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WO2022001998A1 - 用作杀真菌剂的二芳胺衍生物 - Google Patents

用作杀真菌剂的二芳胺衍生物 Download PDF

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Publication number
WO2022001998A1
WO2022001998A1 PCT/CN2021/102896 CN2021102896W WO2022001998A1 WO 2022001998 A1 WO2022001998 A1 WO 2022001998A1 CN 2021102896 W CN2021102896 W CN 2021102896W WO 2022001998 A1 WO2022001998 A1 WO 2022001998A1
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spot
acid
blight
disease
leaf
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周银平
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present disclosure relates to the technical field of sterilization, in particular to a diarylamine derivative used as a fungicide.
  • Chinese patents have reported compounds related to antibiotics, the structures of these compounds are quite different from the compounds of this patent, and such structures are only used for bacterial control.
  • the present disclosure provides a diarylamine derivative used as a fungicide, and the structural formula of the diarylamine derivative is as follows:
  • R 1 and R 2 can be the same or different, and are respectively selected from hydrogen, halogen, cyano, C1-C12 alkyl, halogenated C1-C4 alkyl, C1-C4 alkoxy, and halogenated C1-C4 alkoxy base, C1-C4 alkylamino, C1-C4 alkylthio, C1-C4 alkylsulfonyl;
  • R 3 is selected from hydrogen, potassium, sodium, calcium, C1-C4 alkyl, halo C1-C4 alkyl, C1-C4 alkylcarbonyl group, halo C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl group, Halogenated C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, halogenated C1-C4 alkylaminocarbonyl, C1-C4 alkylsulfonyl, halogenated C1-C4 alkylsulfonyl;
  • X is selected from O, S or NR 5 ;
  • R 4 is one or more substituents, each independently selected from halogen, cyano, NO 2 , carboxyl, hydroxyl, C1-C4 alkyl, halogenated C1-C4 alkyl, C1-C4 alkoxy, Halogenated C1-C4 alkoxy, C1-C4 alkyl C1-C4 alkoxy, C1-C4 alkoxy C1-C4 alkoxy, C1-C4 alkoxycarbonyl, halogenated C1-C4 alkoxy Carbonyl, C1-C4 alkylaminocarbonyl, halogenated C1-C4 alkylaminocarbonyl, C1-C4 alkylsulfonyl, halogenated C1-C4 alkylsulfonyl;
  • R 5 is selected from hydrogen, C1-C4 alkyl
  • the diarylamine derivative does not include compound A, and the structural formula of compound A is as follows:
  • R 1 and R 2 may be the same or different, and are respectively selected from hydrogen, halogen, and cyano;
  • Said R 3 is selected from hydrogen, potassium, sodium, calcium, C1-C4 alkyl
  • the X is selected from O or NR 5 ;
  • the R 4 is one or more substituents, each independently selected from halogen, cyano, NO 2 , carboxyl, hydroxyl, C1-C4 alkyl, halogenated C1-C4 alkyl, C1-C4 alkoxy , halogenated C1-C4 alkoxy, C1-C4 alkyl C1-C4 alkoxy, C1-C4 alkoxy C1-C4 alkoxy, C1-C4 alkoxycarbonyl, halogenated C1-C4 alkoxy carbonyl, C1-C4 alkylaminocarbonyl, halogenated C1-C4 alkylaminocarbonyl, C1-C4 alkylsulfonyl, halogenated C1-C4 alkylsulfonyl;
  • R 5 is selected from hydrogen.
  • R 1 and R 2 can be the same or different, and are respectively selected from H, F, Cl, Br, and I;
  • Said R 3 is selected from hydrogen, potassium, sodium;
  • the X is selected from O or NR 5 ;
  • the R 4 is one or more substituents, each independently selected from fluorine, chlorine, bromine or iodine, hydroxyl, cyano, methyl, ethyl, n-propyl, isopropyl, sec-butyl, tertiary Butyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, isopropoxy, trifluoromethoxy, carboxyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, methanesulfonyl acyl;
  • Said R 5 is selected from hydrogen.
  • R 1 and R 2 can be the same or different, and are respectively selected from H, F, Cl, and Br;
  • Said R 3 is selected from hydrogen, potassium, sodium;
  • the X is selected from O or NR 5 ;
  • the R 4 is one or more substituents, each of which is independently selected from fluorine, chlorine, bromine, hydroxyl, cyano, methyl, ethyl, n-propyl, isopropyl, sec-butyl, tert-butyl group, trifluoromethyl, difluoromethyl, methoxy, ethoxy, isopropoxy, trifluoromethoxy, carboxyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, methanesulfonyl ;
  • Said R 5 is selected from hydrogen.
  • R 1 and R 2 can be the same or different, and are respectively selected from H, F, Cl, and Br;
  • Said R 3 is selected from hydrogen, potassium, sodium;
  • the X is selected from O or NR 5 ;
  • the R 4 is one or more substituents, each independently selected from fluorine, chlorine, bromine, hydroxyl, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, iso Propoxy, trifluoromethoxy, carboxyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl;
  • Said R 5 is selected from hydrogen.
  • the present disclosure provides a salt obtained by reacting the diarylamine derivative with an acid or a base.
  • the acid includes at least one of the following: an organic acid or an inorganic acid;
  • the organic acid includes at least one of the following: carboxylic acid, such as acetic acid, propionic acid, butyric acid, oxalic acid, adipic acid, dodecanedioic acid, lauric acid, stearic acid, trifluoroacetic acid, fumaric acid, Maleic, benzoic or phthalic acid, sulfonic acids, such as methanesulfonic acid, 1,3-propanedisulfonic acid, p-toluenesulfonic acid or dodecylbenzenesulfonic acid;
  • carboxylic acid such as acetic acid, propionic acid, butyric acid, oxalic acid, adipic acid, dodecanedioic acid, lauric acid, stearic acid, trifluoroacetic acid, fumaric acid, Maleic, benzoic or phthalic acid
  • sulfonic acids such as methanesulfonic acid, 1,3-
  • the inorganic acid includes at least one of the following: hydrochloric acid, sulfuric acid, nitric acid or carbonic acid.
  • the alkali includes at least one of the following: sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, sodium metal, sodium hydride, Sodium amide, butyl lithium.
  • the present disclosure provides the application of the diarylamine derivative or the salt of claim 6 in controlling fungal diseases.
  • the fungal diseases include downy mildew, white rust, damping off, cotton rot, blight, late blight, fusarium wilt, root rot, blight, anthracnose, verticillium wilt, scab , Botrytis, brown spot, black spot, leaf blight, early blight, ring disease, rice blast, rust, smut, powdery mildew or sclerotinia.
  • the fungal diseases include leaf blight, stem base rot, corn round spot, kenaf lumbar fold disease, millet black sheath disease, sugarcane eye spot disease, cotton boll aspergillosis, peanut crown rot, soybean stem Blight, soybean black spot, melon large spot, peanut net spot, tea red leaf spot, pepper white spot, wax gourd leaf spot, celery black rot, spinach heart rot, kenaf leaf mildew, red leaf spot Hemp spot, jute stem spot, soybean purple spot, sesame leaf spot, castor grey spot, tea-brown leaf spot, eggplant brown spot, kidney bean red spot, bitter gourd white spot, watermelon spot, jute rot Disease, sunflower rhizome rot, bean char rot, soybean target spot disease, eggplant Corynebacterium leaf spot, cucumber target leaf spot, tomato leaf mold, eggplant leaf mold, broad bean red spot.
  • the present disclosure provides a germicidal composition containing the diarylamine derivative as an active component.
  • the weight percentage of the active ingredient in the bactericidal composition is 0.1-99%.
  • the composition includes active ingredients compatible with the diarylamine derivative, the active ingredients include pesticides, fungicides, plant growth regulators, antibiotics, herbicides, fertilizers.
  • the use forms of the composition include dry powders, wettable powders, emulsifiable concentrates, microemulsions, pastes, granules, solutions, suspensions, and water-dispersible granules.
  • the present disclosure provides the application of the fungicidal composition in controlling fungal diseases.
  • the fungal diseases include downy mildew, white rust, damping off, cotton rot, blight, late blight, fusarium wilt, root rot, blight, anthracnose, verticillium wilt, scab , gray mold, brown spot, black spot, leaf blight, early blight, ring disease, rice blast, rust, smut, powdery mildew, sclerotinia, leaf blight, stem rot, corn Round spot disease, kenaf lumbar fold disease, millet black sheath disease, sugarcane eye spot disease, cotton boll aspergillosis, peanut crown rot, soybean stem blight, soybean black spot disease, melon large leaf spot disease, peanut web spot disease, tea Red leaf spot, pepper white spot, wax gourd leaf spot, celery black rot, spinach heart rot, kenaf leaf mold, kenaf spot, jute stem spot, soybean purple spot, sesame leaf spot, castor
  • the present disclosure provides a diarylamine derivative used as a fungicide, which can effectively control diseases caused by downy mildew, blight, anthracnose, rust and the like as a fungicide.
