruit spot, rice bacterial blight disease, rice bacterial leaf spot, rice bacterial brown spot, rice bacterial brown stripe, rice bacterial base rot, tomato bacterial wilt and other Solanaceae bacterial wilt, mulberry bacterial wilt, peanut bacterial wilt , ginger and ginger blast, tomato/chili bacterial spot, pepper bacterial leaf spot, potato black shank, corn bacterial wilt, corn bacterial stalk rot, wheat black grain, soybean bacterial spot , soybean bacterial blight, cassava bacterial wilt, mango angular spot, citrus canker, peach bacterial perforation, sunflower stem rot, peach gum disease, pear fire blight, pear rust water disease, fruit tree bacterial root Cancer, potato ring rot, kidney bean wilt, wheat
  • the object of the present invention is to provide a synergistic bactericidal composition containing a quinolone compound and its application, wherein the bactericidal composition includes active ingredients, and the active ingredients include compound I and compound II, wherein, the compound I is 7-chloro-1-cyclopropyl-6-fluoro-4-oxo-1,4-dihydroquinoline-3-carboxylic acid-2-methoxyethyl ester, the Compound II is zhongshengmycin, kasugamycin, tetramycin, ethiocin, shenazinemycin, aureomycin, hydratomycin, allicin, amino oligosaccharin, neophytomycin, polyantimycin antibiotics, such as streptomycin, agricultural antibiotic 120, Jinggangmycin, pyrimidine nucleoside antibiotics, ningnanmycin, osthole, oligosaccharin and other antibiotic compounds, as well
  • the mixed use of the compound I and the compound II can form a synergistic bactericidal composition, and the effective active ingredients include the compound I and the compound II.
  • the mechanism of action is different, the compound can act on multiple sites of pathogenic bacteria, expand the bactericidal spectrum, improve the control effect, reduce the amount of pesticides used, delay the generation of drug resistance, and reduce costs.
  • the present invention adopts the following scheme:
  • a bactericidal composition comprises an effective active ingredient, the effective active ingredient comprises a compound I and a compound II, and the compound I is 7-chloro-1-cyclopropyl-6-fluoro-4- Oxo-1,4-dihydroquinoline-3-carboxylic acid-2-methoxyethyl ester, the compound II is an antibiotic compound, zinc thiazole, thiamycin, bromoxynil, amino oligosaccharide, At least one of emodin methyl ether, isothiazolinone, and dithiocyanomethane.
  • the antibiotic compound is selected from the group consisting of zhongshengmycin, kasugamycin, tetramycin, ethoxylin, aureomycin, sentazinemycin, hydratomycin, allicin, new plant At least one of pyrimidine, polyantimycin, agricultural streptomycin, agricultural antibiotic 120, Jinggangmycin, pyrimidine nucleoside antibiotics, ningnanmycin, osthole, oligosaccharin and the like.
  • the mass ratio of the compound I and the compound II is 80-1:1-80.
  • the mass ratio of the compound I and the compound II is 50-1:1-50.
  • the mass ratio of the compound I and the compound II is 30-1:1-30.
  • the mass ratio of compound I and compound II is 80:1, 75:1, 70:1, 65:1, 60:1, 55:1, 50:1, 45:1, 40:1, 35:1, 30:1, 25:1, 20:1, 15:1, 10:1, 5:1, 1:1, 1:5, 1:10, 15:1, 1: 20, 25:1, 1:30, 35:1, 1:40, 45:1, 1:50, 55:1, 1:60, 65:1, 1:70, 75:1, 1:80.
  • the mass sum of the compound I and the compound II in the bactericidal composition is 1-80%, preferably 20-60%, For example 1%, 5%, 8%, 10%, 13%, 15%, 18%, 20%, 24%, 30%, 35%, 38%, 42%, 45%, 50%, 55%, 60 %, 65%, 68%, 75%, 80%, 85%, 90%.
  • the bactericidal composition may be prepared as a liquid preparation or a solid preparation.
  • the content range of the effective active ingredient in the formulation is different.
  • the liquid formulation contains 1% to 60% by weight of the effective active ingredient, preferably 5% to 50%.
  • the solid preparation contains 5% to 80% by weight of effective active ingredients, preferably 10% to 70%.
  • the bactericidal composition further includes an emulsifier, a dispersant, a wetting agent, a thickening agent, an antifoaming agent, a stabilizer, a binding agent, a disintegrating agent, an antifreezing agent, an anti-caking agent At least one of additives, suspending agents, film-forming agents, preservatives, colorants, polymer capsule wall materials, pH adjusters or fillers, etc.
  • the germicidal composition may be diluted or used directly by the user prior to use.
  • Its formulation can be prepared by processing methods known to those skilled in the art, namely mixing the active ingredients with deionized water, organic solvents, emulsifiers, dispersants, wetting agents, thickeners, defoaming agents, stabilizers, binders , disintegrating agent, anti-freezing agent, anti-caking agent, suspending agent, film-forming agent, preservative, coloring agent, polymer capsule wall material, pH adjuster or filler, etc. are mixed to prepare the bactericidal composition.
  • the bactericidal composition can be made into various dosage forms, preferably, the dosage forms include water dispersible granules, dispersible liquids, wettable powders, suspensions, water emulsions, microemulsions, Emulsion, microcapsule suspension, microcapsule suspension-suspension, suspension seed coating, emulsifiable concentrate, granule.
  • the bactericidal composition comprises the following components and contents when made into a wettable powder: Compound I 1%-80%, Compound II 1%-80%, dispersant 1%-12%, moisturizing agent 1%-12%, Wetting agent 1% to 8%, the balance is filler.
  • the composition when the composition is made into water dispersible granules, it includes the following components and contents: Compound I 1%-80%, Compound II 1%-80%, dispersant 1%-12%, moisturizing agent 1%-12%, Wetting agent is 1% to 8%, disintegrant is 1% to 10%, and the balance is filler.
  • the composition when the composition is made into a suspending agent, it includes the following components and contents: compound I 1%-50%, compound II 1%-50%, dispersant 1%-12%, wetting agent 1% to 10%, thickener 0.1% to 8%, antifreeze 0.1% to 8%, and the balance is deionized water.
  • the composition when the composition is made into an aqueous emulsion, it includes the following components and contents: Compound I 1%-50%, Compound II 1%-50%, organic solvent 1%-60%, emulsifier 1 % ⁇ 12%, antifreeze 0.1% ⁇ 8%, defoamer 0.01% ⁇ 2%, thickener 0.1% ⁇ 2%, and the balance is deionized water.
  • the composition when the composition is made into a suspension seed coating agent, it includes the following components and contents: Compound I 1%-50%, Compound II 1%-50%, dispersant 1%-12%, moisturizing agent 1%-12%, Wetting agent 1% ⁇ 10%, antifreeze agent 1 ⁇ 10%, anti-caking agent 0.1 ⁇ 10%, suspending agent 0.1-5%, film-forming agent 1 ⁇ 10%, preservative 0.1 ⁇ 5%, coloring agent 1 ⁇ 30%, pH adjuster 0.1% ⁇ 5%, thickener 0.1% ⁇ 8%, and the balance is deionized water.
  • the composition includes the following components and contents when made into a microcapsule suspension: Compound I 1%-50%, Compound II 1%-50%, and polymer capsule wall material 1-30% , dispersant 2% ⁇ 10%, organic solvent 1 ⁇ 50%, emulsifier 1% ⁇ 7%, pH adjuster 0.1% ⁇ 5%, defoamer 0.01% ⁇ 2%, thickener 0.1% ⁇ 8% , Antifreeze 0.1% to 8%, the balance is deionized water.
  • the composition when the composition is made into a microcapsule suspension-suspending agent, it includes the following components and contents: Compound I 1%-50%, Compound II 1%-50%, and polymer capsule wall material 1% ⁇ 12%, dispersant 1% ⁇ 12%, wetting agent 1% ⁇ 8%, organic solvent 1-50%, emulsifier 1% ⁇ 8%, defoamer 0.01% ⁇ 2%, thickener 0.1% ⁇ 8%, pH adjuster 0.1% ⁇ 5%, antifreeze 0.1% ⁇ 8%, and the balance is deionized water.
  • the composition when the composition is made into an emulsifiable concentrate, the composition includes the following components and contents: Compound I 1%-50%, Compound II 1%-50%, organic solvent 1-50%, emulsifier 1-30% %, antifreeze 1% to 10%, stabilizer 0.1% to 5%, and the balance is organic solvent.
  • composition when the composition is made into a microemulsion, the following components and contents are included: Compound I 1%-50%, Compound II 1%-50%, organic solvent 1-50%, emulsifier 1-50% 30%, antifreeze 1% ⁇ 10%, stabilizer 0.1% ⁇ 5%, the balance is deionized water.
  • the composition when the composition is made into a dispersible liquid, it includes the following components and contents: Compound I 1%-50%, Compound II 1%-50%, emulsifier 1-30%, antifreeze 1% to 10% of agent, 0.1% to 5% of stabilizer, and the balance is organic solvent.
  • the composition when the composition is made into granules, it includes the following components and contents: compound I 0.5%-10%, compound II 0.5%-10%, dispersant 1%-12%, wetting agent 1% to 10%, binder 0.1% to 8%, and the balance is filler.
  • the emulsifier can be selected from one of the following: sodium lignosulfonate, agricultural milk, phenylphenol polyoxyethyl ether phosphate, tristyryl phenol polyoxyethylene ether phosphate Triethanolamine salt, benzyl dimethylphenol polyoxyethyl ether, sorbitan fatty acid ester polyoxyethylene ether, sorbitan oleate (Span-80), fatty alcohol polyoxyethylene ether, alkyl One or more of sodium naphthalene sulfonate, sodium isooctyl succinate sulfonate, nonylphenol polyoxyethylene ether phosphate, castor oil polyoxyethylene ether phosphate.
  • the dispersing agent can be selected from: glycerol fatty acid polyoxyethylene ether, polyoxyethylene alkyl aryl ether, sodium lignin sulfonate, naphthalene sulfonate formaldehyde condensate, fatty alcohol polyoxyethylene ether Sulfate, naphthalene sulfonate formaldehyde condensate, naphthalene sulfonate formaldehyde condensate sodium salt, nonylphenol polyoxyethylene ether, polyoxyethylene lanolin alcohol, alkylphenol polyoxyethylene ether formaldehyde condensate, fatty alcohol polyoxyethylene One or more of vinyl ether, fatty alcohol polyoxyethylene ether phosphate, polyoxyethylene sorbitan fatty acid ester, and phosphate ester.
