WO2022089446A1 - Synergistic bactericidal composition containing quinolone compound and copper preparation - Google Patents

Synergistic bactericidal composition containing quinolone compound and copper preparation Download PDF

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Publication number
WO2022089446A1
WO2022089446A1 PCT/CN2021/126495 CN2021126495W WO2022089446A1 WO 2022089446 A1 WO2022089446 A1 WO 2022089446A1 CN 2021126495 W CN2021126495 W CN 2021126495W WO 2022089446 A1 WO2022089446 A1 WO 2022089446A1
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Prior art keywords
compound
copper
bacterial
quinoline
spot
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PCT/CN2021/126495
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French (fr)
Chinese (zh)
Inventor
迟会伟
吴建挺
韩君
刘杰
李颖
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 WO2022089446A1 publication Critical patent/WO2022089446A1/en

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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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal 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
    • A01N43/34—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
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Definitions

  • the invention belongs to the technical field of pesticide compounding, in particular to a synergistic bactericidal composition containing quinolone compounds, and also relates to the application of the bactericidal composition.
  • quinolones 7-chloro-1-cyclopropyl-6-fluoro-4-oxo-1,4-dihydroquinoline-3-carboxylic acid-2-methoxyethyl ester.
  • the above compounds have broad-spectrum bactericidal activity, especially against bacteria, and exhibit excellent activity against both Gram-positive bacteria and Gram-negative bacteria.
  • bacterial diseases such as soft rot of various crops such as Chinese cabbage soft 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 stripe, rice bacterial base rot, tomato bacterial wilt and other Solanaceae bacterial wilt, mulberry bacterial wilt, peanut bacterial wilt, ginger Ginger blast, tomato/chili bacterial spot, pepper bacterial leaf spot, potato blackleg, corn bacterial wilt, corn bacterial stalk rot, wheat blackgrass, soybean bacterial spot, soybean bacterial Sexual blight, cassava bacterial wilt, mango corner spot, citrus canker, peach bacterial perforation, sunflower stem rot, peach gum disease, pear fire
  • the present invention provides a bactericidal composition
  • a bactericidal composition comprising compound I and compound II, wherein compound I is 7-chloro-1-cyclopropyl-6-fluoro-4-oxo-1,4 -dihydroquinoline-3-carboxylic acid-2-methoxyethyl ester, compound II is a copper preparation, such as copper quinoline, copper thiophanate, copper hydroxide, copper tetraammine, copper king, copper calcium sulfate , Ammonium copper, copper sulfate, cuprous oxide, green milk copper, Bordeaux mixture, copper oxychloride, copper rosinate, copper succinate, nonbacterial copper, thiosen copper, copper nitrohumate, prochloraz Any one of copper salt, copper citrate, copper succinate, copper mixed amino acid, basic copper sulfate, copper imidazoquinoline, copper acetate, etc.
  • the effective active ingredients of the bactericidal composition include Compound I and Compound II, wherein the mass ratio of the Compound I and Compound II is 80-1:1-80, preferably 50-1:1- 50, preferably 30 to 1:1 to 30, for example, 60:1, 45:1, 30:1, 20:1, 10:1, 5:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:5, 1:10, 1:20, 1:30, or 1:60.
  • the sum of the content of the compound I and the compound II in the bactericidal composition is 1-90%, preferably 20-60%, for example 5%, 8%, 10%, 13%, 15%, 18%, 20%, 24%, 30%, 35%, 38%, 42%, 45%, 50%, 55%, 60%, 65% , 68%, 75%, 80%, 85%, or 90%.
  • the bactericidal composition may be prepared as a liquid preparation or a solid preparation.
  • the content of active ingredients in the preparation varies according to different preparation types.
  • liquid preparations contain 1% to 60% by weight of active substances, preferably 5% to 50%; solid preparations Contains 5% to 80% by weight of active substance, preferably 10% to 70%.
  • At least one surfactant is included in the composition to facilitate dispersion of the active ingredient in water upon application.
  • the content of the surfactant is 2% to 30% of the total weight of the preparation.
  • the surfactant selected for the composition is selected from one or more of emulsifiers, dispersants, wetting agents, thickeners or defoaming agents.
  • the preparation may also contain stabilizers, disintegrants, antifreeze agents, binders, anti-caking agents, suspending agents, film-forming agents, preservatives, colorants, polymer capsule wall materials, At least one of pH adjusters or fillers.
  • the composition may be diluted or used directly by the user prior to use.
  • Its preparation can be prepared by processing methods known to those skilled in the art, namely after mixing active ingredients with liquid solvents or solid carriers, and then adding surfactants such as dispersants, stabilizers, wetting agents, binders, defoaming agents, etc. one or more of.
  • the composition can be made into various dosage forms, preferably, the dosage forms of the preparation include water dispersible granules, dispersible liquids, wettable powders, suspensions, water emulsions, microemulsions, Suspension, microcapsule suspension, microcapsule suspension-suspension, seed coating, emulsifiable concentrate, granule.
  • the dosage forms of the preparation include water dispersible granules, dispersible liquids, wettable powders, suspensions, water emulsions, microemulsions, Suspension, microcapsule suspension, microcapsule suspension-suspension, seed coating, emulsifiable concentrate, granule.
  • the composition comprises the following components and contents when made into a wettable powder: Compound I 1%-80%, Compound II 1%-80%, dispersant 1%-12%, wetting agent 1% to 8% of fillers and/or fillers, for example, the following wettable powders are prepared: compound I 5%, compound II 25%, sodium dodecylbenzenesulfonate 2%, lignosulfonic acid Sodium 9%, talc 3%, silica 4%, and attapulgite are supplemented to 100%.
  • 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%, Wet agent 1% ⁇ 8%, disintegrant 1% ⁇ 10%, the balance is filler, for example, the following water dispersible granules are prepared: compound I 10%, compound II 30%, sodium alkylnaphthalene sulfonate 2% , 9% sodium lignosulfonate, 3% sodium lauryl sulfate, 4% ammonium sulfate, and kaolin to be supplemented to 100%.
  • compound I 30% compound II 10%, sodium alkylnaphthalene sulfonate 2%, sodium lignosulfonate 7%, sodium lauryl sulfate 3%, ammonium sulfate 4%, kaolin supplemented to 100%.
  • 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%, disintegrant 0.1% to 8%, antifreeze 0.1% to 8%, deionized water to make up to 100%, for example, the following suspending agent is prepared: compound I 5%, compound II 20%, methylnaphthalene sulfonate sodium formaldehyde condensate 5%, xanthan gum 0.2%, naphthalenesulfonic acid formaldehyde condensate sodium salt 3%, ammonium sulfate 4%, propylene glycol 4%, water added to 100%.
  • 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%, optionally organic solvent 1%-60%, 1% to 12% of emulsifier, 0.1% to 8% of antifreeze, 0.01% to 2% of defoamer, 0.1% to 2% of thickener, and deionized water to make up to 100%, for example, the following water emulsion is made : Compound I 10%, Compound II 5%, 2,2,2-trifluoroethanol 35%, propylene carbonate 10%, 150# solvent oil 15%, Span-80 10%, ethylene glycol 3%, organic Silicon 0.5%, polyvinyl alcohol 0.3%, deionized water supplemented to 100%.
  • 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 to 30%, pH adjuster 0.1% to 5%, thickener 0.1% to 8%, and the balance is deionized water.
  • the composition when the composition is made into a microcapsule suspension, it includes the following components and contents: 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%, emulsifier 1-30%, antifreeze 1% ⁇ 10%, stabilizer 0.1% ⁇ 5%, and the balance is organic solvent.
  • the following emulsifiable concentrates compound I 10%, compound II 40%, tristyryl phenol polyoxyethylene ether phosphate triethanolamine salt 4%, fatty polyether 2%, propylene glycol 4%, triethanolamine 0.1%, mineral spirits Replenish to 100%.
  • 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 includes the following components and contents when made into granules: compound I 0.5%-10%, compound II 0.5%-10%, dispersant 1%-12%, wetting agent 1% to 10% of agent, 0.1% to 8% of binder and filler to 100%.
  • the following granules compound I 0.5%, compound II 2.5%, sodium lignosulfonate 3.2%, sodium lauryl sulfate 3.5%, polyvinyl alcohol 3.2%, silica 10%, diatomaceous earth supplemented to 100%.
  • the emulsifier can be selected from at least one of the following: sodium lignosulfonate, agricultural milk, phenylphenol polyoxyethyl ether phosphate, naphthalene sulfonate formaldehyde condensate, benzyl Dimethylphenol polyoxyethyl ether, sorbitan fatty acid ester polyoxyethylene ether, sorbitan oleate (Span 80), fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether phosphate , Castor oil polyoxyethylene ether phosphate, Tween-80, tristyryl phenol polyoxyethylene ether phosphate triethanolamine salt;
  • the dispersing agent can be selected from at least one of the following: glycerol fatty acid polyoxyethylene ether, polyoxyethylene alkyl aryl ether, sodium lignosulfonate, fatty alcohol polyoxyethylene ether sulfate , Naphthalenesulfonate formaldehyde condensate, Naphthalenesulfonate formaldehyde condensate sodium salt, Nonylphenol polyoxyethylene ether, Polyoxyethylene lanolin alcohol, Alkylphenol polyoxyethylene ether formaldehyde condensate, Fatty alcohol polyoxyethylene ether , fatty alcohol polyoxyethylene ether phosphate, polyoxyethylene sorbitan fatty acid ester, phosphate ester, fatty alcohol polyether, sodium alkyl naphthalene sulfonate;
  • the wetting agent can be selected from at least one of the following: trisiloxane polyoxyethylene ether, sodium N-lauroyl glutamate, sodium lauryl sulfate, lauroyl sarcosine Sodium, castor oil polyoxyethylene ether, tristyryl phenol polyoxyethylene ether, sodium dodecylbenzene sulfonate, sodium isooctyl succinate sulfonate, fatty alcohol polyoxyethylene ether, methylnaphthalene sulfonate Sodium formaldehyde condensate;
  • the binder can be selected from at least one of the following: xanthan gum, starch, urea-formaldehyde resin, gelatin, gum arabic, carboxymethyl cellulose, carboxyethyl cellulose, polyvinyl alcohol ;
  • the disintegrant is selected from at least one of the following: sodium bicarbonate, ammonium sulfate, sodium sulfate, calcium sulfate, magnesium chloride;
  • the thickening agent may be selected from at least one of the following: magnesium aluminum silicate, polyvinyl acetate, xanthan gum, gelatin, gum arabic, polyvinyl alcohol;
  • the defoamer can be selected from at least one of the following: silicone oil, n-octanol, silicone, butyl phosphate, isobutyl phosphate, silicone;
  • the antifreeze agent may be at least one of the following: propylene glycol, ethylene glycol, and glycerol;
  • the stabilizer can be selected from at least one of the following: triethanolamine, epichlorohydrin, butyl glycidyl ether, triphenyl phosphite, N-soybean oil-based trimethylenediamine , dialkyl succinate acetate sulfonate;
  • the fillers include solid fillers and liquid fillers, wherein the solid fillers can be selected from at least one of the following: kaolin, attapulgite, diatomite, silica, bentonite, montmorillonite, calcium carbonate.
  • the liquid filler can be selected from at least one of water, soybean oil, castor oil, and mineral oil.
  • the organic solvent can be selected from at least one of the following: ethyl acetate, acetone, isopropanol, 2-2-2 trifluoroethanol, propylene carbonate, benzene, toluene, xylene, Dimethylformamide, dimethyl sulfoxide, dichloromethane, cyclohexane, cyclohexanone, N-methylpyrrolidone, solvent oil (for example, 150# solvent oil).
  • the present invention also provides the above-mentioned preparation method of the bactericidal composition, comprising: mixing the active ingredients compound I, compound II and an auxiliary agent.
  • the present invention also provides the above-mentioned bactericidal composition containing compound I and compound II for controlling pathogenic bacteria and the agricultural diseases caused by them, and is especially suitable for use in bacteria and bacterial diseases of plants caused by bacteria.
  • 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 stripe, rice bacterial base rot, tomato bacterial wilt and other Solanaceae bacterial wilt, mulberry bacterial wilt, peanut bacterial wilt, ginger Ginger blast, tomato/chili bacterial spot, pepper bacterial leaf spot, potato blackleg, corn bacterial wilt, corn bacterial stalk rot, wheat blackgrass, soybean bacterial spot, soybean bacterial Sexual blight, cassava bacterial wilt, mango corner spot, citrus canker, peach bacterial perforation, sunflower stem rot, peach gum disease, pear fire blight, pear water rust, fruit tree bacterial root cancer, Potato ring rot, bean wilt, wheat white leaf spot, potato
  • 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 synergistic bactericidal composition containing compound I and compound II 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 the desired concentration.
  • the method is applied to plants or crops, for example, spraying, plant root irrigation, smearing, etc. are applied to plants or crops. In specific applications, it can also be mixed with other medicaments such as insecticides, growth regulators, soil conditioners, herbicides, nematicides and the like.
  • the synergistic bactericidal composition containing compound I and compound II of the present invention has the following advantages: 1. It has a synergistic effect, which can improve the control effect; 2. The bactericidal spectrum is expanded, and field diseases are often mixed, and the mixed use of the two is effective against bacterial diseases. The effect is stronger; 3. The two active ingredients have different mechanisms of action, and the mixed use can delay the generation of pathogenic bacteria resistance;
  • the present invention adopts the method of combining indoor biological assay and field test.
  • 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, various additives and fillers are mixed uniformly according to the formula ratio, and the wettable 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 formula ratio, and the finished product is obtained after high-speed shearing.
  • 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 into the batching kettle, and the water emulsion is uniformly mixed by a high-speed shearing machine.
  • 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.
  • the active ingredients, various additives and fillers are mixed uniformly according to the formula ratio, and the wettable 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.
  • Test drugs Compound I and Compound II original drugs.
  • the original drug of compound I was dissolved in dimethyl sulfoxide to prepare a mother solution of 10,000 ⁇ g/mL, and the original drug of compound II was directly dissolved in an appropriate solvent to prepare a mother solution of 10,000 ⁇ g/mL.
  • the emulsifier Tween-80 was added at a volume fraction of 0.2%, Store in a refrigerator at 4°C for later use, and dilute with sterile water to an appropriate concentration when using.
  • 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 leaf spot, citrus canker, peach tree bacterial perforation, cassava bacterial fusarium wilt, fruit and vegetable bacterial root cancer and potato scab.
  • the method for determination of bacterial virulence refers to the Agricultural Industry Standard of the People's Republic of China NY/T 1156.16-2008
  • 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 leaf spot, citrus canker, peach tree bacterial perforation, cassava bacterial fusarium wilt, fruit and vegetable bacterial root cancer and potato scab were used as test materials. Its mixed preparations were tested for toxicity.
  • test agents including compound I, compound II
  • a suitable solvent such as acetone, methanol, N,N dimethylformamide and dimethyl sulfoxide, etc.
  • 7 concentration gradients Compound I: 0.5, 1.0, 2.0, 4.0, 8.0, 16.0, 32.0 ⁇ g/mL, etc.
  • Compound II 0.5, 1.0, 2.0, 4.0, 8.0, 16.0, 7 concentration gradients such as 32.0 ⁇ g/mL
  • the compound I and compound II for compounding are respectively set according to their EC 50 value doses and a series of ratios by mass ratio, and are formulated into final mass concentrations according to different ratios (referring to compound I,
  • the total mass of compound II) is 7 series concentrations of 0.5, 1.0, 2.0, 4.0, 8.0, 16.0, 32.0 ⁇ g/mL.
  • NB nutrient broth, containing 10 g peptone and 3 g beef per liter
  • Dip powder, 5g sodium chloride culture solution is divided into test tubes in equal amounts, quantitatively draw the medicinal liquid from low concentration to high concentration in turn, add into the above test tubes respectively, shake well, and then add in equal amounts to be in the logarithmic growth phase.
  • the bacterial suspension was repeated 4 times per treatment. After mixing, the cells were incubated in the dark in a shaking incubator at 25°C, and the OD value was measured in the logarithmic growth phase.
  • a and b are the proportions of compound I and compound II in the combination, respectively;
  • A is compound I;
  • B is selected from compound II, and is one of copper preparations such as copper quinoline, copper thiophanate, copper hydroxide, copper king, Bordeaux mixture, copper quinoline, copper thiosen, and copper imidazoquinoline.
  • the bactericidal composition of the present invention uses compound I and compound II as active ingredients, and is described by using a biological assay example.
  • Embodiment 1 In order to verify the antibacterial effect of compound I and quinoline copper in different proportions on cucumber bacterial angular spot bacterium, the indoor virulence assay of compound I and quinoline copper in different proportions to cucumber bacterial angular spot bacterium 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 2 In order to verify the antibacterial effect of compound I and quinoline copper on the watermelon fruit spot bacteria in different proportions, the indoor toxicity measurement of watermelon fruit spot bacteria in different proportions of compound I and quinoline copper was carried out. 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 3 in order to verify the antibacterial effect of compound I and quinoline copper in different proportions on citrus canker bacteria, carried out the indoor toxicity measurement of compound I and quinoline copper different proportions to citrus canker bacteria, according to the weight percentage in the table Dubbed into corresponding concentrations, the indoor antibacterial test was carried out.
  • the test results are as follows:
  • Embodiment 4 In order to verify the bacteriostatic effect of compound I and different ratios of copper quinoline on the bacterial blight of rice, the indoor virulence assay test of different ratios of compound I and copper quinoline to rice bacterial blight was carried out, According to the weight percentage in the table, the corresponding concentration is made, and the indoor antibacterial test is carried out.
