WO2020034181A1 - Quaternary triphenylphosphonium salt compound, preparation method therefor, and uses thereof - Google Patents

Quaternary triphenylphosphonium salt compound, preparation method therefor, and uses thereof Download PDF

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WO2020034181A1
WO2020034181A1 PCT/CN2018/100964 CN2018100964W WO2020034181A1 WO 2020034181 A1 WO2020034181 A1 WO 2020034181A1 CN 2018100964 W CN2018100964 W CN 2018100964W WO 2020034181 A1 WO2020034181 A1 WO 2020034181A1
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formula
compound represented
compound
catalyst
preparation
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PCT/CN2018/100964
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Chinese (zh)
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WO2020034181A9 (en
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覃兆海
王家尧
刘雪莲
唐大超
肖玉梅
李佳奇
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中国农业大学
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Priority to AU2018436544A priority Critical patent/AU2018436544B2/en
Priority to CA3101114A priority patent/CA3101114C/en
Priority to PCT/CN2018/100964 priority patent/WO2020034181A1/en
Publication of WO2020034181A1 publication Critical patent/WO2020034181A1/en
Publication of WO2020034181A9 publication Critical patent/WO2020034181A9/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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing aromatic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds

Definitions

  • the invention belongs to the technical field of pesticides, and particularly relates to a class of triphenylphosphonium salt compounds, and a preparation method and application thereof.
  • This kind of fungicide has high efficiency, broad spectrum, strong surface activity, strong slime stripping and cleaning effect, low foaming, low dosage, low toxicity, no environmental pollution, good compatibility, wide pH range (pH 2 ⁇ 12) And good chemical stability and other advantages, is the representative of a new generation of cationic surfactant fungicides, widely used in medical and health, oil field extraction, water treatment, food industry, agriculture and daily life and many other fields.
  • the quaternary phosphonium salt has a high affinity for mitochondria, it is widely used in the mitochondrial targeted delivery of drugs in the field of medicine. , Help reduce the amount of drugs used and reduce toxic and side effects.
  • An object of the present invention is to provide a triphenylphosphonium salt compound and a preparation method thereof.
  • X is selected from CH 2 , N, S or O;
  • Y is selected from halogen (Cl, Br or I), CH 3 SO 3 , CF 3 CO 2 , CH 3 CO 2 , CF 3 SO 3 , PhCO 2 , HOC 6 H 4 CO 2 , (CH 2 CO 2 ) 2 , (CHCO 2 ) 2, and any one of Formula W;
  • n is an integer from 0 to 16;
  • Q is selected from Formula Ia or Formula Ib;
  • R 1 represents H or a C 1 to C 12 alkyl group
  • Ar is selected from any one of the following A 1 to A 8
  • Q 1 is selected from any one of H or B 1 to B 11 ;
  • R 2 , R 3 , R 4 , R 5 and R 6 are all selected from hydrogen, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, C 1 -C 8 alkylthio, C 1 -C 8 fluoroalkyl, C 1 -C 8 fluoroalkoxy, halogen, nitro, cyano, benzene At least one of oxy, pyridyloxy, methanesulfonyl, and trifluoromethanesulfonyl, the halogen is selected from any one of fluorine, chlorine, bromine, and iodine; m is an integer from 0-4; o, q and r are both integers of 0-5; p is an integer of 0-3; the binding sites of R 2 , R 3 , R 5 and R 6 are at least one of the remaining 5 binding sites, where, when When When When When When When When When When When When When When When When When When When When When When When When When When
  • R 7 is selected from hydrogen, C 1 -C 5 alkyl, C 1 -C 5 alkoxy, C 1 -C 5 fluoroalkyl, C At least one of 1- C 5 fluoroalkoxy, halogen, nitro, cyano, phenoxy, pyridyloxy, carboxyl, methanesulfonyl, and trifluoromethanesulfonyl, the halogen selected from fluorine Any of chloro, bromo, and iodine, s is an integer from 0 to 5; the binding site of R 7 is at least one of the remaining 5 binding sites, where when s> 1, R 7 may be The same or different; in the formula B 6 , R 8 and R 9 are both selected from hydrogen, C 1 -C 5 alkyl, C 1 -C 5 alkoxy, C 1 -C 5 fluoroalkyl any one fluoroalkyl C alkoxy and
  • Z is selected from N or CH, and M is selected from NH or O.
  • X is selected from CH 2 or O;
  • Y is selected from halogen, AcO (CH 3 CO 2 ) , P-toluenesulfonyl (TsO), PhCO 2 and HOC 6 H 4 CO 2 ;
  • n is an integer of 4 to 11;
  • Q is selected from Ia or Ib.
  • Halogen refers to fluorine, chlorine, bromine, and iodine.
  • Alkyl represents a linear or branched alkyl group, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-pentyl and the like.
  • the aryl group and the aryl part of the aryloxy group include a phenyl group, a pyridyl group, a furyl group, and the like.
  • geometric isomers are formed by carbon-carbon double bonds or carbon-nitrogen double bonds connecting different substituents (respectively different configurations are represented by Z and E).
  • the compound of formula I according to the present invention may be a Z-isomer, an E-isomer, or a mixture of the two in any ratio.
  • the compound of formula I of the present invention may be specifically selected from the following numbered compounds
  • the compound of formula I of the present invention may be specifically selected from the following numbered compounds
  • Another object of the present invention is to provide a method for preparing the above-mentioned phosphonium salt compound (compound represented by Formula I).
  • the method for preparing a sulfonium salt compound (compound represented by Formula I) provided by the present invention includes the following steps: under a catalyst or catalyst-free condition, a compound represented by Formula VII and triphenylphosphine are subjected to a nucleophilic reaction in an organic solvent To obtain a compound represented by formula I.
  • the definitions of Y, Q, X and n are the same as those in the formula I; in the above preparation method, the catalyst is sodium iodide or potassium iodide.
  • the molar ratio of the catalyst to the compound represented by formula VII is (0.01-0.1): 1.
  • the reaction temperature of the nucleophilic reaction is 25-180 ° C, preferably 80-115 ° C, specifically 82 ° C, and the reaction time is 4-24h, and specifically 8-12h.
  • the molar ratio of the compound represented by Formula VII to triphenylphosphine is 1: (1-2), and specifically, 1: (1-1.3).
  • the organic solvent is selected from at least one of acetonitrile, ethylene glycol dimethyl ether, benzene, toluene, and 1,2-dichloroethane.
  • the nucleophilic reaction can be specifically carried out according to the following steps: evacuating the catalyst, triphenylphosphine and the compound represented by formula VII and magnetons, filling with nitrogen; adding an organic solvent under nitrogen protection, and stirring at room temperature for 5-10 minutes, and then This is reacted at 80-115 ° C for 8-12 hours to obtain a compound represented by formula I.
  • the compound represented by the formula VII is prepared as follows: the compound represented by the formula IV (or the compound represented by the formula V) in the presence of a catalyst (or the presence of an acid-binding agent) in an organic solvent and the compound represented by the formula VI The compound shown is reacted to obtain a compound represented by formula VII.
  • the definition of Q 1 and Ar is the same as Formula Ia; in Formula V, the definition of Q 2 is the same as Formula Ib; in Formula VI, the definitions of X, Y, and n are the same as those of Formula I, U The definitions are all the same as Ib.
  • U is a COO group.
  • the acid-binding agent is pyridine, triethylamine, ethylenediamine, potassium carbonate, cesium carbonate, NMM (N-methylmorpholine), and NaH; and the catalyst is EDCI / HOBT, CDI, DMAP / DCC, HATU / DIPEA, and DIC.
  • the molar ratio of the acid binding agent to the compound represented by Formula IV is (2-5): 1, and specifically, it may be: (2-3): 1.
  • the molar ratio of the catalyst to the compound represented by Formula IV is (1-2.5): 1, and specifically, it can be: (1.2-2): 1.
  • the molar ratio of the compound represented by IV to the compound represented by Formula VI is 1: (1-2), and specifically, it can be 1: 1.05.
  • the molar ratio of the acid binding agent to the compound represented by Formula V is (2-5): 1, and specifically, it can be: (2-3): 1.
  • the molar ratio of the catalyst to the compound represented by Formula V is (1-2.5): 1, and specifically, it can be: (1.2-2): 1.
  • the molar ratio of the compound represented by V and the compound represented by Formula VI is 1: (1-2), and specifically may be 1: 1.05.
  • the reaction temperature of the reaction is -20-35 ° C, and the reaction time is 1-6h.
  • the organic solvents are dichloromethane, tetrahydrofuran, acetonitrile, N, N-dimethylformamide (DMF), 1,4-dioxane, and toluene.
  • the reaction is selected according to the following steps (taking the reaction of the compound represented by Formula IV and the compound represented by VI as an example): the compound represented by Formula IV, the catalyst DMAP / DCC and the magnetons are evacuated and filled with nitrogen; under the protection of nitrogen Add an organic solvent, lower the temperature of the ice-salt bath to -10 ° C, and stir for 5-10 min. Then dilute Formula V in the solvent and slowly drop it into the reaction flask for 0.5-4 h to obtain the compound represented by Formula VII.
  • the compound represented by formula IV is prepared as follows: the compound represented by formula II and an acid binding agent are reacted with a compound represented by formula III in an organic solvent to obtain a compound represented by formula IV.
  • the definition of Ar is the same as Formula I; in Formula III, R 1 is the same as Formula I.
  • the acid-binding agent is pyridine, triethylamine, ethylenediamine, potassium carbonate, cesium carbonate, and NaH.
  • the molar ratio of the catalyst to the compound represented by Formula II is (2-5): 1, and specifically may be: (2-3): 1.
  • the molar ratio between the compound represented by II and the compound represented by formula III is 1: (1-1.2), and specifically, it can be 1: 1.05.
  • the reaction temperature of the reaction is -20-35 ° C, and the reaction time is 1-6h.
  • the organic solvents are dichloromethane, tetrahydrofuran, acetonitrile, N, N-dimethylformamide (DMF), 1,4-dioxane, and toluene.
  • the reaction can be specifically carried out according to the following steps: evacuating the acid binding agent, the compound represented by Formula II and the magnet, and filling it with nitrogen; adding an organic solvent under the protection of nitrogen, cooling the ice-salt bath to -10 ° C and stirring for 5-10 minutes, Dilute the formula III with the solvent and slowly drop it into the reaction flask for 0.5-4 h to obtain the compound represented by the formula IV.
  • the compounds represented by formula II, formula III, formula V and formula VI in the present invention can be purchased through commercial routes or obtained by one-step reaction of raw materials.
  • the compound represented by formula II can be biphenyl containing various substituents. 2-Amine, arylpyridylamine, aniline, benzylamine and various heterocyclic amines.
  • the compound represented by formula III can be specifically obtained from various substituted benzoic acid, phenylacetic acid, and various substituted heterocyclic formic acid in one step.
  • the invention also protects a bactericide composition and a preparation method thereof.
  • the composition includes a sulfonium salt compound (compound represented by Formula I) and an agriculturally acceptable carrier, wherein the mass percentage content of the sulfonium salt compound (active ingredient) in the single agent is 0.1 to 99%, specifically, It is 30 to 60%.
  • the phosphonium salt compound may be a single compound of the present invention or a mixture of several compounds of the present invention.
  • the preparation method of the fungicide composition provided by the present invention includes the following steps: the sulfonium salt compound (the compound represented by the formula I) and an agriculturally acceptable carrier are mixed uniformly to obtain the preparation.
  • the agriculturally acceptable carrier has the following characteristics: 1) after being formulated with the active ingredient, it is convenient to apply to the site to be treated, such as: plants, seeds or soil; 2) it is convenient for storage, transportation or handling; 3) it can be Is a solid or liquid, including substances that are usually gas but have been compressed into a liquid. In short, carriers commonly used in formulating bactericidal preparations for agricultural use can be used.
  • the agriculturally acceptable carrier may be specifically selected from a solid carrier and / or a liquid carrier.
  • the solid support is selected from at least one of natural or synthetic silicate, ammonium sulfate, calcium sulfate, aluminum oxide silicate, natural or synthetic resin, polychlorophenol, starch, bentonite, and wax, wherein, the The natural or synthetic silicate may be specifically selected from at least one of attapulgite, talc, aluminum silicate, diatomaceous earth, mica, montmorillonite, and calcium silicate, and the natural or synthetic resin may be specifically selected from At least one of a benzofuran resin, a styrene polymer (molecular weight of 50,000 to 200,000), and a styrene copolymer (such as a styrene-butadiene copolymer); the wax may be specifically selected from beeswax and / Or paraffin.
  • natural or synthetic silicate may be specifically selected from at least one of attapulgite, talc, aluminum silicate, diatomaceous earth, mica, montmorillonite,
  • the liquid carrier is selected from at least one of water, a C1-C4 alcohol, a C3-C8 ketone, an aromatic hydrocarbon, a petroleum fraction, and a C6-C12 chlorinated hydrocarbon, wherein the alcohol may specifically be ethanol and / or Ethylene glycol, the ketone may be at least one of acetophenone, acetone, methyl ethyl ketone, and cyclohexanone, the aromatic hydrocarbon may be at least one of benzene, toluene, and xylene, and the petroleum fraction may be specifically It may be kerosene and / or mineral oil, and the chlorinated hydrocarbon may specifically be at least one of carbon tetrachloride, dichloromethane, and trichloroethane.
  • the alcohol may specifically be ethanol and / or Ethylene glycol
  • the ketone may be at least one of acetophenone, acetone, methyl ethyl ket
  • the fungicide composition is processed into a concentrate and used for transportation, which is diluted by the user before application.
  • the fungicide composition provided by the present invention may further include a surfactant.
  • the added amount of the surfactant may be an acceptable amount in agricultural fungicides.
  • the surfactant may be selected from at least one of an emulsifier, a dispersant, a wetting agent, and a penetrant.
  • the emulsifier may be specifically selected from agricultural milk 500 # (calcium alkyl phenyl luteinate), agricultural milk 600 # phosphate (phenylphenol polyoxyethyl ether), agricultural milk 700 # (alkylphenol formaldehyde resin polyoxylate) Ethyl ether), agricultural milk 1600 # (phenethylphenol polyoxyethyl polypropylene ether), polyoxyalkylene alkyl aryl ether, and at least one of ethylene oxide-propylene oxide block copolymer Species.
  • the dispersant may be specifically selected from the group consisting of polycarboxylate, ligninsulfonate, alkylphenol polyoxyethylene formaldehyde condensate sulfate, calcium alkylbenzenesulfonate calcium salt, benzenesulfonic acid formaldehyde condensate sodium salt, and lauryl sulfate At least one of sodium, sulfonated castor oil sodium salt, sodium alkylaryl sulfonate, alkylphenol polyoxyethylene pyrimide, fatty acid polyoxyethylene ester, and ester polyoxyethylene pyrimide.
  • the wetting agent may be at least one selected from the group consisting of sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, BX powder, saponin powder, silkworm sand, and sapindus powder.
  • the penetrant may be at least one selected from the group consisting of silicone polyoxyethylene ether, alkylaryl sulfonate, alcohol ether succinate, and phenol ether succinate.
  • auxiliaries may be added to the fungicide composition according to the present invention as appropriate.
  • the addition amount of the other auxiliary agents may be an acceptable amount in agricultural fungicides.
  • the other auxiliary agent may be selected from at least one of a disintegrant, an antifoaming agent, an antifreezing agent, and a thickener.
  • the disintegrant is selected from at least one of bentonite, urea, ammonium sulfate, aluminum chloride, and glucose.
  • the antifoaming agent is at least one selected from the group consisting of silicone oil, silicone compounds, C10-C20 saturated fatty acid compounds, and C8-C10 fatty alcohol compounds.
  • the antifreeze is selected from at least one of ethylene glycol, propylene glycol, glycerol, and polyethylene glycol.
  • the thickener is selected from at least one of xanthan gum, polyvinyl alcohol, and polyethylene glycol.
  • the fungicide composition prepared by the present invention may be added with corresponding ingredients according to methods known to those skilled in the art to prepare wettable powders, powders, granules, concentrated emulsions, emulsifiable concentrates, suspensions, aerosols or Aerosol and other dosage forms.
  • an effective amount of the fungicide composition of the present invention can be applied according to different crops and diseases, and can be implemented by foliar spraying, seed treatment or soil treatment.
  • the invention also protects a composition containing at least two active ingredients.
  • the active composition of the composition includes a phosphonium salt compound (a compound represented by Formula I) and at least one other active compound.
  • the other active compound may be at least one of known fungicides, acaricides, nematicides, insecticides, herbicides, fertilizers, growth regulators, safeners, and chemical pheromones, and more preferably bactericidal Agents and pesticides.
  • the composition is a bactericidal composition, which refers to a composition prepared by a compound represented by Formula I and one or more other bactericides and a preparation thereof, which are used to expand the scope of product control.
  • the other fungicides include: 2- (thiocyanomethylthio) benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, azoxystrobin, amisole, antimycin, and powdery parasitic spores , Azaconazole, azoxystrobin, Bacillus subtilis, benomyl, benzylcarb, fenthiapyr, benfifluconazole, biphenyl, thiacumid, biphenyltriazole, biphenylpyridine Myclosporin, blasticidin-S, borax, Bordeaux solution, boscalid, furfurazol, butanil sulfonate, dicarbendazim, carbendazim, carbendazim, verrudin
  • the composition is a bactericidal and insecticidal composition, which refers to a composition prepared by a compound represented by Formula I and one or more other pesticides and a preparation thereof, which are used to expand the scope of product control.
  • the other insecticides include: Avermectin, Acephate, Acetamiprid, Housefly Phosphorus, Acetonitrile, Pyrethrin, Cotton Lingwei, Aldicarb, Aldicarb, Acrymethrin , Aloxin, dichlorcarb, alpha-cypermethrin, alpha-ecdysone, endosulfan, thiothion, fendicarb, amine phosphate, sothothion, bismetham, pseudoequiline, beta Dimethophos, Azadirachtin, Pyridoxine, Pamphosphos, Azinphos-methyl, Azophos, Permethrin, Cephalcarb, Promethazol, Pesticide,
  • the compound of the formula I provided by the present invention has a broad spectrum and excellent bactericidal activity, and can be used to prevent and control a variety of crops caused by fungi of the four classes of ascomycetes, ascomycetes, basidiomycetes, and oomycetes. Disease. Good control results can be obtained at very low doses.