  • One embodiment of the present disclosure provides a diarylamine derivative used as a fungicide, and the general structural formula is as follows:
  • R 1 and R 2 may be the same or different, and are each independently selected from hydrogen, halogen, cyano, C1-C12 alkyl, halogenated C1-C4 alkyl, C1-C4 alkoxy, and halogenated C1-C4 alkane Oxy group, C1-C4 alkylamino group, C1-C4 alkylthio group, C1-C4 alkylsulfonyl group;
  • R 3 is selected from hydrogen, potassium, sodium, calcium, C1-C4 alkyl, halo C1-C4 alkyl, C1-C4 alkylcarbonyl group, halo C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl group, Halogenated C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, halogenated C1-C4 alkylaminocarbonyl, C1-C4 alkylsulfonyl, halogenated C1-C4 alkylsulfonyl;
  • X is selected from O, S or NR 5 ;
  • R 4 is one or more substituents, each independently selected from halogen, cyano, NO2, carboxyl, hydroxyl, C1-C4 alkyl, halogenated C1-C4 alkyl, C1-C4 alkoxy, halogenated C1-C4 alkoxy, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkoxy, C1-C4 alkoxy, C1-C4 alkoxycarbonyl, halogenated C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, halogenated C1-C4 alkylaminocarbonyl, C1-C4 alkylsulfonyl, halogenated C1-C4 alkylsulfonyl;
  • R 5 is selected from hydrogen, C1-C4 alkyl
  • the diarylamine derivative does not include compound A, and the structural formula of compound A is as follows:
  • the diarylamine derivative is:
  • R 1 and R 2 may be the same or different, and are independently selected from hydrogen, halogen and cyano;
  • R 3 is selected from hydrogen, potassium, sodium, calcium, C1-C4 alkyl
  • X is selected from O or NR 5 ;
  • R 4 is one or more substituents, each independently selected from halogen, cyano, NO2, carboxyl, hydroxyl, C1-C4 alkyl, halogenated C1-C4 alkyl, C1-C4 alkoxy, halogenated C1-C4 alkoxy, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkoxy, C1-C4 alkoxy, C1-C4 alkoxycarbonyl, halogenated C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, halogenated C1-C4 alkylaminocarbonyl, C1-C4 alkylsulfonyl, halogenated C1-C4 alkylsulfonyl;
  • R 5 is selected from hydrogen.
  • the diarylamine derivative is:
  • R 1 and R 2 can be the same or different, and are independently selected from H, F, Cl, Br, and I;
  • R 3 is selected from hydrogen, potassium, sodium
  • X is selected from O or NR 5 ;
  • R 4 is one or more substituents, each independently selected from fluorine, chlorine, bromine or iodine, hydroxy, cyano, methyl, ethyl, n-propyl, isopropyl, sec-butyl, tert-butyl , trifluoromethyl, difluoromethyl, methoxy, ethoxy, isopropoxy, trifluoromethoxy, carboxyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, methanesulfonyl;
  • R 5 is selected from hydrogen.
  • the diarylamine derivative is:
  • R 1 and R 2 can be the same or different, and are respectively selected from H, F, Cl, and Br;
  • R 3 is selected from hydrogen, potassium, sodium
  • X is selected from O or NR 5 ;
  • R 4 is one or more substituents, each independently selected from fluorine, chlorine, bromine, hydroxyl, cyano, methyl, ethyl, n-propyl, isopropyl, sec-butyl, tert-butyl, tri- Fluoromethyl, difluoromethyl, methoxy, ethoxy, isopropoxy, trifluoromethoxy, carboxyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, methanesulfonyl;
  • R 5 is selected from hydrogen.
  • the diarylamine derivative is:
  • R 1 and R 2 may be the same or different, and are independently selected from H, F, Cl, and Br;
  • R 3 is selected from hydrogen, potassium, sodium
  • X is selected from O or NR 5 ;
  • R 4 is one or more substituents, each independently selected from fluorine, chlorine, bromine, hydroxy, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, isopropoxy , trifluoromethoxy, carboxyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl;
  • R 5 is selected from hydrogen.
  • stereoisomers can be formed due to the attachment of different groups or substituents to chiral carbons or nitrogens (R and S represent different configurations, respectively).
  • R and S represent different configurations, respectively.
  • the present disclosure includes the R-isomer and S-isomer and mixtures thereof in any ratio.
  • halogen refers to fluorine, chlorine, bromine or iodine.
  • alkyl straight chain, branched chain or cyclized alkyl such as methyl, ethyl, propyl, isopropyl, tert-butyl or cyclopropyl.
  • Haloalkyl straight or branched chain haloalkyl, the hydrogen atoms on these alkyl groups may be partially or fully substituted by halogen atoms, for example, haloalkyl groups such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl group, difluoromethyl or trifluoromethyl.
  • Alkoxy Linear, branched or cyclic alkoxy, for example methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy or cyclopropoxy.
  • Haloalkoxy straight or branched chain haloalkoxy, the hydrogen atoms in these alkoxy groups may be partially or fully substituted by halogen atoms, for example, haloalkyl groups such as chloromethoxy, dichloromethoxy, trichloro Methoxy, fluoromethoxy, difluoromethoxy or trifluoromethoxy.
  • Alkylthio A straight or branched chain alkyl group attached to the structure via a sulfur atom bond.
  • Halogenated alkylthio group straight-chain or branched-chain alkylthio group, the hydrogen atoms on these alkylthio groups may be partially or totally substituted by halogen atoms.
  • halogen atoms for example, chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio and the like.
  • the diarylamine derivatives are salts obtained by reacting with acids or bases.
  • the acids that can form salts with the diarylamine derivatives of the present disclosure include at least one of the following: organic acids, such as carboxylic acids, such as acetic acid, propionic acid, butyric acid, Oxalic acid, adipic acid, dodecanedioic acid, lauric acid, stearic acid, trifluoroacetic acid, fumaric acid, maleic acid, benzoic or phthalic acid, sulfonic acids such as methanesulfonic acid, 1,3- propanedisulfonic acid, p-toluenesulfonic acid or dodecylbenzenesulfonic acid; and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid or carbonic acid.
  • organic acids such as carboxylic acids, such as acetic acid, propionic acid, butyric acid, Oxalic acid, adipic acid, dodecanedioic acid, lauric acid, stearic acid,
  • bases that can form salts with the diarylamine derivatives of the present disclosure include at least one of the following: sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, carbonic acid Potassium, sodium carbonate, sodium bicarbonate, potassium bicarbonate, sodium metal, sodium hydride, sodium amide, butyllithium, etc.
  • the diarylamine derivatives of the present disclosure can be prepared according to the following methods:
  • L is an easily leaving group such as F, Cl, and Br.
  • (formula a) is reacted with a substituted pyridazineamine (formula b) in the presence or absence of a base, preferably using a solvent.
  • the reaction temperature is preferably 0 to 150°C, and the reaction time is 30 minutes to 20 hours, preferably 0.5 to 10 hours.
  • the solvent is any inert solvent that has no direct effect on the reaction, including aromatic hydrocarbons, such as benzene, toluene, and xylene; ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; halogenated hydrocarbons, such as dichloromethane, chloroform, and dichloromethane.
  • Ethyl chloride lipids such as methyl acetate and ethyl acetate; and polar solvents such as tetrahydrofuran, acetonitrile, dioxane, N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide and pyridine.
  • lipids such as methyl acetate and ethyl acetate
  • polar solvents such as tetrahydrofuran, acetonitrile, dioxane, N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide and pyridine.
  • the bases include metal hydrides such as sodium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium amide; organic amines such as pyridine and triethylamine.
  • the solvent is distilled off under reduced pressure, water is added to the resulting residue, and water-insoluble aromatic hydrocarbons such as benzene, toluene are used. and xylene; halogenated alkanes such as chloroform and dichloromethane; and esters such as ethyl acetate.
  • the resulting extract was dried and the solvent was removed under reduced pressure.
  • the diarylamine derivatives of the present disclosure show excellent activity against various diseases in the agricultural field.
  • the examples of diseases mentioned below are only used to illustrate the present disclosure, but in no way limit the present disclosure.
  • the diarylamine derivatives of the present disclosure can be used to control the following diseases: Oomycetes diseases, such as downy mildew (cucumber downy mildew, rape downy mildew, soybean downy mildew, sugar beet downy mildew, sugarcane downy mildew, tobacco downy mildew Downy mildew, pea downy mildew, loofah downy mildew, wax gourd downy mildew, melon downy mildew, cabbage downy mildew, spinach downy mildew, radish downy mildew, grape downy mildew, onion downy mildew) , White rust (rape white rust, cabbage-like white rust), damping off (rape damping, tobacco damping, tomato damping, pepper damping, eggplant damping, cucumber damping, cotton seedlings Damping disease), cotton rot (hot pepper cotton rot, loofah cotton rot, wax gourd cotton rot), blight (broad bean
  • the diarylamine derivatives of the present disclosure have good bactericidal activity, and can be advantageously used to protect crops, livestock and breeding animals important to agriculture and horticulture, as well as environments frequented by humans from pathogens.