  • the test results are as follows:
  • Embodiment 5 in order to verify the bacteriostatic effect of compound I and different ratios of copper quinoline on tomato bacterial wilt bacteria, the indoor virulence assays of different proportions of compound I and copper quinoline to tomato bacterial wilt bacteria were carried out, 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 6 In order to verify the bacteriostatic effect of compound I and different ratios of copper quinoline on Chinese cabbage soft rot bacteria, the indoor toxicity measurement of compound I and different ratios of quinoline copper to Chinese cabbage soft rot bacteria was carried out, 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 7 In order to verify the antibacterial effect of compound I and thiophanate-copper on watermelon fruit spot bacteria in different proportions, the indoor virulence assay of compound I and thiophanate-copper different ratios to watermelon fruit blotch was carried out, 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:
  • test drug Proportion EC 50 ( ⁇ g/mL) (measured value)
  • EC 50 ( ⁇ g/mL) theoretical value
  • SR Compound I - 2.6518
  • copper thiophanate - 42.15 Compound I: copper thiophanate 60:1 1.6106 2.6932 1.6722 Compound I: copper thiophanate 45:1 1.7229 2.7069 1.5712 Compound I: copper thiophanate 30:1 1.7318 2.7345 1.5790 Compound I: copper thiophanate 20:1 1.7458 2.7757 1.5899 Compound I: copper thiophanate 10:1 1.7325 2.8987 1.6732 Compound I: copper thiophanate 5:1 1.7718 3.1426 1.7737 Compound I: copper thiophanate 3:1 1.8055 3.4631 1.9181 Compound I: copper thiophanate 2:1 1.9679 3.8564 1.9596 Compound I: copper thiophanate 1:1 2.6012 4.9897 1.9182 Compound I: copper thiophanate 1:2 3.4915 7.0663 2.0239 Compound I: copper thiophanate 1:3 3.9529 8.9231 2.2573 Compound I: copper thiophan
  • Example 8 In order to verify the antibacterial effect of compound I and thiossen copper on the bacteriostatic effect of different ratios of compound I and thiosin copper on B. oryzae, the indoor virulence assay of compound I and thiosin copper in different ratios to B. oryzae was carried out. , 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:
  • Embodiment 9 for verifying compound I and copper hydroxide different proportioning dosages to potato scab bacteriostatic effect, carried out compound I and different proportions of copper hydroxide to the indoor virulence measurement of 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 10 in order to verify the antibacterial effect of compound I and different proportioning dosages of nonbacterial copper on mango angular spot bacteria, carried out the indoor virulence measurement of compound I and nonobacterial copper different proportions to mango angular 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 11 In order to verify the bacteriostatic effect of compound I and copper imidazoquinoline in different proportions and dosages on B. oryzae, the indoor toxicity of compound I and copper imidazoquinoline in different proportions of B. oryzae 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:
  • Embodiment 12 in order to verify the antibacterial effect of compound I and different proportioning dosages of Bordeaux mixture to Bacteroides potato, carried out the indoor virulence measurement of different proportions of Compound I and Bordeaux mixture to Bacteroides potato, 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 13 in order to verify that compound I and Wang copper different proportioning dosages are to the bacteriostatic effect of peach bacterial perforation bacteria, carried out the indoor virulence assay of compound I and Wang copper different proportions to peach bacterial perforation 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:
  • the preparation methods of the reagents in the following examples are shown in the above formulation examples 1-7.
  • the preparation method of the 30% Compound I ⁇ Copper quinoline wettable powder (1:5) of Example 1 is the same as the Formulation Example 1, since the content of Compound I in this formulation example is 5% and the content of Compound II is 25%, it is called 30% Compound I ⁇ Copper quinoline wettable powder (1:5), as shown in the following table. analogy.
  • the preparation methods of the control agents in the following comparative examples are also shown in the above-mentioned formulation examples 1-7, except that the content of the active components may be different.
  • the filler or solvent in the Make up to 100% for example, the preparation method of 10% compound I water dispersible granules of comparative agent 1 refers to formulation example 2, wherein 10% compound I replaces 10% compound I and 30% compound II in formulation example 2, and the content difference is through the filler to fill or adjust.
  • the preparation method of the 33.5% copper quinoline suspension of control agent 2 refers to formulation example 3, wherein 33.5% copper quinoline replaces 5% compound I and 20% compound II in formulation example 3, and the difference in content is determined by Filler to fill or adjust.
  • Test method According to the application method stipulated in "National Standard of the People's Republic of China GB/T 17980.110-2004", apply the medicine when the lesions are first seen, and apply the medicine for the second time after 7 days. Second-rate.
  • 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.
  • 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 11% to 20% of the entire leaf area
  • 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.
  • Test method According to the application method stipulated in "National Standard of the People's Republic of China GB/T 17980.19-2000", apply the medicine when the lesions are first seen, and apply the medicine for the second time after 7 days. Second-rate.
  • 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 1 sporadic disease or central disease
  • Grade 3 The diseased area accounts for about a quarter of the total area
  • Grade 5 The incidence area accounts for about one-third of the total area
  • Grade 7 The incidence area accounts for about 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 1 There are 1 to 5 diseased spots on each leaf;
  • Grade 3 There are 6 to 10 diseased spots on each leaf
  • Grade 9 Each leaf has more than 21 diseased spots
  • Test method refer to the spraying method specified in "National Standard of the People's Republic of China GB/T 17980.110-2004".
  • 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 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 11% to 20% of the entire leaf area
  • 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.
  • 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 spray when the diseased plants are first seen, granules are sprayed when the diseased plants are first seen, and the second spray 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 lesions are first seen, and apply the medicine for the second time after 7 days.
  • compound I and copper succinate are compounded and single-dose, and under the same dosage of active ingredients, compound I + copper succinate has a 7-day preventive effect on peach bacterial perforation.
  • 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 80.7%, and the lasting period is longer.
  • 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.
  • Grade 0 The whole plant is disease-free
  • Grade 1 The lesion area accounts for less than 5% of the entire leaf area
  • Grade 3 The lesion area accounts for 6% to 20% of the entire leaf area
  • Grade 5 The lesion area accounts for 21% to 50% of the entire leaf area
  • Grade 7 The lesion area accounts for 51% to 80% of the entire leaf area
  • Grade 9 The lesion area accounts for more than 81% of the entire leaf area.
  • 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 succulent stem symptoms were surveyed for each plant, and the total number of surveyed plants was recorded. , The number of diseased plants at all levels.
  • Grade 0 The whole plant is disease-free
  • Grade 3 11% to 30% of the leaves turn yellow, the leaf margins are slightly rolled, and the fleshy stems appear water-soaked spots;
  • Grade 5 31% to 50% of the leaves turn yellow, the leaf margins are curled, the plants are dwarfed, and the fleshy stems are partially rotted;
  • Grade 7 more than 51% of the leaves are withered, the plants are wilted, and most of the fleshy stems are rotten;
  • Grade 9 Plants die, fleshy stems rot or only filamentous vascular bundles remain.
  • 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 spraying before germination, the second spraying after 7 days, a total of twice spraying, repeated 4 times.
  • Test method spray at the first sight of the diseased plant, and apply the medicine for the second time after 7 days.
  • Survey method random sampling survey in each plot, survey 50 plants at each point, and record the disease grade index. The control effect was investigated 7 days and 14 days after the second application.
  • 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 for each plant. The total number of investigated plants and the number of diseased plants at all levels were recorded.
  • 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 20 leaves were surveyed for each plant. The total number of leaves and the number of diseased leaves at all levels were recorded.
  • Test method When the disease spots are first seen, the foliar spray is applied, the root is irrigated, and the second application is applied after 7 days.
  • Investigation method Investigate all plants in each plot. Record the total number of investigated plants and the number of diseased plants.
  • Test method irrigate the roots when the diseased plants are first seen, and apply the medicine for the second time after 7 days.
  • 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 When the diseased plants were first seen, the leaves were sprayed, the roots were irrigated, and the second application was applied 7 days later, with a total of two applications and 4 repetitions.
  • 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 at the first sight of the diseased plant, and apply the medicine for the second time after 7 days.
  • 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 refer to the application method specified in "The Agricultural Industry Standard of the People's Republic of China NY/T 1464.49-2010", 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.
  • Investigation method Referring to the investigation method stipulated in "The Agricultural Industry Standard of the People's Republic of China NY/T 1464.49-2010", the control effect was investigated 7 days and 14 days after the second application.
  • Grade 0 The whole plant is disease-free.
  • Grade 1 Occasional chlorotic spots on the stem, or withered leaves below 1/2 of the diseased side;
  • Grade 3 Black streaks on the stem, but not more than 1/2 of the stem height, or withered leaves on the diseased side 1/2-2/3;
  • Grade 5 Black streaks on the stem exceed 1/2 of the stem height, but do not reach the top of the stem, or more than 2/3 of the leaves on the diseased side wither;
  • Level 7 black streaks on the stem reach the top of the stem, or all the leaves of the diseased plant wither
  • Level 9 The diseased plants basically die.

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Abstract

Provided are a bactericidal composition containing a compound I and a compound II, and an application of the bactericidal composition. The compound I is 7-chloro-1-cyclopropyl-6-fluoro-4-oxo-1,4-dihydroquinoline-3-carboxylic-2-methoxyethyl ester, and the compound II is any one of copper preparations. The bactericidal composition has the following advantages: a synergistic effect is provided, and prevention and treatment effects are improved; a bactericidal spectrum is expanded, and since diseases in field often occur in a mixed manner, mixing the two compounds for use has a stronger disease effect on bacteria; the two active ingredients have different action mechanisms, and mixed use can delay generation of drug resistance of pathogenic bacteria; the pesticide application amount is reduced, the use frequency is reduced, and the use cost is reduced.

Description

一种含喹诺酮类化合物和铜制剂的增效杀菌组合物A kind of synergistic bactericidal composition containing quinolone compound and copper preparation 技术领域technical field
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，还涉及该杀菌组合物的应用。The invention belongs to the technical field of pesticide compounding, in particular to a synergistic bactericidal composition containing quinolone compounds, and also relates to the application of the bactericidal composition.
背景技术Background technique
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。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另一种药剂，这种不科学的用药方式，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。In recent years, the occurrence of various crop bacterial diseases has been increasing year by year, and the incidence area has increased year by year, which has brought great harm to agricultural production. At present, there is a lack of high-efficiency drugs for the prevention and control of bacterial diseases on the market. In order to improve the control effect, farmers increase the amount of the drug or mix another drug at will. This unscientific method of drug use not only fails to achieve synergistic effects, but leads to The waste of pesticides, excessive residues, pollute the environment, and cause bacteria to develop resistance to pesticides and other problems. Therefore, there is an urgent need to develop a synergistic bactericidal composition for bacterial diseases, which can achieve the effects of expanding the scope of control objects, reducing the dosage of drugs, and delaying the generation of resistance.
在农业生产的实际过程中，长期连续单一的使用一种药剂，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。In the actual process of agricultural production, if a single agent is used continuously for a long time, the pathogenic bacteria will soon develop drug resistance, resulting in a decrease in the control effect, an increase in the use of pesticides, and aggravation of pesticide residues in agricultural products and damage to the ecological environment. It is an effective way to delay the generation of drug resistance of pathogenic bacteria, expand the bactericidal spectrum, prolong the service life and reduce the amount of pesticides used. However, it is a major difficulty in how to compound so that each drug has a synergistic rather than antagonistic effect.
喹诺酮类化合物化学名称为：7-氯-1-环丙基-6-氟代-4-氧-1,4-二氢喹啉-3-羧酸-2-甲氧基乙酯。The chemical name of quinolones is: 7-chloro-1-cyclopropyl-6-fluoro-4-oxo-1,4-dihydroquinoline-3-carboxylic acid-2-methoxyethyl ester.
上述化合物具有广谱的杀菌活性，尤其对细菌活性突出，对革兰氏阳性菌、革兰氏阴性菌均表现出优秀的活性。对多种作物病害尤其是细菌性病害例如大白菜软腐病等各作物软腐病、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、美国冬青叶疫病等均具有较好活性。The above compounds have broad-spectrum bactericidal activity, especially against bacteria, and exhibit excellent activity against both Gram-positive bacteria and Gram-negative bacteria. For a variety of crop diseases, especially bacterial diseases such as soft rot of various crops such as Chinese cabbage soft 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 stripe, rice bacterial base rot, tomato bacterial wilt and other Solanaceae bacterial wilt, mulberry bacterial wilt, peanut bacterial wilt, ginger Ginger blast, tomato/chili bacterial spot, pepper bacterial leaf spot, potato blackleg, corn bacterial wilt, corn bacterial stalk rot, wheat blackgrass, soybean bacterial spot, soybean bacterial Sexual blight, cassava bacterial wilt, mango corner spot, citrus canker, peach bacterial perforation, sunflower stem rot, peach gum disease, pear fire blight, pear water rust, fruit tree bacterial root cancer, Potato ring rot, kidney bean wilt, wheat white leaf spot, potato scab, tomato canker, American holly leaf blight, etc. have good activity.
喹啉铜、噻菌铜、氢氧化铜、四氨合铜、王铜、硫酸铜钙、络氨铜、硫酸铜、氧化亚铜、绿乳铜、波尔多液、氧氯化铜、松脂酸铜、琥珀酸铜、壬菌铜、噻森铜、硝基腐殖酸铜、咪鲜胺铜盐、柠檬酸铜、琥胶肥酸铜、混合氨基酸铜、碱式硫酸铜、咪唑喹啉铜、乙酸铜等铜制剂为目前防治细菌性病害 的药剂，由于长期单一使用，均不同程度出现抗性，防效下降。Copper quinoline, copper thiophanate, copper hydroxide, tetraammine copper, copper king, calcium copper sulfate, copper ammonia, copper sulfate, cuprous oxide, green milk copper, Bordeaux mixture, copper oxychloride, copper rosinate , copper succinate, copper nonbacteria, copper thiosen, copper nitrohumate, copper prochloraz, copper citrate, copper succinate, mixed amino acid copper, basic copper sulfate, copper imidazoquinoline, Copper preparations such as copper acetate are currently used to prevent and control bacterial diseases. Due to long-term single use, resistance occurs to varying degrees, and the control effect decreases.
现有技术中，尚未见有关于化合物I和铜制剂或两者类似物质的复配及应用的相关报道。In the prior art, there is no relevant report on the compounding and application of compound I and copper preparation or both similar substances.
发明内容SUMMARY OF THE INVENTION
为了改善现有技术的不足，本发明提供一种包含化合物I和化合物II的杀菌组合物，其中化合物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，化合物II为铜制剂，例如为喹啉铜、噻菌铜、氢氧化铜、四氨合铜、王铜、硫酸铜钙、络氨铜、硫酸铜、氧化亚铜、绿乳铜、波尔多液、氧氯化铜、松脂酸铜、琥珀酸铜、壬菌铜、噻森铜、硝基腐殖酸铜、咪鲜胺铜盐、柠檬酸铜、琥胶肥酸铜、混合氨基酸铜、碱式硫酸铜、咪唑喹啉铜、乙酸铜等中任意一种。In order to improve the deficiencies of the prior art, the present invention provides a bactericidal composition comprising compound I and compound II, wherein compound I is 7-chloro-1-cyclopropyl-6-fluoro-4-oxo-1,4 -dihydroquinoline-3-carboxylic acid-2-methoxyethyl ester, compound II is a copper preparation, such as copper quinoline, copper thiophanate, copper hydroxide, copper tetraammine, copper king, copper calcium sulfate , Ammonium copper, copper sulfate, cuprous oxide, green milk copper, Bordeaux mixture, copper oxychloride, copper rosinate, copper succinate, nonbacterial copper, thiosen copper, copper nitrohumate, prochloraz Any one of copper salt, copper citrate, copper succinate, copper mixed amino acid, basic copper sulfate, copper imidazoquinoline, copper acetate, etc.
根据本发明的实施方案，所述杀菌组合物的有效活性成分包括化合物I和化合物II，其中所述化合物I和化合物II的质量比为80～1:1～80，优选50～1:1～50，还优选30～1:1～30，例如为60:1、45:1、30:1、20:1、10:1、5:1、3:1、2:1、1:1、1:2、1:3、1:5、1:10、1:20、1:30、或1:60。According to an embodiment of the present invention, the effective active ingredients of the bactericidal composition include Compound I and Compound II, wherein the mass ratio of the Compound I and Compound II is 80-1:1-80, preferably 50-1:1- 50, preferably 30 to 1:1 to 30, for example, 60:1, 45:1, 30:1, 20:1, 10:1, 5:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:5, 1:10, 1:20, 1:30, or 1:60.
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在杀菌组合物中的含量之和为1～90％，优选20～60％，例如5％、8％、10％、13％、15％、18％、20％、24％、30％、35％、38％、42％、45％、50％、55％、60％、65％、68％、75％、80％、85％、或90％。According to an embodiment of the present invention, based on 100% of the total weight of the bactericidal composition, the sum of the content of the compound I and the compound II in the bactericidal composition is 1-90%, preferably 20-60%, for example 5%, 8%, 10%, 13%, 15%, 18%, 20%, 24%, 30%, 35%, 38%, 42%, 45%, 50%, 55%, 60%, 65% , 68%, 75%, 80%, 85%, or 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。According to an embodiment of the present invention, the bactericidal composition may be prepared as a liquid preparation or a solid preparation.
根据本发明的实施方案，根据不同的制剂类型，制剂中活性成分含量范围有所不同，通常，液体制剂含有按重量计1％～60％的活性物质，优选为5％～50％；固体制剂含有按重量计5％～80％的活性物质，优选为10％～70％。According to an embodiment of the present invention, the content of active ingredients in the preparation varies according to different preparation types. Generally, liquid preparations contain 1% to 60% by weight of active substances, preferably 5% to 50%; solid preparations Contains 5% to 80% by weight of active substance, preferably 10% to 70%.
根据本发明的实施方案，所述组合物中至少含有一种表面活性剂，以利于施用时活性成分在水中的分散。所述表面活性剂含量为制剂总重量的2％～30％。According to an embodiment of the present invention, at least one surfactant is included in the composition to facilitate dispersion of the active ingredient in water upon application. The content of the surfactant is 2% to 30% of the total weight of the preparation.
根据本发明的实施方案，所述组合物所选用的表面活性剂选自乳化剂、分散剂、润湿剂、增稠剂或消泡剂中的一种或几种。According to an embodiment of the present invention, the surfactant selected for the composition is selected from one or more of emulsifiers, dispersants, wetting agents, thickeners or defoaming agents.
根据不同剂型，所述制剂中还可以含有稳定剂、崩解剂、抗冻剂、粘结剂、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。According to different dosage forms, the preparation may also contain stabilizers, disintegrants, antifreeze agents, binders, anti-caking agents, suspending agents, film-forming agents, preservatives, colorants, polymer capsule wall materials, At least one of pH adjusters or fillers.