  • the wetting agent can be selected from: trisiloxane polyoxyethylene ether, sodium N-lauroyl glutamate, sodium lauryl sulfate, sodium lauroyl sarcosinate, methylnaphthalene Sodium sulfonate formaldehyde condensate, castor oil polyoxyethylene ether, tristyryl phenol polyoxyethylene ether, sodium dodecylbenzene sulfonate, sodium alkylnaphthalene sulfonate, sodium isooctyl succinate sulfonate, One or more of polyoxyethylene alkyl aryl ether, fatty alcohol polyether glycerol fatty acid polyoxyethylene ether, and fatty alcohol polyoxyethylene ether.
  • the binder can be selected from: one or more of xanthan gum, starch, urea-formaldehyde resin, gelatin, gum arabic, carboxymethyl cellulose, carboxyethyl cellulose, and polyvinyl alcohol kind.
  • the disintegrating agent can be selected from one or more of sodium bicarbonate, ammonium sulfate, sodium sulfate, calcium sulfate, and magnesium chloride.
  • the thickener can be selected from one or more of magnesium aluminum silicate, polyvinyl acetate, xanthan gum, gelatin, gum arabic, and polyvinyl alcohol.
  • the defoamer can be selected from one or more of silicone oil, n-octanol, silicone, butyl phosphate, isobutyl phosphate, and the like.
  • the antifreeze agent can be selected from one or more of propylene glycol, ethylene glycol, glycerol and the like.
  • the stabilizer can be selected from: triethanolamine, epichlorohydrin, butyl glycidyl ether, triphenyl phosphite, N-soybean oil-based trimethylenediamine, dialkyl butanediamine One or more of acetic acid acetic acid sulfonate and the like.
  • the fillers include solid fillers and liquid fillers, wherein the solid fillers can be selected from: kaolin, attapulgite, diatomite, silica, bentonite, montmorillonite, calcium carbonate, talc one or more of the powders.
  • the liquid filler can be selected from one or more of soybean oil, castor oil and mineral oil.
  • the organic solvent can be selected from: ethyl acetate, acetone, isopropanol, 2,2,2-trifluoroethanol, propylene carbonate, benzene, toluene, xylene, dimethylformamide , one or more of dimethyl sulfoxide, dichloromethane, cyclohexane, cyclohexanone, N-methylpyrrolidone, solvent oil (such as 150# solvent oil).
  • the bactericidal composition of the present invention is used for preventing and treating pathogenic bacteria and agricultural diseases caused by them, and is especially suitable for bacteria and bacterial diseases of plants caused by bacteria.
  • the bactericidal composition is used for preventing and treating soft rot of various crops such as Chinese cabbage soft rot, Chinese cabbage black rot, cucumber bacterial angular spot, sesame angular spot, western/melon fruit Spot, rice bacterial blight, rice bacterial leaf spot, rice bacterial brown spot, rice bacterial brown spot, rice bacterial base rot, tomato bacterial wilt and other Solanaceae bacterial wilt, mulberry green Blight, peanut bacterial wilt, ginger and ginger blast, tomato/capsicum bacterial spot, capsicum bacterial leaf spot, potato blackleg, corn bacterial wilt, corn bacterial stalk rot, wheat blackgrass , soybean bacterial spot disease, soybean bacterial blight, cassava bacterial wilt, mango angular spot, citrus canker, peach bacterial perforation, sunflower stem rot, peach gum disease, pear fire blight, pear Rust water disease, fruit tree bacterial root cancer,
  • the present invention also provides a method for preventing and treating pathogenic bacteria and agricultural diseases caused by them, especially bacteria and bacterial diseases of plants caused by bacteria, comprising applying the above bactericidal composition to plants with diseases.
  • the bactericidal composition of the present invention can be provided in the form of a finished preparation, or can be provided in the form of a single dose, which can be directly mixed before use, and then mixed with water to make a desired concentration, and can be applied to plants or crops in any way, such as spraying Application, plant root irrigation, smear, etc. In specific applications, it can also be mixed with other medicaments such as insecticides, growth regulators, soil conditioners, herbicides, nematicides and the like.
  • the invention adopts the method of combining indoor biological assay and field test to test the performance of the bactericidal composition for the bactericidal effect. It should be pointed out that any modifications, equivalent replacements and improvements made within the spirit and principle of the present invention should be included within the protection scope of the present invention.
  • the above materials are coarsely pulverized according to the proportion and then mixed uniformly in the mixer, and then the finished product is obtained after being pulverized by air flow.
  • the active ingredients and various additives are mixed evenly according to the proportion of the formula, and the powder is obtained after jet pulverization, and then a certain amount of water is added to mix and extrude to granulate, and the finished product is obtained after drying and screening.
  • the active ingredients and various additives are mixed uniformly according to the proportion of the formula, and the finished product is obtained after high-speed shearing and sanding.
  • the above-mentioned raw materials are mixed in proportion to dissolve into a uniform oil phase; after passing the inspection, the finished product is obtained by measuring and sub-packing.
  • the above raw materials are added to the batching kettle, and the water emulsion is uniformly mixed by a high-speed shearing machine. After passing the inspection, the finished product is measured and packed.
  • the above-mentioned raw materials are mixed in proportion to dissolve into a uniform oil phase; after passing the inspection, the finished product is obtained by measuring and sub-packing.
  • the components are fully mixed according to the formula ratio, pulverized, mixed with water and then fully stirred, and then granulated by a screw extruder granulator, dried and sieved to obtain the finished product.
  • Test pathogens Chinese cabbage soft rot, cucumber bacterial angular spot, watermelon fruit spot, rice bacterial blight, rice bacterial streak, tomato bacterial wilt, potato blackleg, mango Bacterial diseases such as angular spot, citrus canker, peach tree bacterial perforator and potato scab.
  • the virulence of pathogenic bacteria was determined with Chinese cabbage soft rot, cucumber bacterial angular leaf spot, watermelon fruit leaf spot, rice bacterial blight, rice bacterial stripe, tomato bacterial wilt, potato blackleg, mango horn. Bacterial diseases such as Spotella, citrus canker, peach tree bacterial perforator and potato scab were used as test materials. The virulence of compound I, compound II and their mixed preparations was determined by in vitro turbidity method.
  • compound II 7 concentration gradients such as 0.5, 1.0, 2.0, 4.0, 8.0, 16.0, 32.0 ⁇ g/mL, etc.
  • the final mass concentration (referring to the total mass of compound I and compound II) was formulated into 7 series concentrations of 0.5, 1.0, 2.0, 4.0, 8.0, 16.0, and 32.0 ⁇ g/mL with different ratios.
  • NB nutrient broth, containing 10g peptone per liter, 3g beef dipping powder, 5g sodium chloride
  • the medicinal liquids were respectively added to the above test tubes, shaken well, and then the bacterial suspensions in the logarithmic growth phase were added in equal amounts respectively, and each treatment was repeated 4 times. After mixing, the cells were cultured in the dark in a shaking incubator at 25°C, and the OD value was measured in the logarithmic growth phase.
  • A is compound I
  • B is compound II
  • a and b are the proportions of compound I and compound II in the bactericidal composition, respectively;
  • the bactericidal composition of the present invention uses compound I and compound II as effective active ingredients, and is illustrated by using a biological assay example.
  • Embodiment 1 In order to verify the antibacterial effect of compound I and different proportioning dosages of zhongshengxin on cucumber bacterial angular spot bacterium, the indoor toxicity of compound 1 and zhongshengmycin different proportions on cucumber bacterial angular spot bacterium was carried out. Force measurement, according to the weight percentage in the table to be made into the corresponding concentration, carry out the indoor antibacterial test, the test results are as follows:
  • Table 1 The results of the determination of the virulence of compound I and the single agent of neutrophil and its mixture to Cucumber Bacterial angularis
  • Embodiment 2 In order to verify the antibacterial effect of compound I and different proportions of zhongshengmycin on watermelon fruit spot bacteria, the indoor virulence assay of compound I and zhongshengmycin different proportions to watermelon fruit leaf spot bacteria was carried out , according to the weight percentage in the table into the corresponding concentration, carry out the indoor antibacterial test, the test results are as follows:
  • Embodiment 3 in order to verify the antibacterial effect of compound I and zhongshengmycin different proportioning dosages on citrus canker bacterium, carried out the indoor virulence assay of compound 1 and zhongshengmycin different proportioning to citrus canker bacterium, according to the table. The weight percentage is made into the corresponding concentration, and the indoor antibacterial test is carried out.
  • the test results are as follows:
  • Example 4 In order to verify the bacteriostatic effect of compound I and different proportions of zhongshengmycin on the bacterial blight of rice, the indoor virulence assay of different proportions of compound I and zhongshengmycin on rice bacterial blight was carried out , according to the weight percentage in the table into the corresponding concentration, carry out the indoor antibacterial test, the test results are as follows:
  • Embodiment 5 In order to verify the antibacterial effect of compound I and different proportions of Zhongshengxin on tomato R. solanacearum, the indoor virulence assay of different proportions of Compound I and Zhongshengxin was carried out on tomato R. solanacearum, according to The weight percentage in the table is made into the corresponding concentration, and the indoor antibacterial test is carried out. The test results are as follows:
  • Embodiment 6 In order to verify the bacteriostatic effect of compound I and different proportions of zhongshengmycin on Chinese cabbage soft rot bacteria, the indoor virulence assay of compound I and different proportions of zhongshengmycin on Chinese cabbage soft rot bacteria was carried out , according to the weight percentage in the table into the corresponding concentration, carry out the indoor antibacterial test, the test results are as follows:
  • Embodiment 7 in order to verify the antibacterial effect of compound I and different ratios of allicin on cucumber bacterial keratosis fungus, carried out the indoor virulence assay of compound I and allicin different ratios to cucumber bacterial keratosis bacterium, according to The weight percentage in the table is made into the corresponding concentration, and the indoor antibacterial test is carried out.