  • the diarylamine derivatives are used to prepare fungicides for controlling fungal diseases.
  • the fungal diseases are downy mildew, white rust, damping-off, cotton rot, blight, late blight, fusarium wilt, root rot, blight, anthracnose, verticillium wilt, scab, botrytis , brown spot, black spot, leaf blight, early blight, ring disease, rice blast, rust, smut, powdery mildew or sclerotinia.
  • the fungal diseases further include leaf blight, stem base rot, corn blight, kenaf lumbar fold, millet black sheath disease, sugarcane eye spot disease, cotton boll aspergillosis, peanut crown rot , soybean stem blight, soybean black spot, melon large spot, peanut net spot, tea red leaf spot, pepper white spot, wax gourd leaf spot, celery black rot, spinach heart rot, kenaf leaf mold Disease, kenaf spot, jute stem spot, soybean purple spot, sesame leaf spot, castor gray spot, tea-brown leaf spot, eggplant brown spot, kidney bean red spot, bitter gourd white spot, watermelon spot, Jute blight rot, sunflower rhizome rot, bean char rot, soybean target spot disease, eggplant corynebacterium leaf spot, cucumber target spot disease, tomato leaf mold, eggplant leaf mold, broad bean red spot.
  • the amount of compound to be used to obtain the desired effect will vary depending on factors such as compound used, crop to be protected, type of pest, degree of infestation, climatic conditions, method of application, dosage form employed.
  • dosages of 10 grams to 1000 grams of the diarylamine derivative per hectare provide adequate control.
  • One embodiment of the present disclosure provides a method of diarylamine derivatives for controlling agricultural and horticultural important crops and/or phytopathogenic fungi in environments frequented by livestock and breeding stock and/or humans.
  • the dosage of the compound varied from 10 grams to 1000 grams per hectare.
  • compositions containing one or more of the diarylamine derivatives of the present disclosure For practical use in agriculture, it is often beneficial to use compositions containing one or more of the diarylamine derivatives of the present disclosure.
  • an embodiment of the present disclosure provides a bactericidal composition containing one or more diarylamine derivatives as an active ingredient, and the weight percentage of the active ingredient in the composition is 0.1-99%.
  • An embodiment of the present disclosure provides the use of the bactericidal composition for preparing and controlling fungal diseases.
  • the fungal diseases are the same as the types of fungal diseases controlled by the diarylamine derivatives described above.
  • composition can be used in the form of dry powder, wettable powder, emulsifiable concentrate, microemulsion, paste, granule, solution, suspension, water dispersible granule, etc.
  • the choice of composition type depends on the specific application.
  • compositions are prepared by known methods, eg by diluting or dissolving the active substance with a solvent medium and/or solid diluent, optionally in the presence of a surfactant.
  • useful solid diluents or carriers are, for example, silica, kaolin, bentonite, talc, diatomaceous earth, dolomite, calcium carbonate, magnesium oxide, chalk, clay, synthetic silicates, magnesium silicates Soil, sepiolite, etc.
  • useful liquid diluents in addition to water include, for example, aromatic organic solvents (mixtures of xylenes or alkylbenzenes, chlorobenzene, etc.), paraffins (petroleum fractions), alcohols (methanol, propanol) , butanol, octanol, glycerol), esters (ethyl acetate, isobutyl acetate, etc.), ketones (cyclohexanone, acetone, acetophenone, isophorone, ethyl amyl ketone, etc.), Amides (N,N-dimethylformamide, N-methylpyrrolidone, etc.).
  • aromatic organic solvents mixture of xylenes or alkylbenzenes, chlorobenzene, etc.
  • paraffins petroleum fractions
  • alcohols methanol, propanol
  • butanol, octanol glycerol
  • useful surfactants include sodium such as alkylsulfonates, alkylarylsulfonates, polyoxyethylene alkylphenols, polyoxyethylene esters of sorbitol, lignosulfonates, and the like , calcium, triethylamine or triethanolamine salts.
  • the composition may also contain specific additives for specific purposes, such as binders such as gum arabic, polyvinyl alcohol, polyvinylpyrrolidone, and the like.
  • binders such as gum arabic, polyvinyl alcohol, polyvinylpyrrolidone, and the like.
  • the concentration of the active ingredient in the above compositions can vary widely depending on, for example, the active ingredient, the purpose of use, the environmental conditions and the type of formulation employed.
  • the active ingredient concentration is usually in the range of 0.1-99%, preferably 5-60%.
  • other active ingredients compatible with the diarylamine derivatives of the present disclosure such as other acaricides/insecticides, fungicides, plant growth regulators, Antibiotics, herbicides, fertilizers.
  • the form of the composition is not limited thereto, and one or two or more of the compounds in combination may be mixed as an active ingredient.
  • suspending agent The active ingredient content in common formula is 5-35%.
  • Solvents with water as medium such as water suspension, microemulsion, water emulsion, add the original drug, dispersing agent, suspending agent and antifreeze into a sand mill, and grind to make a suspension.
  • Preparation of water emulsion add the original drug, solvent and emulsifier together to dissolve into a homogeneous oil phase. Mix together water, antifreeze, etc. to form a homogeneous aqueous phase. Under high-speed stirring, the water phase is added to the oil phase or the oil phase is added to the water phase to form a water emulsion with good dispersibility.
  • the active ingredient content of the aqueous emulsion of the present disclosure is generally 5% to 15%.
  • the diarylamine derivatives of the present disclosure can be dissolved in one or several mixed solvents, and then an emulsifier can be added to enhance the dispersion effect of the compound in water.
  • Preparation of wettable powder According to the requirements of the formula, fully mix the original drug, various surfactants and solid diluents, etc., and pulverize by an ultra-fine pulverizer to obtain a wettable powder with a predetermined content (for example, 10-60%). product.
  • a predetermined content for example, 10-60%.
  • the diarylamine derivatives of the present disclosure can be mixed with finely divided solid powders such as clays, inorganic silicates, carbonates and wetting, binder and/or dispersing agents Make up the mixture.
  • Preparation of water-dispersible granules Mix and pulverize the original drug, powdered solid diluent, wetting and spreading agent, and binder, add water and knead, and then add it to a granulator equipped with a certain size of screen. Granulated, then dried and sieved (according to the screen range).
  • the original drug, dispersing agent, disintegrating agent, wetting agent and solid diluent can also be added to a sand mill, ground with water as a medium to make a suspension, and then spray-dried and granulated.
  • the preparation content is 20- 30% granular product.
  • the components of 30% wettable powder are as follows:
  • Compound 2 and other components listed in this example are thoroughly mixed, and after being pulverized by an ultrafine pulverizer, a 30% wettable powder product is obtained.
  • the components of the 40% suspension concentrate are as follows:
  • Compound 1 and the other components listed in this example are thoroughly mixed to obtain a concentrated suspending agent, which can be diluted with water to obtain a dilution of any desired concentration.
  • Compound 23 and other components listed in this example were mixed and pulverized, and after adding water and kneading, added to a granulator with a 10-100 mesh screen for granulation, and then dried and sieved (according to the range of the screen mesh). ).
  • the diarylamine derivatives disclosed in the present disclosure have good activity against various pathogens in the agricultural field.
  • the activity test method and some measurement results are as follows.
  • the in vivo potted assay method was used.
  • the original drug of the compound to be tested is dissolved with a small amount of acetone (the volume ratio of acetone to the sprayed liquid is equal to 0.05), and diluted with water containing 0.1% Tween 80 to the desired concentration.
  • Spray application to plant test material, and disease inoculation is carried out 24 hours later.
  • the plants were cultured in an artificial climate chamber, and 24 hours later, the plant specimens were transferred to a greenhouse for culture. After the control is fully developed (usually one week), the evaluation of the compound's disease prevention effect is carried out.
  • the evaluation method of compound disease prevention effect is as follows:
  • ⁇ fungal infection percentage of treated crops
  • ⁇ fungal infection percentage of untreated (blank) crops
  • An efficacy of "0" indicates that the infestation level of the treated crop is the same as that of the untreated control crop; an efficacy of "100" indicates that the treated crop is not infested.
  • the compounds of the present disclosure have good control effects on important diseases that endanger agricultural production, and have broad application prospects.
  • the present disclosure provides a diarylamine derivative used as a fungicide, a salt thereof, and a bactericidal composition, which have good control effects on important diseases that endanger agricultural production, especially cucumber downy mildew and blight , rust and other diseases are very effective, with good technical effects of low dose and high efficiency, and has broad application prospects.