根据本发明的实施方案，所述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，即将活性成分与液体溶剂或固体载体混合后，再加入表面活性剂如分散剂、稳定剂、润湿剂、粘结剂、消泡剂等中的一种或多种。According to embodiments of the present invention, the composition may be diluted or used directly by the user prior to use. Its preparation can be prepared by processing methods known to those skilled in the art, namely after mixing active ingredients with liquid solvents or solid carriers, and then adding surfactants such as dispersants, stabilizers, wetting agents, binders, defoaming agents, etc. one or more of.
根据本发明的实施方案，所述组合物可以制作成各种剂型，优选地，所述制剂的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、种衣剂、乳油、颗粒剂。According to the embodiment of the present invention, the composition can be made into various dosage forms, preferably, the dosage forms of the preparation include water dispersible granules, dispersible liquids, wettable powders, suspensions, water emulsions, microemulsions, Suspension, microcapsule suspension, microcapsule suspension-suspension, seed coating, emulsifiable concentrate, granule.
根据本发明的实施方案，所述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％、余量为填料和/或填充剂，例如制成如下的可 湿性粉剂：化合物I 5％、化合物II 25％、十二烷基苯磺酸钠2％、木质素磺酸钠9％、滑石粉3％、白炭黑4％、凹凸棒土补充至100％。According to an embodiment of the present invention, the composition comprises the following components and contents when made into a wettable powder: Compound I 1%-80%, Compound II 1%-80%, dispersant 1%-12%, wetting agent 1% to 8% of fillers and/or fillers, for example, the following wettable powders are prepared: compound I 5%, compound II 25%, sodium dodecylbenzenesulfonate 2%, lignosulfonic acid Sodium 9%, talc 3%, silica 4%, and attapulgite are supplemented to 100%.
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，例如制成如下的水分散粒剂：化合物I 10％、化合物II 30％、烷基萘磺酸钠2％、木质素磺酸钠9％、十二烷基硫酸钠3％、硫酸铵4％、高岭土补充至100％。According to an embodiment of the present invention, 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%, Wet agent 1%～8%, disintegrant 1%～10%, the balance is filler, for example, the following water dispersible granules are prepared: compound I 10%, compound II 30%, sodium alkylnaphthalene sulfonate 2% , 9% sodium lignosulfonate, 3% sodium lauryl sulfate, 4% ammonium sulfate, and kaolin to be supplemented to 100%.
或，化合物I 30％、化合物II 10％、烷基萘磺酸钠2％、木质素磺酸钠7％、十二烷基硫酸钠3％、硫酸铵4％、高岭土补充至100％。Or, compound I 30%, compound II 10%, sodium alkylnaphthalene sulfonate 2%, sodium lignosulfonate 7%, sodium lauryl sulfate 3%, ammonium sulfate 4%, kaolin supplemented to 100%.
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％、崩解剂0.1％～8％、抗冻剂0.1％～8％、去离子水补至100％，例如制成如下的悬浮剂：化合物I 5％、化合物II 20％、甲基萘磺酸钠甲醛缩合物5％、黄原胶0.2％、萘磺酸甲醛缩合物钠盐3％、硫酸铵4％、丙二醇4％、水补充至100％。According to an embodiment of the present invention, 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%, disintegrant 0.1% to 8%, antifreeze 0.1% to 8%, deionized water to make up to 100%, for example, the following suspending agent is prepared: compound I 5%, compound II 20%, methylnaphthalene sulfonate sodium formaldehyde condensate 5%, xanthan gum 0.2%, naphthalenesulfonic acid formaldehyde condensate sodium salt 3%, ammonium sulfate 4%, propylene glycol 4%, water added to 100%.
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％、任选地有机溶剂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％、去离子水补至100％，例如制成如下的水乳剂：化合物I 10％、化合物II 5％、2,2,2-三氟乙醇35％、碳酸丙烯酯10％、150#溶剂油15％、斯盘-80 10％、乙二醇3％、有机硅0.5％、聚乙烯醇0.3％、去离子水补充至100％。According to an embodiment of the present invention, when the composition is made into an aqueous emulsion, it includes the following components and contents: Compound I 1%-50%, Compound II 1%-50%, optionally organic solvent 1%-60%, 1% to 12% of emulsifier, 0.1% to 8% of antifreeze, 0.01% to 2% of defoamer, 0.1% to 2% of thickener, and deionized water to make up to 100%, for example, the following water emulsion is made : Compound I 10%, Compound II 5%, 2,2,2-trifluoroethanol 35%, propylene carbonate 10%, 150# solvent oil 15%, Span-80 10%, ethylene glycol 3%, organic Silicon 0.5%, polyvinyl alcohol 0.3%, deionized water supplemented to 100%.
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。According to an embodiment of the present invention, 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 to 30%, pH adjuster 0.1% to 5%, thickener 0.1% to 8%, and the balance is deionized water.
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。According to an embodiment of the present invention, when the composition is made into a microcapsule suspension, it includes the following components and contents: 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.
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。According to an embodiment of the present invention, 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.
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％，乳化剂1～30％，抗冻剂1％～10％，稳定剂0.1％～5％，余量为有机溶剂。例如如下的乳油：化合物I 10％、化合物II 40％、三苯乙烯基苯酚聚氧乙烯醚磷酸酯三乙醇胺盐4％、脂肪醇聚醚2％、丙二醇4％、三乙醇胺0.1％、溶剂油补充至100％。According to an embodiment of the present invention, 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%, emulsifier 1-30%, antifreeze 1% ～10%, stabilizer 0.1%～5%, and the balance is organic solvent. For example, the following emulsifiable concentrates: compound I 10%, compound II 40%, tristyryl phenol polyoxyethylene ether phosphate triethanolamine salt 4%, fatty polyether 2%, propylene glycol 4%, triethanolamine 0.1%, mineral spirits Replenish to 100%.
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。According to an embodiment of the present invention, 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.
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。According to an embodiment of the present invention, 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.
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II0.5％～10％、分散剂1％～12％、润湿剂1％～10％、粘结剂0.1％～8％及填料补足至100％。例如如下的颗粒剂：化合物I 0.5％、化合物II 2.5％、木质素磺酸钠3.2％、十二烷基硫酸钠3.5％、聚乙烯醇3.2％、白炭黑10％、硅藻土补足至100％。According to an embodiment of the present invention, the composition includes the following components and contents when made into granules: compound I 0.5%-10%, compound II 0.5%-10%, dispersant 1%-12%, wetting agent 1% to 10% of agent, 0.1% to 8% of binder and filler to 100%. For example, the following granules: compound I 0.5%, compound II 2.5%, sodium lignosulfonate 3.2%, sodium lauryl sulfate 3.5%, polyvinyl alcohol 3.2%, silica 10%, diatomaceous earth supplemented to 100%.
根据本发明的实施方案，所述乳化剂可以选用如下中的至少一种：木质素磺酸钠、农乳、苯基酚聚氧乙基醚磷酸酯、萘磺酸盐甲醛缩合物、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、壬基酚聚氧乙烯醚磷酸酯、蓖麻油聚氧乙烯醚磷酸酯、Tween-80、三苯乙烯基苯酚聚氧乙烯醚磷酸酯三乙醇胺盐；According to an embodiment of the present invention, the emulsifier can be selected from at least one of the following: sodium lignosulfonate, agricultural milk, phenylphenol polyoxyethyl ether phosphate, naphthalene sulfonate formaldehyde condensate, benzyl Dimethylphenol polyoxyethyl ether, sorbitan fatty acid ester polyoxyethylene ether, sorbitan oleate (Span 80), fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether phosphate , Castor oil polyoxyethylene ether phosphate, Tween-80, tristyryl phenol polyoxyethylene ether phosphate triethanolamine salt;
根据本发明的实施方案，所述分散剂可以选用如下中的至少一种：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、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、脂肪醇聚醚，烷基萘磺酸钠；According to an embodiment of the present invention, the dispersing agent can be selected from at least one of the following: glycerol fatty acid polyoxyethylene ether, polyoxyethylene alkyl aryl ether, sodium lignosulfonate, fatty alcohol polyoxyethylene ether sulfate , Naphthalenesulfonate formaldehyde condensate, Naphthalenesulfonate formaldehyde condensate sodium salt, Nonylphenol polyoxyethylene ether, Polyoxyethylene lanolin alcohol, Alkylphenol polyoxyethylene ether formaldehyde condensate, Fatty alcohol polyoxyethylene ether , fatty alcohol polyoxyethylene ether phosphate, polyoxyethylene sorbitan fatty acid ester, phosphate ester, fatty alcohol polyether, sodium alkyl naphthalene sulfonate;
根据本发明的实施方案，所述润湿剂可以选用如下中的至少一种：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、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、异辛醇琥珀酸酯磺酸钠、脂肪醇聚氧乙烯醚、甲基萘磺酸钠甲醛缩合物；According to an embodiment of the present invention, the wetting agent can be selected from at least one of the following: trisiloxane polyoxyethylene ether, sodium N-lauroyl glutamate, sodium lauryl sulfate, lauroyl sarcosine Sodium, castor oil polyoxyethylene ether, tristyryl phenol polyoxyethylene ether, sodium dodecylbenzene sulfonate, sodium isooctyl succinate sulfonate, fatty alcohol polyoxyethylene ether, methylnaphthalene sulfonate Sodium formaldehyde condensate;
根据本发明的实施方案，所述粘结剂可以选用如下中的至少一种：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；According to an embodiment of the present invention, the binder can be selected from at least one of the following: xanthan gum, starch, urea-formaldehyde resin, gelatin, gum arabic, carboxymethyl cellulose, carboxyethyl cellulose, polyvinyl alcohol ;
根据本发明的实施方案，所述崩解剂选自如下中的至少一种：碳酸氢钠、硫酸铵、硫酸钠、硫酸钙、氯化镁；According to an embodiment of the present invention, the disintegrant is selected from at least one of the following: sodium bicarbonate, ammonium sulfate, sodium sulfate, calcium sulfate, magnesium chloride;
根据本发明的实施方案，所述增稠剂可以选自如下中的至少一种：硅酸镁铝、聚乙酸乙烯酯、黄原胶、明胶、阿拉伯胶、聚乙烯醇；According to an embodiment of the present invention, the thickening agent may be selected from at least one of the following: magnesium aluminum silicate, polyvinyl acetate, xanthan gum, gelatin, gum arabic, polyvinyl alcohol;
根据本发明的实施方案，所述消泡剂可以选用如下中的至少一种：硅油，正-辛醇、硅酮、磷酸丁酯、磷酸异丁酯，有机硅；According to an embodiment of the present invention, the defoamer can be selected from at least one of the following: silicone oil, n-octanol, silicone, butyl phosphate, isobutyl phosphate, silicone;
根据本发明的实施方案，所述抗冻剂可以如下中的至少一种：丙二醇、乙二醇、丙三醇；According to an embodiment of the present invention, the antifreeze agent may be at least one of the following: propylene glycol, ethylene glycol, and glycerol;
根据本发明的实施方案，所述稳定剂可以选用如下中的至少一种：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；According to an embodiment of the present invention, the stabilizer can be selected from at least one of the following: triethanolamine, epichlorohydrin, butyl glycidyl ether, triphenyl phosphite, N-soybean oil-based trimethylenediamine , dialkyl succinate acetate sulfonate;
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，固体填料可以选用如下中的至少一种：高岭土、凹凸棒土、硅藻土、白炭黑、膨润土、蒙脱石、碳酸钙。液体填料可以选用水、 大豆油、蓖麻油、矿物油中的至少一种。According to an embodiment of the present invention, the fillers include solid fillers and liquid fillers, wherein the solid fillers can be selected from at least one of the following: kaolin, attapulgite, diatomite, silica, bentonite, montmorillonite, calcium carbonate. The liquid filler can be selected from at least one of water, soybean oil, castor oil, and mineral oil.
根据本发明的实施方案，所述有机溶剂可以选用如下中的至少一种：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(例如150#溶剂油)。According to an embodiment of the present invention, the organic solvent can be selected from at least one of the following: ethyl acetate, acetone, isopropanol, 2-2-2 trifluoroethanol, propylene carbonate, benzene, toluene, xylene, Dimethylformamide, dimethyl sulfoxide, dichloromethane, cyclohexane, cyclohexanone, N-methylpyrrolidone, solvent oil (for example, 150# solvent oil).
本发明还提供如上所述杀菌组合物的制备方法，包括：将活性成分化合物I、化合物II与助剂进行混合。The present invention also provides the above-mentioned preparation method of the bactericidal composition, comprising: mixing the active ingredients compound I, compound II and an auxiliary agent.
本发明还提供如上所述含化合物I与化合物II的杀菌组合物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中的用途。The present invention also provides the above-mentioned bactericidal composition containing compound I and compound II for controlling pathogenic bacteria and the agricultural diseases caused by them, and is especially suitable for use in bacteria and bacterial diseases of plants caused by bacteria.
优选地，在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、烟草病毒病等真菌和病毒病害方面有一定防效。Preferably, in the control of 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 stripe, rice bacterial base rot, tomato bacterial wilt and other Solanaceae bacterial wilt, mulberry bacterial wilt, peanut bacterial wilt, ginger Ginger blast, tomato/chili bacterial spot, pepper bacterial leaf spot, potato blackleg, corn bacterial wilt, corn bacterial stalk rot, wheat blackgrass, soybean bacterial spot, soybean bacterial Sexual blight, cassava bacterial wilt, mango corner spot, citrus canker, peach bacterial perforation, sunflower stem rot, peach gum disease, pear fire blight, pear water rust, fruit tree bacterial root cancer, Potato ring rot, bean wilt, wheat white leaf spot, potato scab, tomato canker, American holly leaf blight and other pathogenic bacteria, as well as cucumber downy mildew, cucumber target spot, rice blast, rice sheath blight , Tobacco virus disease and other fungal and viral diseases have certain control effect.
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。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.
本发明的含化合物I和化合物II的增效杀菌组合物，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，例如采用喷施、植株根部灌施、涂抹等方式施用于植物或作物上。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。The synergistic bactericidal composition containing compound I and compound II 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 the desired concentration. The method is applied to plants or crops, for example, spraying, plant root irrigation, smearing, etc. are applied to plants or crops. In specific applications, it can also be mixed with other medicaments such as insecticides, growth regulators, soil conditioners, herbicides, nematicides and the like.
本发明含化合物I与化合物II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，两者混用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。The synergistic bactericidal composition containing compound I and compound II of the present invention has the following advantages: 1. It has a synergistic effect, which can improve the control effect; 2. The bactericidal spectrum is expanded, and field diseases are often mixed, and the mixed use of the two is effective against bacterial diseases. The effect is stronger; 3. The two active ingredients have different mechanisms of action, and the mixed use can delay the generation of pathogenic bacteria resistance;
具体实施方式Detailed ways
以下结合实施例进一步说明本发明，下述实施例仅用于说明本发明而对本发明没有限制。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。The present invention is further described below with reference to the examples, which are only used to illustrate the present invention and do not limit the present invention. 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.
如下实施例中的配比均为重量百分比。The proportions in the following examples are all weight percentages.
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。The experimental methods used in the following examples are conventional methods unless otherwise specified; the reagents, materials, etc. used in the following examples can be obtained from commercial sources unless otherwise specified.
本发明采用室内生物测定和田间试验相结合的方法。The present invention adopts the method of combining indoor biological assay and field test.
1、制剂实施例：1. Formulation example:
以下所使用到的药剂均为山东中农联合生物科技股份有限公司研发中心提供。The chemicals used below are provided by the R&D center of Shandong Zhongnong United Biotechnology Co., Ltd.
制剂实施例1：可湿性粉剂Formulation Example 1: Wettable Powder
Figure PCTCN2021126495-appb-000001
Figure PCTCN2021126495-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。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.
制剂实施例2：水分散粒剂Formulation Example 2: Water Dispersible Granules
Figure PCTCN2021126495-appb-000002
Figure PCTCN2021126495-appb-000002
将活性成分及各种助剂及填料等按配方比例混合均匀，经气流粉碎后得到可湿性粉剂，再加入一定量的水混合挤压造粒，经干燥筛分后得到成品。The active ingredients, various additives and fillers are mixed uniformly according to the formula ratio, and the wettable 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.
制剂实施例3：悬浮剂Formulation Example 3: Suspension Agent
Figure PCTCN2021126495-appb-000003
Figure PCTCN2021126495-appb-000003
将活性成分及各种助剂按配方比例混合均匀，经高速剪切后得到成品。The active ingredients and various additives are mixed uniformly according to the formula ratio, and the finished product is obtained after high-speed shearing.
制剂实施例4：乳油Formulation Example 4: Emulsifiable Concentrate
Figure PCTCN2021126495-appb-000004
Figure PCTCN2021126495-appb-000004
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。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.
制剂实施例5：水乳剂Formulation Example 5: Aqueous Emulsion
Figure PCTCN2021126495-appb-000005
Figure PCTCN2021126495-appb-000005
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，进行计量分装即得成品。According to the requirements of the formula, the above raw materials are added into the batching kettle, and the water emulsion is uniformly mixed by a high-speed shearing machine.
制剂实施例6：颗粒剂Formulation Example 6: Granules
Figure PCTCN2021126495-appb-000006
Figure PCTCN2021126495-appb-000006
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。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.
制剂实施例7：水分散粒剂Formulation Example 7: Water Dispersible Granules
Figure PCTCN2021126495-appb-000007
Figure PCTCN2021126495-appb-000007
Figure PCTCN2021126495-appb-000008
Figure PCTCN2021126495-appb-000008
将活性成分及各种助剂及填料等按配方比例混合均匀，经气流粉碎后得到可湿性粉剂，再加入一定量的水混合挤压造粒，经干燥筛分后得到成品。The active ingredients, various additives and fillers are mixed uniformly according to the formula ratio, and the wettable 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.