  • the test results are as follows:
  • Embodiment 8 in order to verify the antibacterial effect of compound I and zinc thiazole in different proportions on watermelon fruit spot bacteria, carried out the indoor virulence measurement of compound I and thiazole zinc different proportions to watermelon fruit leaf spot bacteria, according to the table. The weight percentage is made into the corresponding concentration, and the indoor antibacterial test is carried out. The test results are as follows:
  • Example 9 In order to verify the bacteriostatic effect of compound I and tetramycin in different proportions on B. oryzae, the indoor virulence assay of different proportions of compound I and tetramycin on B. oryzae was carried out. , according to the weight percentage in the table into the corresponding concentration, carry out the indoor antibacterial test, the test results are as follows:
  • Embodiment 10 in order to verify the antibacterial effect of compound I and different proportioning dosages of thiamycin on potato scab bacteria, carried out the indoor virulence measurement of compound I and different proportions of thiamdazole to potato scab bacteria, according to the weight percentage in the table Dubbed into corresponding concentrations, the indoor antibacterial test was carried out, and the test results were as follows:
  • Embodiment 11 in order to verify the antibacterial effect of compound I and kasugamycin different proportioning dosages on potato blackleg, carry out the indoor virulence assay of compound I and kasugamycin different proportioning to potato blackleg, according to the table. The weight percentage is made into the corresponding concentration, and the indoor antibacterial test is carried out.
  • the test results are as follows:
  • Embodiment 12 In order to verify the antibacterial effect of Compound I and Neophytomycin different ratios and dosages on Mango keratosis fungus, the indoor virulence assays of Compound I and Neophytomycin different ratios were carried out on Mango keratosis fungus. The weight percentage in the table is made into the corresponding concentration, and the indoor antibacterial test is carried out. The test results are as follows:
  • Embodiment 13 In order to verify the antibacterial effect of compound I and different proportions of aureomycin on the bacterial perforation pathogen of peach tree, the indoor toxicity of compound I and the different proportions of aureomycin to the bacterial perforation pathogen of peach tree was carried out. Force measurement, according to the weight percentage in the table to be made into the corresponding concentration, carry out the indoor antibacterial test, the test results are as follows:
  • preparation methods of the reagents in the following examples are shown in the above-mentioned preparation examples 1-8.
  • the preparation method of the 10% compound I ⁇ zhongshengmycin wettable powder of example 1 is the same as that of preparation example 1, wherein Compound II is selected from zhongshengmycin
  • the preparation method of 10% compound I ⁇ zinc thiazole wettable powder in Example 8 is the same as that of Preparation Example 1, wherein compound II is selected from zinc thiazole
  • the preparation of other embodiments refers to the above-mentioned Preparation Examples 1-8.
  • the preparation methods of the reagents in the following comparative examples are also shown in the above-mentioned preparation examples 1-8, except that the content of the active components may be different.
  • the fillers or water in the preparations complement the components. to 100%.
  • the preparation method of 10% Compound I water dispersible granules in Comparative Example 1 refers to Preparation Example 2, wherein 10% Compound I replaces 20% Compound I and 10% Compound II in Preparation Example 2, and the difference in content is filled by fillers .
  • the preparation method of the 3% neutropenin wettable powder of comparative example 2 refers to preparation example 1, wherein 3% neutropenin replaces 5% of compound I and 5% of compound II in preparation example 1, and the content is different. Fill it with stuffing.
  • Test method According to the application method stipulated in the "National Standard of the People's Republic of China GB/T 17980.110-2004", the application was applied when the lesions were first seen, and the second application was applied 7 days later.
  • Investigation method According to the investigation method stipulated in "National Standard of the People's Republic of China GB/T 17980.110-2004", the control effect was investigated 7 days and 14 days after the second application. Each plot was sampled at 3 points on the diagonal, with 5 plants per point, all leaves were investigated, and the percentage of diseased spot area per leaf to the entire leaf area was graded.
  • Grade 0 no lesions
  • Grade 1 the lesion area accounts for less than 5% of the entire leaf area
  • Grade 3 the lesion area accounts for 6% to 10% of the entire leaf area
  • Grade 5 the lesion area accounts for 5% of the entire leaf area. 11% to 20%
  • Grade 7 The lesion area accounts for 21% to 50% of the entire leaf area
  • Grade 9 The lesion area accounts for more than 51% of the entire leaf area.
  • the compound I and kasugamycin compound is compared with a single agent, and under the same amount of active ingredients, the compound I and kasugamycin compound is effective against cucumber bacterial keratosis.
  • the 7-day and 14-day control effects of spot disease were significantly higher than those of a single dose. Among them, the 14-day prevention effect can still reach more than 78.9%, and the lasting period is longer.
  • Test method According to the application method stipulated in the "National Standard of the People's Republic of China GB/T 17980.19-2000", the application was applied when the lesions were first seen, and the second application was applied 7 days later.
  • Investigation method According to the investigation method stipulated in "National Standard of the People's Republic of China GB/T 17980.19-2000", the control effect was investigated 7 days and 14 days after the second application.
  • Grade 0 no disease
  • grade 1 sporadic disease or central disease
  • grade 3 the incidence area accounts for about a quarter of the total area
  • grade 5 the disease area accounts for about one-third of the total area
  • grade 7 the disease area It accounts for about one-half of the total area
  • grade 9 the incidence area accounts for more than three-quarters of the total area.
  • the spraying method should be sprayed for the first time before flowering, and sprayed for the second time after the occurrence of diseases.
  • the pesticides were applied twice, and the area of each treatment plot was 3 mature fruit trees, and the number of repetitions was 4 times. Record the times of application and the date of each application and the growth period of fruit trees.
  • Grade 0 no disease
  • Grade 1 1-5 lesions per leaf
  • Grade 3 6-10 lesions per leaf
  • Grade 5 11-15 lesions per leaf
  • Grade 7 per leaf There are 15 to 20 lesions
  • grade 9 more than 21 lesions per leaf
  • the compound I and zhongshengmycin combination has a 7-day prevention of citrus canker.
  • the efficacy and 14-day control effect were significantly higher than that of a single dose. Among them, the 14-day prevention effect can still reach more than 78.5%, and the lasting period is longer.
  • Test method Referring to the application method stipulated in "National Standard of the People's Republic of China GB/T 17980.110-2004", the application was applied when the lesions were first seen, and the second application was applied 7 days later.
  • Investigation method Referring to the investigation method stipulated in "National Standard of the People's Republic of China GB/T 17980.110-2004", the control effect was investigated 7 days and 14 days after the second application.
  • Grade 0 no lesions
  • Grade 1 the lesion area accounts for less than 5% of the entire leaf area
  • Grade 3 the lesion area accounts for 6% to 10% of the entire leaf area
  • Grade 5 the lesion area accounts for 5% of the entire leaf area. 11% to 20%
  • Grade 7 The lesion area accounts for 21% to 50% of the entire leaf area
  • Grade 9 The lesion area accounts for more than 51% of the entire leaf area.
  • Table 21 The efficacy test of compound I and Zhongshengmycin on watermelon fruit spot disease field
  • Test method Refer to the application method specified in "The Agricultural Industry Standard of the People's Republic of China NY/T 1464.32-2010", irrigate the roots when the diseased plants are first seen, and apply the granules when the diseased plants are first seen, and the second application after 7 days , a total of two applications, repeated 4 times.
  • Survey method Referring to the survey method stipulated in "The Agricultural Industry Standard of the People's Republic of China NY/T 1464.32-2010", all plants were surveyed in each plot, and the total number of plants and the number of diseased plants were recorded. The control effect was investigated 7 days and 14 days after the second application.
  • Test method Referring to the application method stipulated in "The Agricultural Industry Standard of the People's Republic of China NY/T 1464.44-2012", the application was performed when the lesions were first seen, and the second application was applied 7 days later. .
  • Survey method Referring to the survey method stipulated in "The Agricultural Industry Standard of the People's Republic of China NY/T 1464.44-2012", 5 points were randomly surveyed in each plot, 1 plant was surveyed at each point, and all leaves were surveyed for each plant. The percentage of the entire leaf lesion area was graded, and the total number of leaves and the number of diseased leaves at all levels were recorded.
  • Test method Referring to the application method stipulated in "The Agricultural Industry Standard of the People's Republic of China NY/T 1464.31-2010", the application was applied when the disease spots were first seen, and the second application after 7 days, a total of twice application, repeated 4 times .
  • Survey method Referring to the survey method stipulated in "The Agricultural Industry Standard of the People's Republic of China NY/T 1464.31-2010", 5 points were randomly surveyed in each plot, 10 plants were surveyed at each point, all leaves and fleshy stem symptoms were surveyed for each plant, and the total number of surveyed plants was recorded. , The number of diseased plants at all levels.
  • Test method Apply the medicine when the lesions are first seen, and apply the medicine for the second time after 7 days. The medicine is applied twice and repeated 4 times.
  • Survey method 5 points were randomly surveyed in each plot, 10 plants were surveyed at each point, and 10 branches were surveyed per plant. The total number of investigated plants and the number of diseased plants at all levels were recorded.
  • Test method The roots were irrigated when the diseased plants were first seen, and the granules were applied when the diseased plants were first seen, and the second application was applied 7 days later.
  • Investigation method Investigate all plants in each plot, and record the total number of plants and the number of diseased plants. The control effect was investigated 7 days and 14 days after the second application.
  • Test method spraying before germination, the second spraying after 7 days, a total of twice spraying, repeated 4 times.
  • Test method spray when the diseased plants are first seen, granules are applied when the diseased plants are first seen, and the second application is applied 7 days later.
  • Investigation method Investigate all plants in each plot, and record the total number of plants and the number of diseased plants. The control effect was investigated 7 days and 14 days after the second application.
  • Test method irrigate the roots when the diseased plants are first seen, granules are applied when the diseased plants are first seen, and the second application is applied 7 days later.
  • Investigation method Investigate all plants in each plot, and record the total number of plants and the number of diseased plants. The control effect was investigated 7 days and 14 days after the second application.
  • Test method spray when the diseased plants are first seen, granules are applied when the diseased plants are first seen, and the second application is applied 7 days later.
  • Investigation method Investigate all plants in each plot, and record the total number of plants and the number of diseased plants. The control effect was investigated 7 days and 14 days after the second application.
  • the compound I and oligosaccharin compound and single dose are compared with the same effective ingredient dosage, and the compound I and oligosaccharin compound can prevent tomato canker disease for 7 days.
  • the efficacy and 14-day control effect were significantly higher than that of a single dose. Among them, the 14-day prevention effect can still reach more than 78.4%, and the lasting period is longer.
  • Test method irrigate the roots when the diseased plants are first seen, granules are applied when the diseased plants are first seen, and the second application is applied 7 days later.
  • Investigation method Investigate all plants in each plot, and record the total number of plants and the number of diseased plants. The control effect was investigated 7 days and 14 days after the second application.