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Abstract

本公开公开了一种用作杀真菌剂的二芳胺衍生物，结构通式如图所示。本公开的化合物具有很好的杀菌活性，对黄瓜霜霉病、疫病、锈病等引致的病害十分有效，特别是对黄瓜霜霉病、疫病防效更好，在很低的剂量下就可以获得很好的效果，具有广阔应用前景。

Description

用作杀真菌剂的二芳胺衍生物
相关申请的交叉引用
本公开要求于2020年07月01日提交中国专利局的申请号为“202010629681.3”名称为“用作杀真菌剂的二芳胺衍生物”的中国专利申请的优先权，其全部内容通过引用结合在本公开中。
技术领域
本公开涉及杀菌技术领域，尤其是涉及一种用作杀真菌剂的二芳胺衍生物。
背景技术
病菌对作物，尤其是对于能够满足人类基本需求的粮食和纤维等农产品，如棉花，水稻，玉米，小麦，大豆等造成很大的损害。杀死或抑制病菌生长的同时避免或减少对作物的损害是一种改进农业生产的有效途径。因此需要不断开发更有效的新型杀菌剂。虽然中国专利已经报道了有关抗生素的化合物，但该类化合物均与本专利化合物结构差别较大，并且该类结构仅用于细菌防治。
公开内容
有鉴于此，特提出本公开。
本公开提供一种用作杀真菌剂的二芳胺衍生物，所述二芳胺衍生物的结构式如下所示：
Figure PCTCN2021102896-appb-000001
其中，R 1、R 2可相同或不同，分别选自氢、卤素、氰基、C1-C12烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C1-C4烷胺基、C1-C4烷硫基、C1-C4烷基磺酰基；
R 3选自氢、钾、钠、钙、C1-C4烷基、卤代C1-C4烷基、C1-C4烷基羰基、卤代C1-C4烷基羰基、C1-C4烷氧基羰基、卤代C1-C4烷氧基羰基、C1-C4烷胺基羰基、卤代C1-C4烷胺基羰基、C1-C4烷基磺酰基、卤代C1-C4烷基磺酰基；
X选自O、S或NR 5；
R 4为一种或多种的取代基，各自独立地选自卤素、氰基、NO 2、羧基、羟基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C1-C4烷基C1-C4烷氧基、C1-C4烷氧基C1-C4烷氧基、C1-C4烷氧基羰基、卤代C1-C4烷氧基羰基、C1-C4烷胺基羰基、卤代C1-C4烷胺基羰基、C1-C4烷基磺酰基、卤代C1-C4烷基磺酰基；
R 5选自氢、C1-C4烷基；
所述二芳胺衍生物不包括化合物A，化合物A的结构式如下所示：
Figure PCTCN2021102896-appb-000002
可选地，所述R 1、R 2可相同或不同，分别选自氢、卤素、氰基；
所述R 3选自氢、钾、钠、钙、C1-C4烷基；
所述X选自O或NR 5；
所述R 4为一种或多种取代基，各自独立地选自卤素、氰基、NO 2、羧基、羟基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C1-C4烷基C1-C4烷氧基、C1-C4烷氧基C1-C4烷氧基、C1-C4烷氧基羰基、卤代C1-C4烷氧基羰基、C1-C4烷胺基羰基、卤代C1-C4烷胺基羰基、C1-C4烷基磺酰基、卤代C1-C4烷基磺酰基；
R 5选自氢。
可选地，所述R 1、R 2可相同或不同，分别选自H、F、Cl、Br、I；
所述R 3选自氢、钾、钠；
所述X选自O或NR 5；
所述R 4为一种或多种取代基，各自独立地选自氟、氯、溴或碘，羟基、氰基、甲基、乙基、正丙基、异丙基、仲丁基、叔丁基、三氟甲基、二氟甲基、甲氧基、乙氧基、异丙氧基、三氟甲氧基、羧基、甲氧基羰基、乙氧基羰基、甲氨基羰基、甲磺酰基；
所述R 5选自氢。
可选地，所述R 1、R 2可相同或不同，分别选自H、F、Cl、Br；
所述R 3选自氢、钾、钠；
所述X选自O或NR 5；
所述R 4为一种或多种取代基，其各自独立地选自氟、氯、溴，羟基、氰基、甲基、乙基、正丙基、异丙基、仲丁基、叔丁基、三氟甲基、二氟甲基、甲氧基、乙氧基、异丙氧基、三氟甲氧基、羧基、甲氧基羰基、乙氧基羰基、甲氨基羰基、甲磺酰基；
所述R 5选自氢。
可选地，所述R 1、R 2可相同或不同，分别选自H、F、Cl、Br；
所述R 3选自氢、钾、钠；
所述X选自O或NR 5；
所述R 4为一种或多种取代基，其各自独立地选自氟、氯、溴，羟基、氰基、甲基、乙基、三氟甲基、甲氧基、乙氧基、异丙氧基、三氟甲氧基、羧基、甲氧基羰基、乙氧基羰基、甲氨基羰基；
所述R 5选自氢。
本公开提供一种所述的二芳胺衍生物与酸或碱反应得到的盐。
可选地，所述酸包括以下的至少一种：有机酸或无机酸；
所述有机酸包括以下的至少一种：羧酸，如乙酸、丙酸、丁酸、草酸、己二酸、十二烷二酸、月桂酸、硬脂酸、三氟乙酸、富马酸、马来酸、苯甲酸或苯二甲酸、磺酸，如甲磺酸、1，3-丙二磺酸、对甲苯磺酸或十二烷基苯磺酸；
及所述无机酸包括以下的至少一种：盐酸、硫酸、硝酸或碳酸。
可选地，所述碱包括以下的至少一种：氢氧化钠、氢氧化钾、氢氧化钙、氢氧化锂、碳酸钾、碳酸钠、碳酸氢钠、碳酸氢钾、金属钠、氢化钠、氨基钠、丁基锂。
本公开提供所述的二芳胺衍生物或权利要求6所述的盐在防治真菌病害中的应用。
可选地，所述真菌病害包括霜霉病、白锈病、猝倒病、绵腐病、疫病、晚疫病、枯萎病、根腐病、立枯病、炭疽病、黄萎病、黑星病、灰霉病、褐斑病、黑斑病、斑枯病、早疫病、轮纹病、稻瘟病、锈病、黑穗病、白粉病或菌核病。
可选地，所述真菌病害包括叶枯病、茎基腐病、玉米圆斑病、红麻腰折病、粟黑鞘病、甘蔗眼斑病、棉铃曲霉病、花生冠腐病、大豆茎枯病、大豆黑点病、甜瓜大斑病、花生网斑病、茶赤叶斑病、辣椒白星病、冬瓜叶斑病、芹菜黑腐病、菠菜心腐病、红麻叶霉病、红麻斑点病、黄麻茎斑病、大豆紫斑病、芝麻叶斑病、蓖麻灰斑病、茶褐色叶 斑病、茄子褐色圆星病、菜豆红斑病、苦瓜白斑病、西瓜斑点病、黄麻枯腐病、向日葵根茎腐病、菜豆炭腐病、大豆靶点病、茄子棒孢叶斑病、黄瓜靶斑病、番茄叶霉病、茄子叶霉病、蚕豆赤斑病。
本公开提供一种杀菌组合物，所述杀菌组合物含有所述的二芳胺衍生物作为活性组分。
可选地，所述活性组分在杀菌组合物中的重量百分含量为0.1-99％。
可选地，所述组合物中包括与所述二芳胺衍生物兼容的活性成分，所述活性成分包括杀虫剂、杀真菌剂、植物生长调节剂、抗生素、除草剂、肥料。
可选地，所述组合物的使用形式包括干粉、可湿性粉剂、乳油、微乳剂、糊剂、颗粒剂、溶液、悬浮剂、水分散性粒剂。
本公开提供所述的杀菌组合物在防治真菌病害中的应用。
可选地，所述真菌病害包括霜霉病、白锈病、猝倒病、绵腐病、疫病、晚疫病、枯萎病、根腐病、立枯病、炭疽病、黄萎病、黑星病、灰霉病、褐斑病、黑斑病、斑枯病、早疫病、轮纹病、稻瘟病、锈病、黑穗病、白粉病、菌核病、叶枯病、茎基腐病、玉米圆斑病、红麻腰折病、粟黑鞘病、甘蔗眼斑病、棉铃曲霉病、花生冠腐病、大豆茎枯病、大豆黑点病、甜瓜大斑病、花生网斑病、茶赤叶斑病、辣椒白星病、冬瓜叶斑病、芹菜黑腐病、菠菜心腐病、红麻叶霉病、红麻斑点病、黄麻茎斑病、大豆紫斑病、芝麻叶斑病、蓖麻灰斑病、茶褐色叶斑病、茄子褐色圆星病、菜豆红斑病、苦瓜白斑病、西瓜斑点病、黄麻枯腐病、向日葵根茎腐病、菜豆炭腐病、大豆靶点病、茄子棒孢叶斑病、黄瓜靶斑病、番茄叶霉病、茄子叶霉病或蚕豆赤斑病。
实施方式
I.二芳胺衍生物