  • the compounds of the formula I have a certain systemic property and can be used as foliar and soil fungicides to prevent and cure diseases on many crops.
  • the following diseases can be controlled: pepper blight, tomato early blight, tomato late blight, tomato gray mold, rice blast, wheat leaf spot, apple rot, rice sheath blight, rice blast, rice blast disease, Rice blight, wheat powdery mildew, wheat scab, rape sclerotinia, cucumber downy mildew, cucumber wilt, cucumber gray mold, cucumber powdery mildew, apple powdery mildew, watermelon anthracnose, peanut brown spot, Melon fruit rot, cotton fusarium wilt, cotton verticillium wilt, and cotton blight.
  • FIG. 1 is a flow chart for the preparation of a compound represented by Formula I.
  • the compounds numbered Ia 4-11 a-81 to Ia 4-11 b-81 to Ia 4-11 a-184 to Ia 4-11 b-184 were all prepared according to the method in Example 1; numbered Ia 4-11
  • the compounds of a-185 to Ia 4-11 b-185 to Ia 4-11 a-553 to Ia 4-11 b-553 were all prepared by referring to the methods in Examples 1 and 2.
  • composition containing the compound represented by the formula I is as follows: (the following components are based on mass percentage content, the active component is metered after adding 100%)
  • Composition of wettable powder 50% of the compound of formula I, 5% of dispersant polycarboxylate, 3% of sodium dodecyl wetting agent, 42% of solid carrier or disintegrant bentonite; The proportions are mixed to obtain a mixture, which is subjected to jet milling to obtain a 50% wettable powder.
  • Composition of emulsifiable concentrate 30% of the compound represented by Formula I, 12% of an emulsifier polyoxyalkylene alkylaryl ether, 10% of an alkylaryl sulfonate sulphonate, and 48% of cyclohexanone as a liquid carrier. The ratios were mixed to obtain a clear solution of 30% of the compound.
  • composition of water-dispersible granules 70% of the compound represented by Formula I, 3% calcium alkylbenzene sulfonate as dispersant, 3% lignin sulfonate as dispersant, 4% sodium dodecyl sulfate as wetting agent, and solid Carrier or filler starch 20%; 70% water-dispersible granules of the compound of formula I are prepared by mixing the components according to the ratio.
  • Example 8 Determination of bactericidal activity:
  • the compounds of formula I of the present invention are used to test various bacterial diseases in plants.
  • the test methods are as follows:
  • the diameter of each treated colony is measured by the cross method, and the colony growth diameter is calculated using formula (1), and the average value is taken.
  • Colony growth diameter colony diameter-bacteria cake diameter
  • the growth inhibitory rate of each compound against the pathogenic bacteria was calculated from the blank control colony growth diameter and the treated colony growth diameter, see formula (2) below.
  • Mycelial growth inhibition rate (%) (control colony growth diameter-chemical treatment colony growth diameter) / control colony growth diameter ⁇ 100 (2)
  • the triphenylphosphonium salt compound represented by the formula I provided by the present invention has a broad spectrum and excellent bactericidal activity, and can be used to control four broadly pathogenic fungi in various crops: ascomycetes, basidiomycetes, semi-strains, and eggs. Diseases caused by mycobacterial diseases. Good control effects can be obtained at low doses, and they are widely used in plant protection agents.

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Abstract

Disclosed are a quaternary triphenylphosphonium salt compound, a preparation method therefor, and the uses thereof. The structure of the quaternary compound is as shown in formula I. The preparation method comprises carrying out a nucleophilic reaction of the compound shown of formula VII and triphenylphosphine in an organic solvent with or without a catalyst to obtain the compound as shown in formula I. The compound as shown in formula I can be used for preventing and treating diseases caused by a plurality of germs such as oomycetes, basidiomycetes, ascomycetes and semi-known fungi on a variety of plants. Excellent results have been obtained in powdery mildew, corn rust, watermelon anthracnose and the like, and a good control effect can be ensured at low concentrations.

Description

一类三苯基鏻盐化合物及其制备方法与应用A class of triphenylphosphonium salt compounds and preparation method and application thereof 技术领域Technical field
本发明属于农药技术领域，尤其涉及一类三苯基鏻盐化合物及其制备方法与应用。The invention belongs to the technical field of pesticides, and particularly relates to a class of triphenylphosphonium salt compounds, and a preparation method and application thereof.
背景技术Background technique
自1888年Messinger等合成四羟甲基鏻盐以来，季鏻盐及其衍生物得到了很快的发展。1990年左右开始生产和使用的烷基季鏻盐化合物是新一代的高效、广谱杀菌剂。这类杀菌剂具有高效、广谱、强表面活性、强黏泥剥离清洗效果、低发泡性、低剂量、低毒、无环境污染、配伍性好、宽pH值使用范围(pH2～12)和化学稳定性好等优点，是新一代阳离子表面活性剂杀菌剂的代表，广泛应用于医疗卫生、油田开采、水处理、食品工业、农业及日常生活等众多领域。Since the synthesis of tetramethylolium phosphonium salt by Messinger et al. In 1888, quaternary phosphonium salt and its derivatives have developed rapidly. Alkyl quaternary phosphonium compounds, which were produced and used around 1990, are a new generation of high-efficiency, broad-spectrum fungicides. This kind of fungicide has high efficiency, broad spectrum, strong surface activity, strong slime stripping and cleaning effect, low foaming, low dosage, low toxicity, no environmental pollution, good compatibility, wide pH range (pH 2 ～ 12) And good chemical stability and other advantages, is the representative of a new generation of cationic surfactant fungicides, widely used in medical and health, oil field extraction, water treatment, food industry, agriculture and daily life and many other fields.
同时也由于季鏻盐对线粒体有着高度的亲合力，在医药领域被广泛用于药物的线粒体靶向投送，其在线粒体内部的靶向聚集能力相比于非靶向药物可提高上1000倍，有助于降低药物的使用量和减小毒副作用。At the same time, because the quaternary phosphonium salt has a high affinity for mitochondria, it is widely used in the mitochondrial targeted delivery of drugs in the field of medicine. , Help reduce the amount of drugs used and reduce toxic and side effects.
发明公开Invention Disclosure
本发明的一个目的是提供一种三苯基鏻盐类化合物及其制备方法。An object of the present invention is to provide a triphenylphosphonium salt compound and a preparation method thereof.
本发明所提供的鏻盐类化合物的结构通式如式I所示：The structural formula of the phosphonium salt compound provided by the present invention is shown in Formula I:
Figure PCTCN2018100964-appb-000001
Figure PCTCN2018100964-appb-000001
所述式I中，X选自CH 2、N、S或O；Y选自卤素(Cl、Br或I)、CH 3SO 3、CF 3CO 2、CH 3CO 2、CF 3SO 3、PhCO 2、HOC 6H 4CO 2、(CH 2CO 2) 2、(CHCO 2) 2和式W中的任一种；n为0～16的整数；Q选自式Ia或式Ib； In the formula I, X is selected from CH 2 , N, S or O; Y is selected from halogen (Cl, Br or I), CH 3 SO 3 , CF 3 CO 2 , CH 3 CO 2 , CF 3 SO 3 , PhCO 2 , HOC 6 H 4 CO 2 , (CH 2 CO 2 ) 2 , (CHCO 2 ) 2, and any one of Formula W; n is an integer from 0 to 16; Q is selected from Formula Ia or Formula Ib;
Figure PCTCN2018100964-appb-000002
Figure PCTCN2018100964-appb-000002
所述式W中，R 1代表H或C 1～C 12的烷基； In the formula W, R 1 represents H or a C 1 to C 12 alkyl group;
所述式Ia中，Ar选自下述A 1～A 8中的任意一种，Q 1选自H或B 1～B 11中的任意一种； In the formula Ia, Ar is selected from any one of the following A 1 to A 8 , and Q 1 is selected from any one of H or B 1 to B 11 ;
Figure PCTCN2018100964-appb-000003
Figure PCTCN2018100964-appb-000003
所述式Ib中U选自O、NH、S、OCO、SC＝O、NHC＝O、NHC＝S中的任意一种，Q 2选自C 1～C 4中的任一种； In the formula Ib, U is selected from any one of O, NH, S, OCO, SC = O, NHC = O, NHC = S, and Q 2 is selected from any one of C 1 to C 4 ;
Figure PCTCN2018100964-appb-000004
Figure PCTCN2018100964-appb-000004
其中，A 1-A 8所述式A 1、A 2和A 5中，R 2、R 3、R 4、R 5和R 6均选自氢、C 1-C 8的烷基、C 1-C 8的烷氧基、C 1-C 8的烷硫基、C 1-C 8的氟代烷基、C 1-C 8的氟代烷氧基、卤素、硝基、氰基、苯氧基、吡啶氧基、甲磺酰基和三氟甲磺酰基中的至少一种，所述卤素选自氟、氯、溴和碘中的任一种；m为0-4的整数；o、q和r均为0-5的整数；p为0-3的整数；R 2、R 3、R 5和R 6的结合位点为剩余的5个结合位点中的至少一个，其中，当m、o、q和r>1时，R 2、R 3、R 5和R 6可相同或不同；R 4的结合位点为剩余3个结合位点中的至少一个，其中，当p>1时，R 4可相同或不同；式A 2中，N可位于3、4、5和6位中的任一处。 Wherein, in the formulas A 1 , A 2 and A 5 described in A 1 to A 8 , R 2 , R 3 , R 4 , R 5 and R 6 are all selected from hydrogen, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, C 1 -C 8 alkylthio, C 1 -C 8 fluoroalkyl, C 1 -C 8 fluoroalkoxy, halogen, nitro, cyano, benzene At least one of oxy, pyridyloxy, methanesulfonyl, and trifluoromethanesulfonyl, the halogen is selected from any one of fluorine, chlorine, bromine, and iodine; m is an integer from 0-4; o, q and r are both integers of 0-5; p is an integer of 0-3; the binding sites of R 2 , R 3 , R 5 and R 6 are at least one of the remaining 5 binding sites, where, when When m, o, q, and r> 1, R 2 , R 3 , R 5, and R 6 may be the same or different; the binding site of R 4 is at least one of the remaining three binding sites, where when p> At 1, R 4 may be the same or different; in Formula A 2 , N may be located at any of the 3, 4, 5 and 6 positions.
其中B 1-B 10所述式B 1中，R 7选自氢、C 1-C 5的烷基、C 1-C 5的烷氧基、C 1-C 5的氟代烷基、C 1-C 5的氟代烷氧基、卤素、硝基、氰基、苯氧基、吡啶氧基、羧基、甲磺酰基和三氟甲磺酰基中的至少一种，所述卤素选自氟、氯、溴和碘中的任 一种，s为0-5的整数；R 7的结合位点为剩余的5个结合位点中的至少一个，其中，当s>1时，R 7可相同或不同；所述式B 6中，R 8和R 9均选自氢、C 1-C 5的烷基、C 1-C 5的烷氧基、C 1-C 5的氟代烷基、C 1-C 5的氟代烷氧基和卤素中的任意一种。 Wherein, in Formula B 1 described in B 1 -B 10 , R 7 is selected from hydrogen, C 1 -C 5 alkyl, C 1 -C 5 alkoxy, C 1 -C 5 fluoroalkyl, C At least one of 1- C 5 fluoroalkoxy, halogen, nitro, cyano, phenoxy, pyridyloxy, carboxyl, methanesulfonyl, and trifluoromethanesulfonyl, the halogen selected from fluorine Any of chloro, bromo, and iodine, s is an integer from 0 to 5; the binding site of R 7 is at least one of the remaining 5 binding sites, where when s> 1, R 7 may be The same or different; in the formula B 6 , R 8 and R 9 are both selected from hydrogen, C 1 -C 5 alkyl, C 1 -C 5 alkoxy, C 1 -C 5 fluoroalkyl any one fluoroalkyl C alkoxy and halogen 1 -C 5 in.
其中C 1-C 4所述式C 1和C 3中，Z选自N或CH，M选自NH或O。 In formulas C 1 and C 3 described in C 1 -C 4 , Z is selected from N or CH, and M is selected from NH or O.
本发明所提供的鏻盐类化合物的结构通式如式I所示，优选为如下结构：所述式I中，X选自CH 2或O；Y选自卤素、AcO(CH 3CO 2)、对甲苯甲磺酰基(TsO)、PhCO 2和HOC 6H 4CO 2中的任一种；n为4～11的整数；Q选自Ia或Ib。 The structural formula of the sulfonium salt compounds provided by the present invention is shown in Formula I, and preferably has the following structure: In Formula I, X is selected from CH 2 or O; Y is selected from halogen, AcO (CH 3 CO 2 ) , P-toluenesulfonyl (TsO), PhCO 2 and HOC 6 H 4 CO 2 ; n is an integer of 4 to 11; Q is selected from Ia or Ib.
更优选的结构为：所述式Ia中，Ar选自A 1、A 3、A 4或A 6，Q 1选自H；所述式Ib中，U选自O、OCO和SC＝O中的任意一种，Q 2选自C 1～C 4中的任一种。 A more preferred structure is: In the formula Ia, Ar is selected from A 1 , A 3 , A 4 or A 6 , and Q 1 is selected from H; in the formula Ib, U is selected from O, OCO, and SC = 0. Q 2 is selected from any one of C 1 to C 4 .
本发明的所述的式I化合物的定义中所涉及到的术语代表如下取代基：The terms involved in the definition of the compound of formula I of the present invention represent the following substituents:
卤素：指氟、氯、溴、碘。Halogen: refers to fluorine, chlorine, bromine, and iodine.
烷基：代表直链或支链烷基，例如：甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、叔戊基等。Alkyl: represents a linear or branched alkyl group, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-pentyl and the like.
芳基以及芳氧基中的芳基部分包括苯基、吡啶基、呋喃基等。The aryl group and the aryl part of the aryloxy group include a phenyl group, a pyridyl group, a furyl group, and the like.
此外，本发明所述的式I化合物中，因碳-碳双键或碳-氮双键连接不同取代基而形成几何异构体(分别以Z和E来表示不同的构型)。本发明所述的式I化合物可为Z型异构体，亦可为E型异构体，或者两者任何比例的混合物。In addition, in the compound of the formula I according to the present invention, geometric isomers are formed by carbon-carbon double bonds or carbon-nitrogen double bonds connecting different substituents (respectively different configurations are represented by Z and E). The compound of formula I according to the present invention may be a Z-isomer, an E-isomer, or a mixture of the two in any ratio.
本发明的所述的式I化合物具体可选自如下编号的化合物The compound of formula I of the present invention may be specifically selected from the following numbered compounds
Figure PCTCN2018100964-appb-000005
Figure PCTCN2018100964-appb-000005
Figure PCTCN2018100964-appb-000006
Figure PCTCN2018100964-appb-000006
Figure PCTCN2018100964-appb-000007
Figure PCTCN2018100964-appb-000007
Figure PCTCN2018100964-appb-000008
Figure PCTCN2018100964-appb-000008
Figure PCTCN2018100964-appb-000009
Figure PCTCN2018100964-appb-000009
Figure PCTCN2018100964-appb-000010
Figure PCTCN2018100964-appb-000010
Figure PCTCN2018100964-appb-000011
Figure PCTCN2018100964-appb-000011
Figure PCTCN2018100964-appb-000012
Figure PCTCN2018100964-appb-000012
Figure PCTCN2018100964-appb-000013
Figure PCTCN2018100964-appb-000013
Figure PCTCN2018100964-appb-000014
Figure PCTCN2018100964-appb-000014
Figure PCTCN2018100964-appb-000015
Figure PCTCN2018100964-appb-000015
Figure PCTCN2018100964-appb-000016
Figure PCTCN2018100964-appb-000016
Figure PCTCN2018100964-appb-000017
Figure PCTCN2018100964-appb-000017
Figure PCTCN2018100964-appb-000018
Figure PCTCN2018100964-appb-000018
Figure PCTCN2018100964-appb-000019
Figure PCTCN2018100964-appb-000019
Figure PCTCN2018100964-appb-000020
Figure PCTCN2018100964-appb-000020
Figure PCTCN2018100964-appb-000021
Figure PCTCN2018100964-appb-000021
Figure PCTCN2018100964-appb-000022
Figure PCTCN2018100964-appb-000022
Figure PCTCN2018100964-appb-000023
Figure PCTCN2018100964-appb-000023
Figure PCTCN2018100964-appb-000024
Figure PCTCN2018100964-appb-000024
Figure PCTCN2018100964-appb-000025
Figure PCTCN2018100964-appb-000025
Figure PCTCN2018100964-appb-000026
Figure PCTCN2018100964-appb-000026
Figure PCTCN2018100964-appb-000027
Figure PCTCN2018100964-appb-000027
Figure PCTCN2018100964-appb-000028
Figure PCTCN2018100964-appb-000028
Figure PCTCN2018100964-appb-000029
Figure PCTCN2018100964-appb-000029
Figure PCTCN2018100964-appb-000030
Figure PCTCN2018100964-appb-000030
本发明的所述的式I化合物具体可选自如下编号的化合物The compound of formula I of the present invention may be specifically selected from the following numbered compounds
Figure PCTCN2018100964-appb-000031
Figure PCTCN2018100964-appb-000031
Figure PCTCN2018100964-appb-000032
Figure PCTCN2018100964-appb-000032
Figure PCTCN2018100964-appb-000033
Figure PCTCN2018100964-appb-000033
Figure PCTCN2018100964-appb-000034
Figure PCTCN2018100964-appb-000034
本发明的另一个目的是提供上述鏻盐类化合物(式I所示化合物)的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned phosphonium salt compound (compound represented by Formula I).
本发明所提供的鏻盐类化合物(式I所示化合物)的制备方法，包括如下步骤：在催化剂或无催化剂条件下，将式VII所示化合物和三苯基膦于有机溶剂中进行亲核反应，得到式I所示化合物。The method for preparing a sulfonium salt compound (compound represented by Formula I) provided by the present invention includes the following steps: under a catalyst or catalyst-free condition, a compound represented by Formula VII and triphenylphosphine are subjected to a nucleophilic reaction in an organic solvent To obtain a compound represented by formula I.
Figure PCTCN2018100964-appb-000035
Figure PCTCN2018100964-appb-000035
所述式VII中，Y、Q、X和n的定义均同式I；上述制备方法中，所述催化剂为碘化钠或碘化钾。In the formula VII, the definitions of Y, Q, X and n are the same as those in the formula I; in the above preparation method, the catalyst is sodium iodide or potassium iodide.