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Abstract

一种含有喹诺酮类化合物的增效杀菌组合物及其应用。所述杀菌剂组合物包括有效活性成分，所述有效活性成分包括化合物I和化合物II，所述化合物I为7-氯-1-环丙基-6-氟-4-氧代-1,4-二氢喹啉-3-羧酸-2-甲氧基乙酯，所述化合物II为抗生素类化合物、噻唑锌、噻霉酮、溴菌腈、氨基寡糖素、大黄素甲醚、异噻唑啉酮、二硫氰甲烷中的至少一种。所述增效杀菌组合物，具有以下优点：1)具有协同增效作用，可提高防治效果；2)扩大杀菌谱，田间病害多混合发生，对细菌病害作用更强；3)两种有效成分作用机理不同，混配使用可延缓病原菌抗药性的产生；4)降低施药量，减少使用次数，降低使用成本。

Description

一种含喹诺酮类化合物的增效杀菌组合物及其应用 技术领域
本发明属于农药复配的技术领域，特别是涉及一种含有喹诺酮类化合物的增效杀菌组合物及其应用。
背景技术
近年来，各种作物细菌性病害的发生呈现逐年加重的趋势，发生面积逐年增长，给农业生产带来巨大危害，例如粮食作物中的水稻细菌性条斑病、水稻白叶枯病，果树中的柑橘溃疡病，茄科蔬菜青枯病，黄瓜细菌性角斑病，十字花科蔬菜软腐病、姜瘟病等都给作物造成了严重的损失。
目前市场上欠缺用于防治细菌性病害的高效药剂，农民为了提高防治效果加大用药量或者随意混配药剂，这种不科学用药，不仅达不到增效作用，反而导致农药的浪费、残留超标、污染环境、导致病菌对农药产生抗性等问题。因此，亟需研制一种针对细菌病害的增效杀菌组合物，能达到扩大防治对象范围、降低用药量、延缓抗性产生的效果。
在农业生产的实际过程中，长期连续单一的使用同一种药剂，病原菌很快就会产生抗药性，导致防效降低，农药使用量增加，加剧农产品农药残留和生态环境的破坏。通过与作用机理完全不同的杀菌剂品种进行复配，是延缓病原菌产生抗药性、扩大杀菌谱、延长使用寿命、降低农药使用量的有效途径。但如何进行复配，使得各药物之间产生协同而非拮抗作用是一大难点。
喹诺酮类化合物的化学名称为：7-氯-1-环丙基-6-氟-4-氧代-1,4-二氢喹啉-3-羧酸-2-甲氧基乙酯，其具有广谱的杀菌活性，尤其对细菌活性更高，对革兰氏阳性菌、革兰氏阴性菌均表现出优异的活性。对多种作物细菌性病害例如大白菜软腐病等各作物软腐病、大白菜黑腐病、黄瓜细菌性角斑病、芝麻角斑病、西/甜瓜果斑病、水稻白叶枯病、水稻细菌性条斑病、水稻细菌性褐斑病、水稻细菌性褐条病、水稻细菌性基腐病、番茄青枯病等茄科青枯病、桑青枯病、花生青枯病、大姜姜瘟病、番茄/辣椒细菌性斑点病、辣椒细菌性叶斑病、马铃薯黑胫病、玉米细菌性枯萎病、玉米细菌性茎腐病、小麦黑颖病、大豆细菌性斑疹病、大豆细菌性疫病、木薯细菌性枯萎病、芒果角斑病、柑橘溃疡病、桃树细菌性穿孔病、向日葵茎腐病、桃流胶 病、梨火疫病、梨锈水病、果树细菌性根癌病、马铃薯环腐病、菜豆萎蔫病、小麦白叶条斑病、马铃薯疮痂病、番茄溃疡病、美国冬青叶疫病等病原细菌均具有优异活性。
中生菌素、春雷霉素、噻霉酮、四霉素、乙蒜素、金核霉素、噻唑锌、申嗪霉素、水合霉素、溴菌腈、新植霉素、多抗霉素、农用链霉素、农抗120、井冈霉素、嘧啶核苷类抗菌素、宁南霉素、蛇床子素、低聚糖素、氨基寡糖素、大蒜素、大黄素甲醚为目前防治细菌性病害的常用药剂，但由于长期单一使用，均不同程度出现抗性，防效下降。
现有技术中，尚未见有关于喹诺酮类化合物和中生菌素、春雷霉素、噻唑锌、噻霉酮、四霉素、乙蒜素、申嗪霉素、金核霉素、水合霉素、溴菌腈、新植霉素、多抗霉素、农用链霉素、农抗120、井冈霉素、嘧啶核苷类抗菌素、宁南霉素、蛇床子素、低聚糖素、氨基寡糖素、大蒜素、大黄素甲醚的复配及应用的相关报道，也未见类似的物质进行复配的报道。
发明内容
为了改善现有技术的不足，本发明的目的在于提供一种含有喹诺酮类化合物的增效杀菌组合物及其应用，所述杀菌组合物包括有效成分，所述有效成分包括化合物I和化合物II，其中，所述化合物I为7-氯-1-环丙基-6-氟-4-氧代-1,4-二氢喹啉-3-羧酸-2-甲氧基乙酯，所述化合物II为中生菌素、春雷霉素、四霉素、乙蒜素、申嗪霉素、金核霉素、水合霉素、大蒜素、氨基寡糖素、新植霉素、多抗霉素、农用链霉素、农抗120、井冈霉素、嘧啶核苷类抗菌素、宁南霉素、蛇床子素、低聚糖素等抗生素类化合物以及噻唑锌、噻霉酮、溴菌腈、大黄素甲醚、异噻唑啉酮、二硫氰甲烷中至少一种。
所述化合物I和所述化合物II的混合使用可以形成增效杀菌组合物，有效活性成分包括化合物I和化合物II，二者的混合使用具有明显的增效互补作用，利用病菌作用位点的不同，作用机理的不同，复配可对病原菌多位点作用，扩大杀菌谱，提高防效，降低农药使用量，延缓抗药性的产生，还可以降低成本。
本发明采取以下方案：
一种杀菌组合物，所述杀菌剂组合物包括有效活性成分，所述有效活性成分包括化合物I和化合物II，所述化合物I为7-氯-1-环丙基-6-氟-4-氧代-1,4-二氢喹啉-3-羧酸-2-甲氧基乙酯，所述化合物II为抗生素类化合物、噻唑锌、噻霉酮、溴菌腈、氨基寡糖素、大黄素甲醚、异噻唑啉酮、二硫氰甲烷中的至少一种。
根据本发明的实施方案，所述抗生素类化合物选自中生菌素、春雷霉素、四霉素、乙蒜素、金核霉素、申嗪霉素、水合霉素、大蒜素、新植霉素、多抗霉素、农用链霉素、农抗120、井冈霉素、嘧啶核苷类抗菌素、宁南霉素、蛇床子素、低聚糖素等中的至少一种。
根据本发明的实施方案，所述化合物I和化合物II的质量比为80～1:1～80。
根据本发明的实施方案，所述化合物I和化合物II的质量比为50～1:1～50。
根据本发明的实施方案，所述化合物I和化合物II的质量比为30～1:1～30。
根据本发明的实施方案，所述化合物I和化合物II的质量比为80:1、75:1、70:1、65:1、60:1、55:1、50:1、45:1、40:1、35:1、30:1、25:1、20:1、15:1、10:1、5:1、1:1、1:5、1:10、15:1、1:20、25:1、1:30、35:1、1:40、45:1、1:50、55:1、1:60、65:1、1:70、75:1、1:80。
根据本发明的实施方案，以所述杀菌组合物的总重量为100％计，所述化合物I与化合物II在杀菌组合物中的质量之和为1～80％，优选为20～60％，例如1％、5％、8％、10％、13％、15％、18％、20％、24％、30％、35％、38％、42％、45％、50％、55％、60％、65％、68％、75％、80％、85％、90％。
根据本发明的实施方案，所述杀菌组合物可制备成液体制剂或固体制剂。
根据本发明的实施方案，根据不同的制剂类型，制剂中有效活性成分含量范围有所不同，通常，液体制剂中含有按重量计1％～60％的有效活性成分，优选为5％～50％；固体制剂中含有按重量计5％～80％的有效活性成分，优选为10％～70％。
根据本发明的实施方案，所述杀菌组合物中还包括乳化剂、分散剂、润湿剂、增稠剂、消泡剂、稳定剂、粘结剂、崩解剂、抗冻剂、抗结剂、助悬剂、成膜剂、防腐剂、着色剂、高分子囊壁材料、pH调节剂或填料等中的至少一种。
根据本发明的实施方案，所述杀菌组合物可以由使用者在使用前经稀释或直接使用。其配制可由本领域技术人员所公知的加工方法制备，即将有效活性成分与去离子水、有机溶剂、乳化剂、分散剂、润湿剂、增稠剂、消泡剂、稳定剂、粘结剂、崩解剂、抗冻剂、抗结剂、助悬剂、成膜剂、防腐剂、着色剂、高分子囊壁材料、pH调节剂或填料等中的一种或多种混合，制备得到所述杀菌组合物。
根据本发明提供的制剂，所述杀菌组合物可以制作成各种剂型，优选地，所述剂型包括水分散粒剂、可分散液剂、可湿性粉剂、悬浮剂、水乳剂、微乳剂、悬乳剂、微囊悬浮剂、微囊悬浮-悬浮剂、悬浮种衣剂、乳油、颗粒剂。
根据本发明的实施方案，所述杀菌组合物制成可湿性粉剂时包含如下组分及含量：化合物I 1％～80％，化合物II 1％～80％，分散剂1％～12％，润湿剂1％～8％，余量为填料。
根据本发明的实施方案，所述组合物制成水分散粒剂时包括如下组分及含量：化合物I 1％～80％，化合物II 1％～80％，分散剂1％～12％，润湿剂1％～8％，崩解剂1％～10％，余量为填料。
根据本发明的实施方案，所述组合物制成悬浮剂时包括如下组分及含量：化合物I 1％～50％，化合物II 1％～50％，分散剂1％～12％，润湿剂1％～10％，增稠剂0.1％～8％，抗冻剂0.1％～8％，余量为去离子水。
根据本发明的实施方案，所述组合物制成水乳剂时包括如下组分及含量：化合物I 1％～50％，化合物II 1％～50％，有机溶剂1％～60％，乳化剂1％～12％，抗冻剂0.1％～8％，消泡剂0.01％～2％，增稠剂0.1％～2％，余量为去离子水。
根据本发明的实施方案，所述组合物制成悬浮种衣剂时包括如下组分及含量：化合物I 1％～50％，化合物II 1％～50％，分散剂1％～12％，润湿剂1％～10％，抗冻剂1～10％，抗结剂0.1～10％，助悬剂0.1-5％，成膜剂1～10％，防腐剂0.1～5％，着色剂1～30％，pH调节剂0.1％～5％，增稠剂0.1％～8％，余量为去离子水。