为了满足农业上的要求，本公开提供了一种用作杀真菌剂的二芳胺衍生物，该化合物作为杀菌剂可有效控制霜霉病病菌、疫病、炭疽病、锈病病菌等引起的病害。
本公开的技术方案如下：
本公开一实施方式提供一种用作杀真菌剂的二芳胺衍生物，结构通式如下所示：
Figure PCTCN2021102896-appb-000003
式中：
R 1、R 2可相同或不同，分别各自独立地选自氢、卤素、氰基、C1-C12烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C1-C4烷胺基、C1-C4烷硫基、C1-C4烷基磺酰基；
R 3选自氢、钾、钠、钙、C1-C4烷基、卤代C1-C4烷基、C1-C4烷基羰基、卤代C1-C4烷基羰基、C1-C4烷氧基羰基、卤代C1-C4烷氧基羰基、C1-C4烷胺基羰基、卤代C1-C4烷胺基羰基、C1-C4烷基磺酰基、卤代C1-C4烷基磺酰基；
X选自O、S或NR 5；
R 4为一种或多种取代基，各自独立地选自卤素、氰基、NO2、羧基、羟基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C1-C4烷基C1-C4烷氧基、C1-C4烷氧基C1-C4烷氧基、C1-C4烷氧基羰基、卤代C1-C4烷氧基羰基、C1-C4烷胺基羰基、卤代C1-C4烷胺基羰基、C1-C4烷基磺酰基、卤代C1-C4烷基磺酰基；
R 5选自氢、C1-C4烷基；
所述二芳胺衍生物不包括化合物A，化合物A的结构式如下所示：
Figure PCTCN2021102896-appb-000004
在一些实施方式中，二芳胺衍生物为：
R 1、R 2可相同或不同，分别各自独立地选自氢、卤素、氰基；
R 3选自氢、钾、钠、钙、C1-C4烷基；
X选自O或NR 5；
R 4为一种或多种取代基，各自独立地选自卤素、氰基、NO2、羧基、羟基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C1-C4烷基C1-C4烷氧基、C1-C4烷氧基C1-C4烷氧基、C1-C4烷氧基羰基、卤代C1-C4烷氧基羰基、C1-C4烷胺基羰基、卤代C1-C4烷胺基羰基、C1-C4烷基磺酰基、卤代C1-C4烷基磺酰基；
R 5选自氢。
在一种或多种示例性实施方式中，二芳胺衍生物为：
R 1、R 2可相同或不同，分别各自独立地选自H、F、Cl、Br、I；
R 3选自氢、钾、钠；
X选自O或NR 5；
R 4为一种或多种取代基，各自独立地选自氟、氯、溴或碘，羟基、氰基、甲基、乙基、正丙基、异丙基、仲丁基、叔丁基、三氟甲基、二氟甲基、甲氧基、乙氧基、异丙氧基、三氟甲氧基、羧基、甲氧基羰基、乙氧基羰基、甲氨基羰基、甲磺酰基；
R 5选自氢。
在一种或多种示例性实施方式中，二芳胺衍生物为：
R 1、R 2可相同或不同，分别选自H、F、Cl、Br；
R 3选自氢、钾、钠；
X选自O或NR 5；
R 4为一种或多种取代基，各自独立地选自氟、氯、溴，羟基、氰基、甲基、乙基、正丙基、异丙基、仲丁基、叔丁基、三氟甲基、二氟甲基、甲氧基、乙氧基、异丙氧基、三氟甲氧基、羧基、甲氧基羰基、乙氧基羰基、甲氨基羰基、甲磺酰基；
R 5选自氢。
在一种或多种示例性实施方式中，二芳胺衍生物为：
R 1、R 2可相同或不同，分别各自独立地选自H、F、Cl、Br；
R 3选自氢、钾、钠；
X选自O或NR 5；
R 4为一种或多种取代基，各自独立地选自氟、氯、溴，羟基、氰基、甲基、乙基、三氟甲基、甲氧基、乙氧基、异丙氧基、三氟甲氧基、羧基、甲氧基羰基、乙氧基羰基、甲氨基羰基；
R 5选自氢。
在本公开的二芳胺衍生物中，由于手性碳或氮连接不同的基团或取代基而可以形成立体异构体(分别以R和S来表示不同的构型)。本公开包括R型异构体和S型异构体及其任何比例的混合物。
上面给出的二芳胺衍生物中，汇集所用术语一般定义如下：
未取代表示所有取代基都为氢。
如本文所用，卤素：指氟、氯、溴或碘。
如本文所用，烷基：直链、支链或环化烷基，例如甲基、乙基、丙基、异丙基、叔丁基或环丙基。
卤代烷基：直链或支链卤代烷基，在这些烷基上的氢原子可部分或全部被卤原子所取代，例如，卤代烷基诸如氯甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基或三氟甲基。
烷氧基：直链、支链或环化烷氧基，例如甲氧基、乙氧基、丙氧基、异丙氧基、叔丁氧基或环丙氧基。
卤代烷氧基：直链或支链卤代烷氧基，在这些烷氧基上的氢原子可部分或全部被卤原子所取代，例如，卤代烷基诸如氯甲氧基、二氯甲氧基、三氯甲氧基、氟甲氧基、二氟甲氧基或三氟甲氧基。
烷硫基：直链或支链烷基，经硫原子键连接到结构上。
卤代烷硫基：直链或支链烷硫基，在这些烷硫基上的氢原子可部分或全部被卤原子所取代。例如，氯甲硫基、二氯甲硫基、三氯甲硫基、氟甲硫基、二氟甲硫基、三氟甲硫基、氯氟甲硫基等。
II.二芳胺衍生物的盐
在一些实施方式中，所述的二芳胺衍生物与酸或碱反应得到的盐。
在一种或多种示例性实施方式中，可以与本公开的二芳胺类衍生物成盐的酸包括以下的至少一种：有机酸，诸如羧酸，如乙酸、丙酸、丁酸、草酸、己二酸、十二烷二酸、月桂酸、硬脂酸、三氟乙酸、富马酸、马来酸、苯甲酸或苯二甲酸、磺酸，如甲磺酸、1，3-丙二磺酸、对甲苯磺酸或十二烷基苯磺酸；及无机酸，诸如盐酸、硫酸、硝酸或碳酸。
在一种或多种示例性实施方式中，可以与本公开的二芳胺衍生物成盐的碱包括以下的至少一种：氢氧化钠、氢氧化钾、氢氧化钙、氢氧化锂、碳酸钾、碳酸钠、碳酸氢钠、碳酸氢钾、金属钠、氢化钠、氨基钠、丁基锂等。
本公开的部分二芳胺衍生物可以用表1中列出的具体化合物来说明，但并不限定本公开。
表1本公开部分二芳胺衍生物举例
Figure PCTCN2021102896-appb-000005
Figure PCTCN2021102896-appb-000006
Figure PCTCN2021102896-appb-000007
Figure PCTCN2021102896-appb-000008
III.二芳胺衍生物的合成方法：
在一些实施方式中，本公开的二芳胺衍生物可按照以下方法制备：
路线一、
Figure PCTCN2021102896-appb-000009
L为F、Cl、Br等易离去基团。
根据上述反应方程式，在有碱或无碱存在的情况下，(式a)和取代哒嗪胺(式b)反应，所述反应优选使用溶剂。反应温度优选0至150℃，反应时间为30分钟至20小时，优选0.5～10小时。所述溶剂是对反应无直接影响的任何惰性溶剂，包括芳烃，如苯、甲苯和二甲苯；酮类，如丙酮甲乙酮和甲基异丁酮；卤代烃，如二氯甲烷、氯仿和二氯乙烷；脂类，如乙酸甲酯和乙酸乙酯；及极性溶剂，如四氢呋喃、乙腈、二噁烷、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、二甲亚砜和吡啶。
所述的碱包括金属氢化物，如氢化钠；碱金属氢氧化物，如氢氧化钠和氢氧化钾；碱金属碳酸盐，如碳酸钠和碳酸钾；氨基钠；有机胺类，如吡啶和三乙胺。
为了在反应后分离二芳胺衍生物，在使用可溶于水的溶剂的情况下，减压蒸除所述溶剂，在所得残余物中加水，用不溶于水的芳香烃，如苯、甲苯和二甲苯；卤代烷烃如氯仿和二氯甲烷；以及酯类，如乙酸乙酯萃取上述残余物，并用饱和氯化钠水溶液冲洗萃取液，再用干燥剂如无水硫酸镁或无水硫酸钠干燥所得萃取液，然后减压除溶剂。当用不溶于水的溶剂时，则向反应混合物中加水，震荡分离，用饱和氯化钠水溶液冲洗所得有机层，再用干燥剂如无水硫酸镁或无水硫酸钠干燥，然后减压除溶剂。通过重结晶、悬浮和冲洗以及柱层析对所得残余物纯化处理，得到二芳胺衍生物。