2、室内毒力测定实施例2. Example of Indoor Toxicity Assay
(1)供试药剂：化合物I以及化合物II原药。化合物I原药用二甲基亚砜溶解配成10000μg/mL的母液，化合物II原药直接用适当溶剂溶解配成10000μg/mL的母液，以0.2％的体积分数加入乳化剂Tween-80，于冰箱中4℃下贮藏备用，使用时以无菌水稀释至适当浓度。(1) Test drugs: Compound I and Compound II original drugs. The original drug of compound I was dissolved in dimethyl sulfoxide to prepare a mother solution of 10,000 μg/mL, and the original drug of compound II was directly dissolved in an appropriate solvent to prepare a mother solution of 10,000 μg/mL. The emulsifier Tween-80 was added at a volume fraction of 0.2%, Store in a refrigerator at 4°C for later use, and dilute with sterile water to an appropriate concentration when using.
(2)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、木薯细菌性枯萎病菌、果蔬细菌性根癌病菌和马铃薯疮痂病菌等细菌性病害。(2) 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 leaf spot, citrus canker, peach tree bacterial perforation, cassava bacterial fusarium wilt, fruit and vegetable bacterial root cancer and potato scab.
(3)测定方法：(3) Measurement method:
细菌毒力测定方法参照中华人民共和国农业行业标准NY/T 1156.16-2008The method for determination of bacterial virulence refers to the Agricultural Industry Standard of the People's Republic of China NY/T 1156.16-2008
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、木薯细菌性枯萎病菌、果蔬细菌性根癌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。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 leaf spot, citrus canker, peach tree bacterial perforation, cassava bacterial fusarium wilt, fruit and vegetable bacterial root cancer and potato scab were used as test materials. Its mixed preparations were tested for toxicity.
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值剂量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，将根据上述行业标准NY/T 1156.16-2008测得的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： First, the test agents (including compound I, compound II) are prepared with a suitable solvent (such as acetone, methanol, N,N dimethylformamide and dimethyl sulfoxide, etc.), and according to their ability to dissolve the sample And select) is formulated into 7 concentration gradients (Compound I: 0.5, 1.0, 2.0, 4.0, 8.0, 16.0, 32.0 μg/mL, etc. 7 concentration gradients; Compound II: 0.5, 1.0, 2.0, 4.0, 8.0, 16.0, 7 concentration gradients such as 32.0 μg/mL), the compound I and compound II for compounding are respectively set according to their EC 50 value doses and a series of ratios by mass ratio, and are formulated into final mass concentrations according to different ratios (referring to compound I, The total mass of compound II) is 7 series concentrations of 0.5, 1.0, 2.0, 4.0, 8.0, 16.0, 32.0 μg/mL. Under sterile operating conditions, NB (nutrient broth, containing 10 g peptone and 3 g beef per liter) Dip powder, 5g sodium chloride) culture solution is divided into test tubes in equal amounts, quantitatively draw the medicinal liquid from low concentration to high concentration in turn, add into the above test tubes respectively, shake well, and then add in equal amounts to be in the logarithmic growth phase. The bacterial suspension was repeated 4 times per treatment. After mixing, the cells were incubated in the dark in a shaking incubator at 25°C, and the OD value was measured in the logarithmic growth phase. Take the average value of 4 effective repetitions as the measurement result, calculate the relative inhibition rate, and convert the inhibition rate measured according to the above-mentioned industry standard NY/T 1156.16-2008 into a probability value (y), and the concentration of the medicinal solution (μg/mL) Converted to logarithmic value (x), the virulence regression equation (y=a+bx) was obtained by the least squares method, and the EC50 value of each agent was calculated therefrom. At the same time, the synergistic ratio (SR) of the two drugs in different proportions was calculated according to the Wadley method. SR<0.5 was the antagonistic effect, 0.5≤SR≤1.5 was the additive effect, and SR>1.5 was the synergistic effect. Calculated as follows:
SR＝EC 50(理论值)/EC 50(实测值) SR=EC 50 (theoretical value)/EC 50 (measured value)
EC 50(理论值)＝(a+b)/[(a/A的EC 50)+(b/B的EC 50) EC50 (theoretical)=(a+b)/[( EC50 of a/A)+( EC50 of b/B)
其中：a、b分别为化合物I与化合物II在组合中所占的比例；Where: a and b are the proportions of compound I and compound II in the combination, respectively;
A为化合物I；A is compound I;
B选自化合物II，为喹啉铜、噻菌铜、氢氧化铜、王铜、波尔多液、壬菌铜、噻森铜、咪唑喹啉铜等铜制剂中的一种。B is selected from compound II, and is one of copper preparations such as copper quinoline, copper thiophanate, copper hydroxide, copper king, Bordeaux mixture, copper quinoline, copper thiosen, and copper imidazoquinoline.
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。After mixing different varieties of pesticides, there are usually three types of action, namely additive action, synergistic action and antagonistic action, but the specific action cannot be predicted.
本发明所述杀菌组合物以化合物I与化合物II为有效成分，采用生物测定实例加以说明。The bactericidal composition of the present invention uses compound I and compound II as active ingredients, and is described by using a biological assay example.
实施例1：为验证化合物I和喹啉铜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和喹啉铜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：Embodiment 1: In order to verify the antibacterial effect of compound I and quinoline copper in different proportions on cucumber bacterial angular spot bacterium, the indoor virulence assay of compound I and quinoline copper in different proportions to cucumber bacterial angular spot bacterium 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:
表1 化合物I和喹啉铜单剂及其混剂对黄瓜细菌性角斑病菌毒力测定结果Table 1 The results of the determination of the virulence of compound I and copper quinoline and their mixtures against Cucumber bacterial keratosis
供试药剂test drug 配比Proportion EC 50(μg/mL)(实测值) EC 50 (μg/mL) (measured value) EC 50(μg/mL)(理论值) EC 50 (μg/mL) (theoretical value) SRSR
化合物ICompound I -- 1.61051.6105    ——
喹啉铜copper quinoline -- 49.810649.8106    ——
化合物I:喹啉铜Compound I: Copper Quinoline 60:160:1 0.99050.9905 1.63651.6365 1.65221.6522
化合物I:喹啉铜Compound I: Copper Quinoline 45:145:1 1.03071.0307 1.64511.6451 1.59611.5961
化合物I:喹啉铜Compound I: Copper Quinoline 30:130:1 1.06781.0678 1.66241.6624 1.55681.5568
化合物I:喹啉铜Compound I: Copper Quinoline 20:120:1 1.06551.0655 1.68831.6883 1.58451.5845
化合物I:喹啉铜Compound I: Copper Quinoline 10:110:1 1.06851.0685 1.76581.7658 1.65261.6526
化合物I:喹啉铜Compound I: Copper Quinoline 5:15:1 1.09561.0956 1.92021.9202 1.75261.7526
化合物I:喹啉铜Compound I: Copper Quinoline 3:13:1 1.02551.0255 2.12442.1244 2.07162.0716
化合物I:喹啉铜Compound I: Copper Quinoline 2:12:1 1.05261.0526 2.37732.3773 2.25852.2585
化合物I:喹啉铜Compound I: Copper Quinoline 1:11:1 1.07081.0708 3.12013.1201 2.91382.9138
化合物I:喹啉铜Compound I: Copper Quinoline 1:21:2 1.95151.9515 4.53804.5380 2.32542.3254
化合物I:喹啉铜Compound I: Copper Quinoline 1:31:3 2.39152.3915 5.87245.8724 2.45552.4555
化合物I:喹啉铜Compound I: Copper Quinoline 1:51:5 2.95152.9515 8.31838.3183 2.81832.8183
化合物I:喹啉铜Compound I: Copper Quinoline 1:101:10 5.78155.7815 13.387113.3871 2.31552.3155
化合物I:喹啉铜Compound I: Copper Quinoline 1:201:20 7.65137.6513 20.539020.5390 2.68442.6844
化合物I:喹啉铜Compound I: Copper Quinoline 1:301:30 9.95159.9515 25.343225.3432 2.54672.5467
化合物I:喹啉铜Compound I: Copper Quinoline 1:601:60 13.561513.5615 33.415733.4157 2.46402.4640
由表1结果可知，化合物I和喹啉铜不同配比用量混配对抑制黄瓜细菌性角斑病菌均具有明显增效作用。It can be seen from the results in Table 1 that compound I and copper quinoline in different proportions and dosages have obvious synergistic effects on inhibiting the bacterial keratosis of cucumber.
实施例2：为验证化合物I和喹啉铜不同配比用量对西瓜果斑病菌抑菌效果，进行了化合物I和喹啉铜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：Embodiment 2: In order to verify the antibacterial effect of compound I and quinoline copper on the watermelon fruit spot bacteria in different proportions, the indoor toxicity measurement of watermelon fruit spot bacteria in different proportions of compound I and quinoline copper was carried out. 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:
表2 化合物I和喹啉铜单剂及其混剂对西瓜果斑病菌毒力测定结果Table 2 Compound I and single agent of copper quinoline and its mixture to the virulence test results of watermelon fruit spot
供试药剂test drug 配比Proportion EC 50(μg/mL)(实测值) EC 50 (μg/mL) (measured value) EC 50(μg/mL)(理论值) EC 50 (μg/mL) (theoretical value) SRSR
化合物ICompound I -- 2.65862.6586    ——
喹啉铜copper quinoline -- 40.351640.3516    ——
化合物I:喹啉铜Compound I: Copper Quinoline 60:160:1 1.41051.4105 2.69992.6999 1.91421.9142
化合物I:喹啉铜Compound I: Copper Quinoline 45:145:1 1.42261.4226 2.71372.7137 1.90761.9076
化合物I:喹啉铜Compound I: Copper Quinoline 30:130:1 1.43151.4315 2.74122.7412 1.91491.9149
化合物I:喹啉铜Compound I: Copper Quinoline 20:120:1 1.43551.4355 2.78242.7824 1.93831.9383
化合物I:喹啉铜Compound I: Copper Quinoline 10:110:1 1.72451.7245 2.90532.9053 1.68471.6847
化合物I:喹啉铜Compound I: Copper Quinoline 5:15:1 1.76591.7659 3.14883.1488 1.78311.7831
化合物I:喹啉铜Compound I: Copper Quinoline 3:13:1 1.78161.7816 3.46863.4686 1.94691.9469
化合物I:喹啉铜Compound I: Copper Quinoline 2:12:1 1.99931.9993 3.86073.8607 1.93101.9310
化合物I:喹啉铜Compound I: Copper Quinoline 1:11:1 2.65262.6526 4.98854.9885 1.88061.8806
化合物I:喹啉铜Compound I: Copper Quinoline 1:21:2 2.98252.9825 7.04727.0472 2.36282.3628
化合物I:喹啉铜Compound I: Copper Quinoline 1:31:3 3.26153.2615 8.87938.8793 2.72252.7225
化合物I:喹啉铜Compound I: Copper Quinoline 1:51:5 4.15194.1519 11.998811.9988 2.89002.8900
化合物I:喹啉铜Compound I: Copper Quinoline 1:101:10 6.45056.4505 17.629417.6294 2.73302.7330
化合物I:喹啉铜Compound I: Copper Quinoline 1:201:20 9.12159.1215 24.088624.0886 2.64092.6409
化合物I:喹啉铜Compound I: Copper Quinoline 1:301:30 11.612511.6125 27.688427.6884 2.38442.3844
化合物I:喹啉铜Compound I: Copper Quinoline 1:601:60 13.522513.5225 32.741732.7417 2.42132.4213
由表2结果可知，化合物I和喹啉铜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。It can be seen from the results in Table 2 that compound I and copper quinoline in different proportions and dosages have obvious synergistic effects on the inhibition of watermelon fruit spot.
实施例3：为验证化合物I和喹啉铜不同配比用量对柑橘溃疡病菌抑菌效果，进行了化合物I和喹啉铜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：Embodiment 3: in order to verify the antibacterial effect of compound I and quinoline copper in different proportions on citrus canker bacteria, carried out the indoor toxicity measurement of compound I and quinoline copper different proportions to citrus canker bacteria, according to the weight percentage in the table Dubbed into corresponding concentrations, the indoor antibacterial test was carried out. The test results are as follows:
表3 化合物I和喹啉铜单剂及其混剂对柑橘溃疡病菌毒力测定结果Table 3 The virulence test results of compound I and copper quinoline and their mixtures against citrus canker
供试药剂test drug 配比Proportion EC 50(μg/mL)(实测值) EC 50 (μg/mL) (measured value) EC 50(μg/mL)(理论值) EC 50 (μg/mL) (theoretical value) SRSR
化合物ICompound I -- 2.78152.7815    ——
喹啉铜copper quinoline -- 51.250051.2500    ——
化合物I:喹啉铜Compound I: Copper Quinoline 60:160:1 1.52021.5202 2.82532.8253 1.85851.8585
化合物I:喹啉铜Compound I: Copper Quinoline 45:145:1 1.51161.5116 2.83992.8399 1.87871.8787
化合物I:喹啉铜Compound I: Copper Quinoline 30:130:1 1.51011.5101 2.86902.8690 1.89991.8999
化合物I:喹啉铜Compound I: Copper Quinoline 20:120:1 1.81241.8124 2.91272.9127 1.60711.6071
化合物I:喹啉铜Compound I: Copper Quinoline 10:110:1 1.83161.8316 3.04313.0431 1.66151.6615
化合物I:喹啉铜Compound I: Copper Quinoline 5:15:1 1.94781.9478 3.30203.3020 1.69521.6952
化合物I:喹啉铜Compound I: Copper Quinoline 3:13:1 1.97821.9782 3.64283.6428 1.84151.8415
化合物I:喹啉铜Compound I: Copper Quinoline 2:12:1 1.95121.9512 4.06204.0620 2.08182.0818
化合物I:喹啉铜Compound I: Copper Quinoline 1:11:1 2.15162.1516 5.27665.2766 2.45242.4524
化合物I:喹啉铜Compound I: Copper Quinoline 1:21:2 3.37233.3723 7.52747.5274 2.23212.2321
化合物I:喹啉铜Compound I: Copper Quinoline 1:31:3 3.53153.5315 9.56819.5681 2.70942.7094
化合物I:喹啉铜Compound I: Copper Quinoline 1:51:5 3.45163.4516 13.126813.1268 3.80313.8031
化合物I:喹啉铜Compound I: Copper Quinoline 1:101:10 6.15126.1512 19.832719.8327 3.22423.2242
化合物I:喹啉铜Compound I: Copper Quinoline 1:201:20 10.132910.1329 28.008928.0089 2.76422.7642
化合物I:喹啉铜Compound I: Copper Quinoline 1:301:30 15.751615.7516 32.808332.8083 2.08292.0829
化合物I:喹啉铜Compound I: Copper Quinoline 1:601:60 19.821619.8216 39.862839.8628 2.01112.0111
由表3结果可知，化合物I和喹啉铜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。It can be seen from the results in Table 3 that compound I and copper quinoline in different proportions and dosages have obvious synergistic effects on the inhibition of citrus canker.
实施例4：为验证化合物I和喹啉铜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和喹啉铜不同配比对水稻白叶枯病菌的室内毒力测定试验，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：Embodiment 4: In order to verify the bacteriostatic effect of compound I and different ratios of copper quinoline on the bacterial blight of rice, the indoor virulence assay test of different ratios of compound I and copper quinoline to rice bacterial blight was carried out, According to the weight percentage in the table, the corresponding concentration is made, and the indoor antibacterial test is carried out. The test results are as follows:
表4 化合物I和喹啉铜单剂及其混剂对水稻白叶枯病菌毒力测定结果Table 4 The results of the determination of the virulence of compound I and copper quinoline and their mixtures against B. oryzae
供试药剂test drug 配比Proportion EC 50(μg/mL)(实测值) EC 50 (μg/mL) (measured value) EC 50(μg/mL)(理论值) EC 50 (μg/mL) (theoretical value) SRSR
化合物ICompound I -- 2.62132.6213    ——
喹啉铜copper quinoline -- 41.351041.3510    ——
化合物I:喹啉铜Compound I: Copper Quinoline 60:160:1 1.68161.6816 2.66222.6622 1.58311.5831
化合物I:喹啉铜Compound I: Copper Quinoline 45:145:1 1.69151.6915 2.67582.6758 1.58191.5819
化合物I:喹啉铜Compound I: Copper Quinoline 30:130:1 1.61261.6126 2.70302.7030 1.67621.6762
化合物I:喹啉铜Compound I: Copper Quinoline 20:120:1 1.62251.6225 2.74372.7437 1.69101.6910
化合物I:喹啉铜Compound I: Copper Quinoline 10:110:1 1.63101.6310 2.86532.8653 1.75681.7568
化合物I:喹啉铜Compound I: Copper Quinoline 5:15:1 1.63811.6381 3.10623.1062 1.89621.8962
化合物I:喹啉铜Compound I: Copper Quinoline 3:13:1 1.77761.7776 3.42273.4227 1.92551.9255
化合物I:喹啉铜Compound I: Copper Quinoline 2:12:1 2.21272.2127 3.81123.8112 1.72241.7224
化合物I:喹啉铜Compound I: Copper Quinoline 1:11:1 2.21262.2126 4.93014.9301 2.22822.2282
化合物I:喹啉铜Compound I: Copper Quinoline 1:21:2 2.38582.3858 6.97916.9791 2.92532.9253
化合物I:喹啉铜Compound I: Copper Quinoline 1:31:3 3.26243.2624 8.80988.8098 2.70042.7004
化合物I:喹啉铜Compound I: Copper Quinoline 1:51:5 3.15183.1518 11.942511.9425 3.78913.7891
化合物I:喹啉铜Compound I: Copper Quinoline 1:101:10 8.59158.5915 17.647417.6474 2.05412.0541
化合物I:喹啉铜Compound I: Copper Quinoline 1:201:20 11.961811.9618 24.273124.2731 2.02922.0292
化合物I:喹啉铜Compound I: Copper Quinoline 1:301:30 16.512616.5126 28.004028.0040 1.69591.6959
化合物I:喹啉铜Compound I: Copper Quinoline 1:601:60 19.102319.1023 33.288233.2882 1.74261.7426
由表4结果可知，化合物I和喹啉铜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。It can be seen from the results in Table 4 that compound I and quinoline copper in different proportions and dosages have obvious synergistic effects on the inhibition of bacterial blight of rice.