根据本发明的实施方案，所述组合物制成微囊悬浮剂时包括如下组分及含量：化合物I 1％～50％，化合物II 1％～50％，高分子囊壁材料1-30％，分散剂2％～10％，有机溶剂1～50％，乳化剂1％～7％，pH调节剂0.1％～5％，消泡剂0.01％～2％，增稠剂0.1％～8％，抗冻剂0.1％～8％，余量为去离子水。
根据本发明的实施方案，所述组合物制成微囊悬浮-悬浮剂时包括如下组分及含量：化合物I 1％～50％，化合物II 1％～50％，高分子囊壁材料1％～12％，分散剂1％～12％，润湿剂1％～8％，有机溶剂1-50％，乳化剂1％～8％，消泡剂0.01％～2％，增稠剂0.1％～8％，pH调节剂0.1％～5％，抗冻剂0.1％～8％，余量为去离子水。
根据本发明的实施方案，所述组合物制成乳油时包括如下组分及含量：化合物I 1％～50％，化合物II 1％～50％，有机溶剂1～50％，乳化剂1～30％，抗冻剂1％～10％，稳定剂0.1％～5％，余量为有机溶剂。
根据本发明的实施方案，所述组合物制成微乳剂时包括如下组分及含量：化合物I 1％～50％，化合物II 1％～50％，有机溶剂1～50％，乳化剂1～30％，抗冻剂1％～10％，稳定剂0.1％～5％，余量为去离子水。
根据本发明的实施方案，所述组合物制成可分散液剂时包括如下组分及含量：化合物I 1％～50％，化合物II 1％～50％，乳化剂1～30％，抗冻剂1％～10％，稳定剂0.1％～5％，余量为有机溶剂。
根据本发明的实施方案，所述组合物制成颗粒剂时包括如下组分及含量：化合物I 0.5％～10％，化合物II 0.5％～10％，分散剂1％～12％，润湿剂1％～10％，粘结剂0.1％～8％，余量为填料。
根据本发明的实施方案，所述乳化剂可以选用如下中的一种：木质素磺酸钠、农乳、苯基酚聚氧乙基醚磷酸酯、三苯乙烯基苯酚聚氧乙烯醚磷酸酯三乙醇胺盐、苄基二甲基酚聚氧乙基醚、失水山梨醇脂肪酸酯聚氧乙烯醚、山梨醇酐油酸酯(斯盘-80)、脂肪醇聚氧乙烯醚、烷基萘磺酸钠、异辛醇琥珀酸酯磺酸钠、壬基酚聚氧乙烯醚磷酸酯、蓖麻油聚氧乙烯醚磷酸酯中的一种或多种。
根据本发明的实施方案，所述分散剂可以选用：甘油脂肪酸聚氧乙烯醚、聚氧乙烯烷基芳基醚、木质素磺酸钠、萘磺酸盐甲醛缩合物、脂肪醇聚氧乙烯醚硫酸盐、萘磺酸盐甲醛缩合物、萘磺酸甲醛缩合物钠盐、壬基酚聚氧乙烯醚、聚氧乙烯羊毛脂醇、烷基酚聚氧乙烯醚甲醛缩合物、脂肪醇聚氧乙烯醚、脂肪醇聚氧乙烯醚磷酸酯、聚氧乙烯山梨聚糖脂肪酸酯、磷酸酯中的一种或多种。
根据本发明的实施方案，所述润湿剂可以选用：三硅氧烷聚氧乙烯醚，N-月桂酰基谷氨酸钠、十二烷基硫酸钠、月桂酰基肌氨酸钠、甲基萘磺酸钠甲醛缩合物、蓖麻油聚氧乙烯醚、三苯乙基苯酚聚氧乙烯醚、十二烷基苯磺酸钠、烷基萘磺酸钠、异辛醇琥珀酸酯磺酸钠、聚氧乙烯烷基芳基醚、脂肪醇聚醚甘油脂肪酸聚氧乙烯醚、脂肪醇聚氧乙烯醚中的一种或多种。
根据本发明的实施方案，所述粘结剂可以选用：黄原胶、淀粉、脲醛树脂、明胶、阿拉伯胶、羧甲基纤维素、羧乙基纤维素、聚乙烯醇中的一种或多种。
根据本发明的实施方案，所述崩解剂可以选用：碳酸氢钠、硫酸铵、硫酸钠、硫酸钙、氯化镁中的一种或多种。
根据本发明的实施方案，所述增稠剂可以选用：硅酸镁铝、聚乙酸乙烯酯、黄原胶、明胶、阿拉伯胶、聚乙烯醇中的一种或多种。
根据本发明的实施方案，所述消泡剂可以选用：硅油、正-辛醇、硅酮、磷酸丁酯、磷酸异丁酯等中的一种或多种。
根据本发明的实施方案，所述抗冻剂可以选用：丙二醇、乙二醇、丙三醇等中的一种或多种。
根据本发明的实施方案，所述稳定剂可以选用：三乙醇胺、环氧氯丙烷、丁基缩水甘油醚、亚磷酸三苯酯、N-大豆油基三亚甲基二胺、二烷基丁二酸醋磺酸盐等中的一种或多种。
根据本发明的实施方案，所述填料包括固体填料和液体填料，其中，所述固体填料可以选用：高岭土、凹凸棒土、硅藻土、白炭黑、膨润土、蒙脱石、碳酸钙、滑石粉中的一种或多种。所述液体填料可以选用大豆油、蓖麻油、矿物油中的一种或多种。
根据本发明的实施方案，所述有机溶剂可以选用：乙酸乙酯、丙酮、异丙醇、2,2,2-三氟 乙醇、碳酸丙烯酯、苯、甲苯、二甲苯、二甲基甲酰胺、二甲基亚砜、二氯甲烷、环己烷、环己酮、N-甲基吡咯烷酮、溶剂油(如150#溶剂油)中的一种或多种。
本发明的杀菌组合物用于防治病原菌及其引起的农业病害，尤其适用于细菌及细菌引起的植物细菌性病害。
根据本发明的实施方案，所述杀菌组合物用于防治大白菜软腐病等各作物软腐病、大白菜黑腐病、黄瓜细菌性角斑病、芝麻角斑病、西/甜瓜果斑病、水稻白叶枯病、水稻细菌性条斑病、水稻细菌性褐斑病、水稻细菌性褐条病、水稻细菌性基腐病、番茄青枯病等茄科青枯病、桑青枯病、花生青枯病、大姜姜瘟病、番茄/辣椒细菌性斑点病、辣椒细菌性叶斑病、马铃薯黑胫病、玉米细菌性枯萎病、玉米细菌性茎腐病、小麦黑颖病、大豆细菌性斑疹病、大豆细菌性疫病、木薯细菌性枯萎病、芒果角斑病、柑橘溃疡病、桃树细菌性穿孔病、向日葵茎腐病、桃流胶病、梨火疫病、梨锈水病、果树细菌性根癌病、马铃薯环腐病、菜豆萎蔫病、小麦白叶条斑病、马铃薯疮痂病、番茄溃疡病、美国冬青叶疫病等病原细菌以及黄瓜霜霉病、黄瓜靶斑病、水稻稻瘟病、水稻纹枯病、番茄病毒病等病原真菌和病毒病。
本发明还提供一种防治病原菌及其引起的农业病害，尤其是细菌及细菌引起的植物细菌性病害的方法，包括将如上杀菌组合物施用于存在病害的植物上。
本发明的杀菌组合物可以以成品制剂形式提供，也可以以单剂形式提供，使用前直接混合，然后兑水混匀配成所需浓度，可以以任何方式施用于植物或作物上，例如喷施、植株根部灌施、涂抹等。具体应用时，也可以与其它药剂如杀虫剂、生长调节剂、土壤调节剂、除草剂、杀线虫剂等混合使用。
本发明的有益效果：
本发明的增效杀菌组合物，具有以下优点：
1)具有协同增效作用，可提高防治效果；2)扩大杀菌谱，田间病害多混合发生，对细菌病害作用更强；3)两种有效成分作用机理不同，混配使用可延缓病原菌抗药性的产生；4)降低施药量，减少使用次数，降低使用成本。
具体实施方式
下文将结合具体实施例对本发明做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法；下述实施例中所用的试剂、材料等，如无特殊说明，均可从商业途径得到。
本发明采用室内生物测定和田间试验相结合的方法对所述杀菌组合物的杀菌效果进行性能测试。应当指出的是，凡在本发明的精神和原则之内所做的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
一、制剂制备例：
制备例1：可湿性粉剂
Figure PCTCN2021126496-appb-000001
将上述材料按比例粗粉碎后进入混合器中混合均匀，再经气流粉碎后即制得成品。
制备例2：水分散粒剂
Figure PCTCN2021126496-appb-000002
将有效活性成分及各种助剂等按配方的比例混合均匀，经气流粉碎后得到粉料，再加入一定量的水混合挤压造粒，经干燥筛分后得到成品。
制备例3：悬浮剂
Figure PCTCN2021126496-appb-000003
Figure PCTCN2021126496-appb-000004
将有效活性成分及各种助剂按配方的比例混合均匀，经高速剪切后并砂磨得到成品。
制备例4：乳油
Figure PCTCN2021126496-appb-000005
将上述原料按比例混合，使其溶解为均匀油相；经检验合格后，进行计量分装即成品。
制备例5：水乳剂
Figure PCTCN2021126496-appb-000006
按配方要求，将以上原料加入到配料釜中，经高速剪切机混合均匀制成水乳剂，经检验合格后，进行计量分装即成品。
制备例6：乳油
Figure PCTCN2021126496-appb-000007
Figure PCTCN2021126496-appb-000008
将上述原料按比例混合，使其溶解为均匀油相；经检验合格后，进行计量分装即成品。
制备例7：乳油
Figure PCTCN2021126496-appb-000009
将上述原料按比例混合，使其溶解为均匀油相；经检验合格后，进行计量分装即成品。制备例8：颗粒剂
Figure PCTCN2021126496-appb-000010
按配方比例将各组分充分混合，粉碎，加水润湿后再充分搅拌均匀，再用螺杆挤压造粒机造粒，干燥后过筛，即得成品。
二、室内毒力测定实施例
(1)供试病原菌：大白菜软腐病菌、黄瓜细菌性角斑病菌、西瓜果斑病菌、水稻白叶枯病菌、水稻细菌性条斑病菌、番茄青枯病菌、马铃薯黑胫病菌、芒果角斑病菌、柑橘溃疡病菌、桃树细菌性穿孔病菌和马铃薯疮痂病菌等细菌性病害。
(2)测定方法：
细菌毒力测定方法
病原细菌毒力测定以大白菜软腐病菌、黄瓜细菌性角斑病菌、西瓜果斑病菌、水稻白叶枯病菌、水稻细菌性条斑病菌、番茄青枯病菌、马铃薯黑胫病菌、芒果角斑病菌、柑橘溃疡病菌、桃树细菌性穿孔病菌和马铃薯疮痂病菌等细菌性病害为试验材料，采用离体浑浊度法对化合物I、化合物II及其混配制剂进行毒力测定。
参照中华人民共和国农业行业标准NY/T 1156.16-2008，先将供试药剂(包括化合物I、化合物II)用合适的溶剂(溶剂的种类如丙酮、甲醇、N,N二甲基甲酰胺和二甲基亚砜等，并且依据其对样品的溶解能力而选择)配制成7个浓度梯度(化合物I：0.5,1.0,2.0,4.0,8.0,16.0,32.0μg/mL等7个浓度梯度；化合物II：0.5,1.0,2.0,4.0,8.0,16.0,32.0μg/mL等7个浓度梯度)，将供混配的化合物I、化合物II分别按其EC 50值按质量比例设置一系列比例，按不同配比配制成最终质量浓度(指化合物I、化合物II的总质量)为0.5,1.0,2.0,4.0,8.0,16.0,32.0μg/mL7个系列浓度。