作为合成二芳胺衍生物的中间体(式a)以及(式b)，由市场购买得到。
IV.二芳胺衍生物及其盐的用途和使用方法
有害生物防治剂：
本公开的二芳胺衍生物对农业领域中的多种病害显示出优异的活性。下面提及的病害的例子仅用来说明本公开，但绝不限定本公开。
本公开的二芳胺衍生物可用于防治下列病害：卵菌纲病害，如霜霉病(黄瓜霜霉病、油菜霜霉病、大豆霜霉病、甜菜霜霉病、甘蔗霜霉病、烟草霜霉病、豌豆霜霉病、丝瓜霜霉病、冬瓜霜霉病、甜瓜霜霉病、白菜类霜霉病、菠菜霜霉病、萝卜霜霉病、葡萄霜霉病、葱霜霉病)，白锈病(油菜白锈病、白菜类白锈病)，猝倒病(油菜猝倒病、烟草猝倒病、番茄猝倒病、辣椒猝倒病、茄子猝倒病、黄瓜猝倒病、棉苗猝倒病)，绵腐病(辣椒绵腐病、丝瓜绵腐病、冬瓜绵腐病)，疫病(蚕豆疫病、黄瓜疫病、南瓜疫病、冬瓜疫病、西瓜疫病、甜瓜疫病、辣椒疫病、韭菜疫病、大蒜疫病、棉花疫病)，晚疫病(马铃薯晚疫病、番茄晚疫病)等；半知菌病害，如枯萎病(甘薯枯萎病、棉花枯萎病、芝麻枯萎病、蓖麻枯萎病、番茄枯萎病、菜豆枯萎病、黄瓜枯萎病、丝瓜枯萎病、南瓜枯萎病、冬瓜枯萎病、西瓜枯萎病、甜瓜枯萎病、辣椒枯萎病、蚕豆枯萎病、油菜枯萎病、大豆枯萎病)，根腐病(辣椒根腐病、茄子根腐病、菜豆根腐病、黄瓜根腐病、苦瓜根腐病、棉黑根腐病、蚕豆根腐病)，立枯病(棉苗立枯病、芝麻立枯病、辣椒立枯病、黄瓜立枯病、白菜立枯病)，炭疽病(高粱炭疽病、棉花炭疽病、红麻炭疽病、黄麻炭疽病、亚麻炭疽病、烟草炭疽病、桑炭疽病、辣椒炭疽病、茄子炭疽病、菜豆炭疽病、黄瓜炭疽病、苦瓜炭疽病、西葫芦炭疽病、冬瓜炭疽病、西瓜炭疽病、甜瓜炭疽病、荔枝炭疽病)，黄萎病(棉花黄萎病、向日葵黄萎病、番茄黄萎病、辣椒黄萎病、茄子黄萎病)，黑星病(西葫芦黑星病、冬瓜黑星病、甜瓜黑星病)，灰霉病(棉铃灰霉病、红麻灰霉病、番茄灰霉病、辣椒灰霉病、菜豆灰霉病、芹菜灰霉病、菠菜灰霉病、猕猴桃灰霉病)，褐斑病(棉花褐斑病、黄麻褐斑病、甜菜褐斑病、花生褐斑病、辣椒褐斑病、冬瓜褐斑病、大豆褐斑病、向日葵褐斑病、豌豆褐斑病、蚕豆褐斑病)，黑斑病(亚麻假黑斑病、油菜黑斑病、芝麻黑斑病、向日葵黑斑病、蓖麻黑斑病、番茄黑斑病、辣椒黑斑病、茄子黑斑病、菜豆黑斑病、黄瓜黑斑病、芹菜黑斑病、胡萝卜黑腐病、胡萝卜黑斑病、苹果黑斑病、花生黑斑病)，斑枯病(番茄斑枯病、辣椒斑枯病、芹菜斑枯病)，早疫病(番茄早疫病、辣椒早疫病、茄子早疫病、马铃薯早疫病、芹菜早疫病)，轮纹病(大豆轮纹病、芝麻轮纹病、菜豆轮纹病)，叶枯病(芝麻叶枯病、向日葵叶枯病、西瓜叶枯病、甜瓜叶枯病)，茎基腐病(番茄茎基腐病、菜豆茎基腐病)，及其他(玉米圆斑病、红麻腰折病、稻瘟病、粟黑鞘病、甘蔗眼斑病、棉铃曲霉病、花生冠腐病、大豆茎枯病、大豆黑点病、甜瓜大斑病、花生网斑病、茶赤叶斑病、辣椒白星病、冬瓜叶斑病、芹菜黑腐病、菠菜心腐病、红麻叶霉病、红麻斑点病、黄麻茎斑病、大豆紫斑病、芝麻叶斑病、蓖麻灰斑病、茶褐色叶斑病、茄子褐色圆星病、菜豆红斑病、苦 瓜白斑病、西瓜斑点病、黄麻枯腐病、向日葵根茎腐病、菜豆炭腐病、大豆靶点病、茄子棒孢叶斑病、黄瓜靶斑病、番茄叶霉病、茄子叶霉病、蚕豆赤斑病等)等；担子菌病害，如锈病(小麦条锈病、小麦杆锈病、小麦叶锈病、花生锈病、向日葵锈病、甘蔗锈病、韭菜锈病、葱锈病、栗锈病、大豆锈病)，黑穗病(玉米丝黑穗病、玉米黑粉病、高粱丝黑穗病、高粱散黑穗病、高粱坚黑穗病、高梁柱黑粉病、栗粒黑穗病、甘蔗黑穗病、菜豆锈病)及其他(如小麦纹枯病、水稻纹枯病等)等；子囊菌病害，如白粉病(小麦白粉病、油菜白粉病、芝麻白粉病、向日葵白粉病、甜菜白粉病、茄子白粉病、豌豆白粉病、丝瓜白粉病、南瓜白粉病、西葫芦白粉病、冬瓜白粉病、甜瓜白粉病、葡萄白粉病、蚕豆白粉病)，菌核病(亚麻菌核病、油菜菌核病、大豆菌核病、花生菌核病、烟草菌核病、辣椒菌核病、茄子菌核病、菜豆菌核病、豌豆菌核病、黄瓜菌核病、苦瓜菌核病、冬瓜菌核病、西瓜菌核病、芹菜菌核病)，黑星病(苹果黑星病、梨黑星病)等。
本公开的二芳胺衍生物具有很好的杀菌活性，可有利地用于保护农业和园艺业重要的作物、家畜和种畜，以及人类常去的环境免于病菌的伤害。
在一些实施方式中，所述二芳胺衍生物用于制备防治真菌病害的杀菌剂。
所述真菌病害为霜霉病、白锈病、猝倒病、绵腐病、疫病、晚疫病、枯萎病、根腐病、立枯病、炭疽病、黄萎病、黑星病、灰霉病、褐斑病、黑斑病、斑枯病、早疫病、轮纹病、稻瘟病、锈病、黑穗病、白粉病或菌核病。
在一些实施方式中，所述真菌病害还包括叶枯病、茎基腐病、玉米圆斑病、红麻腰折病、粟黑鞘病、甘蔗眼斑病、棉铃曲霉病、花生冠腐病、大豆茎枯病、大豆黑点病、甜瓜大斑病、花生网斑病、茶赤叶斑病、辣椒白星病、冬瓜叶斑病、芹菜黑腐病、菠菜心腐病、红麻叶霉病、红麻斑点病、黄麻茎斑病、大豆紫斑病、芝麻叶斑病、蓖麻灰斑病、茶褐色叶斑病、茄子褐色圆星病、菜豆红斑病、苦瓜白斑病、西瓜斑点病、黄麻枯腐病、向日葵根茎腐病、菜豆炭腐病、大豆靶点病、茄子棒孢叶斑病、黄瓜靶斑病、番茄叶霉病、茄子叶霉病、蚕豆赤斑病。
为获得理想效果，化合物的用量因各种因素而改变，例如所用化合物、被保护的作物、有害生物的类型、感染程度、气候条件、施药方法、采用的剂型。
在一些实施方式中，每公顷10克－1000克的二芳胺衍生物剂量能提供充分的防治。
本公开一实施方式提供二芳胺衍生物，防治农业和园艺业重要的作物和/或家畜和种畜和/或人类常去的环境中的植物致病性真菌的方法。尤其是，化合物的用量在每公顷10克－1000克内变化。
V.杀菌组合物及其用途
为了实际应用于农业，使用含一种或多种本公开的二芳胺衍生物的组合物通常是有益的。
因此，本公开一实施方式提供含一种或多种二芳胺衍生物作为活性成分的杀菌组合物，组合物中活性成分的重量百分含量为0.1-99％。
本公开一实施方式提供所述杀菌组合物用于制备防治真菌病害的用途。
所述真菌病害同上文所述二芳胺衍生物防治真菌病害的种类。
组合物的使用形式可以是干粉、可湿性粉剂、乳油、微乳剂、糊剂、颗粒剂、溶液、悬浮剂、水分散性粒剂等，组合物类型的选择取决于具体的应用。
组合物是以已知方法制备的，例如任选在表面活性剂的存在下，通过用溶剂介质和/或固体稀释剂稀释或溶解活性物质。
在一些实施方式中，可用的固体稀释剂或载体例如是：二氧化硅、高岭土、膨润土、滑石、硅藻土、白云石、碳酸钙、氧化镁、白垩、粘土、合成硅酸盐、硅镁土、海泡石等。
在一些实施方式中，除水以外，可用的液体稀释剂还包括如芳族有机溶剂(二甲苯或烷基苯的混合物、氯苯等)，石蜡(石油馏分)，醇类(甲醇、丙醇、丁醇、辛醇、甘油)，酯类(乙酸乙酯、乙酸异丁酯等)，酮类(环己酮、丙酮、苯乙酮、异佛尔酮、乙基戊基酮等)，酰胺类(N,N-二甲基甲酰胺、N-甲基吡咯烷酮等)。
在一些实施方式中，可用的表面活性剂包括诸如烷基磺酸盐、烷基芳基磺酸盐、聚氧乙烯烷基酚、山梨醇的聚氧乙烯酯、木质素磺酸盐等的钠、钙、三乙基胺或三乙醇胺盐。
在一些实施方式中，组合物还可含特殊的添加剂用于特定的目的，例如含有粘合剂如阿拉伯胶、聚乙烯醇、聚乙烯吡咯烷酮等。
上述组合物中活性成分的浓度可根据例如活性成分、使用目的、环境条件和采用的制剂类型而在宽范围内改变。活性成分浓度范围通常为0.1-99％，优选5-60％。