实施例5：为验证化合物I和喹啉铜不同配比用量对番茄青枯病菌抑菌效果，进行了化合物I和喹啉铜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：Embodiment 5: in order to verify the bacteriostatic effect of compound I and different ratios of copper quinoline on tomato bacterial wilt bacteria, the indoor virulence assays of different proportions of compound I and copper quinoline to tomato bacterial wilt bacteria were carried out, 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:
表5 化合物I和喹啉铜单剂及其混剂对番茄青枯病菌毒力测定结果Table 5 The results of the determination of the virulence of compound I and copper quinoline and its mixture to tomato bacterial wilt
供试药剂test drug 配比Proportion EC 50(μg/mL)(实测值) EC 50 (μg/mL) (measured value) EC 50(μg/mL)(理论值) EC 50 (μg/mL) (theoretical value) SRSR
化合物ICompound I -- 2.65292.6529    ——
喹啉铜copper quinoline -- 45.281545.2815    ——
化合物I:喹啉铜Compound I: Copper Quinoline 60:160:1 1.61351.6135 2.69452.6945 1.67001.6700
化合物I:喹啉铜Compound I: Copper Quinoline 45:145:1 1.62151.6215 2.70832.7083 1.67031.6703
化合物I:喹啉铜Compound I: Copper Quinoline 30:130:1 1.62291.6229 2.73602.7360 1.68591.6859
化合物I:喹啉铜Compound I: Copper Quinoline 20:120:1 1.63011.6301 2.77742.7774 1.70381.7038
化合物I:喹啉铜Compound I: Copper Quinoline 10:110:1 1.73251.7325 2.90122.9012 1.67461.6746
化合物I:喹啉铜Compound I: Copper Quinoline 5:15:1 1.75191.7519 3.14663.1466 1.79611.7961
化合物I:喹啉铜Compound I: Copper Quinoline 3:13:1 1.88591.8859 3.46943.4694 1.83971.8397
化合物I:喹啉铜Compound I: Copper Quinoline 2:12:1 1.91681.9168 3.86613.8661 2.01702.0170
化合物I:喹啉铜Compound I: Copper Quinoline 1:11:1 2.78192.7819 5.01225.0122 1.80171.8017
化合物I:喹啉铜Compound I: Copper Quinoline 1:21:2 3.38163.3816 7.12407.1240 2.10672.1067
化合物I:喹啉铜Compound I: Copper Quinoline 1:31:3 4.05264.0526 9.02539.0253 2.22702.2270
化合物I:喹啉铜Compound I: Copper Quinoline 1:51:5 4.23164.2316 12.311112.3111 2.90932.9093
化合物I:喹啉铜Compound I: Copper Quinoline 1:101:10 7.36147.3614 18.401218.4012 2.49972.4997
化合物I:喹啉铜Compound I: Copper Quinoline 1:201:20 11.012611.0126 25.652725.6527 2.32942.3294
化合物I:喹啉铜Compound I: Copper Quinoline 1:301:30 16.012116.0121 29.822929.8229 1.86251.8625
化合物I:喹啉铜Compound I: Copper Quinoline 1:601:60 19.102419.1024 35.840435.8404 1.87621.8762
由表5结果可知，化合物I和喹啉铜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。It can be seen from the results in Table 5 that compound I and copper quinoline in different proportions and dosages have obvious synergistic effects on the inhibition of tomato bacterial wilt.
实施例6：为验证化合物I和喹啉铜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和喹啉铜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：Embodiment 6: In order to verify the bacteriostatic effect of compound I and different ratios of copper quinoline on Chinese cabbage soft rot bacteria, the indoor toxicity measurement of compound I and different ratios of quinoline copper to Chinese cabbage soft rot bacteria was carried out, 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:
表6 化合物I和喹啉铜单剂及其混剂对大白菜软腐病菌毒力测定结果Table 6 The virulence test results of compound I and copper quinoline and their mixtures against Chinese cabbage soft rot bacteria
供试药剂test drug 配比Proportion EC 50(μg/mL)(实测值) EC 50 (μg/mL) (measured value) EC 50(μg/mL)(理论值) EC 50 (μg/mL) (theoretical value) SRSR
化合物ICompound I -- 2.66122.6612    ——
喹啉铜copper quinoline -- 46.152846.1528    ——
化合物I:喹啉铜Compound I: Copper Quinoline 60:160:1 1.74231.7423 2.70302.7030 1.55141.5514
化合物I:喹啉铜Compound I: Copper Quinoline 45:145:1 1.73161.7316 2.71692.7169 1.56901.5690
化合物I:喹啉铜Compound I: Copper Quinoline 30:130:1 1.74151.7415 2.74462.7446 1.57601.5760
化合物I:喹啉铜Compound I: Copper Quinoline 20:120:1 1.75081.7508 2.78622.7862 1.59141.5914
化合物I:喹啉铜Compound I: Copper Quinoline 10:110:1 1.72161.7216 2.91052.9105 1.69061.6906
化合物I:喹啉铜Compound I: Copper Quinoline 5:15:1 1.76121.7612 3.15703.1570 1.79251.7925
化合物I:喹啉铜Compound I: Copper Quinoline 3:13:1 1.79151.7915 3.48143.4814 1.94331.9433
化合物I:喹啉铜Compound I: Copper Quinoline 2:12:1 2.13652.1365 3.87993.8799 1.81601.8160
化合物I:喹啉铜Compound I: Copper Quinoline 1:11:1 2.26172.2617 5.03225.0322 2.22502.2250
化合物I:喹啉铜Compound I: Copper Quinoline 1:21:2 3.25153.2515 7.15817.1581 2.20152.2015
化合物I:喹啉铜Compound I: Copper Quinoline 1:31:3 4.02164.0216 9.07509.0750 2.25662.2566
化合物I:喹啉铜Compound I: Copper Quinoline 1:51:5 4.29024.2902 12.394012.3940 2.88892.8889
化合物I:喹啉铜Compound I: Copper Quinoline 1:101:10 7.58157.5815 18.567218.5672 2.44902.4490
化合物I:喹啉铜Compound I: Copper Quinoline 1:201:20 10.521910.5219 25.954325.9543 2.46672.4667
化合物I:喹啉铜Compound I: Copper Quinoline 1:301:30 16.120516.1205 30.220830.2208 1.87471.8747
化合物I:喹啉铜Compound I: Copper Quinoline 1:601:60 20.521520.5215 36.400536.4005 1.77381.7738
由上表可知，化合物I和喹啉铜不同配比用量混配对大白菜软腐病菌的抑制均具有明显增效作用。It can be seen from the above table that compound I and copper quinoline in different proportions and dosages have obvious synergistic effects on the inhibition of Chinese cabbage soft rot pathogen.
实施例7：为验证化合物I和噻菌铜不同配比用量对西瓜果斑病菌抑菌效果，进行了化合物I和噻菌铜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：Embodiment 7: In order to verify the antibacterial effect of compound I and thiophanate-copper on watermelon fruit spot bacteria in different proportions, the indoor virulence assay of compound I and thiophanate-copper different ratios to watermelon fruit blotch was carried out, 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:
表7 化合物I和噻菌铜单剂及其混剂对西瓜果斑病菌毒力测定结果Table 7 The results of the determination of the virulence of compound I and the single agent of copper thiophanate and its mixture to watermelon fruit spot bacterium
供试药剂test drug 配比Proportion EC 50(μg/mL)(实测值) EC 50 (μg/mL) (measured value) EC 50(μg/mL)(理论值) EC 50 (μg/mL) (theoretical value) SRSR
化合物ICompound I -- 2.65182.6518    ——
噻菌铜copper thiophanate -- 42.1542.15    ——
化合物I:噻菌铜Compound I: copper thiophanate 60:160:1 1.61061.6106 2.69322.6932 1.67221.6722
化合物I:噻菌铜Compound I: copper thiophanate 45:145:1 1.72291.7229 2.70692.7069 1.57121.5712
化合物I:噻菌铜Compound I: copper thiophanate 30:130:1 1.73181.7318 2.73452.7345 1.57901.5790
化合物I:噻菌铜Compound I: copper thiophanate 20:120:1 1.74581.7458 2.77572.7757 1.58991.5899
化合物I:噻菌铜Compound I: copper thiophanate 10:110:1 1.73251.7325 2.89872.8987 1.67321.6732
化合物I:噻菌铜Compound I: copper thiophanate 5:15:1 1.77181.7718 3.14263.1426 1.77371.7737
化合物I:噻菌铜Compound I: copper thiophanate 3:13:1 1.80551.8055 3.46313.4631 1.91811.9181
化合物I:噻菌铜Compound I: copper thiophanate 2:12:1 1.96791.9679 3.85643.8564 1.95961.9596
化合物I:噻菌铜Compound I: copper thiophanate 1:11:1 2.60122.6012 4.98974.9897 1.91821.9182
化合物I:噻菌铜Compound I: copper thiophanate 1:21:2 3.49153.4915 7.06637.0663 2.02392.0239
化合物I:噻菌铜Compound I: copper thiophanate 1:31:3 3.95293.9529 8.92318.9231 2.25732.2573
化合物I:噻菌铜Compound I: copper thiophanate 1:51:5 3.21033.2103 12.103512.1035 3.77023.7702
化合物I:噻菌铜Compound I: copper thiophanate 1:101:10 6.45166.4516 17.905117.9051 2.77532.7753
化合物I:噻菌铜Compound I: copper thiophanate 1:201:20 9.65159.6515 24.659524.6595 2.55502.5550
化合物I:噻菌铜Compound I: copper thiophanate 1:301:30 13.651213.6512 28.470528.4705 2.08562.0856
化合物I:噻菌铜Compound I: copper thiophanate 1:601:60 20.152420.1524 33.877833.8778 1.68111.6811
由上表可知，化合物I和噻菌铜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。It can be seen from the above table that compound I and thiophanate-copper in different proportions have obvious synergistic effects on the inhibition of watermelon fruit spot.
实施例8：为验证化合物I和噻森铜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和噻森铜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：Example 8: In order to verify the antibacterial effect of compound I and thiossen copper on the bacteriostatic effect of different ratios of compound I and thiosin copper on B. oryzae, the indoor virulence assay of compound I and thiosin copper in different ratios to B. oryzae was carried out. , 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:
表8 化合物I和噻森铜单剂及其混剂对水稻细菌性条斑病菌毒力测定结果Table 8 The results of the determination of the virulence of Compound I and Thiossencopper and their mixtures against S. oryzae
供试药剂test drug 配比Proportion EC 50(μg/mL)(实测值) EC 50 (μg/mL) (measured value) EC 50(μg/mL)(理论值) EC 50 (μg/mL) (theoretical value) SRSR
化合物ICompound I -- 2.51532.5153    ——
噻森铜Thiossen copper -- 45.162545.1625    ——
化合物I:噻森铜Compound I: Copper Thiossen 50:150:1 1.55081.5508 2.56282.5628 1.65251.6525
化合物I:噻森铜Compound I: Copper Thiossen 30:130:1 1.65191.6519 2.59432.5943 1.57051.5705
化合物I:噻森铜Compound I: Copper Thiossen 20:120:1 1.65121.6512 2.63372.6337 1.59501.5950
化合物I:噻森铜Compound I: Copper Thiossen 10:110:1 1.62281.6228 2.75152.7515 1.69551.6955
化合物I:噻森铜Compound I: Copper Thiossen 5:15:1 1.80251.8025 2.98512.9851 1.65611.6561
化合物I:噻森铜Compound I: Copper Thiossen 3:13:1 1.88521.8852 3.29263.2926 1.74661.7466
化合物I:噻森铜Compound I: Copper Thiossen 2:12:1 2.02152.0215 3.67073.6707 1.81581.8158
化合物I:噻森铜Compound I: Copper Thiossen 1:11:1 2.56892.5689 4.76524.7652 1.85501.8550
化合物I:噻森铜Compound I: Copper Thiossen 1:21:2 3.42153.4215 6.78966.7896 1.98441.9844
化合物I:噻森铜Compound I: Copper Thiossen 1:31:3 3.95133.9513 8.62088.6208 2.18182.1818
化合物I:噻森铜Compound I: Copper Thiossen 1:51:5 3.52173.5217 11.804611.8046 3.35193.3519
化合物I:噻森铜Compound I: Copper Thiossen 1:101:10 7.98127.9812 17.770917.7709 2.22662.2266
化合物I:噻森铜Compound I: Copper Thiossen 1:201:20 11.121611.1216 24.987724.9877 2.24682.2468
化合物I:噻森铜Compound I: Copper Thiossen 1:301:30 16.521816.5218 29.194729.1947 1.76701.7670
化合物I:噻森铜Compound I: Copper Thiossen 1:501:50 22.161522.1615 33.894233.8942 1.52941.5294
由上表可知，化合物I和噻森铜不同配比用量混配对水稻细菌性条斑病菌的抑制均具有明显增效作用。It can be seen from the above table that the compound I and the different proportions and dosages of thiossen copper have obvious synergistic effects on the inhibition of B. oryzae.
实施例9：为验证化合物I和氢氧化铜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和氢氧化铜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：Embodiment 9: for verifying compound I and copper hydroxide different proportioning dosages to potato scab bacteriostatic effect, carried out compound I and different proportions of copper hydroxide to the indoor virulence measurement of 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:
表9 化合物I和氢氧化铜单剂及其混剂对马铃薯疮痂病菌毒力测定结果Table 9 Compound I and single agent of copper hydroxide and its mixture to potato scab virulence test results
供试药剂test drug 配比Proportion EC 50(μg/mL)(实测值) EC 50 (μg/mL) (measured value) EC 50(μg/mL)(理论值) EC 50 (μg/mL) (theoretical value) SRSR
化合物ICompound I -- 1.52191.5219    ——
氢氧化铜copper hydroxide -- 48.160548.1605    ——
化合物I:氢氧化铜Compound I: Copper Hydroxide 50:150:1 1.02061.0206 1.55141.5514 1.52001.5200
化合物I:氢氧化铜Compound I: Copper Hydroxide 30:130:1 1.04161.0416 1.57101.5710 1.50821.5082
化合物I:氢氧化铜Compound I: Copper Hydroxide 20:120:1 1.05151.0515 1.59551.5955 1.51731.5173
化合物I:氢氧化铜Compound I: Copper Hydroxide 10:110:1 1.05121.0512 1.66881.6688 1.58751.5875
化合物I:氢氧化铜Compound I: Copper Hydroxide 5:15:1 1.07191.0719 1.81481.8148 1.69311.6931
化合物I:氢氧化铜Compound I: Copper Hydroxide 3:13:1 1.22161.2216 2.00802.0080 1.64381.6438
化合物I:氢氧化铜Compound I: Copper Hydroxide 2:12:1 1.42181.4218 2.24732.2473 1.58061.5806
化合物I:氢氧化铜Compound I: Copper Hydroxide 1:11:1 1.93251.9325 2.95062.9506 1.52681.5268
化合物I:氢氧化铜Compound I: Copper Hydroxide 1:21:2 2.68152.6815 4.29434.2943 1.60151.6015
化合物I:氢氧化铜Compound I: Copper Hydroxide 1:31:3 3.12163.1216 5.56055.5605 1.78131.7813
化合物I:氢氧化铜Compound I: Copper Hydroxide 1:51:5 3.02143.0214 7.88557.8855 2.60992.6099
化合物I:氢氧化铜Compound I: Copper Hydroxide 1:101:10 6.98166.9816 12.721012.7210 1.82211.8221
化合物I:氢氧化铜Compound I: Copper Hydroxide 1:201:20 10.521810.5218 19.583119.5831 1.86121.8612
化合物I:氢氧化铜Compound I: Copper Hydroxide 1:301:30 14.521614.5216 24.218924.2189 1.66781.6678
化合物I:氢氧化铜Compound I: Copper Hydroxide 1:501:50 19.522319.5223 30.083730.0837 1.54101.5410
由上表可知，化合物I和氢氧化铜不同配比用量混配对马铃薯疮痂病菌的抑制均具有明显增效作用。It can be seen from the above table that compound I and copper hydroxide in different proportions and dosages have obvious synergistic effects on the inhibition of potato scab bacteria.
实施例10：为验证化合物I和壬菌铜不同配比用量对芒果角斑病菌抑菌效果，进行了化合物I和壬菌铜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：Embodiment 10: in order to verify the antibacterial effect of compound I and different proportioning dosages of nonbacterial copper on mango angular spot bacteria, carried out the indoor virulence measurement of compound I and nonobacterial copper different proportions to mango angular 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:
表10 化合物I和壬菌铜单剂及其混剂对芒果角斑病菌毒力测定结果Table 10 The virulence determination results of compound I and non-bacterial copper single agent and its mixture to Mango angularis
供试药剂test drug 配比Proportion EC 50(μg/mL)(实测值) EC 50 (μg/mL) (measured value) EC 50(μg/mL)(理论值) EC 50 (μg/mL) (theoretical value) SRSR
化合物ICompound I -- 1.75261.7526    ——
壬菌铜Nonbacterial copper -- 56.7956.79    ——
化合物I:壬菌铜Compound I: Nonbacterium 50:150:1 1.10251.1025 1.78651.7865 1.62051.6205
化合物I:壬菌铜Compound I: Nonbacterium 30:130:1 1.10131.1013 1.80921.8092 1.64271.6427
化合物I:壬菌铜Compound I: Nonbacterium 20:120:1 1.15161.1516 1.83741.8374 1.59551.5955
化合物I:壬菌铜Compound I: Nonbacterium 10:110:1 1.20151.2015 1.92191.9219 1.59961.5996
化合物I:壬菌铜Compound I: Nonbacterium 5:15:1 1.30121.3012 2.09022.0902 1.60641.6064
化合物I:壬菌铜Compound I: Nonbacterium 3:13:1 1.31551.3155 2.31302.3130 1.75831.7583
化合物I:壬菌铜Compound I: Nonbacterium 2:12:1 1.50151.5015 2.58902.5890 1.72421.7242
化合物I:壬菌铜Compound I: Nonbacterium 1:11:1 2.05162.0516 3.40033.4003 1.65741.6574
化合物I:壬菌铜Compound I: Nonbacterium 1:21:2 2.78252.7825 4.95214.9521 1.77971.7797
化合物I:壬菌铜Compound I: Nonbacterial copper 1:31:3 3.56133.5613 6.41646.4164 1.80171.8017
化合物I:壬菌铜Compound I: Nonbacterium 1:51:5 3.12163.1216 9.10999.1099 2.91832.9183
化合物I:壬菌铜Compound I: Nonbacterium 1:101:10 7.01587.0158 14.732114.7321 2.09982.0998
化合物I:壬菌铜Compound I: Nonbacterium 1:201:20 11.012511.0125 22.757922.7579 2.06662.0666
化合物I:壬菌铜Compound I: Nonbacterium 1:301:30 15.013615.0136 28.211528.2115 1.87911.8791
化合物I:壬菌铜Compound I: Nonbacterium 1:501:50 20.132920.1329 35.147735.1477 1.74581.7458
由上表可知，化合物I和壬菌铜不同配比用量混配对芒果角斑病菌的抑制均具有明显增效作用。It can be seen from the above table that compound I and different proportions and dosages of nonbacterial copper have obvious synergistic effects on the inhibition of Mango angularis.
