WO2023284761A1 - Composé pyrazole éther, son procédé de préparation et son utilisation - Google Patents

Composé pyrazole éther, son procédé de préparation et son utilisation Download PDF

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WO2023284761A1
WO2023284761A1 PCT/CN2022/105331 CN2022105331W WO2023284761A1 WO 2023284761 A1 WO2023284761 A1 WO 2023284761A1 CN 2022105331 W CN2022105331 W CN 2022105331W WO 2023284761 A1 WO2023284761 A1 WO 2023284761A1
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methyl
hydrogen
hours
reaction
butyl
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PCT/CN2022/105331
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Chinese (zh)
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吕亮
李宏伟
庞俊倩
杜永磊
张扬
陈晨
袁硕
周飞
郑斐
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南通泰禾化工股份有限公司
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Publication of WO2023284761A1 publication Critical patent/WO2023284761A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms

Definitions

  • the present application relates to the field of agricultural fungicides, such as a pyrazole ether compound and its preparation method and application.
  • Amide fungicides are a kind of commonly used fungicides, which account for a considerable proportion of fungicides. They have attracted attention for their high-efficiency biological activity. However, after a period of use of these fungicides, diseases will become resistant Therefore, there is a constant need to invent new and improved compounds and compositions with fungicidal activity.
  • CN101631460A discloses KC1, KC2, and KC2 (respectively compounds 595, 596 and 599 in the patent). These disclosed compounds have herbicidal activity, but no pyrazole ethers have been reported. Bactericidal activity of compounds.
  • the application provides a pyrazole ether compound and its preparation method and application.
  • the application provides a pyrazole ether compound, the pyrazole ether compound has the structure shown in formula I:
  • R is selected from phenyl, pyridyl, pyrimidinyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl substituted by at least one R 10 ;
  • R 2 and R 3 are independently selected from hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy;
  • R is selected from C1 - C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy;
  • R is selected from hydrogen, methyl ;
  • R is selected from hydrogen, halogen, C1- C6 alkyl or C1-C6 haloalkyl
  • R 7 is selected from hydrogen, methyl
  • R 8 is selected from hydrogen, C1-C6 alkyl
  • R9 is selected from C1-C8 alkyl, hydroxy C1-C6 alkyl, C1-C6 cycloalkyl, C1-C6 cycloalkylC1-C6 alkyl; or
  • R 8 and R 9 together with the nitrogen atom they are connected to form a three-membered to six-membered saturated ring group, the ring group may optionally contain an oxygen atom or a sulfur atom;
  • R 10 is selected from hydrogen, halogen, cyano, nitro, hydroxyl, amino, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkyl Substituted amino, C1-C6 alkylcarbonylamino, C1-C6 alkylsulfoxide, C1-C6 alkylsulfone, C1-C6 haloalkylsulfoxide, C1-C6 haloalkylsulfoxide.
  • the pyrazole ether compound has the structure shown in formula II:
  • R 2 and R 3 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, difluoromethyl, trifluoromethyl, methoxy, trifluoromethoxy, difluoromethoxy;
  • R is selected from methyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy ;
  • R is selected from hydrogen, methyl ;
  • R is selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, difluoromethyl, trifluoromethyl ;
  • R 7 is selected from hydrogen, methyl
  • R is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 2 -pentyl, neopentyl, isopentyl, 4 -Methyl-2-pentyl, n-hexyl;
  • R is selected from methyl, ethyl, hydroxyethyl, n-propyl, isopropyl, 1 -methylpropyl, 1-ethylpropyl, 2-methylpropyl, 3-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, n-butyl, tert-butyl, 3-methylbutyl, 1,1-dimethyl-3,3-dimethyl Butyl, n-pentyl, 4-methyl-2-pentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-hexyl, 2- Ethylhexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl; or
  • R 8 and R 9 together with the nitrogen atom to which they are attached form pyrrole, piperidine or morpholine;
  • R is selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxyl, amino, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, Difluoromethyl, trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl, methoxy, difluoromethoxy, trifluoromethoxy, methylamino, acetylamino, methylsulfonyl, trifluoromethyl Sulfonyl;