所述催化剂和式VII所示化合物的摩尔比为(0.01-0.1):1。The molar ratio of the catalyst to the compound represented by formula VII is (0.01-0.1): 1.
所述亲核反应的反应温度为25～180℃，优选为80～115℃，具体可为82℃，反应时间为4-24h，具体可为8-12h。The reaction temperature of the nucleophilic reaction is 25-180 ° C, preferably 80-115 ° C, specifically 82 ° C, and the reaction time is 4-24h, and specifically 8-12h.
所述式VII所示化合物和三苯基膦的摩尔比为1：(1-2)，具体可为1：(1-1.3)。The molar ratio of the compound represented by Formula VII to triphenylphosphine is 1: (1-2), and specifically, 1: (1-1.3).
所述有机溶剂选自乙腈、乙二醇二甲醚、苯、甲苯和1,2-二氯乙烷中的至少一种。The organic solvent is selected from at least one of acetonitrile, ethylene glycol dimethyl ether, benzene, toluene, and 1,2-dichloroethane.
所述亲核反应具体可按如下步骤进行：将催化剂、三苯基膦和式VII所示化合物和磁子抽真空，充氮气；在氮气保护下加有机溶剂，于室温下搅拌5-10min，再将其于80～115℃下反应8-12h，得到式I所示化合物。The nucleophilic reaction can be specifically carried out according to the following steps: evacuating the catalyst, triphenylphosphine and the compound represented by formula VII and magnetons, filling with nitrogen; adding an organic solvent under nitrogen protection, and stirring at room temperature for 5-10 minutes, and then This is reacted at 80-115 ° C for 8-12 hours to obtain a compound represented by formula I.
上述制备法中，式VII所示化合物按如下方法制备得到：将式IV所示化合物(或式V所示化合物)在催化剂存在下(或缚酸剂存在下)于有机溶剂中与式VI所示化合物进行反应，得到式VII所示化合物。In the above preparation method, the compound represented by the formula VII is prepared as follows: the compound represented by the formula IV (or the compound represented by the formula V) in the presence of a catalyst (or the presence of an acid-binding agent) in an organic solvent and the compound represented by the formula VI The compound shown is reacted to obtain a compound represented by formula VII.
Figure PCTCN2018100964-appb-000036
Figure PCTCN2018100964-appb-000036
所述式IV中，Q 1和Ar的定义同式Ia；所述式V中，Q 2的定义同式Ib；所述式VI中，X、Y和n的定义均同式I，U的定义均同式Ib。当式IV与式VI反应时，U为COO基团。上述制备方法中，所述缚酸剂为吡啶、三乙胺、乙二胺、碳酸钾、碳酸铯、NMM(N-甲基***啉)和NaH；所述催化剂为EDCI/HOBT、CDI、DMAP/DCC、HATU/DIPEA和DIC等。 In Formula IV, the definition of Q 1 and Ar is the same as Formula Ia; in Formula V, the definition of Q 2 is the same as Formula Ib; in Formula VI, the definitions of X, Y, and n are the same as those of Formula I, U The definitions are all the same as Ib. When Formula IV reacts with Formula VI, U is a COO group. In the above preparation method, the acid-binding agent is pyridine, triethylamine, ethylenediamine, potassium carbonate, cesium carbonate, NMM (N-methylmorpholine), and NaH; and the catalyst is EDCI / HOBT, CDI, DMAP / DCC, HATU / DIPEA, and DIC.
所述缚酸剂和式IV所示化合物的摩尔比为(2-5):1，具体可为：(2-3):1。所述催化剂和式IV所示化合物的摩尔比为(1-2.5):1，具体可为：(1.2-2):1。其中，IV所示化合物和式VI所示化合物的摩尔比为1：(1-2)，具体可为1:1.05。The molar ratio of the acid binding agent to the compound represented by Formula IV is (2-5): 1, and specifically, it may be: (2-3): 1. The molar ratio of the catalyst to the compound represented by Formula IV is (1-2.5): 1, and specifically, it can be: (1.2-2): 1. The molar ratio of the compound represented by IV to the compound represented by Formula VI is 1: (1-2), and specifically, it can be 1: 1.05.
所述缚酸剂和式V所示化合物的摩尔比为(2-5):1，具体可为：(2-3):1。所述催化剂和式V所示化合物的摩尔比为(1-2.5):1，具体可为：(1.2-2):1。其中，V所示化合物和式VI所示化合物的摩尔比为1：(1-2)，具体可为1:1.05。The molar ratio of the acid binding agent to the compound represented by Formula V is (2-5): 1, and specifically, it can be: (2-3): 1. The molar ratio of the catalyst to the compound represented by Formula V is (1-2.5): 1, and specifically, it can be: (1.2-2): 1. Wherein, the molar ratio of the compound represented by V and the compound represented by Formula VI is 1: (1-2), and specifically may be 1: 1.05.
所述反应的反应温度为-20～35℃，反应时间为1-6h。The reaction temperature of the reaction is -20-35 ° C, and the reaction time is 1-6h.
所述有机溶剂为二氯甲烷、四氢呋喃、乙腈、N,N-二甲基甲酰胺(DMF)、1,4-二氧六环和甲苯。The organic solvents are dichloromethane, tetrahydrofuran, acetonitrile, N, N-dimethylformamide (DMF), 1,4-dioxane, and toluene.
所述反应选为按如下步骤进行(以式IV所示化合物与VI所示化合物反应为例)：将式IV所示化合物、催化剂DMAP/DCC和磁子抽真空，充氮气；在氮气保护下加有机溶剂，冰盐浴降温至-10℃搅拌5-10min，再将式V稀释于溶剂中慢慢滴入反应瓶中，反应0.5-4h，得到式VII所示化合物。The reaction is selected according to the following steps (taking the reaction of the compound represented by Formula IV and the compound represented by VI as an example): the compound represented by Formula IV, the catalyst DMAP / DCC and the magnetons are evacuated and filled with nitrogen; under the protection of nitrogen Add an organic solvent, lower the temperature of the ice-salt bath to -10 ° C, and stir for 5-10 min. Then dilute Formula V in the solvent and slowly drop it into the reaction flask for 0.5-4 h to obtain the compound represented by Formula VII.
Figure PCTCN2018100964-appb-000037
Figure PCTCN2018100964-appb-000037
上述制备法中，式IV所示化合物按如下方法制备得到：将式II所示化合物和缚酸剂于有机溶剂中与式III所示化合物进行反应，得到式IV所示化合物。In the above preparation method, the compound represented by formula IV is prepared as follows: the compound represented by formula II and an acid binding agent are reacted with a compound represented by formula III in an organic solvent to obtain a compound represented by formula IV.
所述式II中，Ar的定义同式I；所述式III中，R 1的定义均同式I。上述制备方法中，所述缚酸剂为吡啶、三乙胺、乙二胺、碳酸钾、碳酸铯和NaH。 In Formula II, the definition of Ar is the same as Formula I; in Formula III, R 1 is the same as Formula I. In the above preparation method, the acid-binding agent is pyridine, triethylamine, ethylenediamine, potassium carbonate, cesium carbonate, and NaH.
所述催化剂和式II所示化合物的摩尔比为(2-5):1，具体可为：(2-3):1。其中，II所示化合物和式III所示化合物的摩尔比为1：(1-1.2)，具体可为1:1.05。The molar ratio of the catalyst to the compound represented by Formula II is (2-5): 1, and specifically may be: (2-3): 1. The molar ratio between the compound represented by II and the compound represented by formula III is 1: (1-1.2), and specifically, it can be 1: 1.05.
所述反应的反应温度为-20～35℃，反应时间为1-6h。The reaction temperature of the reaction is -20-35 ° C, and the reaction time is 1-6h.
所述有机溶剂为二氯甲烷、四氢呋喃、乙腈、N,N-二甲基甲酰胺(DMF)、1,4-二氧六环和甲苯。The organic solvents are dichloromethane, tetrahydrofuran, acetonitrile, N, N-dimethylformamide (DMF), 1,4-dioxane, and toluene.
所述反应具体可按如下步骤进行：将缚酸剂和式II所示化合物和磁子抽真空，充氮气；在氮气保护下加有机溶剂，冰盐浴降温至-10℃搅拌5-10min，再将式III稀释与溶剂中慢慢滴入反应瓶中，反应0.5-4h，得到式IV所示化合物。The reaction can be specifically carried out according to the following steps: evacuating the acid binding agent, the compound represented by Formula II and the magnet, and filling it with nitrogen; adding an organic solvent under the protection of nitrogen, cooling the ice-salt bath to -10 ° C and stirring for 5-10 minutes, Dilute the formula III with the solvent and slowly drop it into the reaction flask for 0.5-4 h to obtain the compound represented by the formula IV.
本发明中所述式II、式III、式V和式VI所示化合物可通过商业途径购得或经原料一步反应得到，如：式II所示化合物具体可为含各种取代基的联苯-2-胺、芳基吡啶胺、苯胺、苄胺以及各种杂环胺。式III所示化合物具体可由各种取代的苯甲酸、苯乙酸以及各种取代是的杂环甲酸等经一步反应得到。The compounds represented by formula II, formula III, formula V and formula VI in the present invention can be purchased through commercial routes or obtained by one-step reaction of raw materials. For example, the compound represented by formula II can be biphenyl containing various substituents. 2-Amine, arylpyridylamine, aniline, benzylamine and various heterocyclic amines. The compound represented by formula III can be specifically obtained from various substituted benzoic acid, phenylacetic acid, and various substituted heterocyclic formic acid in one step.
本发明还保护一种杀菌剂组合物及其制备方法。The invention also protects a bactericide composition and a preparation method thereof.
该组合物包括鏻盐类化合物(式I所示化合物)和农业上可接受的载体，其中，该单剂中鏻盐类化合物(活性成分)的质量百分含量为0.1～99％，具体可为30～60％。The composition includes a sulfonium salt compound (compound represented by Formula I) and an agriculturally acceptable carrier, wherein the mass percentage content of the sulfonium salt compound (active ingredient) in the single agent is 0.1 to 99%, specifically, It is 30 to 60%.
所述鏻盐类化合物既可为本发明的单一化合物，也可为本发明几种化合物的混合物。The phosphonium salt compound may be a single compound of the present invention or a mixture of several compounds of the present invention.
本发明所提供的杀菌剂组合物的制备方法，包括如下步骤：将鏻盐类化合物(式I所示化合物)和农业上可接受的载体混合均匀即可制备得到。The preparation method of the fungicide composition provided by the present invention includes the following steps: the sulfonium salt compound (the compound represented by the formula I) and an agriculturally acceptable carrier are mixed uniformly to obtain the preparation.
所述农业上可接受的载体具有如下特点：1)与活性成分配制后便于施用于待处理的位点，例如：植物、种子或土壤；2)有利于贮存、运输或操作；3)可为是固体或液体，包括通常为气体但已压缩成液体的物质。总之，在配制农业上所用杀菌制剂中常用的载体均可使用。The agriculturally acceptable carrier has the following characteristics: 1) after being formulated with the active ingredient, it is convenient to apply to the site to be treated, such as: plants, seeds or soil; 2) it is convenient for storage, transportation or handling; 3) it can be Is a solid or liquid, including substances that are usually gas but have been compressed into a liquid. In short, carriers commonly used in formulating bactericidal preparations for agricultural use can be used.
所述农业上可接受的载体具体可选自固体载体和/或液体载体。The agriculturally acceptable carrier may be specifically selected from a solid carrier and / or a liquid carrier.
所述固体载体选自天然或合成的硅酸盐、硫酸铵、硫酸钙、氧化硅酸铝、天然或合成的树脂、多氯苯酚、淀粉、膨润土和蜡中的至少一种，其中，所述天然或合成的硅酸盐具体可选自硅镁土、滑石、硅酸铝、硅藻土、云母、蒙脱石和硅酸钙中的至少一种，所述天然或合成的树脂具体可选自苯并呋喃树脂、苯乙烯聚合物(分子量为5-20万)和苯乙烯共聚物(如：苯乙烯-丁二烯共聚物)中的至少一种；所述蜡具体可选自蜂蜡和/或石蜡。The solid support is selected from at least one of natural or synthetic silicate, ammonium sulfate, calcium sulfate, aluminum oxide silicate, natural or synthetic resin, polychlorophenol, starch, bentonite, and wax, wherein, the The natural or synthetic silicate may be specifically selected from at least one of attapulgite, talc, aluminum silicate, diatomaceous earth, mica, montmorillonite, and calcium silicate, and the natural or synthetic resin may be specifically selected from At least one of a benzofuran resin, a styrene polymer (molecular weight of 50,000 to 200,000), and a styrene copolymer (such as a styrene-butadiene copolymer); the wax may be specifically selected from beeswax and / Or paraffin.
所述液体载体选自水、C1-C4的醇、C3-C8的酮、芳烃、石油馏分和C6-C12的氯代烃中的至少一种，其中，所述醇具体可为乙醇和/或乙二醇，所述酮具体可为苯乙酮、丙酮、甲乙酮和环己酮中的至少一种，所述芳烃具体可为苯、甲苯和二甲苯中的至少一种，所述石油馏分具体可为煤油和/或矿物油，所述氯代烃具体可为四氯化碳、二氯甲烷和三氯乙烷中的至少一种。The liquid carrier is selected from at least one of water, a C1-C4 alcohol, a C3-C8 ketone, an aromatic hydrocarbon, a petroleum fraction, and a C6-C12 chlorinated hydrocarbon, wherein the alcohol may specifically be ethanol and / or Ethylene glycol, the ketone may be at least one of acetophenone, acetone, methyl ethyl ketone, and cyclohexanone, the aromatic hydrocarbon may be at least one of benzene, toluene, and xylene, and the petroleum fraction may be specifically It may be kerosene and / or mineral oil, and the chlorinated hydrocarbon may specifically be at least one of carbon tetrachloride, dichloromethane, and trichloroethane.
一般杀菌剂组合物通常会被加工成浓缩物的形式，并以此用于运输，在施 用之前由使用者将其稀释。Generally, the fungicide composition is processed into a concentrate and used for transportation, which is diluted by the user before application.
为了利于稀释，本发明所提供的杀菌剂组合物，还可包括表面活性剂。In order to facilitate dilution, the fungicide composition provided by the present invention may further include a surfactant.
所述表面活性剂的添加量为农业上用杀菌剂中可接受的量即可。The added amount of the surfactant may be an acceptable amount in agricultural fungicides.
所述表面活性剂可选自乳化剂、分散剂、润湿剂和渗透剂中的至少一种。The surfactant may be selected from at least one of an emulsifier, a dispersant, a wetting agent, and a penetrant.
所述乳化剂具体可选自农乳500#(烷基苯黄酸钙)，农乳600#磷酸酯(苯基酚聚氧乙基醚)、农乳700#(烷基酚甲醛树脂聚氧乙基醚)、农乳1600#(苯乙基酚聚氧乙基聚丙烯基醚)、聚氧化烯基烷基芳基醚和环氧乙烷-环氧丙烷嵌段共聚物中的至少一种。The emulsifier may be specifically selected from agricultural milk 500 # (calcium alkyl phenyl luteinate), agricultural milk 600 # phosphate (phenylphenol polyoxyethyl ether), agricultural milk 700 # (alkylphenol formaldehyde resin polyoxylate) Ethyl ether), agricultural milk 1600 # (phenethylphenol polyoxyethyl polypropylene ether), polyoxyalkylene alkyl aryl ether, and at least one of ethylene oxide-propylene oxide block copolymer Species.
所述分散剂具体可选自聚羧酸盐、木质素磺酸盐、烷基酚聚氧乙烯甲醛缩合物硫酸盐、烷基苯磺酸钙盐、苯磺酸甲醛缩合物钠盐、硫酸月桂酸钠，磺化蓖麻油钠盐、磺酸烷基芳基酯钠，烷基酚聚氧乙烯嘧、脂肪酸聚氧乙烯酯和酯聚氧乙烯嘧中的至少一种。The dispersant may be specifically selected from the group consisting of polycarboxylate, ligninsulfonate, alkylphenol polyoxyethylene formaldehyde condensate sulfate, calcium alkylbenzenesulfonate calcium salt, benzenesulfonic acid formaldehyde condensate sodium salt, and lauryl sulfate At least one of sodium, sulfonated castor oil sodium salt, sodium alkylaryl sulfonate, alkylphenol polyoxyethylene pyrimide, fatty acid polyoxyethylene ester, and ester polyoxyethylene pyrimide.
所述润湿剂具体可选自十二烷基硫酸钠、十二烷基苯磺酸钠、拉开粉BX、皂角粉、蚕沙和无患子粉中的至少一种。The wetting agent may be at least one selected from the group consisting of sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, BX powder, saponin powder, silkworm sand, and sapindus powder.
所述渗透剂具体可选自硅氧烷聚氧乙烯醚、磺酸烷基芳酯、醇醚琥珀酸盐和酚醚琥珀酸盐中的至少一种。The penetrant may be at least one selected from the group consisting of silicone polyoxyethylene ether, alkylaryl sulfonate, alcohol ether succinate, and phenol ether succinate.
当然，本发明所述杀菌剂组合物中，还可适当添加其他助剂。Of course, other auxiliaries may be added to the fungicide composition according to the present invention as appropriate.
所述其他助剂的添加量为农业上用杀菌剂中可接受的量即可。The addition amount of the other auxiliary agents may be an acceptable amount in agricultural fungicides.
所述其他助剂可选自崩解剂、消泡剂、抗冻剂和增稠剂中的至少一种。The other auxiliary agent may be selected from at least one of a disintegrant, an antifoaming agent, an antifreezing agent, and a thickener.
所述崩解剂选自膨润土、尿素、硫酸铵、氯化铝和葡萄糖中的至少一种。The disintegrant is selected from at least one of bentonite, urea, ammonium sulfate, aluminum chloride, and glucose.
所述消泡剂选自硅油、硅酮类化合物、C10-C20饱和脂肪酸类化合物、C8-C10脂肪醇类化合物中的至少一种。The antifoaming agent is at least one selected from the group consisting of silicone oil, silicone compounds, C10-C20 saturated fatty acid compounds, and C8-C10 fatty alcohol compounds.
所述抗冻剂选自乙二醇、丙二醇、丙三醇和聚乙二醇中的至少一种。The antifreeze is selected from at least one of ethylene glycol, propylene glycol, glycerol, and polyethylene glycol.