实施例11：为验证化合物I和咪唑喹啉铜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和咪唑喹啉铜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：Example 11: In order to verify the bacteriostatic effect of compound I and copper imidazoquinoline in different proportions and dosages on B. oryzae, the indoor toxicity of compound I and copper imidazoquinoline in different proportions of B. oryzae 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:
表11 化合物I和咪唑喹啉铜单剂及其混剂对水稻细菌性条斑病菌毒力测定结果Table 11 The results of the determination of the virulence of compound I and imidazoquinoline copper single agent and its mixture to S. oryzae
供试药剂test drug 配比Proportion EC 50(μg/mL)(实测值) EC 50 (μg/mL) (measured value) EC 50(μg/mL)(理论值) EC 50 (μg/mL) (theoretical value) SRSR
化合物ICompound I -- 1.50261.5026    ——
咪唑喹啉铜copper imidazoquinoline -- 45.012545.0125    ——
化合物I:咪唑喹啉铜Compound I: copper imidazoquinoline 50:150:1 0.95210.9521 1.53161.5316 1.60871.6087
化合物I:咪唑喹啉铜Compound I: copper imidazoquinoline 30:130:1 0.90150.9015 1.55101.5510 1.72041.7204
化合物I:咪唑喹啉铜Compound I: copper imidazoquinoline 20:120:1 0.95260.9526 1.57511.5751 1.65351.6535
化合物I:咪唑喹啉铜Compound I: copper imidazoquinoline 10:110:1 0.95550.9555 1.64741.6474 1.72411.7241
化合物I:咪唑喹啉铜Compound I: copper imidazoquinoline 5:15:1 0.91230.9123 1.79121.7912 1.96331.9633
化合物I:咪唑喹啉铜Compound I: copper imidazoquinoline 3:13:1 0.98210.9821 1.98141.9814 2.01752.0175
化合物I:咪唑喹啉铜Compound I: copper imidazoquinoline 2:12:1 0.99550.9955 2.21692.2169 2.22692.2269
化合物I:咪唑喹啉铜Compound I: copper imidazoquinoline 1:11:1 1.01151.0115 2.90812.9081 2.87512.8751
化合物I:咪唑喹啉铜Compound I: copper imidazoquinoline 1:21:2 1.52651.5265 4.22574.2257 2.76822.7682
化合物I:咪唑喹啉铜Compound I: copper imidazoquinoline 1:31:3 1.72141.7214 5.46335.4633 3.17373.1737
化合物I:咪唑喹啉铜Compound I: copper imidazoquinoline 1:51:5 2.55252.5525 7.72617.7261 3.02693.0269
化合物I:咪唑喹啉铜Compound I: copper imidazoquinoline 1:101:10 3.95233.9523 12.391912.3919 3.13543.1354
化合物I:咪唑喹啉铜Compound I: copper imidazoquinoline 1:201:20 6.02156.0215 18.921718.9217 3.14243.1424
化合物I:咪唑喹啉铜Compound I: copper imidazoquinoline 1:301:30 7.02167.0216 23.273423.2734 3.31453.3145
化合物I:咪唑喹啉铜Compound I: copper imidazoquinoline 1:501:50 9.02169.0216 28.711128.7111 3.18253.1825
由上表可知，化合物I和咪唑喹啉铜不同配比用量混配对水稻细菌性条斑病菌的抑制均具有明显增效作用。It can be seen from the above table that compound I and imidazoquinoline copper in different proportions and dosages have obvious synergistic effects on the inhibition of bacterial leaf spot of rice.
实施例12：为验证化合物I和波尔多液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和波尔多液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：Embodiment 12: in order to verify the antibacterial effect of compound I and different proportioning dosages of Bordeaux mixture to Bacteroides potato, carried out the indoor virulence measurement of different proportions of Compound I and Bordeaux mixture to Bacteroides potato, 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:
表12 化合物I和波尔多液单剂及其混剂对马铃薯黑胫病菌毒力测定结果Table 12 Compound I and Bordeaux mixture single agent and its mixture to the virulence test result of potato blackleg
供试药剂test drug 配比Proportion EC 50(μg/mL)(实测值) EC 50 (μg/mL) (measured value) EC 50(μg/mL)(理论值) EC 50 (μg/mL) (theoretical value) SRSR
化合物ICompound I -- 2.02592.0259    ——
波尔多液Bordeaux mixture -- 58.065258.0652    ——
化合物I:波尔多液Compound I: Bordeaux mixture 50:150:1 1.02561.0256 2.06502.0650 2.01342.0134
化合物I:波尔多液Compound I: Bordeaux mixture 30:130:1 1.06251.0625 2.09102.0910 1.96801.9680
化合物I:波尔多液Compound I: Bordeaux mixture 20:120:1 1.16251.1625 2.12352.1235 1.82671.8267
化合物I:波尔多液Compound I: Bordeaux mixture 10:110:1 0.96530.9653 2.22072.2207 2.30062.3006
化合物I:波尔多液Compound I: Bordeaux mixture 5:15:1 0.99570.9957 2.41422.4142 2.42472.4247
化合物I:波尔多液Compound I: Bordeaux mixture 3:13:1 1.05241.0524 2.67012.6701 2.53722.5372
化合物I:波尔多液Compound I: Bordeaux mixture 2:12:1 1.15201.1520 2.98672.9867 2.59272.5927
化合物I:波尔多液Compound I: Bordeaux mixture 1:11:1 1.35291.3529 3.91523.9152 2.89392.8939
化合物I:波尔多液Compound I: Bordeaux mixture 1:21:2 1.59561.5956 5.68135.6813 3.56063.5606
化合物I:波尔多液Compound I: Bordeaux mixture 1:31:3 2.05292.0529 7.33587.3358 3.57343.5734
化合物I:波尔多液Compound I: Bordeaux mixture 1:51:5 2.95262.9526 10.349910.3499 3.50533.5053
化合物I:波尔多液Compound I: Bordeaux mixture 1:101:10 4.25164.2516 16.520816.5208 3.88583.8858
化合物I:波尔多液Compound I: Bordeaux mixture 1:201:20 7.12037.1203 25.058225.0582 3.51933.5193
化合物I:波尔多液Compound I: Bordeaux mixture 1:301:30 8.95238.9523 30.684930.6849 3.42763.4276
化合物I:波尔多液Compound I: Bordeaux mixture 1:501:50 11.022611.0226 37.646537.6465 3.41543.4154
由上表可知，化合物I和波尔多液不同配比用量混配对马铃薯黑胫病菌的抑制均具有明显增效作用。It can be seen from the above table that compound I and Bordeaux mixture with different proportions and dosages have obvious synergistic effects on the inhibition of potato blackleg.
实施例13：为验证化合物I和王铜不同配比用量对桃细菌性穿孔病菌抑菌效果，进行了化合物I和王铜不同配比对桃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：Embodiment 13: in order to verify that compound I and Wang copper different proportioning dosages are to the bacteriostatic effect of peach bacterial perforation bacteria, carried out the indoor virulence assay of compound I and Wang copper different proportions to peach bacterial perforation 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:
表13 化合物I和王铜单剂及其混剂对桃细菌性穿孔病菌毒力测定结果Table 13 Compound I and Wangtong single agent and its mixture to peach bacterial perforating bacteria virulence test results
供试药剂test drug 配比Proportion EC 50(μg/mL)(实测值) EC 50 (μg/mL) (measured value) EC 50(μg/mL)(理论值) EC 50 (μg/mL) (theoretical value) SRSR
化合物ICompound I -- 2.51232.5123    ——
王铜Wang Tong -- 46.211246.2112    ——
化合物I:王铜Compound I: Wang Copper 50:150:1 1.15291.1529 2.55982.5598 2.22032.2203
化合物I:王铜Compound I: Wang Copper 30:130:1 1.25161.2516 2.59132.5913 2.07042.0704
化合物I:王铜Compound I: Wang Copper 20:120:1 1.20161.2016 2.63082.6308 2.18942.1894
化合物I:王铜Compound I: Wang Copper 10:110:1 1.52041.5204 2.74862.7486 1.80781.8078
化合物I:王铜Compound I: Wang Copper 5:15:1 1.30251.3025 2.98232.9823 2.28972.2897
化合物I:王铜Compound I: Wang Copper 3:13:1 1.40121.4012 3.29013.2901 2.34812.3481
化合物I:王铜Compound I: Wang Copper 2:12:1 1.50141.5014 3.66873.6687 2.44352.4435
化合物I:王铜Compound I: Wang Copper 1:11:1 1.62101.6210 4.76554.7655 2.93992.9399
化合物I:王铜Compound I: Wang Copper 1:21:2 1.95261.9526 6.79786.7978 3.48143.4814
化合物I:王铜Compound I: Wang Copper 1:31:3 2.72162.7216 8.64008.6400 3.17463.1746
化合物I:王铜Compound I: Wang Copper 1:51:5 3.59853.5985 11.852111.8521 3.29363.2936
化合物I:王铜Compound I: Wang Copper 1:101:10 5.25365.2536 17.902517.9025 3.40773.4077
化合物I:王铜Compound I: Wang Copper 1:201:20 7.25987.2598 25.275725.2757 3.48163.4816
化合物I:王铜Compound I: Wang Copper 1:301:30 10.523510.5235 29.601829.6018 2.81292.8129
化合物I:王铜Compound I: Wang Copper 1:501:50 12.512012.5120 34.458834.4588 2.75412.7541
由上表可知，化合物I和王铜不同配比用量混配对桃细菌性穿孔病菌的抑制均具有明显增效作用。It can be seen from the above table that compound I and Wang copper in different proportions and dosages have obvious synergistic effects on the inhibition of peach bacterial perforation bacteria.
3、大田药效实施例3. Examples of medicinal effects in the field
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、马铃薯黑胫病、桃细菌性穿孔病、烟草野火病、大姜姜瘟病、番茄溃疡病、猕猴桃溃疡病、花生青枯病、水稻细菌性褐斑病、梨火疫病、番茄细菌病斑点病、木薯细菌性枯萎病、果树细菌性根癌病、柑橘黄龙病、甘薯茎腐病和水稻白叶枯等细菌性病害的防治效果，在国内不同地区开展了多次药效试验。In order to clarify the effects of compound I and compound II single agent and mixture on cucumber bacterial keratosis, citrus canker, potato black shank, peach bacterial perforation, tobacco wildfire, ginger and ginger blast, tomato canker, kiwi canker Disease, peanut bacterial wilt, rice bacterial brown spot, pear fire blight, tomato bacterial spot, cassava bacterial wilt, fruit tree bacterial root cancer, citrus Huanglongbing, sweet potato stem rot and rice bacterial blight, etc. The control effect of bacterial diseases has been carried out for many times in different regions of the country.
下述各实施例中的试剂的制备方法如上述制剂实施例1-7所示，示例性地，实施例1的30％化合物I·喹啉铜可湿性粉剂(1:5)的制备方法同制剂实施例1，由于该制剂实施例中化合物I含量为5％，化合物II含量为25％，故称为30％化合物I·喹啉铜可湿性粉剂(1:5)，如下表格中以此类推。The preparation methods of the reagents in the following examples are shown in the above formulation examples 1-7. Exemplarily, the preparation method of the 30% Compound I·Copper quinoline wettable powder (1:5) of Example 1 is the same as the Formulation Example 1, since the content of Compound I in this formulation example is 5% and the content of Compound II is 25%, it is called 30% Compound I·Copper quinoline wettable powder (1:5), as shown in the following table. analogy.
下述各对比例中的对照药剂的制备方法同样如上述制剂实施例1-7所示，只是其中的活性组分的含量可能会有所不同，相应的，制剂中的填料或溶剂将组分补齐至100％。例如，对比药剂1的10％化合物I水分散粒剂的制备方法参照制剂实施例2，其中10％化合物I替换制剂实施例2中的10％化合物I和30％化合物II，含量的差异通过填料来填补或调整。又例如，对照药剂2的33.5％喹啉铜悬浮剂的制备方法参照制剂实施例3，其中33.5％喹啉铜替换制剂实施例3中的5％化合物I和20％化合物II，含量的差异通过填料来填补或调整。The preparation methods of the control agents in the following comparative examples are also shown in the above-mentioned formulation examples 1-7, except that the content of the active components may be different. Correspondingly, the filler or solvent in the Make up to 100%. For example, the preparation method of 10% compound I water dispersible granules of comparative agent 1 refers to formulation example 2, wherein 10% compound I replaces 10% compound I and 30% compound II in formulation example 2, and the content difference is through the filler to fill or adjust. For another example, the preparation method of the 33.5% copper quinoline suspension of control agent 2 refers to formulation example 3, wherein 33.5% copper quinoline replaces 5% compound I and 20% compound II in formulation example 3, and the difference in content is determined by Filler to fill or adjust.
黄瓜细菌性角斑病大田药效试验(于山东聊城冠县开展)：Field efficacy test of cucumber bacterial angular spot disease (carried out in Guan County, Liaocheng, Shandong):
试验方法：根据《中华人民共和国国家标准GB/T 17980.110-2004》规定的施药方法，在初见病斑时施药，7天后第2次施药，共施药两次，重复次数为4次。Test method: According to the application method stipulated in "National Standard of the People's Republic of China GB/T 17980.110-2004", apply the medicine when the lesions are first seen, and apply the medicine for the second time after 7 days. Second-rate.
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。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.
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。Each plot was sampled at 3 diagonal points, 5 plants per point, all leaves were investigated, and the percentage of diseased spot area per leaf to the entire leaf area was graded.
分级方法：Grading method:
0级:无病斑；Grade 0: no lesions;
1级:病斑面积占整个叶面积的5％以下；Grade 1: The lesion area accounts for less than 5% of the entire leaf area;
3级:病斑面积占整个叶面积的6％～10％；Grade 3: The lesion area accounts for 6% to 10% of the entire leaf area;
5级:病斑面积占整个叶面积的11％～20％；Grade 5: The lesion area accounts for 11% to 20% of the entire leaf area;
7级:病斑面积占整个叶面积的21％～50％；Grade 7: The lesion area accounts for 21% to 50% of the entire leaf area;
9级:病斑面积占整个叶面积的51％以上。Grade 9: The lesion area accounts for more than 51% of the entire leaf area.
表14 化合物I与喹啉铜复配对黄瓜细菌性角斑病大田药效试验Table 14 Pharmacodynamic test of compound I and copper quinoline on cucumber bacterial angular spot disease
Figure PCTCN2021126495-appb-000009
Figure PCTCN2021126495-appb-000009
Figure PCTCN2021126495-appb-000010
Figure PCTCN2021126495-appb-000010
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。Different letters after the data in the same column indicate significant differences at the P<0.05 level by Duncan's new multiple range test, the same below.
由测定结果可知，在防治黄瓜细菌性角斑病时，化合物I与喹啉铜复配和单剂相比，在同等有效成分用量下，化合物I+喹啉铜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79.8％以上，持效期较长。It can be seen from the measurement results that, in the prevention and treatment of cucumber bacterial keratosis, compound I and quinoline copper compound and single agent, under the same amount of active ingredients, compound I + quinoline copper on cucumber bacterial keratosis 7%. The day control effect and 14-day control effect were significantly higher than the single dose. Among them, the 14-day prevention effect can still reach more than 79.8%, and the effective period is longer.
表15 化合物I与噻菌铜复配对黄瓜细菌性角斑病大田药效试验Table 15 Pharmacodynamic test of compound I and thiophanate-copper complex on cucumber bacterial angular spot disease
Figure PCTCN2021126495-appb-000011
Figure PCTCN2021126495-appb-000011
由测定结果可知，在防治黄瓜细菌性角斑病时，化合物I与噻菌铜复配和单剂相比，在同等有效成分用量下，化合物I+噻菌铜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77.3％以上，持效期较长。It can be seen from the determination results that, in the control of cucumber bacterial angular spot, compound I and thiophanate-copper compound and single agent, under the same dosage of active ingredients, compound I + thiophanate-copper on cucumber bacterial angular spot disease are 7 times more effective. The day control effect and 14-day control effect were significantly higher than the single dose. Among them, the 14-day prevention effect can still reach more than 77.3%, and the lasting period is longer.
表16 化合物I与壬菌铜复配对黄瓜细菌性角斑病大田药效试验Table 16 Field efficacy test of compound I and non-bacterial copper compound on cucumber bacterial angular spot disease
Figure PCTCN2021126495-appb-000012
Figure PCTCN2021126495-appb-000012
Figure PCTCN2021126495-appb-000013
Figure PCTCN2021126495-appb-000013
由测定结果可知，在防治黄瓜细菌性角斑病时，化合物I与壬菌铜复配和单剂相比，在同等有效成分用量下，化合物I+壬菌铜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79.8％以上，持效期较长。It can be seen from the measurement results that when controlling cucumber bacterial angular spot, compound I and non-bacterial copper compound and single agent, under the same amount of active ingredients, compound I + non-bacterial angular leaf spot disease of cucumber is 7 times more effective. The day control effect and 14-day control effect were significantly higher than the single dose. Among them, the 14-day prevention effect can still reach more than 79.8%, and the effective period is longer.