在无菌操作条件下，将NB(营养肉汤，每升中含有10g蛋白胨、3g牛肉浸粉、5g氯化钠)培养液等量分装至试管中，从低浓度到高浓度依次定量吸取药液，分别加入上述试管中，充分摇匀，然后分别等量加入处于对数生长期的菌悬液，每处理重复4次。混匀后，放于25℃振荡培养箱黑暗培养，待对数生长期测量OD值。取有效的4个重复的平均值为测定结果，计算相对抑制率，将抑制率换算成机率值(y)，药液浓度(μg/mL)转换成对数值(x)，以最小二乘法求得毒力回归方程(y＝a+bx)，并由此计算出每种药剂的EC 50值。同时根据Wadley法计算两药剂不同配比联合增效比值(SR)，SR<0.5为拮抗作用，0.5≤SR≤1.5为相加作用，SR>1.5为增效作用。计算公式如下：
SR＝EC 50(理论值)/EC 50(实测值)
EC 50(理论值)＝(a+b)/[(a/A的EC 50)+(b/B的EC 50)
式中：A为化合物I，B为化合物II；a、b分别为化合物I与化合物II在杀菌组合物中所占的比例；
不同品种的农药混合后，通常表现出三种作用类型，即相加作用、增效作用和拮抗作用，但具体为何种作用，无法预测。本发明所述的杀菌组合物以化合物I与化合物II为有效活性成分，采用生物测定实例加以说明。
实施例1：为验证化合物I和中生菌素不同配比用量对黄瓜细菌性角斑病菌抑菌效果，进行了化合物I和中生菌素不同配比对黄瓜细菌性角斑病菌的室内毒力测定，按照表内重量百分比配成相应浓度，进行室内抑菌试验，试验结果如下：
表1化合物I和中生菌素单剂及其混剂对黄瓜细菌性角斑病菌毒力测定结果
Figure PCTCN2021126496-appb-000011
Figure PCTCN2021126496-appb-000012
由表1结果可知，化合物I和中生菌素不同配比用量混配对黄瓜细菌性角斑病菌的抑制均具有明显增效作用。
实施例2：为验证化合物I和中生菌素不同配比用量对西瓜果斑病菌抑菌效果，进行了化合物I和中生菌素不同配比对西瓜果斑病菌的室内毒力测定，按照表内重量百分比配成相应浓度，进行室内抑菌试验，试验结果如下：
表2化合物I和中生菌素单剂及其混剂对西瓜果斑病菌毒力测定结果
Figure PCTCN2021126496-appb-000013
Figure PCTCN2021126496-appb-000014
由表2结果可知，化合物I和中生菌素不同配比用量混配对西瓜果斑病菌的抑制均具有明显增效作用。
实施例3：为验证化合物I和中生菌素不同配比用量对柑橘溃疡病菌抑菌效果，进行了化合物I和中生菌素不同配比对柑橘溃疡病菌的室内毒力测定，按照表内重量百分比配成相应浓度，进行室内抑菌试验，试验结果如下：
表3化合物I和中生菌素单剂及其混剂对柑橘溃疡病菌毒力测定结果
Figure PCTCN2021126496-appb-000015
由表3结果可知，化合物I和中生菌素不同配比用量混配对柑橘溃疡病菌的抑制均具有明显增效作用。
实施例4：为验证化合物I和中生菌素不同配比用量对水稻白叶枯病菌抑菌效果，进行了化合物I和中生菌素不同配比对水稻白叶枯病菌的室内毒力测定，按照表内重量百分比配成相应浓度，进行室内抑菌试验，试验结果如下：
表4化合物I和中生菌素单剂及其混剂对水稻白叶枯病菌毒力测定结果
Figure PCTCN2021126496-appb-000016
Figure PCTCN2021126496-appb-000017
由表4结果可知，化合物I和中生菌素不同配比用量混配对水稻白叶枯病菌的抑制均具有明显增效作用。
实施例5：为验证化合物I和中生菌素不同配比用量对番茄青枯病菌抑菌效果，进行了化合物I和中生菌素不同配比对番茄青枯病菌的室内毒力测定，按照表内重量百分比配成相应浓度，进行室内抑菌试验，试验结果如下：
表5化合物I和中生菌素单剂及其混剂对番茄青枯病菌毒力测定结果
Figure PCTCN2021126496-appb-000018
Figure PCTCN2021126496-appb-000019
由表5结果可知，化合物I和中生菌素不同配比用量混配对番茄青枯病菌的抑制均具有明显增效作用。
实施例6：为验证化合物I和中生菌素不同配比用量对大白菜软腐病菌抑菌效果，进行了化合物I和中生菌素不同配比对大白菜软腐病菌的室内毒力测定，按照表内重量百分比配成相应浓度，进行室内抑菌试验，试验结果如下：
表6化合物I和中生菌素单剂及其混剂对大白菜软腐病菌毒力测定结果
Figure PCTCN2021126496-appb-000020
由上表可知，化合物I、中生菌素及其混配制剂对大白菜软腐病菌的抑制均具有明显增效作用。
实施例7：为验证化合物I和大蒜素不同配比用量对黄瓜细菌性角斑病菌抑菌效果，进行了化合物I和大蒜素不同配比对黄瓜细菌性角斑病菌的室内毒力测定，按照表内重量百分比配成相应浓度，进行室内抑菌试验，试验结果如下：
表7化合物I和大蒜素单剂及其混剂对黄瓜细菌性角斑病菌毒力测定结果
Figure PCTCN2021126496-appb-000021
Figure PCTCN2021126496-appb-000022
由上表可知，化合物I、大蒜素及其混配制剂对黄瓜细菌性角斑病菌的抑制均具有明显增效作用。
实施例8：为验证化合物I和噻唑锌不同配比用量对西瓜果斑病菌抑菌效果，进行了化合物I和噻唑锌不同配比对西瓜果斑病菌的室内毒力测定，按照表内重量百分比配成相应浓度，进行室内抑菌试验，试验结果如下：
表8化合物I和噻唑锌单剂及其混剂对西瓜果斑病菌毒力测定结果
Figure PCTCN2021126496-appb-000023
由上表可知，化合物I、噻唑锌及其混配制剂对西瓜果斑病菌的抑制均具有明显增效作用。
实施例9：为验证化合物I和四霉素不同配比用量对水稻细菌性条斑病菌抑菌效果，进行了化合物I和四霉素不同配比对水稻细菌性条斑病菌的室内毒力测定，按照表内重量百分比配成相应浓度，进行室内抑菌试验，试验结果如下：
表9化合物I和四霉素单剂及其混剂对水稻细菌性条斑病菌毒力测定结果
Figure PCTCN2021126496-appb-000024
由上表可知，化合物I、四霉素及其混配制剂对水稻细菌性条斑病菌的抑制均具有明显增效作用。
实施例10：为验证化合物I和噻霉酮不同配比用量对马铃薯疮痂病菌抑菌效果，进行了化合物I和噻霉酮不同配比对马铃薯疮痂病菌的室内毒力测定，按照表内重量百分比配成相应浓度，进行室内抑菌试验，试验结果如下：
表10化合物I和噻霉酮单剂及其混剂对马铃薯疮痂病菌毒力测定结果
Figure PCTCN2021126496-appb-000025
Figure PCTCN2021126496-appb-000026
由上表可知，化合物I、噻霉酮及其混配制剂对马铃薯疮痂病菌的抑制均具有明显增效作用。
实施例11：为验证化合物I和春雷霉素不同配比用量对马铃薯黑胫病菌抑菌效果，进行了化合物I和春雷霉素不同配比对马铃薯黑胫病菌的室内毒力测定，按照表内重量百分比配成相应浓度，进行室内抑菌试验，试验结果如下：
表11化合物I和春雷霉素单剂及其混剂对马铃薯黑胫病菌毒力测定结果
Figure PCTCN2021126496-appb-000027
由上表可知，化合物I、春雷霉素及其混配制剂对马铃薯黑胫病菌的抑制均具有明显增效作用。
实施例12：为验证化合物I和新植霉素不同配比用量对芒果角斑病菌抑菌效果，进行了化 合物I和新植霉素不同配比对芒果角斑病菌的室内毒力测定，按照表内重量百分比配成相应浓度，进行室内抑菌试验，试验结果如下：
表12化合物I和新植霉素单剂及其混剂对芒果角斑病菌毒力测定结果
Figure PCTCN2021126496-appb-000028
由上表可知，化合物I、新植霉素及其混配制剂对芒果角斑病菌的抑制均具有明显增效作用。
实施例13：为验证化合物I和金核霉素不同配比用量对桃树细菌性穿孔病菌抑菌效果，进行了化合物I和金核霉素不同配比对桃树细菌性穿孔病菌的室内毒力测定，按照表内重量百分比配成相应浓度，进行室内抑菌试验，试验结果如下：
表13化合物I和金核霉素单剂及其混剂对桃树细菌性穿孔病菌毒力测定结果
Figure PCTCN2021126496-appb-000029
Figure PCTCN2021126496-appb-000030
由上表可知，化合物I、金核霉素及其混配制剂对桃树细菌性穿孔病菌的抑制均具有明显增效作用。
三、大田药效实施例
为了明确化合物I和化合物II单剂和混剂对黄瓜细菌性角斑病、柑橘溃疡病、西瓜果斑病、烟草野火病、大姜姜瘟病、猕猴桃溃疡病、梨火疫病、果树细菌性根癌病、玉米细菌性茎腐病、柑橘黄龙病、番茄溃疡病、玉米细菌性枯萎病、番茄青枯病和水稻白叶枯等细菌性病害防治效果，在国内不同地区开展了多次药效试验。
下述各实施例中的试剂的制备方法如上述制备例1-8所示，示例性地，实施例1的10％化合物I·中生菌素可湿性粉剂的制备方法同制备例1，其中化合物II选自中生菌素，实施例8的10％化合物I·噻唑锌可湿性粉剂的制备方法同制备例1，其中化合物II选自噻唑锌，同理，其他的实施例的制备参考上述制备例1-8。