所述增稠剂选自黄原酸胶、聚乙烯醇和聚乙二醇中的至少一种。The thickener is selected from at least one of xanthan gum, polyvinyl alcohol, and polyethylene glycol.
本发明所制备得到的杀菌剂组合物，可按照本领域技术人员所公知的方法，加入相应成分，从而制备得到可湿性粉剂、粉剂、颗粒剂、浓乳剂、乳油，悬浮剂、气雾剂或烟雾剂等多种剂型。同时，可根据不同的作物及病害施用有效量的本发明的杀菌剂组合物，可用叶面喷雾、种子处理或土壤处理的方法实施。The fungicide composition prepared by the present invention may be added with corresponding ingredients according to methods known to those skilled in the art to prepare wettable powders, powders, granules, concentrated emulsions, emulsifiable concentrates, suspensions, aerosols or Aerosol and other dosage forms. At the same time, an effective amount of the fungicide composition of the present invention can be applied according to different crops and diseases, and can be implemented by foliar spraying, seed treatment or soil treatment.
本发明还保护一种含有至少两种活性组分的组合物。The invention also protects a composition containing at least two active ingredients.
所述组合物的活性组合物包括鏻盐类化合物(式I所示化合物)和其它至少一种具有活性的化合物。所述其它活性化合物可为已知的杀菌剂、杀螨剂、杀线虫剂、杀虫剂、除草剂、肥料、生长调节剂、安全剂和化学信息素种的至少一种，进一步优选为杀菌剂和杀虫剂。The active composition of the composition includes a phosphonium salt compound (a compound represented by Formula I) and at least one other active compound. The other active compound may be at least one of known fungicides, acaricides, nematicides, insecticides, herbicides, fertilizers, growth regulators, safeners, and chemical pheromones, and more preferably bactericidal Agents and pesticides.
所述组合物为杀菌组合物是指式I所示化合物与一种或数种其他杀菌剂制备的组合物及其制剂，用于扩大产品的防治范围。所述其他杀菌剂包括：2-(硫氰基甲硫基)苯并噻唑,2-苯基苯酚,8-羟基喹啉硫酸盐,唑嘧菌胺,安美速,抗霉素,白粉寄生孢,阿扎康唑,嘧菌酯,枯草芽孢杆菌,苯霜灵,苯菌灵,苯噻菌胺,苯并烯氟菌唑，联苯,噻枯唑,联苯***醇,联苯吡菌胺,杀稻瘟菌素-S,硼砂,波尔多液,啶酰菌胺,糠菌唑,磺酸丁嘧啶,敌菌丹,克菌丹,多菌灵,萎锈灵,环内酰亚胺,香芹酮,地茂散,百菌清,乙菌利,盾壳霉,氢氧化铜,异辛酸铜,王铜,硫酸铜,氧化亚铜,氰霜唑,环氟菌胺,霜脲氰,环唑醇,嘧菌环胺,棉隆,咪菌威,二乙双胍,抑菌灵,二氯芬,双氯氰菌胺,哒菌清,氯硝胺,乙霉威,苯醚甲环唑,氟嘧菌胺,烯酰吗啉,醚菌胺,烯唑醇,烯唑醇-M,敌螨通,敌螨普,二苯胺,二噻农,吗菌灵,多果定,克瘟散,烯肟菌酯,氟环唑,噻唑菌胺,乙氧喹,氯喹灵,噁唑菌酮,咪唑菌酮,氯苯嘧啶醇,腈苯唑,甲呋酰胺,环酰菌胺,氰菌胺,拌种咯,苯锈啶,丁苯吗啉,胺苯吡菌酮,三苯锡,福美铁,嘧菌腙,氟啶胺,咯菌腈,氟吗啉,氟吡菌胺,氟吡菌酰胺,氟酰亚胺,氟嘧菌酯,氟喹唑,氟硅唑,磺菌胺,flutianil,氟酰胺,粉唑醇,氟唑菌酰胺,灭菌丹,乙磷铝,呋线威,呋霜灵,呋吡菌胺,双辛胍,双辛胍乙酸盐,六氯苯,己唑醇,恶霉灵,抑霉唑,酰胺唑,种菌唑,异稻瘟净,异菌脲,异丙菌胺,稻瘟灵,吡唑萘菌胺,异噻菌胺,春雷霉素,醚菌酯,海带多糖,代森锰铜,代森锰锌,双炔酰菌胺,代森锰,甲霜灵，精甲霜灵,嘧菌胺，灭锈胺,威百亩,叶菌唑,磺菌威,异硫氰酸甲酯,代森联,苯氧菌胺,苯菌酮,灭粉霉素,腈菌唑,代森钠,酞菌酯,氟苯嘧啶醇,辛异噻唑酮,甲呋酰胺,油酸,肟醚菌胺,恶霜灵,喹啉铜,咪唑富马酸盐,氧化萎锈灵,稻瘟酯,戊菌唑,戊菌隆,戊苯吡菌胺,五氯酚,五氯酚月桂酸酯,吡噻菌胺,苯酞,啶氧菌酯,多抗霉素,多氧霉素,噻菌灵,咪鲜胺,腐霉利,霜霉威,丙环唑,甲基代森锌,碘喹唑酮,丙硫菌唑,唑菌胺酯,唑胺菌酯,唑菌酯,定菌磷,pyribencarb,稗草畏,啶斑肟,嘧霉胺,丁吡吗啉,pyriofenone,氯喹酮,灭藻醌,喹氧灵,五氯硝基苯,sedaxane,硫硅菌胺,硅氟唑,五氯酚钠,螺环菌胺,硫,戊唑醇,异丁乙氧喹啉,四氯硝基苯,氟醚唑,噻苯达唑,噻呋酰胺,甲基硫菌灵,福美双,噻酰菌胺,甲基立枯磷,对甲抑菌灵,粉锈宁,***醇,咪唑嗪,三环唑,十三吗啉,肟菌酯,氟菌唑,嗪胺灵,灭菌唑,有效霉素,缬菌胺,霜霉灭,烯菌酮,代森锌,福美锌,苯酰菌胺,尖孢镰刀菌,麦锈灵,醌肟腙,氰烯菌酯，抑菌啉,乐杀螨,丁硫啶,吗菌威,chlobenthiazone,粉净胺,苯咪唑菌,四氯喹噁啉,环菌胺,氰菌灵, 酯菌胺,癸磷锡,二氯萘醌,菌核利,苄氯***醇,甲菌定,敌菌消,硝辛酯,硝丁酯,双硫氧吡啶,灭菌磷,多地辛,敌菌酮,乙环唑,敌克松,丙烷腈,种衣酯,氟苯***,呋萎灵,呋菌唑,拌种胺,呋甲硫菌灵,灰黄霉素,丙烯酸喹啉酯,环己硫磷,异派磷,氯苯咪菌酮,灭锈胺,苯并威,间氯敌菌酮,三甲呋菌胺,噻菌胺,代森环,粘氯酸酐,甲菌利,游霉素,氯瘟磷,胺丙威，吡喃灵,啶菌腈,甲氧氯吡啶,氯吡呋醚,羟基喹啉基乙酮,喹唑胺，氟喹唑,吡咪唑,水杨酰苯胺,戊苯砜,噻二呋,噻菌腈,硫氯苯亚胺,克杀螨,硫氰苯甲酰胺,威菌磷,嘧菌醇,丁***,水杨菌胺,福美甲胂,氰菌胺等。The composition is a bactericidal composition, which refers to a composition prepared by a compound represented by Formula I and one or more other bactericides and a preparation thereof, which are used to expand the scope of product control. The other fungicides include: 2- (thiocyanomethylthio) benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, azoxystrobin, amisole, antimycin, and powdery parasitic spores , Azaconazole, azoxystrobin, Bacillus subtilis, benomyl, benzylcarb, fenthiapyr, benfifluconazole, biphenyl, thiacumid, biphenyltriazole, biphenylpyridine Myclosporin, blasticidin-S, borax, Bordeaux solution, boscalid, furfurazol, butanil sulfonate, dicarbendazim, carbendazim, carbendazim, verrudin, cyclamide Amine, carvone, diazepam, chlorothalonil, acetolide, scutellum spp., Copper hydroxide, copper isooctanoate, king copper, copper sulfate, cuprous oxide, cyanamide, ciclosporin, cream Urocyanide, cycloconazole, azoxystrobin, methalonol, midazolam, diformin, bacteriochlor, dichlorophen, diclofenac, pyridazole, clonamide, etamcarb, benzene Trimethoprim, fluoxastrobin, dimethomorph, dimethoxam, enazol, enazol-M, dibentox, difenox, diphenylamine, dithianon, morphin, multi-fruit Ding, Kewensan, fenoxystrobin, fluconazole, thiabendazole, ethoxyquin, chloroquineline, oxazosin, imidaclostrole, chlorobenzimidol, nitrilazole, methylfuramide, cyclyl Bacteramide, cyanamide, seed dressing, fenpropidin, butan Benmorpholine, amphetamine, triphenyltin, formoferox, azoxystrobin, fluazinam, flupronil, flumorph, fluoxastrobin, fluopyram, fluimide, fluoxazim Myclostrobin, fluquinazole, flusilazol, sulfasalazine, flutianil, fluamide, fluconazole, fluoxastrobin, sterilant, acephate, furavir, furasyl, furazolid, Bisectidine, Bisectidine Acetate, Hexachlorobenzene, Tetraconazole, Mycoxalol, Imazalil, Amidazole, Myclobutanil, Isobaricin, Isoxuron, Isoprofen, Rice Blast Aspirin, pyraclostrobin, isotianil, kasugamycin, triclostrobin, kelp polysaccharides, mancozeb, mancozeb, dimethylam, mancozeb, metalaxyl, refined nails Metalaxyl, azoxystrobin, fenastylamine, carbaminophen, tebuconazole, sulfoxycarb, methyl isothiocyanate, Daisenlian, phenoxystrobin, fenoxystrobin, fenamicin, nitriles Azole, sodium substitute, phthalate, flubenazol, octazolidone, methylfuramide, oleic acid, oxystrobin, oxamethoxam, copper quinoline, imidazolium fumarate, oxanil , Rice blast ester, penconazole, pentosalone, penefenpyram, pentachlorophenol, pentachlorophenol laurate, pyrithidin, phthalide, picoxystrobin, polyoxin, polyoxin Chlortetracycline, thiabendazole, prochloraz, humilis, propadicarb, propiconazole , Zinc methyl, iodoquinazolone, prothioconazole, pyraclostrobin, pyraclostrobin, pyraclostrobin, azoxystrobin, pyripencarb, humulone, pyracoxime, pyraclostrobin, butan Pymorpholine, pyriofenone, chloroquinone, chlortetracycline, quinoxaline, pentachloronitrobenzene, sedaxane, thiacillosamine, silylflurazole, sodium pentachlorophene, spirocyclamine, sulfur, tebuconazole, Isobutoxyquinoline, Tetrachloronitrobenzene, Flufenazole, Tibendazole, Thioflavamide, Methionil, Famibis, Thiacidil, Methyl Pyridoxine, Parabens Ling, fentanin, triazol, imidazolid, tricyclazole, tridemorpholine, oxystrobin, fluconazol, azoxystroben, bacterazole, effective mycotoxin, valeryl amine, downy mildew, enone Ketones, zinc substitutes, fomezine, fenoxystrobin, fusarium oxysporum, wheat rust, quinone oxime, cyanoxenil, bacteriocin, acaricid, sulfothim, carbendazim, cholobenthiazone, Dimethoamine, Benzimidazole, Tetrachloroquinoxaline, Cyclosporine, Cyclosporin, Estabron, Decodetin, Dichloronaphthoquinone, Sclerotinia, Benzyltriazol, Methadine, Enemies Diazepam, Nitrooctyl Ester, Nitrobutyl Ester, Dithiopyridine, Sterilized Phosphate, Dodoxin, Diecone, Etocyclazole, Dimethasone, Propanenitrile, Seed Coating Esters, Fluttriazole, Furazone , Furacid, dressing amines, thiomethoxam, ash Mycin, quinolinyl acrylate, cyclohexylphosphine, allylphosphine, chlorfenidone, fenfluramine, benzocarb, m-chlorfendione, trimethoprim, thiabendazim, duracil, Chlorinic anhydride, carbendazim, natamycin, chloramphosphate, amiprovir, pyracloprid, picoxynil, methoxychloropyridine, clopifuryl ether, hydroxyquinolinone, quinazolidine, fluorine Quinazole, pimimidazole, salicylanilide, pentyl sulfone, thiadifuride, thiabendazole, thiochlorobenzimine, chlorfenazole, thiocyanamide, carbendazim, azoxystrobin, butatriazole , Salicylamine, formamidine, cyanamide.
所述组合物为杀菌杀虫组合物是指式I所示化合物与一种或数种其他杀虫剂制备的组合物及其制剂，用于扩大产品的防治范围。所述其他杀虫剂包括：阿维菌素,乙酰甲胺磷,啶虫脒,家蝇磷,乙酰虫腈,杀螨菊酯,棉铃威,涕灭威,涕灭氧威,丙烯菊酯,阿洛氨菌素,除害威,α-氯氰菊酯,α-蜕皮激素,硫丹,赛硫磷,灭害威,胺吸磷,索胺硫磷,双甲脒,假木贼碱,乙基杀扑磷,印楝素,甲基吡啶磷,益棉磷,谷硫磷,偶氮磷,椒菊酯,恶虫威,丙硫克百威,杀虫磺,β-氟氯氰菊酯,β-氯氰菊酯,联苯菊酯,生物丙烯菊酯,bioethanomethrin,生物氯菊酯，双三氟虫脲,溴苯烯磷,溴杀烯,溴硫磷,丁苯氨酯,稻虱净,丁苯甲氨酯,特嘧硫磷,丁酮威,布托酯,丁酮砜威,硫线磷,毒杀芬,氯灭杀威,西维因,虫螨威,二硫磷,呋喃威,巴丹,氯虫苯甲酰胺,冰片丹,氯丹,十氯酮,氯二甲脒,氯氧磷,溴虫腈,毒虫畏,定虫隆,氯甲磷,氯化苦,氯腈肟磷,氯吡唑磷,毒死蜱,甲基毒死蜱,虫螨磷,环虫酰肼,瓜菊酯,顺式苄呋菊酯,除线威,氯生太尔,噻虫胺,蝇毒麟,毒虫磷,克罗米通,丁烯磷,育畜磷,苯腈磷,杀螟腈,果虫磷,氰虫酰胺,环虫菊酯,乙氰菊酯,氟氯氰菊酯,三氟氯氰菊酯,氯氰菊酯,苯醚氰菊酯,环丙氨嗪,赛灭磷,DDT,甲呋喃丹,溴氰菊酯,田乐磷,田乐磷,硫代田乐磷,内吸磷,甲基内吸磷,丁醚脲,氯亚胺硫磷,地亚农,异氯硫磷,除线磷,敌敌畏,百治磷,环虫腈,狄氏剂,除虫脲,四氟甲醚菊酯,甲氟磷,地麦威,乐果,苄菊酯,甲基毒虫畏,敌蝇威,消螨酚,丙消酚,二硝戊酚,呋虫胺,二苯丙醚,蔬果磷,二氧威,敌杀磷,乙拌磷,噻喃磷,多拉克丁,脱皮甾酮,甲维盐,烯炔菊酯,硫丹,因毒麟,异狄氏剂,保幼醚,乙酰氨基阿维菌素,烯丙菊酯,高氰戊菊酯,乙硫苯威,乙硫磷,乙虫腈,丙线磷,醚菊酯,乙嘧硫磷,伐灭磷,克线磷,抗螨唑,皮蝇硫磷,乙苯威,五氟菊酯,杀螟硫磷,仲丁威,氧嘧酰胺,苯氧威,吡氯氰菊酯,甲氰菊酯,丰索磷,倍硫磷,乙基倍硫磷,氰戊菊酯,氟虫腈,氟啶虫酰胺,氟虫双酰胺,氟氯双苯隆,氟螨脲, 氟氰戊菊酯,嘧虫胺,氟虫脲,三氟醚菊酯,氟胺氰菊酯,地虫硫磷,伐虫脒,安果，胺甲威，丁苯硫磷,伐线丹,呋线威,糠醛菊酯,γ-三氟氯氰菊酯,溴氟醚菊酯,氯虫酰肼,七氯,蚜螨磷,速杀硫磷,氟铃脲,氟蚁腙,烯虫乙酯,喹啉威,吡虫啉,炔咪菊酯,茚虫威,氯唑磷,碳氯灵,水胺硫磷,异艾氏剂,异丙胺磷,灭扑威,稻瘟灵,异丙磷,噁唑磷,伊维菌素,茉莉菊酯,碘硫磷,保幼激素I,保幼激素II,保幼激素III,氯戊环,丙诺保幼素,雷皮菌素,对溴磷,啶虫磷,虱螨脲,喹唑啉,马拉硫磷,特螨腈,叠氮磷,灭蚜磷,甲基灭蚜磷,灭蚜松,二噻磷,倍硫磷亚砜,氰氟虫腙,虫螨畏,甲胺磷,杀扑磷,灭虫威,丁烯胺磷,灭多威,烯虫酯,甲氧滴滴涕,甲氧虫酰肼,甲氧苄氟菊酯,速灭威,噁虫酮,速灭磷,治克威,米尔螨素,米尔贝肟,丙烯氟磷，灭蚊灵,杀虫单,久效磷,茂果,莫西菌素,驱虫磷,二溴磷,氟蚁灵,烯啶虫胺,硝虫噻嗪,戊氰威,双苯氟脲,多氟脲,杀线威,亚砜磷,异砜磷,砜拌磷,对硫磷,甲基对硫磷,氟幼脲,氯菊酯,芬硫磷,苯醚菊酯,稻丰散,甲拌磷,伏杀硫磷,棉安磷,亚胺硫磷,对氯硫磷,磷胺,辛硫磷,甲基辛硫磷,甲胺嘧磷,抗蚜磷,乙基虫螨磷,甲基虫螨磷,丙炔菊酯,早熟素I,早熟素II,早熟素III,酰胺嘧啶磷,丙溴磷,氟乐灵,蜱虱威,猛杀威,丙虫磷,胺丙畏,残杀威,乙噻唑膦,丙硫磷,发硫磷,protrifenbute,吡唑硫磷,pyrafluprole,定菌磷,反灭虫菊,除虫菊素,哒螨灵,啶虫丙醚,哒嗪硫磷,pyrifluquinazon,嘧螨醚,嘧啶磷,pyriprole,吡蚜酮，吡丙醚,苦楝素,喹硫磷,甲基喹硫磷,畜宁磷,碘醚柳胺,鱼藤酮,鱼尼丁,沙巴藜芦,八甲磷,司拉克丁,氟硅菊酯,苏果,多杀菌素,乙基多杀菌素,螺螨酯,螺虫乙酯,sulcofuron,sulcofuron-sodium,氟虫胺,治螟磷,氟啶虫胺腈,硫灭克磷,氟胺氰菊酯,噻螨威,虫酰肼,吡螨胺,丁基嘧啶磷,伏虫隆,七氟菊酯,双硫磷,甲烯菊酯,特丁磷,杀虫威,胺菊酯,四氟醚菊酯,高效氯氰菊酯,噻虫啉,噻虫嗪,喹氯磷,抗虫威,杀虫环,杀虫环草酸盐,硫双威,久效威,甲基乙拌磷,杀虫双,苏云金素,唑虫酰胺,四溴菊酯,四氟菊酯,苯螨噻,唑蚜威,***磷,敌百虫,trichlormetaphos-3,毒壤磷,三氯丙氧磷,杀铃脲,混杀威,烯虫硫酯,蚜灭磷,氟吡唑虫,灭杀威,唑虫磷等。