水稻白叶枯病大田药效试验(于江苏南京开展)：Field efficacy test on rice bacterial blight (carried out in Nanjing, Jiangsu):
试验方法：根据《中华人民共和国国家标准GB/T 17980.19-2000》规定的施药方法，在初见病斑时施药，7天后第2次施药，共施药两次，重复次数为4次。Test method: According to the application method stipulated in "National Standard of the People's Republic of China GB/T 17980.19-2000", apply the medicine when the lesions are first seen, and apply the medicine for the second time after 7 days. Second-rate.
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。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.
白叶枯病病情普遍率(以目测分级):The prevalence of bacterial blight disease (graded by visual inspection):
0级:无病；Level 0: no disease;
1级:零星发病或有中心病团；Grade 1: sporadic disease or central disease;
3级:发病面积占总面积四分之一左右；Grade 3: The diseased area accounts for about a quarter of the total area;
5级:发病面积占总面积三分之一左右；Grade 5: The incidence area accounts for about one-third of the total area;
7级:发病面积占总面积二分之一左右；Grade 7: The incidence area accounts for about half of the total area;
9级:发病面积占总面积四分之三以上。Grade 9: The incidence area accounts for more than three-quarters of the total area.
表17 化合物I与喹啉铜复配对水稻白叶枯病大田药效试验Table 17 Pharmacodynamic test of compound I and copper quinoline on rice bacterial blight
Figure PCTCN2021126495-appb-000014
Figure PCTCN2021126495-appb-000014
由测定结果可知，在防治水稻白叶枯病时，化合物I与喹啉铜复配和单剂相比，在同等有效成分用量下，化合物I+喹啉铜防治水稻白叶枯病的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79.8％以上，持效期较长。It can be seen from the determination results that when controlling rice bacterial blight, compound I and quinoline copper compound and single agent are compared with the same effective ingredient dosage, and compound I + quinoline copper can control rice bacterial blight for 7 days. The efficacy and 14-day control effect were significantly higher than that of a single dose. Among them, the 14-day control effect can still reach more than 79.8%, and the lasting effect is longer.
表18 化合物I与噻森铜复配对水稻白叶枯病大田药效试验Table 18 Pharmacodynamic test of compound I and copper thiosate on rice bacterial blight field
Figure PCTCN2021126495-appb-000015
Figure PCTCN2021126495-appb-000015
由测定结果可知，在防治水稻白叶枯病时，化合物I与噻森铜复配和单剂相比，在同等有效成分用量下，化合物I+噻森铜对水稻白叶枯病的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78.5％以上，持效期较长。It can be seen from the determination results that when controlling rice bacterial blight, compound I and thiosin copper compound and single agent, under the same dosage of active ingredients, compound I + thiosin copper 7-day control of rice bacterial blight. 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.
表19 化合物I与王铜复配对水稻白叶枯病大田药效试验Table 19 The efficacy test of compound I and Wang Tongfu on rice bacterial blight field
Figure PCTCN2021126495-appb-000016
Figure PCTCN2021126495-appb-000016
由测定结果可知，在防治水稻白叶枯病时，化合物I与王铜复配和单剂相比，在同等有效成分用量下，化合物I+王铜对水稻白叶枯病的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。It can be seen from the determination results that, in the control of rice bacterial blight, compound I and Wang copper compound and single agent, under the same amount of active ingredients, the 7-day control effect of compound I + Wang copper on rice bacterial blight and the difference. The 14-day control effect was significantly higher than that of a single dose. Among them, the 14-day prevention effect can still reach more than 80.5%, and the lasting period is longer.
柑橘溃疡病大田药效试验(于广西武鸣开展)：Field efficacy test of citrus canker disease (carried out in Wuming, Guangxi):
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，重复次数为4次。记录施药次数和每次施药日期及果树生育期。According to the "Guidelines for Field Efficacy Test of Pesticide (GB/T17980.103-2004)", 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.
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。Investigation method: According to the investigation method stipulated in the "Pesticide Field Efficacy Test Guidelines (GB/T17980.103-2004)", 7d and 14d after the second application, two plants were investigated in each plot, and each plant was based on five points in east, west, north, south, and middle. Sampling, survey all leaves on two shoots at each point, and calculate the control effect.
叶分级方法：Leaf grading method:
0级：无病；Level 0: no disease;
1级：每叶有病斑1～5个；Grade 1: There are 1 to 5 diseased spots on each leaf;
3级：每叶有病斑6～10个；Grade 3: There are 6 to 10 diseased spots on each leaf;
5级：每叶有病斑11～15个；Grade 5: There are 11 to 15 diseased spots on each leaf;
7级：每叶有病斑15～20个；Grade 7: 15 to 20 diseased spots per leaf;
9级：每叶有病斑21个以上；Grade 9: Each leaf has more than 21 diseased spots;
表20 化合物I与喹啉铜复配对柑橘溃疡病大田药效试验Table 20 Compound I and quinoline copper compound on citrus canker field drug efficacy test
Figure PCTCN2021126495-appb-000017
Figure PCTCN2021126495-appb-000017
由测定结果可知，在防治柑橘溃疡病时，化合物I与喹啉铜复配和单剂相比，在同等有效成分用量下，化合物I+喹啉铜对柑橘溃疡病的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80.5％以上，持效期较长。It can be seen from the measurement results that, in the prevention and treatment of citrus canker, compound I and quinoline copper compound and single agent, under the same active ingredient dosage, compound I + quinoline copper on citrus canker 7-day control effect and 14-day control effect. The control effect is significantly higher than that of a single agent. Among them, the 14-day prevention effect can still reach more than 80.5%, and the lasting period is longer.
西瓜果斑病大田药效试验(于潍坊市昌乐县开展)：Field efficacy test of watermelon fruit spot disease (carried out in Changle County, Weifang City):
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Test method: refer to the spraying method specified in "National Standard of the People's Republic of China GB/T 17980.110-2004".
施药，7天后第2次施药，共施药两次，重复次数为4次。Application, the second application after 7 days, a total of two applications, repeated 4 times.
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。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.
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。Each plot was sampled at 3 diagonal points, 5 plants per point, all leaves were investigated, and the percentage of diseased spot area per leaf to the entire leaf area was graded.
分级方法：Grading method:
0级:无病斑；Grade 0: no lesions;
1级:病斑面积占整个叶面积的5％以下；Grade 1: The lesion area accounts for less than 5% of the entire leaf area;
3级:病斑面积占整个叶面积的6％～10％；Grade 3: The lesion area accounts for 6% to 10% of the entire leaf area;
5级:病斑面积占整个叶面积的11％～20％；Grade 5: The lesion area accounts for 11% to 20% of the entire leaf area;
7级:病斑面积占整个叶面积的21％～50％；Grade 7: The lesion area accounts for 21% to 50% of the entire leaf area;
9级:病斑面积占整个叶面积的51％以上。Grade 9: The lesion area accounts for more than 51% of the entire leaf area.
表21 化合物I与喹啉铜复配对西瓜果斑病大田药效试验Table 21 Compound I and quinoline copper compound on watermelon fruit spot disease field efficacy test
Figure PCTCN2021126495-appb-000018
Figure PCTCN2021126495-appb-000018
由测定结果可知，在防治西瓜果斑病时，化合物I与喹啉铜复配和单剂相比，在同等有效成分用量下，化合物I+喹啉铜对西瓜果斑病的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79.5％以上，持效期较长。It can be seen from the measurement results that, in the prevention and treatment of watermelon fruit spot, compound I and quinoline copper compound and single agent, under the same amount of active ingredients, compound I + quinoline copper on watermelon fruit spot 7-day prevention. 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 79.5%, and the lasting period is longer.
表22 化合物I与氢氧化铜复配对西瓜果斑病大田药效试验Table 22 The efficacy test of compound I and copper hydroxide compound on watermelon fruit spot disease field
Figure PCTCN2021126495-appb-000019
Figure PCTCN2021126495-appb-000019
Figure PCTCN2021126495-appb-000020
Figure PCTCN2021126495-appb-000020
由测定结果可知，在防治西瓜果斑病时，化合物I与氢氧化铜复配和单剂相比，在同等有效成分用量下，化合物I+氢氧化铜对西瓜果斑病的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75.8％以上，持效期较长。It can be seen from the measurement results that, in the prevention and control of watermelon fruit spot, compound I and copper hydroxide compound and single agent, under the same amount of active ingredients, compound I + copper hydroxide on watermelon fruit spot 7-day prevention. 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 75.8%, and the lasting period is longer.
番茄青枯病大田药效试验(于潍坊市昌乐县开展)：Field efficacy test of tomato bacterial wilt disease (carried out in Changle County, Weifang City):
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，重复次数为4次。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.
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。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.
表23 化合物I与喹啉铜复配对番茄青枯病大田药效试验Table 23 Compound I and quinoline copper compound on tomato bacterial wilt field efficacy test
Figure PCTCN2021126495-appb-000021
Figure PCTCN2021126495-appb-000021
Figure PCTCN2021126495-appb-000022
Figure PCTCN2021126495-appb-000022
由测定结果可知，在防治番茄青枯病时，化合物I与喹啉铜复配和单剂相比，在同等有效成分用量下，化合物I+喹啉铜对番茄青枯病的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80.5％以上，持效期较长。It can be seen from the determination results that, in the control of tomato bacterial wilt, compound I and quinoline copper compound and single agent, under the same amount of active ingredients, the 7-day control effect of compound I + quinoline copper on tomato bacterial wilt and the difference. The 14-day control effect was significantly higher than that of a single dose. Among them, the 14-day prevention effect can still reach more than 80.5%, and the lasting period is longer.
马铃薯黑胫病大田药效试验(于山东省滕州市开展)：Field efficacy test of potato black shank disease (carried out in Tengzhou City, Shandong Province):
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，重复次数为4次。Test method: spray when the diseased plants are first seen, granules are sprayed when the diseased plants are first seen, and the second spray is applied 7 days later.
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。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.
表24 化合物I与硫酸铜钙复配对马铃薯黑胫病大田药效试验Table 24 The efficacy test of compound I and copper-calcium sulfate complex on potato black shank disease field
Figure PCTCN2021126495-appb-000023
Figure PCTCN2021126495-appb-000023
由测定结果可知，在防治马铃薯黑胫病时，化合物I与硫酸铜钙复配和单剂相比，在同等有效成分用量下，化合物I+硫酸铜钙对马铃薯黑胫病的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80.1％以上，持效期较长。It can be seen from the determination results that when controlling potato black shank, compound I and copper-calcium sulfate compound and single dose are compared under the same dosage of active ingredients, the 7-day control effect of compound I + copper-calcium sulfate on potato black shank disease and The 14-day control effect was significantly higher than that of a single dose. Among them, the 14-day prevention effect can still reach more than 80.1%, and the lasting period is longer.
桃细菌性穿孔病大田药效试验(于山东省肥城市开展)：Field efficacy test of peach bacterial perforation disease (carried out in Feicheng, Shandong Province):
试验方法：在初见病斑时喷雾，7天后第2次施药，共施药两次，重复次数为4次。Test method: spray when the lesions are first seen, and apply the medicine for the second time after 7 days.
调查方法：每小区随机5点取样，每点调查5棵果树，每个果树调查50片叶片。第2次施药后7天和14天调查防治效果。Survey method: 5 random points were sampled in each plot, 5 fruit trees were surveyed at each point, and 50 leaves were surveyed for each fruit tree. The control effect was investigated 7 days and 14 days after the second application.
表25 化合物I与琥珀酸铜复配对桃细菌性穿孔病大田药效试验Table 25 Field efficacy test of compound I and copper succinate on peach bacterial perforation disease
Figure PCTCN2021126495-appb-000024
Figure PCTCN2021126495-appb-000024
Figure PCTCN2021126495-appb-000025
Figure PCTCN2021126495-appb-000025
由测定结果可知，在防治桃细菌性穿孔病时，化合物I与琥珀酸铜复配和单剂相比，在同等有效成分用量下，化合物I+琥珀酸铜对桃细菌性穿孔病的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80.7％以上，持效期较长。It can be seen from the measurement results that, in the prevention and treatment of peach bacterial perforation, compound I and copper succinate are compounded and single-dose, and under the same dosage of active ingredients, compound I + copper succinate has a 7-day preventive effect on peach bacterial perforation. 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 80.7%, and the lasting period is longer.
烟草野火病大田药效试验(于云南省玉溪市开展)：Field efficacy test of tobacco wildfire disease (carried out in Yuxi City, Yunnan Province):
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。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. .
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。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.
分级方法:Grading method:
0级:全株无病；Grade 0: The whole plant is disease-free;
1级:病斑面积占整叶面积的5％以下；Grade 1: The lesion area accounts for less than 5% of the entire leaf area;
3级:病斑面积占整叶面积的6％～20％；Grade 3: The lesion area accounts for 6% to 20% of the entire leaf area;
5级:病斑面积占整叶面积的21％～50％；Grade 5: The lesion area accounts for 21% to 50% of the entire leaf area;
7级:病斑面积占整叶面积的51％～80％；Grade 7: The lesion area accounts for 51% to 80% of the entire leaf area;
9级:病斑面积占整叶面积的81％以上。Grade 9: The lesion area accounts for more than 81% of the entire leaf area.
表26 化合物I与络氨铜复配对烟草野火病大田药效试验Table 26 Pharmacodynamic test of compound I and copper ammonium compound on tobacco wildfire disease field
Figure PCTCN2021126495-appb-000026
Figure PCTCN2021126495-appb-000026
Figure PCTCN2021126495-appb-000027
Figure PCTCN2021126495-appb-000027
由测定结果可知，在防治烟草野火病时，化合物I与络氨铜复配和单剂相比，在同等有效成分用量下，化合物I+络氨铜对烟草野火病的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80.9％以上，持效期较长。It can be seen from the measurement results that, when controlling tobacco wildfire, compound I and copper bromide compound and single dose are compared, and under the same dosage of active ingredients, the 7-day preventive effect and 14-day preventive effect of compound I + bromine copper on tobacco wildfire. The control effect is significantly higher than that of a single agent. Among them, the 14-day prevention effect can still reach more than 80.9%, and the lasting period is longer.
大姜姜瘟病大田药效试验(于山东省安丘市开展)：Field efficacy test of ginger and ginger blast disease (carried out in Anqiu City, Shandong Province):
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。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 .
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。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 succulent stem symptoms were surveyed for each plant, and the total number of surveyed plants was recorded. , The number of diseased plants at all levels.
分级方法:Grading method:
0级:全株无病；Grade 0: The whole plant is disease-free;
1级:10％以下叶片轻微变黄,肉质茎无明显症状；Grade 1: Less than 10% of the leaves turn slightly yellow, and the fleshy stems have no obvious symptoms;
3级:11％～30％叶片变黄,叶缘稍卷,肉质茎出现水渍状斑；Grade 3: 11% to 30% of the leaves turn yellow, the leaf margins are slightly rolled, and the fleshy stems appear water-soaked spots;
5级:31％～50％叶片变黄,叶缘卷曲,植株矮化,肉质茎部分腐烂；Grade 5: 31% to 50% of the leaves turn yellow, the leaf margins are curled, the plants are dwarfed, and the fleshy stems are partially rotted;
7级:51％以上叶片枯黄,植株萎蔫,肉质茎大部分腐烂；Grade 7: more than 51% of the leaves are withered, the plants are wilted, and most of the fleshy stems are rotten;
9级:植株枯死,肉质茎腐烂或仅留丝状维管束。Grade 9: Plants die, fleshy stems rot or only filamentous vascular bundles remain.
试验小区如果发生其他叶、茎部病害,也应调查记载说明。If other leaf and stem diseases occur in the experimental plot, investigation and records should also be made.
表27 化合物I与松脂酸铜复配对大姜姜瘟病大田药效试验Table 27 Compound I and copper rosinate compound the field efficacy test of ginger and ginger blast
Figure PCTCN2021126495-appb-000028
Figure PCTCN2021126495-appb-000028
Figure PCTCN2021126495-appb-000029
Figure PCTCN2021126495-appb-000029
由测定结果可知，在防治大姜姜瘟病时，化合物I与松脂酸铜复配和单剂相比，在同等有效成分用量下，化合物I+松脂酸铜对大姜姜瘟病的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80.5％以上，持效期较长。It can be seen from the measurement results that when controlling the ginger blast of ginger, the compound I and copper rosinate are compounded and single-agent compared, and under the same amount of active ingredients, the 7-day preventive effect of compound I+copper rosinate on ginger and ginger blast and The 14-day control effect was significantly higher than that of a single dose. Among them, the 14-day prevention effect can still reach more than 80.5%, and the lasting period is longer.
番茄溃疡病大田药效试验(于山东省安丘市开展)：Field efficacy test of tomato canker disease (carried out in Anqiu City, Shandong Province):
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。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.
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。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.
表28 化合物I与柠檬酸铜复配对番茄溃疡病大田药效试验Table 28 The efficacy test of compound I and copper citrate on tomato canker field
Figure PCTCN2021126495-appb-000030
Figure PCTCN2021126495-appb-000030
由测定结果可知，在防治番茄溃疡病时，化合物I与柠檬酸铜复配和单剂相比，在同等有效成分用量下，化合物I+柠檬酸铜对番茄溃疡病的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79.3％以上，持效期较长。It can be seen from the measurement results that, in the prevention and treatment of tomato canker, the compound I and copper citrate compound and single dose compared with the same active ingredient dosage, the compound I + copper citrate on tomato canker 7-day control effect and 14-day The control effect is significantly higher than that of a single agent. Among them, the 14-day prevention effect can still reach more than 79.3%, and the lasting period is longer.
猕猴桃溃疡病大田药效试验(于四川省蒲江县开展)：Field efficacy test of kiwifruit canker disease (carried out in Pujiang County, Sichuan Province):
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。Test method: spraying before germination, the second spraying after 7 days, a total of twice spraying, repeated 4 times.
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。Investigation method: 7d and 14d after the second application, two plants were investigated in each plot, each plant was sampled at five points in the east, west, north, south, middle, and 20 branches were investigated for each plant, and the control effect was calculated.