在一些实施方式中，如果需要，可以向组合物中添加能与本公开的二芳胺衍生物兼容的其他活性成分，例如其他杀螨剂/杀虫剂、杀真菌剂、植物生长调节剂、抗生素、除草剂、肥料。
但所述组合物的形式并不仅限于此，也可将一种或两种或更多种组合形式的化合物混合以作为活性成分。
在一种或多种示例性的实施方式中，几种常见剂型的配制方法举例如下：
悬浮剂的配制：常用配方中活性组分含量为5-35％。以水为介质的溶剂诸如水悬浮剂、微乳剂、水乳剂，将原药、分散剂、助悬剂和抗冻剂等加入砂磨机中，进行研磨，制成悬浮剂。
水乳剂的配制：将原药、溶剂和乳化剂加在一起，使溶解成均匀油相。将水、抗冻剂等混合一起，成为均一水相。在高速搅拌下，将水相加入到油相或将油相加入到水相，形成分散性良好的水乳剂。本公开的水乳剂活性组分含量一般为5％-15％。为制备浓乳剂，本公开的二芳胺衍生物可溶解于一种或数种混合溶剂，再加入乳化剂来增强化合物在水中的分散效果。
可湿性粉剂的配制：按配方要求，将原药、各种表面活性剂及固体稀释剂等充分混合，经超细粉碎机粉碎后，即得到预定含量(例如10-60％)的可湿性粉剂产品。为制备适于喷洒用的可湿性粉剂，本公开的二芳胺衍生物可以和研细的固体粉末如粘土、无机硅酸盐、碳酸盐以及润湿剂、粘合剂和/或分散剂组成混合物。
水分散性粒剂的配制：将原药和粉状固体稀释剂、润湿展着剂及粘合剂等进行混合粉碎，再加水捏合后，加入装有一定规格筛网的造粒机中进行造粒，然后再经干燥、筛分(按筛网范围)。也可将原药、分散剂、崩解剂和润湿剂及固体稀释剂加入砂磨机中，以水为介质研磨，制成悬浮剂，然后进行喷雾干燥造粒，通常配制含量为20-30％颗粒状产品。
下面将结合实施方式和实施例对本公开的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施方式和实施例仅用于说明本公开，而不应视为限制本公开的范围。基于本公开中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本公开保护的范围。未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
通过实施例和对比例进一步说明本公开，但是，应当理解为，这些实施例仅仅是用于更详细地说明之用，而不应理解为用于以任何形式限制本公开。
实施例
实施例1：化合物23的制备
Figure PCTCN2021102896-appb-000010
室温搅拌下向含18.8g(0.1mol)2,6-二氯苯并恶唑的150mL乙腈溶液中加入16.4g(0.1mol)3,6-二氯-4-氨基哒嗪、27g碳酸钾，升温回流搅拌反应2-3小时，TLC监测反应完毕后，减压蒸除溶剂，剩余物加入过量水中，搅拌，过滤并依次水洗、石油醚洗得白色固体26.2g，产率83.2％。( 1HNMR，400MHz，内标TMS，溶剂CDCl 3)δppm 8.83(1H,s)，7.82(1H,s)，7.56(1H,d)，7.48(1H,d)，7.35(1H,d)。
实施例2：化合物75的制备
Figure PCTCN2021102896-appb-000011
室温搅拌下向含18.7g(0.1mol)2,6-二氯苯并咪唑的150mL乙腈溶液中加入16.4g(0.1mol)3,6-二氯-4-氨基哒嗪，26g碳酸钾，升温回流搅拌反应2-3小时，TLC监测反应完毕后，减压蒸除溶剂，剩余物加入过量水中，搅拌，过滤并依次水洗、石油醚洗得白色固体26.8g，产率86.4％。( 1HNMR，400MHz，内标TMS，溶剂(CDCl 3)δppm 8.80(1H,s)，7.78(1H,s)，7.50(1H,d)，7.45(1H,d)，7.32(1H,d)。
实施例3化合物23的钠盐制备
Figure PCTCN2021102896-appb-000012
室温搅拌下向含31.6g(0.1mol)化合物23的100mL甲醇溶液中加入4g(0.1mol)氢氧化钠，室温搅拌反应2-3小时，减压蒸除溶剂，得白色固体36.1g，产率99％。( 1HNMR，400MHz，内标TMS，溶剂D 2O)δppm 8.90(1H,s)，7.65(1H,d)，7.52(1H,s)，7.38(1H,d)。
表2部分如通式I所示的本公开化合物的表征结果
Figure PCTCN2021102896-appb-000013
Figure PCTCN2021102896-appb-000014
制剂实施例(各组分加入量均为重量百分含量，活性化合物折百后计量加入)
实施例4：30％可湿性粉剂的制备
30％可湿性粉剂的组分如下：
Figure PCTCN2021102896-appb-000015
Figure PCTCN2021102896-appb-000016
化合物2的制备方法如下：
将化合物2及本实施例中列出的其他组分充分混合，经超细粉碎机粉碎后，即得到30％的可湿性粉剂产品。
实施例5：40％浓悬浮剂的制备
40％浓悬浮剂的组分如下：
Figure PCTCN2021102896-appb-000017
化合物1的制备方法如下：
将化合物1及本实施例中列出的其他组分充分混合，由此得到的浓悬浮剂，用水稀释所得悬浮剂可得到任何所需浓度的稀释液。
实施例6：60％水分散性粒剂的制备
60％水分散性粒剂的组分如下：
Figure PCTCN2021102896-appb-000018
本实施例中的化合物23来源于实施例1的制备。
将化合物23及本实施例中列出的其他组分混合粉碎，再加水捏合后，加入10-100目筛网的造粒机中进行造粒，然后再经干燥、筛分(按筛网范围)。
试验例 杀菌活性测定
本公开二芳胺衍生物对农业领域中的多种病菌都表现出很好的活性，活性测试方法及部分测定结果如下。
活体保护活性测定：采用活体盆栽测定方法。待测化合物原药用少量丙酮(丙酮与喷液量的体积比等于0.05)溶解，用含有0.1％吐温80的水稀释至所需的浓度。喷雾施药到植物试材上，24小时后进行病害接种。接种后，将植物放在人工气候室中培养，24小时后将植物试材移入温室培养。待对照充分发病后(通常为一周时间)进行化合物防病效果评估。
其中，化合物防病效果评估方法如下：
使用Abbot公式计算，即得到观察效力(W)：W＝(1-α/β)×100。
其中，式中：
α：处理作物的真菌侵染百分数；β：未处理(空白对照)作物的真菌侵染百分数；
效力为“0”表示处理作物的侵染水平与未处理对照作物的侵染水平相同；效力为“100”表示处理作物未受侵染。
本公开的二芳胺衍生物抑菌活性测试结果如下：
药液浓度为400ppm时，列表化合物3、23、6、40、41、58、75、78、114对黄瓜霜霉病、番茄晚疫病防效达100％。
药液浓度为25ppm时，列表化合物23、114对黄瓜霜霉病、番茄晚疫病防效达90％以上；化合物75对黄瓜炭疽病防效100％。
本公开的化合物对危害农业生产的重要病害有很好的防治效果，具有广阔的应用前景。
最后应说明的是：以上各实施例仅用以说明本公开的技术方案，而非对其限制；尽管参照前述各实施例对本公开进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本公开各实施例技术方案的范围。
工业实用性
本公开了提供一种用作杀真菌剂的二芳胺衍生物、及其盐和杀菌组合物，其具有对危害农业生产的重要病害有很好的防治效果，特别对黄瓜霜霉病、疫病、锈病等引致的病害十分有效，具有低剂量高效的良好技术效果，具有广阔应用前景。