The composition is a bactericidal and insecticidal composition, which refers to a composition prepared by a compound represented by Formula I and one or more other pesticides and a preparation thereof, which are used to expand the scope of product control. The other insecticides include: Avermectin, Acephate, Acetamiprid, Housefly Phosphorus, Acetonitrile, Pyrethrin, Cotton Lingwei, Aldicarb, Aldicarb, Acrymethrin , Aloxin, dichlorcarb, alpha-cypermethrin, alpha-ecdysone, endosulfan, thiothion, fendicarb, amine phosphate, sothothion, bismetham, pseudoequiline, beta Dimethophos, Azadirachtin, Pyridoxine, Pamphosphos, Azinphos-methyl, Azophos, Permethrin, Cephalcarb, Promethazol, Pesticide, β-cyfluthrin, β -Cypermethrin, bifenthrin, biomethrin, bioethanomethrin, biopermethrin, bistrifluthrin, bromophene, bromofenth, bromothion, bupropionate, rice lice net, butadiene Methocarbamate, Terazofos, Butanone, Butorate, Butanone Sulfate, Parathion, Toxaphen, Chlorfencarb, Cevidin, Indoxacarb, Dithiphos, Furacarb, Badan, Chlorantraniliprole, Borneol, Chlordane, Chlordecone, Chlorodimethoxine, Phosphorus, Bromopyronil, Chlorpyridine, Dipyridam, Chlorophen, Chloranthenium, Chlorimoxime Phosphorus, chlorpyrazole, chlorpyrifos, methyl chlorpyrifos, chlorpyrifos, fenzofen, citrinin, cis-fenfurate, dimethoate, chlorhexidine, clothianidin, methamphetamine, Pythium, Crowe Phosphate, Butenephos, Animal Phosphorus, Benzoz, Pyronitrile, Phosphate, Cypermethrin, Cypermethrin, Cypermethrin, Cyfluthrin, Cyhalothrin, Cypermethrin, Phenmethrin , Cypromazine, Xanthophos, DDT, Mefurandan, Deltamethrin, Tianle Phosphate, Tianle Phosphate, Thio Tian Phosphorus, Systemic Phosphorus, Methyl Systemic Phosphorus, Butyl Urea, Chlorine Amithion, Diazinon, Isochlorothion, Diphosphine, Dichlorvos, Dimethoate, Ciclofenac, Dieldrin, Diflubenzuron, Tetrafluthrin, Methion, Dimethoate, Dimethoate, Permethrin, Methofen, Difencarb, Acarofol, Propron, Dinitros, Pyridoxan, Diphenprofen, Phosphate, Dioxocarb, Difencarb, B Phosphorus, Phosphorate, Dolactin, Ecdysterone, Methanoate, Dimethrin, Endosulfan, Indoxacin, Ordrin, Juvenile Ether, Acetaveraverin, Allyl Chrysanthemum Ester, Fenvalerate, Ethylphene, Ethion, Ethionil, Profenthron, Ethethrin, Ethionthion, Phfenthion, Clenthophyl, Anti-Metazole, Dermatophosphine , Ethylcarb, Pentafluthrin, Fenthion, Sinbutyr, Oxyramid, Phenoxycarb, Permethrin, Fenpropathrin, Fossophos, Fenthion, Ethylfenthion, Cyanide Valproate, fipronil, flubendicarb, fluorid Bisamide, fluclofenon, flufenoxuron, fenvalerate, fenflubenzuron, flufenoxuron, trifluthrin, flufenthrin, fenthion, fenvalerate, angopril , Fenprocarb, Butylthiophos, Phanthin, Furanvir, Furfural, Gamma-cyhalothrin, Deltamethrin, Chlorantrazil, Heptachlor, Aphid, Fast-killer , Flufenuron, flufenazone, fenprofen, quinolincarb, imidacloprid, fenvalerate, indoxacarb, clozafos, chlorpromazine, thiamin, isotrin, isopropylamidron , Metronidazole, rice blast spirit, isopropylphosphine, oxazophos, ivermectin, jasmonate, ithiophosphine, juvenile hormone I, juvenile hormone II, juvenile hormone III, chloropentane, propyl Noborubin, rapidin, parabromophos, acetamiprid, fenuron, quinazoline, malathion, tebufenil, azide, aphid, methylphenid, Aphis pine, dithiphos, fenthion sulfoxide, cyanfludizone, fenflubenzus, methamidophos, fenfos, fenprocarb, butenamiphos, fendicarb, methoprene, methoprene , Methofenozide, Methofluthrin, Sulfadicarb, Xanthomone, Tefendicarb, Zhikwei, Milfenoxin, Milbexime, Acryloflufen, Mosquito, Insecticidal, Monocrotophos, Mogob, Moxidectin, Deworming Phosphorus, Dibromophosphine, Fluoride Aspirin, nitenpyram, nitracloprid, pentacyancarb, fenfluril, polyfluorourea, fenflucarb, sulfoxide, isosulfone, sulfone, parathion, methyl parathion , Fluenuron, Permethrin, Phfenthion, Phenmethrin, Rice Flour Powder, Phosphate, Fufenthion, Cotton Anphosphine, Imithion, Parathion, Phosphamine, Phoxim Phosphorus, Methylphosphine, Methamidophos, Aphis Phosphate, Ethylphos-methyl, Pyrethroids, Propyrmethrin, Precoccus I, Precoccus II, Precoccus III, Amidopyridin, Profenfos, Flulorin, Tevicarb, Methylcarb, Profenfos, Aprofen, Paracetamol, Ethiazole, Prothiophene, Phthionate, Protrifenbute, Pyrazine, Pyrafluprole, Bacterium Phosphorus, pyrethroids, pyrethrins, pyridaben, acetamiprid, pyridazithion, pyrifluquinazon, pyrimidin, pyrimiprole, pyrimiprole, pyridoxine, pyridoxine, arbutin, quinothion, Methylquinothion, Ninephosphine, Iodosalamine, Rotenone, Rootin, Sapora, Octaphos, Silactin, Filthrin, Thresh, Spinosad, Ethoxybin , Spirotetramat, spirotetramat, sulcofuron, sulcofuron-sodium, flubendicarb, fenfosinate, flufenacil, nitril, fenfosin, flufluthrin, thiamethoxam, tebufenozide, pyridoxine Mite, butyl Imidacloprid, flubendicarb, tefluthrin, dithiphos, methenethrin, terbufos, fenflucarb, pyrethrin, tetrafluthrin, beta-cypermethrin, thiamethoxam, thiamethoxam, Quincloxafen, insecticidal ring, insecticidal ring, insecticidal ring oxalate, thiodicarb, monocrotoxyl, methylacetophos, chlorfendione, threonin, pyraclostrobin, tetramethrin, tetrachloride Bifluthrin, benfenthiazate, pyraclostrobin, triazophos, trichlorfos, trichlormetaphos-3, poisonous soil phosphorus, trichloropropoxyphos, fenprofen, chlorfencarb, dimethoate, aphid , Fluflurazole, metronidazole, pyraclostrobin and so on.
此外，本发明所提供的式I所示化合物以及含该式I所示化合物的组合物在制备杀菌剂中的应用也属于本发明的保护范围。In addition, the application of the compound represented by the formula I and the composition containing the compound represented by the formula I in the preparation of a bactericide also belongs to the protection scope of the present invention.
本发明提供的式I所示化合物具有广谱而优异的杀菌活性，可用于防治在多种作物上由四大致病真菌纲：子囊菌、担子菌、半知菌和卵菌纲的真菌引起的病害。在很低的剂量下即可获得很好的防治效果。同时，该类式I所示化合 物具有一定的内吸性并可用作叶面和土壤杀菌剂，防治多种作物上的病害。具体可防治如下病害：辣椒疫病、番茄早疫病、番茄晚疫病、番茄灰霉病、水稻稻瘟病、小麦叶斑病、苹果轮纹病、水稻纹枯病、水稻稻瘟病、水稻稻曲病、水稻恶苗病、小麦白粉病、小麦赤霉病、油菜菌核病、黄瓜霜霉病、黄瓜枯萎病、黄瓜灰霉病、黄瓜白粉病、苹果白粉病、西瓜炭疽病、花生褐斑病、瓜果腐霉病、棉花枯萎病、棉花黄萎病和棉花立枯病。The compound of the formula I provided by the present invention has a broad spectrum and excellent bactericidal activity, and can be used to prevent and control a variety of crops caused by fungi of the four classes of ascomycetes, ascomycetes, basidiomycetes, and oomycetes. Disease. Good control results can be obtained at very low doses. At the same time, the compounds of the formula I have a certain systemic property and can be used as foliar and soil fungicides to prevent and cure diseases on many crops. Specifically, the following diseases can be controlled: pepper blight, tomato early blight, tomato late blight, tomato gray mold, rice blast, wheat leaf spot, apple rot, rice sheath blight, rice blast, rice blast disease, Rice blight, wheat powdery mildew, wheat scab, rape sclerotinia, cucumber downy mildew, cucumber wilt, cucumber gray mold, cucumber powdery mildew, apple powdery mildew, watermelon anthracnose, peanut brown spot, Melon fruit rot, cotton fusarium wilt, cotton verticillium wilt, and cotton blight.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为式I所示化合物的制备流程图。FIG. 1 is a flow chart for the preparation of a compound represented by Formula I.
实施发明的最佳方式The best way to implement the invention
下面通过具体实施例对本发明进行说明，但本发明并不局限于此，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 following describes the present invention through specific embodiments, but the present invention is not limited thereto. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention shall be included in the protection scope of the present invention. within.
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。Unless otherwise specified, the experimental methods used in the following examples are conventional methods.
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。The materials, reagents, etc. used in the following examples can be obtained from commercial sources unless otherwise specified.
一、式I所示化合物的制备实施例如下：相应的制备流程图如图1所示：1. Examples of the preparation of compounds represented by formula I are as follows: The corresponding preparation flow chart is shown in Figure 1:
实施例1、制备化合物Ia 8a-1(即式Ia na中n＝8，Y＝Br，Q 1＝H，Ar＝A 1/[(R 2) m＝H,(R 3) o＝H]的化合物) Example 1 Preparation of Compound Ia 8 a-1 (i.e. formula Ia n a of n = 8, Y = Br, Q 1 = H, Ar = A 1 / [(R 2) m = H, (R 3) o = H] compound)
1、制备N-[(1,1’-联苯)-2-基]-11-溴十一酰胺1. Preparation of N-[(1,1'-biphenyl) -2-yl] -11-bromoundecamide
取250mL三口瓶，加入2-碘苯胺2g(9.13mmol)、1.3g(10.96mmol)苯硼酸和2.5g(18.26mmol)碳酸钾。加入甲苯：乙醇：水＝10:1:1的120ml混合溶液并搅拌，后加入300mg(0.26mmol)四(三苯基膦)钯。加热回流8小时反应完全，得邻氨基联苯1.4g，收率91％。A 250 mL three-necked flask was charged with 2 g (9.13 mmol) of 2-iodoaniline, 1.3 g (10.96 mmol) of phenylboronic acid, and 2.5 g (18.26 mmol) of potassium carbonate. 120 ml of a mixed solution of toluene: ethanol: water = 10: 1: 1 was added and stirred, and then 300 mg (0.26 mmol) of tetrakis (triphenylphosphine) palladium was added. The reaction was completed by heating under reflux for 8 hours to obtain 1.4 g of o-aminobiphenyl with a yield of 91%.
在100ml圆底烧瓶中加入11-溴代十一酸1g(3.77mmol)、EDCI(0.72g，3.77mmol)和HoBT(0.5g，3.77mmol)，加入40ml二氯甲烷反应15min。然后加入邻氨基联苯(0.61g,3.6mmol)和NMM(0.77g,7.55mmol)。反应4h后得1.35g N-[(1,1’-联苯)-2-基]-11-溴十一酰胺{N-[(1,1'-biphenyl)-2-yl]-11-bromoundecanamide}，收率为86％。In a 100 ml round-bottomed flask, 1 g of bromoundecanoic acid (3.77 mmol), EDCI (0.72 g, 3.77 mmol) and HoBT (0.5 g, 3.77 mmol) were added, and 40 ml of dichloromethane was added to react for 15 minutes. Then o-aminobiphenyl (0.61 g, 3.6 mmol) and NMM (0.77 g, 7.55 mmol) were added. After 4 hours of reaction, 1.35 g of N-[(1,1'-biphenyl) -2-yl] -11-bromoundecamide {N-[(1,1'-biphenyl) -2-yl] -11- bromoundecanamide} with a yield of 86%.
1H NMR(300MHz,CDCl 3)δ8.21(d,J＝8.2Hz,1H),7.45–7.24(m,6H),7.17–7.13(m,1H),7.12–7.04(m,2H),3.32(t,J＝6.8Hz,2H),2.10(t,J＝7.5Hz,2H),1.84–1.68(m,2H),1.54–1.42(m,2H),1.38–1.28(m,2H),1.18(s,10H). 1 H NMR (300MHz, CDCl 3 ) δ8.21 (d, J = 8.2Hz, 1H), 7.45–7.24 (m, 6H), 7.17–7.13 (m, 1H), 7.12–7.04 (m, 2H), 3.32 (t, J = 6.8Hz, 2H), 2.10 (t, J = 7.5Hz, 2H), 1.84–1.68 (m, 2H), 1.54–1.42 (m, 2H), 1.38–1.28 (m, 2H) , 1.18 (s, 10H).
13C NMR(75MHz,CDCl 3)δ170.86,137.88,134.45,131.82,129.65,128.95,128.72,128.08,127.63,123.86,121.24,37.48,33.66,32.48,29.01,28.95,28.91,28.74,28.39,27.81,25.10. 13 C NMR (75MHz, CDCl 3 ) δ 170.86, 137.88, 134.45, 131.82, 129.65, 128.95, 128.72, 128.08, 127.63, 123.86, 121.24, 37.48, 33.66, 32.48, 29.01, 28.95, 28.91,28.74, 28.39, 27.81, 25.10 .
2、制备化合物Ia 8a-1 2. Preparation of compound Ia 8 a-1
在100mL三口瓶中加入0.6g(1.45mmol)N-[(1,1’-联苯)-2-基]-11-溴十一酰胺{N-[(1,1'-biphenyl)-2-yl]-11-bromoundecanamide}、0.5g(1.9mmol)三苯基膦、12mg(0.72ummol)碘化钾和磁子，抽真空，充氮气。在氮气保护下加30ml乙腈，于室温下搅拌5-10min，再将其于90℃下加热回流12h，柱层析分离得0.87g白色固体粉末，产率90％。In a 100 mL three-necked flask, 0.6 g (1.45 mmol) of N-[(1,1'-biphenyl) -2-yl] -11-bromoundecamide {N-[(1,1'-biphenyl) -2 -yl] -11-bromoundecanamide}, 0.5 g (1.9 mmol) of triphenylphosphine, 12 mg (0.72 ummol) of potassium iodide and magnetons, evacuate and fill with nitrogen. Under nitrogen protection, 30 ml of acetonitrile was added, and the mixture was stirred at room temperature for 5-10 min, and then heated to reflux at 90 ° C. for 12 h. The column chromatography was used to isolate 0.87 g of a white solid powder with a yield of 90%.
结构式确证数据：Structural Confirmation Data:
1H NMR(300MHz,CDCl 3)δ8.11(d,J＝8.2Hz,1H),7.78–7.59(m,15H),7.43–7.30(m,3H),7.27–7.18(m,4H),7.14(dd,J＝7.6,1.6Hz,1H),7.06(t,J＝7.4Hz,1H),3.47(s,2H),2.08(t,J＝7.5Hz,2H),1.61–1.37(m,6H),1.21–1.04(m,10H). 1 H NMR (300 MHz, CDCl 3 ) δ 8.11 (d, J = 8.2 Hz, 1 H), 7.78–7.59 (m, 15H), 7.43–7.30 (m, 3H), 7.27–7.18 (m, 4H), 7.14 (dd, J = 7.6, 1.6 Hz, 1H), 7.06 (t, J = 7.4 Hz, 1H), 3.47 (s, 2H), 2.08 (t, J = 7.5 Hz, 2H), 1.61-1.37 (m , 6H), 1.21--1.04 (m, 10H).
13C NMR(75MHz,CDCl 3)δ170.94,137.32,134.74,134.69,134.48,133.28,133.14,132.19,130.25,130.08,129.63,129.33,128.62,127.62,123.81,121.38,118.42,117.28,37.25,30.09,29.89,28.77,28.74,28.65,28.57,24.98,22.74,22.23,22.18,22.08. 13 C NMR (75MHz, CDCl 3 ) δ 170.94,137.32,134.74,134.69,134.48,133.28,133.14,132.19,130.25,130.08,129.63,129.33,128.62,127.62,123.81,121.38,118.42,117.28,37.25,30.09,29.89 , 28.77, 28.74, 28.65, 28.57, 24.98, 22.74, 22.23, 22.18, 22.08.