下述各对比例中的试剂的制备方法同样如上述制备例1-8所示，只是其中的活性组分的含量可能会有所不同，相应的，制剂中的填料或水将组分补齐至100％。例如，对比例1的10％化合物I水分散粒剂的制备方法参照制备例2，其中10％化合物I替换制备例2中的20％化合物I和10％化合物II，含量的差异通过填料来填补。又例如，对比例2的3％中生菌素可湿性粉剂的制备方法参照制备例1，其中3％中生菌素替换制备例1中的5％化合物I和5％化合物II，含量的差异通过填料来填补。
黄瓜细菌性角斑病大田药效试验(于山东聊城冠县开展)：
试验方法：根据《中华人民共和国国家标准GB/T 17980.110-2004》规定施药方法，在初见病斑时施药，7天后第2次施药，共施药两次，重复次数4次。
调查方法：根据《中华人民共和国国家标准GB/T 17980.110-2004》规定的调查方法，第2次施药后7天和14天调查防治效果。每小区对角线3点取样，每点5株，调查全部叶片，以每叶片病斑面积占整个叶片面积百分率分级。
分级方法：
0级:无病斑；1级:病斑面积占整个叶面积的5％以下；3级:病斑面积占整个叶面积的6％～10％；5级:病斑面积占整个叶面积的11％～20％；7级:病斑面积占整个叶面积的21％～50％；9级:病斑面积占整个叶面积的51％以上。
表14化合物I与中生菌素复配对黄瓜细菌性角斑病大田药效试验
Figure PCTCN2021126496-appb-000031
注：同列数据后不同字母表示经Duncan氏新复极差法检验在P<0.05水平差异显著，下同。
由表中测定结果可知，在防治黄瓜细菌性角斑病时，化合物I与中生菌素复配和单剂相比，在同等有效成分用量下，化合物I与中生菌素复配对黄瓜细菌性角斑病的7天防效和14天防效明显高于单剂。其中14天防效依然能达到78.5％以上，持效期较长。
表15化合物I与噻唑锌复配对黄瓜细菌性角斑病大田药效试验
Figure PCTCN2021126496-appb-000032
由表中测定结果可知，在防治黄瓜细菌性角斑病时，化合物I与噻唑锌复配和单剂相比，在同等有效成分用量下，化合物I与噻唑锌复配对黄瓜细菌性角斑病的7天防效和14天防效明显高于单剂。其中14天防效依然能达到80.6％以上，持效期较长。
表16化合物I与春雷霉素复配对黄瓜细菌性角斑病大田药效试验
Figure PCTCN2021126496-appb-000033
由表中测定结果可知，在防治黄瓜细菌性角斑病时，化合物I与春雷霉素复配与单剂相比，在同等有效成分用量下，化合物I与春雷霉素复配对黄瓜细菌性角斑病的7天防效和14天防效明显高于单剂。其中14天防效依然能达到78.9％以上，持效期较长。
水稻白叶枯病大田药效试验(于江苏南京开展)：
试验方法：根据《中华人民共和国国家标准GB/T 17980.19-2000》规定施药方法，在初见病斑时施药，7天后第2次施药，共施药两次，重复次数4次。
调查方法：根据《中华人民共和国国家标准GB/T 17980.19-2000》规定的调查方法，第2次施药后7天和14天调查防治效果。
白叶枯病病情普遍率(以目测分级)：
0级:无病；1级:零星发病或有中心病团；3级:发病面积占总面积四分之一左右；5级:发病面积占总面积三分之一左右；7级:发病面积占总面积二分之一左右；9级:发病面积占总面积四分之三以上。
表17化合物I与中生菌素复配对水稻白叶枯病大田药效试验
Figure PCTCN2021126496-appb-000034
Figure PCTCN2021126496-appb-000035
由测定结果可知，在防治水稻白叶枯病时，化合物I与中生菌素复配和单剂相比，在同等有效成分用量下，化合物I与中生菌素对水稻白叶枯病的7天防效和14天防效明显高于单剂。其中14天防效依然能达到80.5％以上，持效期较长。
表18化合物I与四霉素复配对水稻白叶枯病大田药效试验
Figure PCTCN2021126496-appb-000036
由测定结果可知，在防治水稻白叶枯病时，化合物I与四霉素复配和单剂相比，在同等有效成分用量下，化合物I+四霉素复配对对水稻白叶枯病的7天防效和14天防效明显高于单剂。其中14天防效依然能达到78.6％以上，持效期较长。
柑橘溃疡病大田药效试验(于广西武鸣开展)：
根据《农药田间药效试验准则(GB/T17980.103-2004)》规定施药方法，在始见开花之前第一次喷雾施药，出现病害后第二次喷雾施药。共施药两次，每个处理小区面积为成龄果树3株，重复次数4次。记录施药次数和每次施药日期及果树生育期。
调查方法：根据《农药田间药效试验准则(GB/T17980.103-2004)》规定调查方法，第二次施药后7d，14d对每个小区调查两株，每株按东西南北中五点取样，每点调查两个梢上的全部叶片，计算防治防效。
叶分级方法：
0级：无病；1级：每叶有病斑1～5个；3级：每叶有病斑6～10个；5级：每叶有病斑11～15个；7级：每叶有病斑15～20个；9级：每叶有病斑21个以上；
表19化合物I与中生菌素复配对柑橘溃疡病大田药效试验
Figure PCTCN2021126496-appb-000037
Figure PCTCN2021126496-appb-000038
由测定结果可知，在防治柑橘溃疡病时，化合物I与中生菌素复配和单剂相比，在同等有效成分用量下，化合物I与中生菌素复配对柑橘溃疡病的7天防效和14天防效明显高于单剂。其中14天防效依然能达到78.5％以上，持效期较长。
表20化合物I与申嗪霉素复配对柑橘溃疡病大田药效试验
Figure PCTCN2021126496-appb-000039
由测定结果可知，在防治柑橘溃疡病时，化合物I与申嗪霉素复配和单剂相比，在同等有效成分用量下，化合物I与申嗪霉素复配对柑橘溃疡病的7天防效和14天防效明显高于单剂。其中14天防效依然能达到79.3％以上，持效期较长。
西瓜果斑病大田药效试验(于潍坊市昌乐县开展)：
试验方法：参照《中华人民共和国国家标准GB/T 17980.110-2004》规定施药方法，在初见病斑时施药，7天后第2次施药，共施药两次，重复次数4次。
调查方法：参照《中华人民共和国国家标准GB/T 17980.110-2004》规定的调查方法，第2次施药后7天和14天调查防治效果。
每小区对角线3点取样，每点5株，调查全部叶片，以每叶片病斑面积占整个叶片面积百分率分级。
分级方法：
0级:无病斑；1级:病斑面积占整个叶面积的5％以下；3级:病斑面积占整个叶面积的 6％～10％；5级:病斑面积占整个叶面积的11％～20％；7级:病斑面积占整个叶面积的21％～50％；9级:病斑面积占整个叶面积的51％以上。
表21化合物I与中生菌素复配对西瓜果斑病大田药效试验
Figure PCTCN2021126496-appb-000040
由测定结果可知，在防治西瓜果斑病时，化合物I与中生菌素复配和单剂相比，在同等有效成分用量下，化合物I与中生菌素复配对西瓜果斑病的7天防效和14天防效明显高于单剂。其中14天防效依然能达到78.6％以上，持效期较长。
表22化合物I与大蒜素复配对西瓜果斑病大田药效试验
Figure PCTCN2021126496-appb-000041
由测定结果可知，在防治西瓜果斑病时，化合物I与大蒜素复配和单剂相比，在同等有效成分用量下，化合物I与大蒜素复配对西瓜果斑病的7天防效和14天防效明显高于单剂。其中14天防效依然能达到77.4％以上，持效期较长。
番茄青枯病大田药效试验(于潍坊市昌乐县开展)：
试验方法：参照《中华人民共和国农业行业标准NY/T 1464.32-2010》规定施药方法，在初见病株时灌根，颗粒剂在初见病株时撒施，7天后第2次施药，共施药两次，重复次数4次。
调查方法：参照《中华人民共和国农业行业标准NY/T 1464.32-2010》规定的调查方法，每小区调查全部植株，记录总株数和病株数。第2次施药后7天和14天调查防治效果。
表23化合物I与中生菌素复配对番茄青枯病大田药效试验
Figure PCTCN2021126496-appb-000042
由测定结果可知，在防治番茄青枯病时，化合物I与中生菌素复配和单剂相比，在同等有效成分用量下，化合物I与中生菌素复配对番茄青枯病的7天防效和14天防效明显高于单剂。其中14天防效依然能达到78.1％以上，持效期较长。
烟草野火病大田药效试验(于云南省玉溪市开展)：
试验方法：参照《中华人民共和国农业行业标准NY/T 1464.44-2012》规定施药方法，在初见病斑时施药，7天后第2次施药，共施药两次，重复次数4次。
调查方法：参照《中华人民共和国农业行业标准NY/T 1464.44-2012》规定的调查方法，每小区随机调查5点，每点调查1株，每株调查全部叶片，以每片叶病斑面积占整个叶片病斑面积的百分率分级，记录总叶片数、各级病叶数。
表24化合物I与乙蒜素复配对烟草野火病大田药效试验
Figure PCTCN2021126496-appb-000043
Figure PCTCN2021126496-appb-000044
由测定结果可知，在防治烟草野火病时，化合物I与乙蒜素复配和单剂相比，在同等有效成分用量下，化合物I与乙蒜素复配对烟草野火病的7天防效和14天防效明显高于单剂。其中14天防效依然能达到77.5％以上，持效期较长。