表29 化合物I与乙酸铜复配对猕猴桃溃疡病大田药效试验Table 29 Compound I and copper acetate compound efficacy test on kiwifruit canker
Figure PCTCN2021126495-appb-000031
Figure PCTCN2021126495-appb-000031
由测定结果可知，在防治猕猴桃溃疡病时，化合物I与乙酸铜复配和单剂相比，在同等有效成分用量下，化合物I+乙酸铜对猕猴桃溃疡病的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78.6％以上，持效期较长。It can be seen from the determination results that, in the prevention and treatment of kiwifruit canker, the compound I and copper acetate compound and single agent, under the same amount of active ingredients, the 7-day and 14-day preventive effects of compound I+copper acetate on kiwifruit canker. significantly higher than a single dose. Among them, the 14-day prevention effect can still reach more than 78.6%, and the lasting period is longer.
水稻细菌性褐斑病大田药效试验(于山东省鱼台市开展)：Field efficacy test of rice bacterial brown spot disease (carried out in Yutai City, Shandong Province):
试验方法：在初见病株时喷雾，7天后第2次施药，共施药两次，重复次数4次。Test method: spray at the first sight of the diseased plant, and apply the medicine for the second time after 7 days.
调查方法：每小区随机取样调查，每点调查50株植株，记录病级指数。第2次施药后7天和14天调查防治效果。Survey method: random sampling survey in each plot, survey 50 plants at each point, and record the disease grade index. The control effect was investigated 7 days and 14 days after the second application.
表30 化合物I与四氨合铜复配对水稻细菌性褐斑病大田药效试验Table 30 The efficacy test of compound I and tetraammine copper complex on rice bacterial brown spot
Figure PCTCN2021126495-appb-000032
Figure PCTCN2021126495-appb-000032
由测定结果可知，在防治水稻细菌性褐斑病时，化合物I与四氨合铜复配和单剂相比，在同等有效成分用量下，化合物I+四氨合铜对水稻细菌性褐斑病的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76.4％以上，持效期较长。It can be seen from the determination results that, in the control of rice bacterial brown spot, compound I and tetraammine copper compound and single agent, under the same dosage of active ingredients, compound I + tetraammine copper is effective against rice bacterial brown spot disease. The 7-day preventive effect and 14-day preventive effect were significantly higher than those of a single dose. Among them, the 14-day prevention effect can still reach more than 76.4%, and the lasting period is longer.
梨火疫病大田药效试验(于新疆库尔勒开展)：Field efficacy test of pear fire blight (carried out in Korla, Xinjiang):
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。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.
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。Survey method: 5 points were randomly surveyed in each plot, 10 plants were surveyed at each point, and 10 branches were surveyed for each plant. The total number of investigated plants and the number of diseased plants at all levels were recorded.
表31 化合物I与硝基腐殖酸铜复配对梨火疫病大田药效试验Table 31 Compound I and nitro humic acid copper compound on the field efficacy test of pear fire blight
Figure PCTCN2021126495-appb-000033
Figure PCTCN2021126495-appb-000033
由测定结果可知，在防治梨火疫病时，化合物I与硝基腐殖酸铜复配和单剂相比，在同等有效成分用量下，化合物I+硝基腐殖酸铜对梨火疫病的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75.3％以上，持效期较长。It can be seen from the determination results that, in the prevention and treatment of pear fire blight, compound I and copper nitro humate compound and single dose are compared, under the same dosage of active ingredients, compound I + copper nitro humate has 7 effects on pear fire blight. The day control effect and 14-day control effect were significantly higher than the single dose. Among them, the 14-day prevention effect can still reach more than 75.3%, and the lasting period is longer.
番茄细菌性斑点病大田药效试验(于山东济南开展)：Field efficacy test of tomato bacterial spot disease (carried out in Jinan, Shandong):
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。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.
调查方法：每小区随机调查5点，每点调查10株，每株调查20个叶片。记录调查总叶数、各级病叶数。Survey method: 5 points were randomly surveyed in each plot, 10 plants were surveyed at each point, and 20 leaves were surveyed for each plant. The total number of leaves and the number of diseased leaves at all levels were recorded.
表32 化合物I与绿乳铜复配对番茄细菌性斑点病大田药效试验Table 32 Efficacy test of compound I and green lactate copper complex on tomato bacterial spot disease field
Figure PCTCN2021126495-appb-000034
Figure PCTCN2021126495-appb-000034
Figure PCTCN2021126495-appb-000035
Figure PCTCN2021126495-appb-000035
由测定结果可知，在防治番茄细菌性斑点病时，化合物I与绿乳铜复配和单剂相比，在同等有效成分用量下，化合物I+绿乳铜对番茄细菌性斑点病的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76.5％以上，持效期较长。It can be seen from the measurement results that, in the prevention and treatment of tomato bacterial spot, compound I and green milk copper compound and single agent, under the same amount of active ingredients, compound I + green milk copper on tomato bacterial spot 7-day prevention. 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 76.5%, and the effective period is longer.
木薯细菌性枯萎病大田药效试验(于广西玉林开展)：Field efficacy test of cassava bacterial wilt (carried out in Yulin, Guangxi):
试验方法：在初见病斑时施药叶面喷雾，根部灌药，7天后第2次施药，共施药两次，重复次数4次。Test method: When the disease spots are first seen, the foliar spray is applied, the root is irrigated, and the second application is applied after 7 days.
调查方法：每小区调查全部植株。记录调查总株数和病株数。Investigation method: Investigate all plants in each plot. Record the total number of investigated plants and the number of diseased plants.
表33 化合物I与碱式硫酸铜复配对木薯细菌性枯萎病大田药效试验Table 33 Compound I and basic copper sulfate compound efficacy test on cassava bacterial fusarium wilt
Figure PCTCN2021126495-appb-000036
Figure PCTCN2021126495-appb-000036
由测定结果可知，在防治木薯细菌性枯萎病时，化合物I与碱式硫酸铜复配和单剂相比，在同等有效成分用量下，化合物I+碱式硫酸铜对木薯细菌性枯萎病的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77.3％以上，持效期较长。It can be seen from the measurement results that, in the control of cassava bacterial wilt, compound I and basic copper sulfate compound and single agent, under the same amount of active ingredients, compound I + basic copper sulfate on cassava bacterial wilt 7. The day control effect and 14-day control effect were significantly higher than the single dose. Among them, the 14-day prevention effect can still reach more than 77.3%, and the lasting period is longer.
果树细菌性根癌病大田药效试验(于山东烟台开展)：Field efficacy test of fruit tree bacterial root cancer disease (carried out in Yantai, Shandong):
试验方法：在初见病株时灌根，7天后第2次施药，共施药两次，重复次数为4次。Test method: irrigate the roots when the diseased plants are first seen, and apply the medicine for the second time after 7 days.
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。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.
表34 化合物I与氧化亚铜复配对果树细菌性根癌病大田药效试验Table 34 Field efficacy test of compound I and cuprous oxide on bacterial root cancer of fruit trees
Figure PCTCN2021126495-appb-000037
Figure PCTCN2021126495-appb-000037
由测定结果可知，在防治果树细菌性根癌病时，化合物I与氧化亚铜复配和单剂相比，在同等有效成分用量下，化合物I+氧化亚铜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76.8％以上，持效期较长。It can be seen from the measurement results that, in the prevention and treatment of fruit tree bacterial root cancer, compound I and cuprous oxide compound and single agent, under the same amount of active ingredients, compound I + cuprous oxide on fruit tree bacterial root cancer disease 7-day prevention. 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 76.8%, and the lasting period is longer.
柑橘黄龙病大田药效试验(于广西武鸣开展)Field efficacy test of citrus Huanglongbing (in Wuming, Guangxi)
试验方法：在初见病株时叶面喷雾，根部灌根，7天后第2次施药，共施药两次，重复次数4次。Test method: When the diseased plants were first seen, the leaves were sprayed, the roots were irrigated, and the second application was applied 7 days later, with a total of two applications and 4 repetitions.
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。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.
表35 化合物I与混合氨基酸铜复配对柑橘黄龙病大田药效试验Table 35 The efficacy test of compound I and mixed amino acid copper compound on citrus Huanglongbing field
Figure PCTCN2021126495-appb-000038
Figure PCTCN2021126495-appb-000038
由测定结果可知，在防治柑橘黄龙病时，化合物I与混合氨基酸铜复配和单剂相比，在同等有效成分用量下，化合物I+混合氨基酸铜对柑橘黄龙病的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77.2％以上，持效期较长。It can be seen from the determination results that when controlling citrus huanglongbing, compound I and mixed amino acid copper compound and single agent, under the same amount of active ingredients, compound I + mixed amino acid copper have 7-day control effect and 14-day control effect on citrus huanglongbing. The control effect is significantly higher than that of a single agent. Among them, the 14-day prevention effect can still reach more than 77.2%, and the lasting period is longer.
甘薯茎腐病大田药效试验(于山东济南开展)Field efficacy test of sweet potato stem rot disease (carried out in Jinan, Shandong)
试验方法：在初见病株时喷雾，7天后第2次施药，共施药两次，重复次数4次。Test method: spray at the first sight of the diseased plant, and apply the medicine for the second time after 7 days.
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。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.
表36 化合物I与琥胶肥酸铜复配对甘薯茎腐病大田药效试验Table 36 Field efficacy test of compound I and succinic acid copper compound on sweet potato stem rot
Figure PCTCN2021126495-appb-000039
Figure PCTCN2021126495-appb-000039
由测定结果可知，在防治甘薯茎腐病时，化合物I与琥胶肥酸铜复配和单剂相比，在同等有效成分用量下，化合物I+琥胶肥酸铜对甘薯茎腐病的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79.7％以上，持效期较长。.It can be seen from the measurement results that, in the prevention and control of sweet potato stem rot, compound I and succinic acid copper compound and single agent, under the same amount of active ingredients, compound I + succinic acid copper fertile have 7% of sweet potato stem rot. The day control effect and 14-day control effect were significantly higher than the single dose. Among them, the 14-day prevention effect can still reach more than 79.7%, and the lasting period is longer. .
烟草青枯病大田药效试验(于山东济南开展)：Field efficacy test of tobacco bacterial wilt disease (carried out in Jinan, Shandong):
试验方法：参照《中华人民共和国农业行业标准NY/T 1464.49-2010》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，重复次数为4次。Test method: refer to the application method specified in "The Agricultural Industry Standard of the People's Republic of China NY/T 1464.49-2010", 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.
调查方法：参照《中华人民共和国农业行业标准NY/T 1464.49-2010》规定的调查方法，第2次施药后7天和14天调查防治效果。Investigation method: Referring to the investigation method stipulated in "The Agricultural Industry Standard of the People's Republic of China NY/T 1464.49-2010", the control effect was investigated 7 days and 14 days after the second application.
每小区采用5点取样方法，每点固定调查5株-10株，记录调查总株数及各级病株数。以株为单位分级调查。5-point sampling method was adopted in each plot, 5-10 plants were fixedly surveyed at each point, and the total number of surveyed plants and the number of diseased plants at all levels were recorded. Grading survey in units of strains.
0级:全株无病。Grade 0: The whole plant is disease-free.
1级:茎部偶有褪绿斑，或病侧1/2以下叶片凋萎；Grade 1: Occasional chlorotic spots on the stem, or withered leaves below 1/2 of the diseased side;
3级:茎部有黑色条斑.但不超过茎高1/2，或病侧1/2-2/3叶片凋萎；Grade 3: Black streaks on the stem, but not more than 1/2 of the stem height, or withered leaves on the diseased side 1/2-2/3;
5级:茎部黑色条斑超过茎高1/2，但未到达茎顶部，或病侧2/3以上叶片凋萎；Grade 5: Black streaks on the stem exceed 1/2 of the stem height, but do not reach the top of the stem, or more than 2/3 of the leaves on the diseased side wither;
7级:茎部黑色条斑到达茎顶部，或病株叶片全部凋萎；Level 7: black streaks on the stem reach the top of the stem, or all the leaves of the diseased plant wither;
9级:病株基本枯死。Level 9: The diseased plants basically die.
表37 化合物I与硫酸铜复配对烟草青枯病大田药效试验Table 37 Compound I and copper sulfate compound drug effect test on tobacco bacterial wilt field
Figure PCTCN2021126495-appb-000040
Figure PCTCN2021126495-appb-000040
由测定结果可知，在防治烟草青枯病时，化合物I与硫酸铜复配和单剂相比，在同等有效成分用量下，化合物I+硫酸铜对烟草青枯病的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77.4％以上，持效期较长。As can be seen from the measurement results, when controlling tobacco bacterial wilt, compound I and copper sulfate compound and single agent compared, under the same active ingredient dosage, compound I + copper sulfate on tobacco bacterial wilt 7-day control effect and 14 days. The control effect is significantly higher than that of a single agent. Among them, the 14-day prevention effect can still reach more than 77.4%, and the lasting period is longer.
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。The embodiments of the present invention have been described above. However, the present invention is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (10)

  1. 一种包含化合物I和化合物II的杀菌组合物，其中化合物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，化合物II为铜制剂，例如为喹啉铜、噻菌铜、氢氧化铜、四氨合铜、王铜、硫酸铜钙、络氨铜、硫酸铜、氧化亚铜、绿乳铜、波尔多液、氧氯化铜、松脂酸铜、琥珀酸铜、壬菌铜、噻森铜、硝基腐殖酸铜、咪鲜胺铜盐、柠檬酸铜、琥胶肥酸铜、混合氨基酸铜、碱式硫酸铜、咪唑喹啉铜、乙酸铜等中任意一种。A bactericidal composition comprising compound I and compound II, wherein compound I is 7-chloro-1-cyclopropyl-6-fluoro-4-oxo-1,4-dihydroquinoline-3-carboxylic acid- 2-Methoxyethyl ester, compound II is a copper preparation, such as copper quinoline, copper thiophanate, copper hydroxide, copper tetraammine, copper king, calcium copper sulfate, copper bromide, copper sulfate, cuprous oxide , green milk copper, Bordeaux mixture, copper oxychloride, copper rosinate, copper succinate, nonbacterial copper, thiosen copper, copper nitrohumate, prochloraz copper salt, copper citrate, succinic acid Any one of copper, mixed amino acid copper, basic copper sulfate, imidazoquinoline copper, copper acetate, etc.
  2. 根据权利要求1所述的杀菌组合物，其特征在于，所述杀菌组合物的有效活性成分包括化合物I和化合物II，其中所述化合物I和化合物II的质量比为80～1:1～80，例如50～1:1～50，或30～1:1～30；The bactericidal composition according to claim 1, wherein the effective active ingredients of the bactericidal composition include compound I and compound II, wherein the mass ratio of compound I and compound II is 80-1:1-80 , such as 50～1:1～50, or 30～1:1～30;
    优选地，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在杀菌组合物中的含量之和为1～90％。Preferably, based on the total weight of the sterilizing composition as 100%, the sum of the content of the compound I and the compound II in the sterilizing composition is 1-90%.
  3. 根据权利要求1或2所述的杀菌组合物，其特征在于，所述杀菌组合物可制备成液体制剂或固体制剂。The bactericidal composition according to claim 1 or 2, characterized in that, the bactericidal composition can be prepared as a liquid preparation or a solid preparation.
  4. 根据权利要求1-3任一项所述的杀菌组合物，其特征在于，所述杀菌组合物中至少含有一种表面活性剂；优选地，所述表面活性剂含量为制剂总重量的2％～30％；The bactericidal composition according to any one of claims 1-3, characterized in that, the bactericidal composition contains at least one surfactant; preferably, the content of the surfactant is 2% of the total weight of the preparation ~30%;
    所述表面活性剂例如选自乳化剂、分散剂、润湿剂、增稠剂或消泡剂中的一种或多种。The surfactant is, for example, selected from one or more of emulsifiers, dispersants, wetting agents, thickeners or defoaming agents.
  5. 根据权利要求1-4任一项所述的杀菌组合物，其特征在于，所述杀菌组合物中还含有稳定剂、崩解剂、抗冻剂、粘结剂、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。The bactericidal composition according to any one of claims 1-4, characterized in that, the bactericidal composition further contains a stabilizer, a disintegrating agent, an antifreeze agent, a binding agent, an anti-caking agent, and a suspending agent , at least one of film formers, preservatives, colorants, polymer capsule wall materials, pH adjusters or fillers.
  6. 根据权利要求1-5任一项所述的杀菌组合物，其特征在于，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、种衣剂、乳油、颗粒剂。The bactericidal composition according to any one of claims 1-5, wherein the bactericidal composition can be made into water-dispersible granules, dispersible liquids, wettable powders, suspending agents, water emulsions, and microemulsions , suspoemulsion, microcapsule suspension, microcapsule suspension-suspension, seed coating, emulsifiable concentrate, granule.
  7. 权利要求1-6任一项所述杀菌组合物用于防治病原菌及其引起的农业病害。The bactericidal composition of any one of claims 1-6 is used for controlling pathogenic bacteria and agricultural diseases caused by them.
  8. 根据权利要求7所述的用途，其中，所述杀菌组合物用于防治细菌及细菌引起的植物细菌性病害。The use according to claim 7, wherein the bactericidal composition is used to control bacteria and bacterial diseases of plants caused by bacteria.
  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、黄瓜霜霉病、黄瓜靶斑病、水稻稻瘟病、水稻纹枯病。The use according to claim 8, wherein 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, / Melon fruit spot, rice bacterial blight, rice bacterial spot, rice bacterial brown spot, rice bacterial brown spot, rice bacterial base rot, tomato bacterial wilt and other Solanaceae bacterial wilt disease, mulberry bacterial wilt, peanut bacterial wilt, ginger and ginger blast, tomato/chili bacterial spot, pepper bacterial leaf spot, potato blackleg, corn bacterial wilt, corn bacterial stalk rot, Wheat smut, soybean bacterial spot, soybean bacterial blight, cassava bacterial wilt, mango corner spot, citrus canker, peach bacterial perforation, sunflower stem rot, peach gum disease, pear Fire blight, pear rust, bacterial root cancer of fruit trees, potato ring rot, bean wilt, wheat white leaf spot, potato scab, tomato canker, American holly leaf blight, cucumber downy mildew, cucumber target Spot, rice blast, rice sheath blight.
  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1-6任一项所述杀菌组合物施用于存在病害的植物上。A method for preventing and treating pathogenic bacteria and agricultural diseases caused by them, especially bacterial diseases of plants caused by bacteria and bacteria, comprising applying the bactericidal composition according to any one of claims 1 to 6 to plants with diseases.
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