编号Ia 4-11a-1～Ia 4-11b-1至Ia 4-11a-80～Ia 4-11b-80的化合物均参照实施例1中的方法制备得到。其中部分化合物核磁如下： The compounds numbered Ia 4-11 a-1 to Ia 4-11 b-1 to Ia 4-11 a-80 to Ia 4-11 b-80 were all prepared by referring to the method in Example 1. Some of these compounds are as follows:
化合物Ia 8a-3 1H NMR和 13C NMR如下： Compound Ia 8 a-3 1 H NMR and 13 C NMR are as follows:
1H NMR(300MHz,CDCl 3)δ7.93(d,J＝8.0Hz,1H),7.76–7.56(m,15H),7.40–7.27(m,2H),7.25–7.13(m,4H),7.13–7.02(m,2H),3.54–3.35(m,2H),2.10(t,J＝7.5Hz,2H),1.63–1.33(m,6H),1.21–0.99(m,10H). 1 H NMR (300 MHz, CDCl 3 ) δ 7.93 (d, J = 8.0 Hz, 1 H), 7.76–7.56 (m, 15H), 7.40–7.27 (m, 2H), 7.25–7.13 (m, 4H), 7.13--7.02 (m, 2H), 3.54--3.35 (m, 2H), 2.10 (t, J = 7.5Hz, 2H), 1.63--1.33 (m, 6H), 1.21--0.99 (m, 10H).
13C NMR(75MHz,CDCl 3)δ171.22,139.94,134.85,134.82,134.23,134.15,133.27,133.14,130.33,130.16,129.89,129.51,128.77,128.27,127.49,127.01,124.47,122.94,118.19,117.06,37.12,30.11,29.90,28.71,28.61,28.58,25.04,23.02,22.35,22.17,22.11. 13 C NMR (75MHz, CDCl 3 ) δ171.22,139.94,134.85,134.82,134.23,134.15,133.27,133.14,130.33,130.16,129.89,129.51,128.77,128.27,127.49,127.01,124.47,122.94,118.19,117.06,37.12. , 30.11, 29.90, 28.71,28.61,28.58, 25.04, 23.02, 22.35, 22.17, 22.11.
化合物Ia 8a-5  1H NMR和 13C NMR如下： Compound Ia 8 a-5 1 H NMR and 13 C NMR are as follows:
1H NMR(300MHz,CDCl 3)δ7.79–7.57(m,15H),7.37(dd,J＝8.3,5.1Hz,2H),7.24–7.15(m,2H),7.13–7.06(m,2H),3.51–3.30(m,2H),2.15(t,J＝7.5Hz,2H),1.62–1.33(m,6H),1.24–0.97(m,10H). 1 H NMR (300 MHz, CDCl 3 ) δ 7.79–7.57 (m, 15H), 7.37 (dd, J = 8.3, 5.1 Hz, 2H), 7.24–7.15 (m, 2H), 7.13–7.06 (m, 2H ), 3.51--3.30 (m, 2H), 2.15 (t, J = 7.5Hz, 2H), 1.62--1.33 (m, 6H), 1.24--0.97 (m, 10H).
13C NMR(75MHz,CDCl 3)δ171.55,138.69,134.89,134.85,134.20,133.26,133.13,132.35,132.10,131.17,130.50,130.34,130.27,130.18,129.48,128.46,128.33,125.03,124.40,118.18,117.04,36.87,30.09,29.88,28.67,28.59,28.48,25.08,23.03,22.36,22.16,22.10. 13 C NMR (75MHz, CDCl 3 ) δ171.55,138.69,134.89,134.85,134.20,133.26,133.13,132.35,132.10,131.17,130.50,130.34,130.27,130.18,129.48,128.46,128.33,125.03,124.40,118.18,117.11.04. , 36.87, 30.09, 29.88, 28.67, 28.59, 28.48, 25.08, 23.03, 22.36, 22.16, 22.10.
化合物Ia 8a-21  1H NMR和 13C NMR如下： Compound Ia 8 a-21 1 H NMR and 13 C NMR are as follows:
1H NMR(300MHz,CDCl 3)δ8.12(s,1H),7.79–7.59(m,16H),7.51(dd,J＝30.9,8.3Hz,4H),7.22(dd,J＝7.7,4.0Hz,1H),7.14(d,J＝4.2Hz,2H),3.47–3.31(m,2H),2.16(t,J＝7.4Hz,2H),1.67–1.45(m,4H),1.45–1.31(m,2H),1.28–1.01(m,10H). 1 H NMR (300MHz, CDCl 3 ) δ8.12 (s, 1H), 7.79–7.59 (m, 16H), 7.51 (dd, J = 30.9, 8.3Hz, 4H), 7.22 (dd, J = 7.7, 4.0 Hz, 1H), 7.14 (d, J = 4.2Hz, 2H), 3.47–3.31 (m, 2H), 2.16 (t, J = 7.4Hz, 2H), 1.67–1.45 (m, 4H), 1.45–1.31 (m, 2H), 1.28--1.01 (m, 10H).
13C NMR(75MHz,CDCl 3)δ171.75,144.03,134.92,134.88,134.16,133.26,133.13,131.84,130.35,130.18,129.62,129.44,128.66,125.41,118.56,118.18,117.04,110.37,36.60,30.09,29.89,28.67,28.64,28.54,28.41,25.01,22.98,22.32,22.15,22.09. 13 C NMR (75MHz, CDCl 3 ) δ171.75,144.03,134.92,134.88,134.16,133.26,133.13,131.84,130.35,130.18,129.62,129.44,128.66,125.41,118.56,118.18,117.04,110.37,36.60,30.09,29.89.89 , 28.67, 28.64, 28.54, 28.41,25.01,22.98, 22.32, 22.15, 22.09.
化合物Ia 8a-26  1H NMR和 13C NMR如下： Compound Ia 8 a-26 1 H NMR and 13 C NMR are as follows:
1H NMR(300MHz,DMSO)δ8.80(s,1H),7.78–7.57(m,15H),7.47(dd,J＝8.7,5.4Hz,1H),7.37(d,J＝2.0Hz,1H),7.35–7.28(m,1H),7.25(dd,J＝8.3,2.0Hz,1H),6.84(ddd,J＝11.8,8.4,2.9Hz,2H),3.54–3.25(m,2H),2.18(t,J＝7.5Hz,2H),1.65–1.45(m,4H),1.45–1.29(m,2H),1.26–1.00(m,10H). 1 H NMR (300MHz, DMSO) δ8.80 (s, 1H), 7.78–7.57 (m, 15H), 7.47 (dd, J = 8.7, 5.4Hz, 1H), 7.37 (d, J = 2.0Hz, 1H ), 7.35–7.28 (m, 1H), 7.25 (dd, J = 8.3, 2.0 Hz, 1H), 6.84 (ddd, J = 11.8, 8.4, 2.9 Hz, 2H), 3.54-3.25 (m, 2H) 2.18 (t, J = 7.5 Hz, 2H), 1.65--1.45 (m, 4H), 1.45--1.29 (m, 2H), 1.26--1.00 (m, 10H).
13C NMR(75MHz,CDCl 3)δ172.22,161.45,158.20,138.26,136.25,134.85,134.82,133.18,133.05,131.81,131.18,130.61,130.28,130.11,130.02,128.15,118.26,117.12,116.05,115.75,114.88,114.59,36.25,30.00,29.80,28.57,28.51,28.33,25.04,22.78,22.12. 13 C NMR (75MHz, CDCl 3 ) δ172.22,161.45,158.20,138.26,136.25,134.85,134.82,133.18,133.05,131.81,131.18,130.61,130.28,130.11,130.02,128.15,118.26,117.12,116.05,115.75,114.88 , 114.59, 36.25, 30.00, 29.80, 28.57, 28.51,28.33, 25.04, 22.78, 22.12.
实施例2、制备化合物Ia 8a-115(即式Ia na中n＝8，Y＝Br，Q 1＝B 5，Ar＝A 1/[(R 2) m＝H,(R 3) o＝4-Cl]的化合物) Example 2. Preparation of compounds Ia 8 a-115 (that is, n = 8, Y = Br, Q 1 = B 5 in the formula Ia n a, Ar = A 1 / [(R 2 ) m = H, (R 3 ) o = 4-Cl] compound)
1、制备2-氯-N-(4-氯联苯-2-基)-N-(11-溴十一酰基)烟酰胺1.Preparation of 2-chloro-N- (4-chlorobiphenyl-2-yl) -N- (11-bromoundanoyl) nicotinamide
在100ml圆底烧瓶中加入11-溴代十一酸1g(3.77mmol)、EDCI(0.72g，3.77mmol)和HoBT(0.5g，3.77mmol)，加入40ml二氯甲烷反应15min。然后加入Boscalid{2-Chloro-N-(4'-chloro-[1,1'-biphenyl]-2-yl)nicotinamide}1.24g(3.6mmol)。反应4h后得1.5g 2-氯-N-(4-氯联苯-2-基)-N-(11-溴十一酰基)烟酰胺，收率为93％。In a 100 ml round-bottomed flask, 1 g of bromoundecanoic acid (3.77 mmol), EDCI (0.72 g, 3.77 mmol) and HoBT (0.5 g, 3.77 mmol) were added, and 40 ml of dichloromethane was added to react for 15 minutes. Then Boscalid {2-Chloro-N- (4'-chloro- [1,1'-biphenyl] -2-yl) nicotinamide} 1.24 g (3.6 mmol) was added. After 4 hours of reaction, 1.5 g of 2-chloro-N- (4-chlorobiphenyl-2-yl) -N- (11-bromoundanoyl) nicotinamide was obtained in a yield of 93%.
结构式确证数据：Structural Confirmation Data:
1H NMR(300MHz,CDCl 3)δ8.40(dd,J＝4.8,1.9Hz,1H),7.59–7.39(m,7H),7.33–7.24(m,3H),3.42(t,J＝6.8Hz,2H),2.39–2.23(m,1H),2.05(dt,J＝17.3,7.2Hz,1H),1.94–1.80(m,2H),1.50–1.04(m,15H). 1 H NMR (300MHz, CDCl 3 ) δ 8.40 (dd, J = 4.8, 1.9 Hz, 1H), 7.59–7.39 (m, 7H), 7.33–7.24 (m, 3H), 3.42 (t, J = 6.8 (Hz, 2H), 2.39--2.23 (m, 1H), 2.05 (dt, J = 17.3, 7.2Hz, 1H), 1.94--1.80 (m, 2H), 1.50--1.04 (m, 15H).
13C NMR(75MHz,CDCl 3)δ174.45,168.36,149.49,145.31,139.63,136.13,136.05,135.08,134.20,133.52,130.97,129.69,129.64,129.21,129.13,128.60,121.91,36.58,33.71,32.46,28.94,28.84,28.82,28.46,28.34,27.78,23.64. 13 C NMR (75MHz, CDCl 3 ) δ174.45,168.36,149.49,145.31,139.63,136.13,136.05,135.08,134.20,133.52,130.97,129.69,129.64,129.21,129.13,128.60,121.91,36.58,33.71,32.46,28.94. , 28.84, 28.82, 28.46, 28.34, 27.78, 23.64.
2、制备化合物Ia 8a-115 2. Preparation of compound Ia 8 a-115
在100mL三口瓶中加入0.78g(1.32mmol)2-氯-N-(4-氯联苯-2-基)-N-(11-溴十一酰基)烟酰胺{2-Chloro-N-(4'-chloro-[1,1'-biphenyl]-2-yl)-N-(11-bromoundecanoyl)-nicotinamide}、0.53g(2mmol)三苯基膦、12mg(72ummol)碘化钾和磁子，抽真空，充氮气。在氮气保护下加30ml乙腈，于室温下搅拌5-10min，再将其于90℃下加热回流10h，柱层析分离得1g白色固体粉末，产率88％。In a 100 mL three-necked flask, 0.78 g (1.32 mmol) of 2-chloro-N- (4-chlorobiphenyl-2-yl) -N- (11-bromoundanoyl) nicotinamide {2-Chloro-N- ( 4'-chloro- [1,1'-biphenyl] -2-yl) -N- (11-bromoundecanoyl) -nicotinamide}, 0.53g (2mmol) triphenylphosphine, 12mg (72ummol) potassium iodide and magnetons, draw Vacuum and nitrogen. Under nitrogen protection, 30 ml of acetonitrile was added, and the mixture was stirred at room temperature for 5-10 min, and then heated to reflux at 90 ° C. for 10 h. Column chromatography separated 1 g of a white solid powder with a yield of 88%.
结构确证数据：Structural Confirmation Data:
1H NMR(300MHz,CDCl 3)δ8.23(dd,J＝4.8,1.9Hz,1H),7.74–7.57(m,15H),7.47–7.14(m,10H),3.60–3.42(m,2H),2.28–1.79(m,2H),1.48(4,6H),1.25–0.87(m,12H). 1 H NMR (300MHz, CDCl 3 ) δ8.23 (dd, J = 4.8, 1.9Hz, 1H), 7.74–7.57 (m, 15H), 7.47–7.14 (m, 10H), 3.60–3.42 (m, 2H ), 2.28--1.79 (m, 2H), 1.48 (4, 6H), 1.25--0.87 (m, 12H).
13C NMR(75MHz,CDCl 3)δ174.42,168.27,149.35,145.29,139.46,136.01,135.96,134.90,134.73,134.69,134.02,133.47,133.27,133.13,130.94,130.24,130.07,129.66,129.23,129.05,128.49,121.96,118.42,117.29,36.48,30.06,29.86,28.65,28.59,28.29,23.52,22.75,22.25,22.19,22.08. 13 C NMR (75MHz, CDCl 3 ) δ174.42,168.27,149.35,145.29,139.46,136.01,135.96,134.90,134.73,134.69,134.02,133.47,133.27,133.13,130.94,130.24,130.07,129.66,129.23,129.05,128.49. , 121.96, 118.42, 117.29, 36.48, 30.06, 29.86, 28.65, 28.59, 28.29, 23.52, 22.75, 22.25, 22.19, 22.08.
编号Ia 4-11a-81～Ia 4-11b-81至Ia 4-11a-184～Ia 4-11b-184的化合物均按实施例1中的方法制备得到；编号Ia 4-11a-185～Ia 4-11b-185至Ia 4-11a-553～Ia 4-11b-553的化合物均参照实施例1和实施例2中的方法制备得到。 The compounds numbered Ia 4-11 a-81 to Ia 4-11 b-81 to Ia 4-11 a-184 to Ia 4-11 b-184 were all prepared according to the method in Example 1; numbered Ia 4-11 The compounds of a-185 to Ia 4-11 b-185 to Ia 4-11 a-553 to Ia 4-11 b-553 were all prepared by referring to the methods in Examples 1 and 2.
实施例3、制备化合物Ib 6a-2(即式Ib na中n＝6，Y＝Br，Q 2＝C 1b的化合物) Example 3 Preparation of compound Ib 6 a-2 (ie, the compound of formula Ib n a where n = 6, Y = Br, Q 2 = C 1b )
在100mL三口瓶中加入(E)-2-(2-溴甲基)苯基-2-甲氧亚氨基乙酸甲酯2.35g(8.2mmol)和8-溴正辛醇(1.8g,8.61mmol)，THF溶液30mL，降温至5℃以下，加入3.91g(12mmol)Cs 2CO 3，搅拌1h后，升温至室温(25℃)继续反应8h。真空旋干，柱层析得产物(E)-2-[2-(8-溴辛氧基)亚甲基)苯基-2-甲氧亚氨基乙酸甲酯2.7g，收率80％ In a 100 mL three-neck flask, add (E) -2- (2-bromomethyl) phenyl-2-methoxyiminoacetic acid methyl ester 2.35 g (8.2 mmol) and 8-bromo-n-octanol (1.8 g, 8.61 mmol) ), 30 mL of a THF solution, lowered the temperature to below 5 ° C., added 3.91 g (12 mmol) of Cs 2 CO 3 , stirred for 1 h, then raised the temperature to room temperature (25 ° C.) to continue the reaction for 8 h. Spin-dried in vacuum and column chromatography to obtain the product (E) -2- [2- (8-bromooctyloxy) methylene) phenyl-2-methoxyiminoacetic acid methyl ester 2.7g, yield 80%
1H NMR(300MHz,CDCl 3)δ7.49–7.32(m,3H),7.21–7.14(m,1H),4.38(s,2H),4.04(s,3H),3.87(s,3H),3.39(dt,J＝13.6,6.8Hz,4H),1.93–1.79(m,2H),1.49–1.38(m,2H),1.32(s,6H). 1 H NMR (300MHz, CDCl 3 ) δ 7.49–7.32 (m, 3H), 7.21–7.14 (m, 1H), 4.38 (s, 2H), 4.04 (s, 3H), 3.87 (s, 3H), 3.39 (dt, J = 13.6, 6.8 Hz, 4H), 1.93--1.79 (m, 2H), 1.49--1.38 (m, 2H), 1.32 (s, 6H).
在100mL三口瓶中加入(E)-2-[2-(8-溴辛氧基)亚甲基)苯基-2-甲氧亚氨基乙酸甲酯1.07g(2.59mmol)、0.82g(3.1mmol)三苯基膦、18mg(108ummol)碘化钾和磁子，抽真空，充氮气。在氮气保护下加30ml乙腈，于室温下搅拌5-10min，再将其于90℃下加热回流10h，柱层析分离得0.74g白色固体粉末，产率42％。(E) -2- [2- (8-Bromooctyloxy) methylene) phenyl-2-methoxyiminoacetic acid methyl ester 1.07 g (2.59 mmol), 0.82 g (3.1 mmol) of triphenylphosphine, 18 mg (108 ummol) of potassium iodide and magnetons, evacuated and filled with nitrogen. Under nitrogen protection, 30 ml of acetonitrile was added, and the mixture was stirred at room temperature for 5-10 min. Then it was heated to reflux at 90 ° C. for 10 h. Column chromatography separated 0.74 g of a white solid powder with a yield of 42%.
1H NMR(300MHz,CDCl 3)δ7.81–7.59(m,15H),7.36–7.20(m,3H),7.09–7.02(m,1H),4.26(s,2H),3.92(s,3H),3.73(s,3H),3.57(s,2H),3.24(t,J＝6.6Hz, 2H),1.58–1.47(m,2H),1.45–1.34(m,2H),1.24–1.10(m,6H). 1 H NMR (300MHz, CDCl 3 ) δ 7.81-7.59 (m, 15H), 7.36-7.20 (m, 3H), 7.09-7.02 (m, 1H), 4.26 (s, 2H), 3.92 (s, 3H ), 3.73 (s, 3H), 3.57 (s, 2H), 3.24 (t, J = 6.6Hz, 2H), 1.58–1.47 (m, 2H), 1.45–1.34 (m, 2H), 1.24-1.10 ( m, 6H).