Claims (17)

  1. 一种用作杀真菌剂的二芳胺衍生物，其特征在于，所述二芳胺衍生物的结构式如下所示：
    Figure PCTCN2021102896-appb-100001
    其中，R 1、R 2可相同或不同，分别选自氢、卤素、氰基、C1-C12烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C1-C4烷胺基、C1-C4烷硫基、C1-C4烷基磺酰基；
    R 3选自氢、钾、钠、钙、C1-C4烷基、卤代C1-C4烷基、C1-C4烷基羰基、卤代C1-C4烷基羰基、C1-C4烷氧基羰基、卤代C1-C4烷氧基羰基、C1-C4烷胺基羰基、卤代C1-C4烷胺基羰基、C1-C4烷基磺酰基、卤代C1-C4烷基磺酰基；
    X选自O、S或NR 5；
    R 4为一种或多种的取代基，各自独立地选自卤素、氰基、NO 2、羧基、羟基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C1-C4烷基C1-C4烷氧基、C1-C4烷氧基C1-C4烷氧基、C1-C4烷氧基羰基、卤代C1-C4烷氧基羰基、C1-C4烷胺基羰基、卤代C1-C4烷胺基羰基、C1-C4烷基磺酰基、卤代C1-C4烷基磺酰基；
    R 5选自氢、C1-C4烷基；
    所述二芳胺衍生物不包括化合物A，化合物A的结构式如下所示：
    Figure PCTCN2021102896-appb-100002
  2. 根据权利要求1所述的二芳胺衍生物，其特征在于，所述R 1、R 2可相同或不同，分别选自氢、卤素、氰基；
    所述R 3选自氢、钾、钠、钙、C1-C4烷基；
    所述X选自O或NR 5；
    所述R 4为一种或多种取代基，各自独立地选自卤素、氰基、NO 2、羧基、羟基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C1-C4烷基C1-C4 烷氧基、C1-C4烷氧基C1-C4烷氧基、C1-C4烷氧基羰基、卤代C1-C4烷氧基羰基、C1-C4烷胺基羰基、卤代C1-C4烷胺基羰基、C1-C4烷基磺酰基、卤代C1-C4烷基磺酰基；
    R 5选自氢。
  3. 根据权利要求1所述的二芳胺衍生物，其特征在于，所述R 1、R 2可相同或不同，分别选自H、F、Cl、Br、I；
    所述R 3选自氢、钾、钠；
    所述X选自O或NR 5；
    所述R 4为一种或多种取代基，各自独立地选自氟、氯、溴或碘，羟基、氰基、甲基、乙基、正丙基、异丙基、仲丁基、叔丁基、三氟甲基、二氟甲基、甲氧基、乙氧基、异丙氧基、三氟甲氧基、羧基、甲氧基羰基、乙氧基羰基、甲氨基羰基、甲磺酰基；
    所述R 5选自氢。
  4. 根据权利要求1所述的二芳胺衍生物，其特征在于，所述R 1、R 2可相同或不同，分别选自H、F、Cl、Br；
    所述R 3选自氢、钾、钠；
    所述X选自O或NR 5；
    所述R 4为一种或多种取代基，其各自独立地选自氟、氯、溴，羟基、氰基、甲基、乙基、正丙基、异丙基、仲丁基、叔丁基、三氟甲基、二氟甲基、甲氧基、乙氧基、异丙氧基、三氟甲氧基、羧基、甲氧基羰基、乙氧基羰基、甲氨基羰基、甲磺酰基；
    所述R 5选自氢。
  5. 根据权利要求1所述的二芳胺衍生物，其特征在于，所述R 1、R 2可相同或不同，分别选自H、F、Cl、Br；
    所述R 3选自氢、钾、钠；
    所述X选自O或NR 5；
    所述R 4为一种或多种取代基，其各自独立地选自氟、氯、溴，羟基、氰基、甲基、乙基、三氟甲基、甲氧基、乙氧基、异丙氧基、三氟甲氧基、羧基、甲氧基羰基、乙氧基羰基、甲氨基羰基；
    所述R 5选自氢。
  6. 一种由权利要求1-5中任一项所述的二芳胺衍生物与酸或碱反应得到的盐。
  7. 根据权利要求6所述的盐，其特征在于，所述酸包括以下的至少一种：有机酸或无机酸；
    所述有机酸包括以下的至少一种：羧酸，如乙酸、丙酸、丁酸、草酸、己二酸、十二烷二酸、月桂酸、硬脂酸、三氟乙酸、富马酸、马来酸、苯甲酸或苯二甲酸、磺酸，如甲磺酸、1，3-丙二磺酸、对甲苯磺酸或十二烷基苯磺酸；
    及所述无机酸包括以下的至少一种：盐酸、硫酸、硝酸或碳酸。
  8. 根据权利要求6或7所述的盐，其特征在于，所述碱包括以下的至少一种：氢氧化钠、氢氧化钾、氢氧化钙、氢氧化锂、碳酸钾、碳酸钠、碳酸氢钠、碳酸氢钾、金属钠、氢化钠、氨基钠、丁基锂。
  9. 权利要求1-5中任一项所述的二芳胺衍生物或权利要求6-8任一所述的盐在防治真菌病害中的应用。
  10. 根据权利要求9所述的二芳胺衍生物在防治真菌病害中的应用，其特征在于，所述真菌病害包括霜霉病、白锈病、猝倒病、绵腐病、疫病、晚疫病、枯萎病、根腐病、立枯病、炭疽病、黄萎病、黑星病、灰霉病、褐斑病、黑斑病、斑枯病、早疫病、轮纹病、稻瘟病、锈病、黑穗病、白粉病或菌核病。
  11. 根据权利要求9或10所述的二芳胺衍生物在防治真菌病害中的应用，其特征在于，所述真菌病害包括叶枯病、茎基腐病、玉米圆斑病、红麻腰折病、粟黑鞘病、甘蔗眼斑病、棉铃曲霉病、花生冠腐病、大豆茎枯病、大豆黑点病、甜瓜大斑病、花生网斑病、茶赤叶斑病、辣椒白星病、冬瓜叶斑病、芹菜黑腐病、菠菜心腐病、红麻叶霉病、红麻斑点病、黄麻茎斑病、大豆紫斑病、芝麻叶斑病、蓖麻灰斑病、茶褐色叶斑病、茄子褐色圆星病、菜豆红斑病、苦瓜白斑病、西瓜斑点病、黄麻枯腐病、向日葵根茎腐病、菜豆炭腐病、大豆靶点病、茄子棒孢叶斑病、黄瓜靶斑病、番茄叶霉病、茄子叶霉病、蚕豆赤斑病。
  12. 一种杀菌组合物，其特征在于，所述杀菌组合物含有如权利要求1-8任一项所述的二芳胺衍生物作为活性组分。
  13. 根据权利要求12所述的杀菌组合物，其特征在于，所述活性组分在杀菌组合物中的重量百分含量为0.1-99％。
  14. 根据权利要求12或13所述的杀菌组合物，其特征在于，所述组合物中包括与所述二芳胺衍生物兼容的活性成分，所述活性成分包括杀虫剂、杀真菌剂、植物生长调节剂、抗生素、除草剂、肥料。
  15. 根据权利要求12-14中任一所述的杀菌组合物，其特征在于，所述组合物的使用形式包括干粉、可湿性粉剂、乳油、微乳剂、糊剂、颗粒剂、溶液、悬浮剂、水分散性粒剂。
  16. 权利要求12-15中任一所述的杀菌组合物在防治真菌病害中的应用。
  17. 根据权利要求16所述的杀菌组合物在防治真菌病害中的应用，其特征在于，所述真菌病害包括霜霉病、白锈病、猝倒病、绵腐病、疫病、晚疫病、枯萎病、根腐病、立枯病、炭疽病、黄萎病、黑星病、灰霉病、褐斑病、黑斑病、斑枯病、早疫病、轮纹病、稻瘟病、锈病、黑穗病、白粉病、菌核病、叶枯病、茎基腐病、玉米圆斑病、红麻腰折病、粟黑鞘病、甘蔗眼斑病、棉铃曲霉病、花生冠腐病、大豆茎枯病、大豆黑点病、甜瓜大斑病、花生网斑病、茶赤叶斑病、辣椒白星病、冬瓜叶斑病、芹菜黑腐病、菠菜心腐病、红麻叶霉病、红麻斑点病、黄麻茎斑病、大豆紫斑病、芝麻叶斑病、蓖麻灰斑病、茶褐色叶斑病、茄子褐色圆星病、菜豆红斑病、苦瓜白斑病、西瓜斑点病、黄麻枯腐病、向日葵根茎腐病、菜豆炭腐病、大豆靶点病、茄子棒孢叶斑病、黄瓜靶斑病、番茄叶霉病、茄子叶霉病或蚕豆赤斑病。
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