大姜姜瘟病大田药效试验(于山东省安丘市开展)：
试验方法：参照《中华人民共和国农业行业标准NY/T 1464.31-2010》规定施药方法，在初见病斑时施药，7天后第2次施药，共施药两次，重复次数4次。
调查方法：参照《中华人民共和国农业行业标准NY/T 1464.31-2010》规定的调查方法，每小区随机调查5点，每点调查10株，每株调查全部叶片和肉质茎症状，记录调查总株数、各级病株数。
表25化合物I与金核霉素复配对大姜姜瘟病大田药效试验
Figure PCTCN2021126496-appb-000045
由测定结果可知，在防治大姜姜瘟病时，化合物I与金核霉素复配和单剂相比，在同等有效成分用量下，化合物I与金核霉素复配对大姜姜瘟病的7天防效和14天防效明显高于单剂。其中14天防效依然能达到77.9％以上，持效期较长。
梨火疫病大田药效试验(于新疆库尔勒开展)：
试验方法：在初见病斑时施药，7天后第2次施药，共施药两次，重复次数4次。
调查方法：每小区随机调查5点，每点调查10株，每株调查10个枝条。记录调查总株数、各级病株数。
表26化合物I与嘧啶核苷类抗菌素复配对梨火疫病大田药效试验
Figure PCTCN2021126496-appb-000046
Figure PCTCN2021126496-appb-000047
由测定结果可知，在防治梨火疫病时，化合物I与嘧啶核苷类抗菌素复配和单剂相比，在同等有效成分用量下，化合物I与嘧啶核苷类抗菌素复配对梨火疫病的7天防效和14天防效明显高于单剂。其中14天防效依然能达到77.6％以上，持效期较长。
果树细菌性根癌病大田药效试验(于山东烟台开展)：
试验方法：在初见病株时灌根，颗粒剂在初见病株时撒施，7天后第2次施药，共施药两次，重复次数为4次。
调查方法：每小区调查全部植株，记录总株数和病株数。第2次施药后7天和14天调查防治效果。
表27化合物I与氨基寡糖素复配对果树细菌性根癌病大田药效试验
Figure PCTCN2021126496-appb-000048
由测定结果可知，在防治果树细菌性根癌病时，化合物I与氨基寡糖素复配和单剂相比，在同等有效成分用量下，化合物I与氨基寡糖素复配对果树细菌性根癌病的7天防效和14天防效明显高于单剂。其中14天防效依然能达到78.3％以上，持效期较长。
猕猴挑溃疡病大田药效试验(于四川省蒲江县开展)：
试验方法：在发芽前施药，7天后第2次施药，共施药两次，重复次数4次。
调查方法：第二次施药后7d，14d对每个小区调查两株，每株按东西南北中五点取样，每株调查20个枝条，计算防治防效。
表28化合物I与新植霉素复配对猕猴桃溃疡病大田药效试验
Figure PCTCN2021126496-appb-000049
由测定结果可知，在防治猕猴桃溃疡病时，化合物I与新植霉素复配和单剂相比，在同等有效成分用量下，化合物I与新植霉素复配对猕猴桃溃疡病的7天防效和14天防效明显高于单剂。其中14天防效依然能达到77.7％以上，持效期较长。
玉米细菌性茎腐病大田药效试验(于山东济南开展)
试验方法：在初见病株时喷雾，颗粒剂在初见病株时撒施，7天后第2次施药，共施药两次，重复次数4次。
调查方法：每小区调查全部植株，记录总株数和病株数。第2次施药后7天和14天调查防治效果。
表29化合物I与多抗霉素复配对玉米细菌性茎腐病大田药效试验
Figure PCTCN2021126496-appb-000050
Figure PCTCN2021126496-appb-000051
由测定结果可知，在防治玉米细菌性茎腐病时，化合物I与多抗霉素复配和单剂相比，在同等有效成分用量下，化合物I与多抗霉素复配对玉米细菌性茎腐病的7天防效和14天防效明显高于单剂。其中14天防效依然能达到78.4％，持效期较长。
柑橘黄龙病大田药效试验(于广西武鸣开展)
试验方法：在初见病株时灌根，颗粒剂在初见病株时撒施，7天后第2次施药，共施药两次，重复次数4次。
调查方法：每小区调查全部植株，记录总株数和病株数。第2次施药后7天和14天调查防治效果。
表30化合物I与井冈霉素复配对柑橘黄龙病大田药效试验
Figure PCTCN2021126496-appb-000052
由测定结果可知，在防治柑橘黄龙病时，化合物I与井冈霉素复配和单剂相比，在同等有效成分用量下，化合物I与井冈霉素复配对柑橘黄龙病的7天防效和14天防效明显高于单剂。其中14天防效依然能达到79.3％，持效期较长。
番茄溃疡病大田药效试验(于山东济南开展)
试验方法：在初见病株时喷雾，颗粒剂在初见病株时撒施，7天后第2次施药，共施药两次，重复次数4次。
调查方法：每小区调查全部植株，记录总株数和病株数。第2次施药后7天和14天调查防治效果。
表31化合物I与低聚糖素复配对番茄溃疡病大田药效试验
Figure PCTCN2021126496-appb-000053
由测定结果可知，在防治番茄溃疡病时，化合物I与低聚糖素复配和单剂相比，在同等有效成分用量下，化合物I与低聚糖素复配对番茄溃疡病的7天防效和14天防效明显高于单剂。其中14天防效依然能达到78.4％以上，持效期较长。
玉米细菌性枯萎病大田药效试验(于潍坊市昌乐县开展)：
试验方法：在初见病株时灌根，颗粒剂在初见病株时撒施，7天后第2次施药，共施药两次，重复次数4次。
调查方法：每小区调查全部植株，记录总株数和病株数。第2次施药后7天和14天调查防治效果。
表32化合物I与水合霉素复配对玉米细菌性枯萎病大田药效试验
Figure PCTCN2021126496-appb-000054
Figure PCTCN2021126496-appb-000055
由测定结果可知，在防治玉米细菌性枯萎病时，化合物I与水合霉素复配颗粒剂和单剂相比，在同等有效成分用量下，化合物I与水合霉素复配对玉米细菌性枯萎病的7天防效和14天防效明显高于单剂。其中14天防效依然能达到76.3％，持效期较长。
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种杀菌组合物，其中，所述杀菌剂组合物包括有效活性成分，所述有效活性成分包括化合物I和化合物II，所述化合物I为7-氯-1-环丙基-6-氟-4-氧代-1,4-二氢喹啉-3-羧酸-2-甲氧基乙酯，所述化合物II为抗生素类化合物、噻唑锌、噻霉酮、溴菌腈、氨基寡糖素、大黄素甲醚、异噻唑啉酮、二硫氰甲烷中的至少一种。
  2. 根据权利要求1所述的杀菌组合物，其中，所述抗生素类化合物选自中生菌素、春雷霉素、四霉素、乙蒜素、金核霉素、申嗪霉素、水合霉素、大蒜素、新植霉素、多抗霉素、农用链霉素、农抗120、井冈霉素、嘧啶核苷类抗菌素、宁南霉素、蛇床子素、低聚糖素中的至少一种。
  3. 根据权利要求1或2所述的杀菌组合物，其中，所述化合物I和化合物II的质量比为80～1:1～80；
    优选地，所述化合物I和化合物II的质量比为50～1:1～50；
    优选地，所述化合物I和化合物II的质量比为30～1:1～30。
  4. 根据权利要求1-3任一所所述的杀菌组合物，其中，以所述杀菌组合物的总重量为100％计，所述化合物I与化合物II在杀菌组合物中的质量之和为1～80％。
  5. 根据权利要求1-4任一所所述的杀菌组合物，其中，所述杀菌组合物可制备成液体制剂或固体制剂。
    优选地，液体制剂中含有按重量计1％～60％的有效活性成分；固体制剂中含有按重量计5％～80％的有效活性成分。
  6. 根据权利要求1-5任一所所述的杀菌组合物，其中，所述杀菌组合物中还包括乳化剂、分散剂、润湿剂、增稠剂、消泡剂、稳定剂、粘结剂、崩解剂、抗冻剂、抗结剂、助悬剂、成膜剂、防腐剂、着色剂、高分子囊壁材料、pH调节剂或填料中的至少一种。
  7. 根据权利要求1-6任一所述的杀菌组合物，其中，所述杀菌组合物可制作成水分散粒剂、可分散液剂、可湿性粉剂、悬浮剂、水乳剂、微乳剂、悬乳剂、微囊悬浮剂、微囊悬浮-悬浮剂、悬浮种衣剂、乳油、颗粒剂。
  8. 权利要求1-7任一项所述的杀菌组合物用于防治病原菌及其引起的农业病害，尤其适用于细菌及细菌引起的植物细菌性病害。
  9. 根据权利要求8所述的用途，其中，所述杀菌组合物用于防治大白菜软腐病等各作物软腐病、大白菜黑腐病、黄瓜细菌性角斑病、芝麻角斑病、西/甜瓜果斑病、水稻白叶枯病、 水稻细菌性条斑病、水稻细菌性褐斑病、水稻细菌性褐条病、水稻细菌性基腐病、番茄青枯病等茄科青枯病、桑青枯病、花生青枯病、大姜姜瘟病、番茄/辣椒细菌性斑点病、辣椒细菌性叶斑病、马铃薯黑胫病、玉米细菌性枯萎病、玉米细菌性茎腐病、小麦黑颖病、大豆细菌性斑疹病、大豆细菌性疫病、木薯细菌性枯萎病、芒果角斑病、柑橘溃疡病、桃树细菌性穿孔病、向日葵茎腐病、桃流胶病、梨火疫病、梨锈水病、果树细菌性根癌病、马铃薯环腐病、菜豆萎蔫病、小麦白叶条斑病、马铃薯疮痂病、番茄溃疡病、美国冬青叶疫病以及黄瓜霜霉病、黄瓜靶斑病、水稻稻瘟病、水稻纹枯病等。
  10. 一种防治病原菌及其引起的农业病害，尤其是细菌及细菌引起的植物细菌性病害的方法，包括将权利要求1-7任一项所述的杀菌组合物施用于存在病害的植物上。
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