编号Ib 4-11a系列的化合物均按实施例3中的方法制备得到。 The compounds of No. Ib 4-11 a series were all prepared according to the method in Example 3.
实施例4、制备化合物Ib 8b-2(即式Ib nb中n＝8，Y＝Br，Q 2＝C 1b的化合物)： Example 4: Preparation of compound Ib 8 b-2 (that is, a compound in which n = 8, Y = Br, and Q 2 = C 1b in formula Ib n b):
在100mL三口瓶中加入含有2.4g(9mmol)11-溴代十一酸的THF溶液30mL，降温至5℃以下，加入3.91g(12mmol)Cs2CO3，搅拌1h后，加入(E)-2-(2-溴甲基)苯基-2-甲氧亚氨基乙酸甲酯2.35g(8.2mmol)，升温至室温(25℃)继续反应8h。真空旋干，呈黄色粘稠状液体，柱层析得粉色粘稠状液体3.2g，产率83％。30 mL of a THF solution containing 2.4 g (9 mmol) of 11-bromoundecanoic acid was added to a 100 mL three-necked flask, the temperature was lowered to below 5 ° C, 3.91 g (12 mmol) of Cs2CO3 was added, and after stirring for 1 h, (E) -2- ( 2-Bromomethyl) phenyl-2-methoxyiminoacetic acid methyl ester 2.35 g (8.2 mmol), warmed to room temperature (25 ° C.) and continued the reaction for 8 h. It was spin-dried under vacuum to give a yellow viscous liquid. Column chromatography gave 3.2 g of a pink viscous liquid with a yield of 83%.
1H NMR(300MHz,CDCl 3)δ7.47–7.34(m,3H),7.20–7.13(m,1H),4.97(s,2H),4.03(s,3H),3.86(s,3H),3.62(t,J＝6.5Hz,2H),2.28(td,J＝7.6,2.1Hz,2H),1.69–1.50(m,6H),1.27(s,10H). 1 H NMR (300MHz, CDCl 3 ) δ 7.47–7.34 (m, 3H), 7.20–7.13 (m, 1H), 4.97 (s, 2H), 4.03 (s, 3H), 3.86 (s, 3H), 3.62 (t, J = 6.5 Hz, 2H), 2.28 (td, J = 7.6, 2.1 Hz, 2H), 1.69-1.50 (m, 6H), 1.27 (s, 10H).
在100mL三口瓶中加入(E)-2-[2-(11-溴十一酸基)亚甲基)苯基-2-甲氧亚氨基乙酸甲酯1.2g(2.59mmol)、0.82g(3.1mmol)三苯基膦、18mg(108ummol)碘化钾和磁子，抽真空，充氮气。在氮气保护下加30ml乙腈，于室温下搅拌5-10min，再将其于90℃下加热回流10h，柱层析分离得0.99g白色固体粉末，产率52％。(E) -2- [2- (11-bromoundecanoyl) methylene) phenyl-2-methoxyiminoacetic acid methyl ester 1.2 g (2.59 mmol), 0.82 g ( 3.1 mmol) of triphenylphosphine, 18 mg (108 ummol) of potassium iodide and magnetons, evacuated and filled with nitrogen. Under nitrogen protection, 30 ml of acetonitrile was added, and the mixture was stirred at room temperature for 5-10 min. Then it was heated to reflux at 90 ° C. for 10 h. Column chromatography separated 0.99 g of a white solid powder with a yield of 52%.
1H NMR(300MHz,DMSO-d6)δ7.96–7.85(m,3H),7.86–7.71(m,12H),7.48–7.35(m,3H),7.25–7.18(m,1H),4.87(s,2H),3.92(s,3H),3.74(s,3H),3.56(s,2H),2.22(t,J＝7.4Hz,2H),1.46(s,6H),1.33–1.12(m,10H).1HNMR (300MHz, DMSO-d6) δ 7.96–7.85 (m, 3H), 7.86–7.71 (m, 12H), 7.48–7.35 (m, 3H), 7.25–7.18 (m, 1H), 4.87 (s , 2H), 3.92 (s, 3H), 3.74 (s, 3H), 3.56 (s, 2H), 2.22 (t, J = 7.4Hz, 2H), 1.46 (s, 6H), 1.33--1.12 (m, 10H).
13C NMR(75MHz,DMSO-d6)δ172.52,162.77,148.93,134.98(d,J＝3.1Hz),133.69(d,J＝9.8Hz),130.34(d,J＝12.4Hz),129.33,128.90,128.65,128.15,119.28,118.15,63.92,63.45,52.69,33.34,30.00,28.98–28.58(m),28.50,28.16,24.33.13CNMR (75MHz, DMSO-d6) δ172.52, 162.77, 148.93, 134.98 (d, J = 3.1Hz), 133.69 (d, J = 9.8Hz), 130.34 (d, J = 12.4Hz), 129.33, 128.90, 128.65 , 128.15, 119.28, 118.15, 63.92, 63.45, 52.69, 33.34, 30.00, 28.98–28.58 (m), 28.50, 28.16, 24.33.
编号Ib 4-11b和Ib 4-11c的化合物均按实施例4中的方法制备得到。 The compounds numbered Ib 4-11 b and Ib 4-11 c were prepared according to the method in Example 4.
其中，化合物Ib 2b-2：粉色粘稠状液体，产率为53％，1H NMR如下： Among them, compound Ib 2 b-2: a pink viscous liquid with a yield of 53%. The 1H NMR is as follows:
1H NMR(300MHz,Chloroform-d)δ7.69–7.55(m,9H),7.51(td,J＝7.6,3.7Hz,6H),7.23–7.13(m,3H),6.97(dq,J＝5.3,2.5Hz,1H),4.71(s,2H),3.79(s,3H),3.61(s,3H),3.59–3.41(m,2H),2.19(t,J＝6.7Hz,2H),1.80(p,J＝7.1Hz,2H),1.54(p,J＝7.8,7.3Hz,2H).1HNMR (300MHz, Chloroform-d) δ 7.69–7.55 (m, 9H), 7.51 (td, J = 7.6, 3.7Hz, 6H), 7.23–7.13 (m, 3H), 6.97 (dq, J = 5.3 , 2.5Hz, 1H), 4.71 (s, 2H), 3.79 (s, 3H), 3.61 (s, 3H), 3.59-3.41 (m, 2H), 2.19 (t, J = 6.7Hz, 2H), 1.80 (p, J = 7.1 Hz, 2H), 1.54 (p, J = 7.8, 7.3 Hz, 2H).
二、包含式I所示化合物的组合物的实施例如下：(以下各组分均以质量百分含量计，活性组分折百后计量加入)Second, the embodiment of the composition containing the compound represented by the formula I is as follows: (the following components are based on mass percentage content, the active component is metered after adding 100%)
实施例5、制备含有50％式I所示化合物的可湿性粉剂：Example 5. Preparation of a wettable powder containing 50% of the compound represented by Formula I:
可湿性粉剂的组成：式I所示化合物50％、分散剂聚羧酸盐5％、润湿剂十二烷基硫酸钠3％、固体载体或崩解剂膨润土42％；将各组分按所述比例混合得到混合物，对其进行气流粉碎，即可制得50％可湿性粉剂。Composition of wettable powder: 50% of the compound of formula I, 5% of dispersant polycarboxylate, 3% of sodium dodecyl wetting agent, 42% of solid carrier or disintegrant bentonite; The proportions are mixed to obtain a mixture, which is subjected to jet milling to obtain a 50% wettable powder.
实施例6、制备含有30％式I所示化合物的乳油：Example 6. Preparation of an emulsifiable concentrate containing 30% of the compound represented by Formula I:
乳油的组成：式I所示化合物30％、乳化剂聚氧化烯基烷基芳基醚12％、渗透剂磺酸烷基芳酯10％、液体载体环己酮48％；将各组分按所述比例混合得到30％化合物的透明溶液。Composition of emulsifiable concentrate: 30% of the compound represented by Formula I, 12% of an emulsifier polyoxyalkylene alkylaryl ether, 10% of an alkylaryl sulfonate sulphonate, and 48% of cyclohexanone as a liquid carrier. The ratios were mixed to obtain a clear solution of 30% of the compound.
实施例7、制备含有60％式I化合物的水分散粒剂：Example 7. Preparation of water-dispersible granules containing 60% of the compound of formula I:
水分散粒剂的组成：式I所示化合物70％、分散剂烷基苯磺酸钙盐3％、分散剂木质素磺酸盐3％、润湿剂十二烷基硫酸钠4％、固体载体或填料淀粉20％；将各组分按所述比例混合制得70％式I化合物的水分散粒剂。Composition of water-dispersible granules: 70% of the compound represented by Formula I, 3% calcium alkylbenzene sulfonate as dispersant, 3% lignin sulfonate as dispersant, 4% sodium dodecyl sulfate as wetting agent, and solid Carrier or filler starch 20%; 70% water-dispersible granules of the compound of formula I are prepared by mixing the components according to the ratio.
三、生物活性测定：3. Biological activity determination:
实施例8、杀菌活性测定：Example 8: Determination of bactericidal activity:
用本发明式I化合物对植物的各种菌病害进行试验，试验方法如下：The compounds of formula I of the present invention are used to test various bacterial diseases in plants. The test methods are as follows:
采用菌丝生长速率测定方法：本试验按照中华人民共和国农业行业标准(NY/T 1156.2-2006)，采用菌丝生长速率法进行测定。将活化好的各种病原菌，在超净实验台上，无菌条件下用直径5mm的打孔器打孔，切取菌饼，用11号手术刀将菌饼接种于冷却后的含药培养基的中央，盖上皿盖，倒置于25℃培养箱中培养，三个平行，统计结果时取平均值。Using the method of measuring the growth rate of hyphae: This test was carried out in accordance with the standards of the agricultural industry of the People's Republic of China (NY / T 1156.2-2006), using the growth rate method of hyphae. The various pathogenic bacteria that have been activated are punched on a clean bench with a 5mm diameter hole punch under aseptic conditions, the bacteria cake is cut, and the bacteria cake is inoculated into the cooled medicated medium with a No. 11 scalpel. In the center, cover the dish and invert in a 25 ° C incubator. Three parallel cultures are used.
待CK直径达到6-8cm后，以十字交叉法测量处理过的各菌落直径，采用公式(1)计算菌落增长直径，取其平均值。After the diameter of CK reaches 6-8cm, the diameter of each treated colony is measured by the cross method, and the colony growth diameter is calculated using formula (1), and the average value is taken.
菌落增长直径＝菌落直径-菌饼直径   (1)Colony growth diameter = colony diameter-bacteria cake diameter (1)
测定结果，以空白对照菌落增长直径和药剂处理过的菌落增长直径计算各化合物对病原菌的菌丝生长抑制率，参见下面公式(2)。As a result of the measurement, the growth inhibitory rate of each compound against the pathogenic bacteria was calculated from the blank control colony growth diameter and the treated colony growth diameter, see formula (2) below.
菌丝生长抑制率(％)＝(对照菌落增长直径-药剂处理菌落增长直径)/对照菌落增长直径×100   (2)Mycelial growth inhibition rate (%) = (control colony growth diameter-chemical treatment colony growth diameter) / control colony growth diameter × 100 (2)
表1、Ia系列部分化合物杀菌活性对比试验结果Table 1. Results of comparative test of bactericidal activity of some compounds of Ia series
Figure PCTCN2018100964-appb-000038
Figure PCTCN2018100964-appb-000038
Figure PCTCN2018100964-appb-000039
Figure PCTCN2018100964-appb-000039
杀菌实验结果发现，在0.07μM浓度下，11个式I系列的化合物均表现出优秀的广谱性的杀菌活性。与对照药剂啶酰菌胺相比，每个药都有相似甚至优于啶酰菌胺的杀菌活性，尤其是Ia 8a-3、Ia 8a-13、Ia 8a-14、Ia 8a-15和Ia 8a-21在番茄灰霉、辣椒疫霉、西瓜炭疽和番茄晚疫病上均表现出良好杀菌效果。 The results of the bactericidal experiment found that at a concentration of 0.07 μM, all 11 compounds of the formula I series showed excellent broad-spectrum bactericidal activity. Compared with the control agent, boscalid, each drug has similar or even better fungicidal activity than boscalid, especially Ia 8 a-3, Ia 8 a-13, Ia 8 a-14, Ia 8 a -15 and Ia 8 a-21 showed good bactericidal effects on Botrytis cinerea, Phytophthora capsici, anthracnose watermelon and tomato late blight.
表2、Ib系列部分化合物杀菌活性对比试验结果Table 2. Comparative test results of bactericidal activity of some compounds in the Ib series
0.07μM0.07 μM 瓜果腐霉Pythium melon 棉花立枯Cotton stand 番茄灰霉Botrytis cinerea 辣椒疫霉Phytophthora capsici 苹果轮纹Apple wheel pattern 小麦赤霉Gibberella wheat 番茄晚疫Tomato late blight
I b2b-2 I b2b -2 3.603.60 (1.65)(1.65) 47.5047.50 64.7264.72 8.898.89 15.0315.03 6.146.14
I b5b-2 I b5b -2 24.7224.72 0.680.68 69.1769.17 86.8886.88 46.0046.00 20.2620.26 52.4152.41
I b8b-2 I b8b -2 91.2291.22 56.8056.80 78.7578.75 88.0188.01 70.4470.44 24.6224.62 79.8279.82
醚菌酯Etoxystrobin 69.8969.89 50.4450.44 45.3145.31 22.2122.21 47.1147.11 30.0730.07 68.4268.42
杀菌实验结果发现，在0.07μM浓度下，3个式Ib系列的化合物I b8b-2和I b5b-2表现出优秀的广谱性的杀菌活性。与对照药剂醚菌酯相比，I b8b-2和I b5b-2都有相似甚至优于醚菌酯的杀菌活性，尤其是在瓜果腐霉、番茄灰霉、辣椒疫霉、苹果轮纹和番茄晚疫病上I b8b-2表现出良好杀菌效果。 The results of the bactericidal experiment revealed that at a concentration of 0.07 μM, the three compounds of the formula Ib series, I b8 b-2 and I b5 b-2, showed excellent broad-spectrum bactericidal activity. Compared with the control agent triclostrobin , I b8 b-2 and I b5 b-2 have similar or even better fungicidal activity, especially in Pythium melon, Botrytis cinerea, Phytophthora capsici, apple I b8 b-2 on ring pattern and tomato late blight showed good bactericidal effect.
工业应用Industrial applications
本发明提供的式I所示三苯基鏻盐化合物具有广谱而优异的杀菌活性，可用于防治在多种作物上由四大致病真菌纲：子囊菌、担子菌、半知菌和卵菌纲病害引起的病害。在低剂量下即可获得很好的防治效果，在植物保护剂中有广泛的应用。The triphenylphosphonium salt compound represented by the formula I provided by the present invention has a broad spectrum and excellent bactericidal activity, and can be used to control four broadly pathogenic fungi in various crops: ascomycetes, basidiomycetes, semi-strains, and eggs. Diseases caused by mycobacterial diseases. Good control effects can be obtained at low doses, and they are widely used in plant protection agents.

Claims (15)

  1. 结构通式如式I所示的化合物：Compounds having the general formula:
    Figure PCTCN2018100964-appb-100001
    Figure PCTCN2018100964-appb-100001
    所述式I中，X选自CH 2、N、S或O；Y选自卤素、CH 3SO 3、CF 3CO 2、CH 3CO 2、CF 3SO 3、PhCO 2、HOC 6H 4CO 2、(CH 2CO 2) 2、(CHCO 2) 2和式W中的任意一种；所述卤素选自氯、溴和碘中的任意一种；n为0～16的整数；Q选自下述式Ia或式Ib； In the formula I, X is selected from CH 2 , N, S or O; Y is selected from halogen, CH 3 SO 3 , CF 3 CO 2 , CH 3 CO 2 , CF 3 SO 3 , PhCO 2 , HOC 6 H 4 CO 2 , (CH 2 CO 2 ) 2 , (CHCO 2 ) 2 and any one of Formula W; the halogen is selected from any one of chlorine, bromine and iodine; n is an integer from 0 to 16; Q Selected from the following formula Ia or Ib;
    Figure PCTCN2018100964-appb-100002
    Figure PCTCN2018100964-appb-100002
    所述式W中，R 1代表H或C 1～C 12的烷基； In the formula W, R 1 represents H or a C 1 to C 12 alkyl group;
    所述式Ia中，Ar选自下述A 1～A 8中的任意一种，Q 1选自H和B 1～B 11中的任意一种； In the formula Ia, Ar is selected from any one of the following A 1 to A 8 , and Q 1 is selected from any one of H and B 1 to B 11 ;
    Figure PCTCN2018100964-appb-100003
    Figure PCTCN2018100964-appb-100003
    所述式Ib中U选自O、NH、S、OCO、SC＝O、NHC＝O和NHC＝S中的任意一种，Q 2选自C 1～C 4中的任一种； In the formula Ib, U is selected from any one of O, NH, S, OCO, SC = 0, NHC = 0, and NHC = S, and Q 2 is selected from any one of C 1 to C 4 ;
    Figure PCTCN2018100964-appb-100004
    Figure PCTCN2018100964-appb-100004
    其中，A 1-A 8中所述式A 1、A 2和A 5中，R 2、R 3、R 4、R 5和R 6均选自氢、C 1-C 8的烷基、C 1-C 8的烷氧基、C 1-C 8的烷硫基、C 1-C 8的氟代烷基、C 1-C 8的氟代烷氧基、卤素、硝基、氰基、苯氧基、吡啶氧基、甲磺酰基和三氟甲磺酰基中的至少一种，所述卤素选自氟、氯、溴和碘中的任一种；：o、q和r均为0-5的整数；m为0-4的整数；p为0-3的整数；R 2、R 3、R 5和R 6的结合位点为剩余的5个结合位点中的至少一个，其中，当m、o、q和r>1时，R 2、R 3、R 5和R 6相同或不同；R 4的结合位点为剩余3个结合位点中的至少一个，其中，当p>1时，R 4相同或不同；式A 2中，N位于3、4、5和6位中的任一处； Wherein, in the formulas A 1 , A 2 and A 5 described in A 1 -A 8 , R 2 , R 3 , R 4 , R 5 and R 6 are all selected from hydrogen, C 1 -C 8 alkyl, C 1- C 8 alkoxy, C 1 -C 8 alkylthio, C 1 -C 8 fluoroalkyl, C 1 -C 8 fluoroalkoxy, halogen, nitro, cyano, At least one of phenoxy, pyridyloxy, methanesulfonyl, and trifluoromethanesulfonyl, and the halogen is selected from any one of fluorine, chlorine, bromine, and iodine; o, q, and r are all 0 An integer of -5; m is an integer of 0-4; p is an integer of 0-3; the binding sites of R 2 , R 3 , R 5 and R 6 are at least one of the remaining 5 binding sites, wherein When m, o, q, and r> 1, R 2 , R 3 , R 5, and R 6 are the same or different; the binding site of R 4 is at least one of the remaining three binding sites, where when p When> 1, R 4 is the same or different; in formula A 2 , N is located at any of the 3, 4, 5 and 6 positions;
    B 1-B 10中所述式B 1中，R 7选自氢、C 1-C 5的烷基、C 1-C 5的烷氧基、C 1-C 5的氟代烷基、C 1-C 5的氟代烷氧基、卤素、硝基、氰基、苯氧基、吡啶氧基、羧基、甲磺酰基和三氟甲磺酰基中的至少一种，所述卤素选自氟、氯、溴和碘中的任一种，s为0-5的整数；R 7的结合位点为剩余的5个结合位点中的至少一个，其中，当s>1时，R 7相同或不同；所述式B 6中，R 8和R 9均选自氢、C 1-C 5的烷基、C 1-C 5的烷氧基、C 1-C 5的氟代烷基、C 1-C 5的氟代烷氧基和卤素中的任意一种； In Formula B 1 described in B 1 -B 10 , R 7 is selected from hydrogen, C 1 -C 5 alkyl, C 1 -C 5 alkoxy, C 1 -C 5 fluoroalkyl, C At least one of 1- C 5 fluoroalkoxy, halogen, nitro, cyano, phenoxy, pyridyloxy, carboxyl, methanesulfonyl, and trifluoromethanesulfonyl, the halogen selected from fluorine Any of chloro, bromo, and iodine, s is an integer of 0-5; the binding site of R 7 is at least one of the remaining 5 binding sites, wherein when s> 1, R 7 is the same Or different; in the formula B 6 , R 8 and R 9 are both selected from hydrogen, C 1 -C 5 alkyl, C 1 -C 5 alkoxy, C 1 -C 5 fluoroalkyl, Any of C 1 -C 5 fluoroalkoxy and halogen;
    式C 1-C 4所述式C 1和C 3中，Z选自N或CH，M选自NH或O。 The C 1 -C 4 Formula C Formula 1 and C 3, Z chosen from N or CH, M is selected from NH or O.
  2. 根据权利要求1所述的化合物，其特征在于：所述式I中，X选自CH 2或O；Y选自卤素、CH 3CO 2、对甲苯甲磺酰基、PhCO 2和HOC 6H 4CO 2中的任一种；n为4～11的整数。 The compound according to claim 1, wherein in the formula I, X is selected from CH 2 or O; Y is selected from halogen, CH 3 CO 2 , p-toluenesulfonyl, PhCO 2 and HOC 6 H 4 Any of CO 2 ; n is an integer of 4-11.
  3. 根据权利要求1或2所述的化合物，其特征在于：所述式Ia中，Ar选自所述A 1、A 3、A 4和A 6中的任意一种，Q 1选自H；所述式Ib中，U选自O、OCO和SC＝O中的任意一种，Q 2选自所述C 1～C 4中的任一种。 The compound according to claim 1 or 2, wherein, in the formula Ia, Ar is selected from any one of the A 1 , A 3 , A 4 and A 6 , and Q 1 is selected from H; In Formula Ib, U is selected from any one of O, OCO, and SC = O, and Q 2 is selected from any one of C 1 to C 4 .
  4. 权利要求1-3中任一项所述式I所示的化合物的制备方法，包括如下步骤：在催化剂或无催化剂存在条件下，使式VII所示化合物和三苯基膦进行亲核反应，得到式I所示化合物；The method for preparing a compound represented by formula I according to any one of claims 1-3, comprising the steps of: performing a nucleophilic reaction between a compound represented by formula VII and triphenylphosphine in the presence of a catalyst or without a catalyst to obtain A compound represented by formula I;
    Figure PCTCN2018100964-appb-100005
    Figure PCTCN2018100964-appb-100005
    所述式VII中，Y、Q、X和n的定义均同式I。In Formula VII, the definitions of Y, Q, X and n are the same as those in Formula I.
  5. 根据权利要求4所述的制备方法，其特征在于：所述催化剂为碘化钠或碘 化钾；The preparation method according to claim 4, wherein the catalyst is sodium iodide or potassium iodide;
    所述催化剂和式VII所示化合物的摩尔比为(0.01-0.1):1；The molar ratio of the catalyst to the compound represented by formula VII is (0.01-0.1): 1;
    所述亲核反应的反应温度为25～180℃，优选为80～115℃，反应时间为4-24h，优选为8-12h；The reaction temperature of the nucleophilic reaction is 25-180 ° C, preferably 80-115 ° C, and the reaction time is 4-24h, preferably 8-12h;
    所述式VII所示化合物和三苯基膦的摩尔比为1：(1-2)；The molar ratio of the compound represented by Formula VII to triphenylphosphine is 1: (1-2);
    所述亲核反应在有机溶剂中进行，所述有机溶剂选自乙腈、乙二醇二甲醚、苯、甲苯和1,2-二氯乙烷中的至少一种。The nucleophilic reaction is performed in an organic solvent selected from at least one of acetonitrile, ethylene glycol dimethyl ether, benzene, toluene, and 1,2-dichloroethane.
  6. 根据权利要求4或5所述的制备方法，其特征在于：所述亲核反应具体按照如下步骤进行：将所述催化剂、三苯基膦和式VII所示化合物和磁子抽真空，充氮气；在氮气保护下加有机溶剂，于室温下搅拌5-10min，再将其于80～115℃下反应8-12h，得到式I所示化合物。The preparation method according to claim 4 or 5, characterized in that the nucleophilic reaction is specifically performed according to the following steps: evacuating the catalyst, triphenylphosphine, the compound represented by formula VII and magnetons, and filling it with nitrogen; Add an organic solvent under nitrogen protection, stir at room temperature for 5-10min, and then react it at 80-115 ° C for 8-12h to obtain the compound represented by formula I.
  7. 结构通式如式VII所示的化合物：Compounds having the general formula:
    Figure PCTCN2018100964-appb-100006
    Figure PCTCN2018100964-appb-100006
    所述式VII中，Y、Q、X和n的定义均同所述式I中对应的Y、Q、X和n。In the formula VII, the definitions of Y, Q, X and n are the same as the corresponding Y, Q, X and n in the formula I.
  8. 权利要求7所述式VII所示的化合物的制备方法，包括下述步骤：The method for preparing a compound represented by formula VII according to claim 7, comprising the following steps:
    将式IV所示化合物在催化剂存在下与式VI所示化合物进行反应，或将式V所示化合物在缚酸剂存在下与式VI所示化合物进行反应，得到式VII所示化合物；Reacting a compound represented by formula IV with a compound represented by formula VI in the presence of a catalyst, or reacting a compound represented by formula V with a compound represented by formula VI in the presence of an acid binding agent to obtain a compound represented by formula VII;
    Figure PCTCN2018100964-appb-100007
    Figure PCTCN2018100964-appb-100007
    所述式IV中，Q 1和Ar的定义同权利要求1中所述式Ia；所述式V中，Q 2的定义同权利要求1中所述式Ib；所述式VI中，X、Y和n的定义均同式I，U的定义均同权利要求1中所述式Ib；当式IV与式VI反应时，U为COO基团。 In Formula IV, Q 1 and Ar are defined as Formula Ia described in claim 1; in Formula V, Q 2 is defined as Formula Ib described in Claim 1; in Formula VI, X, The definitions of Y and n are the same as those of formula I, and the definitions of U are the same as those of formula Ib described in claim 1; when formula IV reacts with formula VI, U is a COO group.
  9. 根据权利要求8所述的制备方法，其特征在于：The preparation method according to claim 8, characterized in that:
    所述缚酸剂选自下述至少一种：吡啶、三乙胺、乙二胺、碳酸钾、碳酸铯、N-甲基***啉和NaH；所述催化剂选自下述至少一种：EDCI/HOBT、CDI、DMAP/DCC、HATU/DIPEA和DIC；The acid-binding agent is selected from at least one of the following: pyridine, triethylamine, ethylenediamine, potassium carbonate, cesium carbonate, N-methylmorpholine, and NaH; the catalyst is selected from at least one of the following: EDCI / HOBT, CDI, DMAP / DCC, HATU / DIPEA and DIC;
    所述缚酸剂和式IV所示化合物的摩尔比为(2-5):1；The molar ratio of the acid-binding agent and the compound represented by Formula IV is (2-5): 1;
    所述催化剂和式IV所示化合物的摩尔比为(1-2.5):1，其中，IV所示化合物和式VI所示化合物的摩尔比为1：(1-2)；The molar ratio of the catalyst and the compound represented by Formula IV is (1-2.5): 1, wherein the molar ratio of the compound represented by IV and the compound represented by Formula VI is 1: (1-2);
    所述缚酸剂和式V所示化合物的摩尔比为(2-5):1；所述催化剂和式V所示化合物的摩尔比为(1-2.5):1；其中，V所示化合物和式VI所示化合物的摩尔比为1：(1-2)；The molar ratio of the acid binding agent and the compound represented by Formula V is (2-5): 1; the molar ratio of the catalyst and the compound represented by Formula V is (1-2.5): 1; wherein, the compound represented by V is The molar ratio with the compound represented by Formula VI is 1: (1-2);
    所述反应的反应温度为-20～35℃，反应时间为1-6h；The reaction has a reaction temperature of -20 to 35 ° C and a reaction time of 1-6h;
    所述反应在有机溶剂中进行，所述有机溶剂选自下述至少一种：二氯甲烷、四氢呋喃、乙腈、N,N-二甲基甲酰胺、1,4-二氧六环和甲苯。The reaction is performed in an organic solvent selected from at least one of the following: methylene chloride, tetrahydrofuran, acetonitrile, N, N-dimethylformamide, 1,4-dioxane, and toluene.
  10. 一种组合物，包括权利要求1-3中任一项所述的式I所示化合物和农业上可接受的载体。A composition comprising a compound of formula I according to any one of claims 1-3 and an agriculturally acceptable carrier.
  11. 根据权利要求10所述的组合物，其特征在于：所述组合物中式I所示化合物的质量百分含量为0.1～99％，优选为30～60％。The composition according to claim 10, wherein the mass percentage content of the compound represented by Formula I in the composition is 0.1 to 99%, preferably 30 to 60%.
  12. 根据权利要求10或11所述的组合物，其特征在于：所述组合物中还包括至少一种其它具有活性的化合物；所述其它具有活性的化合物为已知的杀菌剂、杀螨剂、杀线虫剂、杀虫剂、除草剂、肥料、生长调节剂、安全剂和化学信息素种的至少一种，进一步优选为杀菌剂和杀虫剂。The composition according to claim 10 or 11, wherein the composition further comprises at least one other active compound; the other active compounds are known fungicides, acaricides, At least one of a nematicide, an insecticide, a herbicide, a fertilizer, a growth regulator, a safener, and a chemical pheromone, and more preferably a fungicide and an insecticide.
  13. 根据权利要求10-12中任一项所述的组合物，其特征在于：所述农业上可接受的载体选自固体载体和/或液体载体；The composition according to any one of claims 10-12, wherein the agriculturally acceptable carrier is selected from a solid carrier and / or a liquid carrier;
    所述固体载体选自天然或合成的硅酸盐、硫酸铵、硫酸钙、氧化硅酸铝、天然或合成的树脂、多氯苯酚、淀粉、膨润土和蜡中的至少一种，其中，所述天然或合成的硅酸盐选自硅镁土、滑石、硅酸铝、硅藻土、云母、蒙脱石和硅酸钙中的至少一种，所述天然或合成的树脂选自苯并呋喃树脂、苯乙烯聚合物和苯乙烯共聚物中的至少一种；所述蜡选自蜂蜡和/或石蜡；The solid support is selected from at least one of natural or synthetic silicate, ammonium sulfate, calcium sulfate, aluminum oxide silicate, natural or synthetic resin, polychlorophenol, starch, bentonite, and wax, wherein, the The natural or synthetic silicate is at least one selected from the group consisting of wollastonite, talc, aluminum silicate, diatomaceous earth, mica, montmorillonite, and calcium silicate. The natural or synthetic resin is selected from benzofuran resin. At least one of styrene polymer and styrene copolymer; the wax is selected from beeswax and / or paraffin;
    所述液体载体选自水、C 1-C 4的醇、C 3-C 8的酮、芳烃、石油馏分和C 6-C 12的氯代烃中的至少一种，其中，所述醇为乙醇和/或乙二醇；所述酮为苯乙酮、丙酮、甲乙酮和环己酮中的至少一种；所述芳烃为苯、甲苯和二甲苯中的至少一种；所述石油馏分为煤油和/或矿物油；所述氯代烃为四氯化碳、二氯甲烷和三氯乙烷中的至少一种； The liquid carrier is at least one selected from the group consisting of water, a C 1 -C 4 alcohol, a C 3 -C 8 ketone, an aromatic hydrocarbon, a petroleum fraction, and a C 6 -C 12 chlorinated hydrocarbon, wherein the alcohol is Ethanol and / or ethylene glycol; the ketone is at least one of acetophenone, acetone, methyl ethyl ketone, and cyclohexanone; the aromatic hydrocarbon is at least one of benzene, toluene, and xylene; the petroleum fraction Kerosene and / or mineral oil; the chlorinated hydrocarbon is at least one of carbon tetrachloride, dichloromethane and trichloroethane;
    所述组合物中，还包括表面活性剂；The composition further includes a surfactant;
    所述表面活性剂选自乳化剂、分散剂、润湿剂和渗透剂中的至少一种；The surfactant is selected from at least one of an emulsifier, a dispersant, a wetting agent, and a penetrant;
    所述乳化剂选自烷基苯黄酸钙、苯基酚聚氧乙基醚、烷基酚甲醛树脂聚氧乙基醚、苯乙基酚聚氧乙基聚丙烯基醚、聚氧化烯基烷基芳基醚和环氧乙烷-环氧丙烷嵌段共聚物中的至少一种；The emulsifier is selected from the group consisting of calcium alkylphenylxanthate, phenylphenol polyoxyethyl ether, alkylphenol formaldehyde resin polyoxyethyl ether, phenethylphenol polyoxyethyl polypropylene ether, and polyoxyalkylene group. At least one of an alkylaryl ether and an ethylene oxide-propylene oxide block copolymer;
    所述分散剂选自聚羧酸盐、木质素磺酸盐、烷基酚聚氧乙烯甲醛缩合物硫酸盐、烷基苯磺酸钙盐、苯磺酸甲醛缩合物钠盐、硫酸月桂酸钠，磺化蓖麻油钠盐、磺酸 烷基芳基酯钠，烷基酚聚氧乙烯嘧、脂肪酸聚氧乙烯酯和酯聚氧乙烯嘧中的至少一种；The dispersant is selected from the group consisting of polycarboxylate, lignin sulfonate, alkylphenol polyoxyethylene formaldehyde condensate sulfate, calcium alkylbenzenesulfonate calcium salt, benzenesulfonic acid formaldehyde condensate sodium salt, sodium laurate sulfate , At least one of sulfonated castor oil sodium salt, sodium alkylaryl sulfonate, alkylphenol polyoxyethylene pyrimide, fatty acid polyoxyethylene ester, and ester polyoxyethylene pyrimide;
    所述润湿剂选自十二烷基硫酸钠、十二烷基苯磺酸钠、拉开粉BX、皂角粉、蚕沙和无患子粉中的至少一种；The wetting agent is at least one selected from the group consisting of sodium lauryl sulfate, sodium dodecylbenzenesulfonate, BX powder, saponin powder, silkworm sand, and sapindus powder.
    所述组合物中，还包括其他助剂；The composition further includes other auxiliaries;
    所述其他助剂选自崩解剂、消泡剂、抗冻剂和增稠剂中的至少一种；The other auxiliary agents are selected from at least one of a disintegrant, an antifoaming agent, an antifreeze agent, and a thickener;
    所述崩解剂选自膨润土、尿素、硫酸铵、氯化铝和葡萄糖中的至少一种；The disintegrant is selected from at least one of bentonite, urea, ammonium sulfate, aluminum chloride, and glucose;
    所述消泡剂选自硅油、硅酮类化合物、C10-C20饱和脂肪酸类化合物、C8-C10脂肪醇类化合物中的至少一种；The defoaming agent is at least one selected from the group consisting of silicone oil, silicone compounds, C10-C20 saturated fatty acid compounds, and C8-C10 fatty alcohol compounds;
    所述抗冻剂选自乙二醇、丙二醇、丙三醇和聚乙二醇中的至少一种；The antifreeze is selected from at least one of ethylene glycol, propylene glycol, glycerol, and polyethylene glycol;
    所述的增稠剂选自黄原酸胶、聚乙烯醇和聚乙二醇中的至少一种。The thickener is selected from at least one of xanthan gum, polyvinyl alcohol and polyethylene glycol.
  14. 权利要求1-3中任一项所述的式I所示化合物和/或权利要求10-13中任一项所述的组合物在制备植物杀菌剂和/或土壤杀菌剂中的应用。Use of the compound of formula I according to any one of claims 1-3 and / or the composition of any one of claims 10-13 in the preparation of a plant fungicide and / or a soil fungicide.
  15. 根据权利要求14所述的应用，其特征在于：所述植物杀菌剂和/或土壤杀菌剂用于防治由下述至少一种真菌纲的真菌引起的病害：子囊菌、担子菌、半知菌和卵菌纲。The application according to claim 14, characterized in that the plant fungicide and / or soil fungicide is used for controlling diseases caused by at least one of the following fungi: Ascomycetes, Basidiomycetes, and Deuteromycetes And Oomycetes.
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