  • n an integer of 0 to 5 (for example, 0, 1, 2, 3, 4, 5).
  • the pyrazole ether compound is any one of the compounds shown in Table 1 below with the general formula I, wherein R 2 and R 3 are selected from hydrogen:
  • R 2 and R 3 are selected from hydrogen
  • R 4 is selected from methyl
  • R is selected from hydrogen ;
  • R 6 is selected from hydrogen, methyl
  • R is selected from hydrogen ;
  • R 8 is selected from hydrogen, methyl
  • R is selected from methyl, ethyl, hydroxyethyl, n-propyl, isopropyl, 1 -methylpropyl, 1-ethylpropyl, 2-methylpropyl, 3-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, n-butyl, tert-butyl, 3-methylbutyl, 1,1-dimethyl-3,3-dimethyl Butyl, n-pentyl, 4-methyl-2-pentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-hexyl, 2- ethylhexyl; or
  • R 8 and R 9 together with the nitrogen atom to which they are attached form pyrrole, piperidine or morpholine;
  • R is selected from hydrogen, fluorine, chlorine, cyano, methoxy, trifluoromethyl ;
  • n 0, 1 or 2.
  • the pyrazole ether compound is any one of the following compounds:
  • alkyl group mentioned in this application refers to a straight chain or a branched chain form, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl , Isopentyl, n-hexyl and other groups.
  • Haloalkyl means a group in which the alkyl group is substituted with one or more halogen atoms.
  • Alkoxy refers to a group with an oxygen atom attached to the end of the alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy and the like.
  • Haloalkoxy means a group in which an alkoxy group is substituted with one or more halogen atoms.
  • Halogen is F, Cl, Br or I.
  • C1-C6 alkyl used in this application refers to a straight or branched chain alkyl group having 1 to 6 carbon atoms, including without limitation methyl, ethyl, n-propyl, isopropyl, n-butyl Base, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, etc.
  • C1-C6 alkoxy refers to a straight or branched chain alkoxy group having 1 to 6 carbon atoms, including without limitation methoxy, ethoxy, n-propoxy, isopropoxy And tert-butoxy, etc.
  • C1-C12 alkoxy has a similar meaning.
  • C3-C8 cycloalkyl used in this application refers to a cyclic alkyl group with 3 to 8 carbon atoms on the ring, including without limitation cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, Cycloheptyl, cyclooctyl, etc.
  • C2-C12, C1-C6, C3-C8, etc. before the specific group indicate the number of carbon atoms contained in the group
  • C2-C12 means that the number of carbon atoms can be 2, 3, or 4 , 5, 6, 7, 8, 9, 10, 11 or 12 groups
  • C1-C6 represents a group with 1, 2, 3, 4, 5 or 6 carbon atoms
  • C3-C8 represents a carbon atom
  • C2-C4 represents a group whose number of carbon atoms can be 2, 3 or 4, etc., and so on.
  • the group Represents the attachment position of the group.
  • the present application provides the preparation method of the above-mentioned pyrazole ether compounds, the preparation method is:
  • R 11 is selected from C1-C6 alkyl.
  • the molar ratio of the compound represented by the formula II to the compound represented by the formula III is 0.5-2:1, such as 0.5:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 1.8:1 or 2:1.
  • the solvent for the reaction is dichloromethane, chloroform, ethyl acetate, toluene, acetonitrile, tetrahydrofuran, dioxane, ethanol, methanol, N,N-dimethylformamide or dimethylsulfoxide, etc. Any one or a combination of at least two of them.
  • the reaction temperature is greater than or equal to room temperature and less than or equal to the boiling point of the reaction solvent, such as 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 60°C, 70°C, 75°C, 80°C, 85°C, 90°C, etc., or react at the boiling point of the solvent, that is, under reflux.
  • the boiling point of the reaction solvent such as 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 60°C, 70°C, 75°C, 80°C, 85°C, 90°C, etc.
  • the reaction time is 0.5-48 hours, such as 0.5 hours, 1 hour, 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 23 hours, 25 hours , 28 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 44 hours, or 48 hours.
  • the compound shown in formula III is prepared by the following method: the compound shown in formula IV reacts with the compound of formula V in the presence of a catalyst to obtain the compound shown in formula III, and the reaction formula is as follows:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 11 are as described above, and will not be repeated here.
  • the reaction is carried out in the presence of an acidic substance, and the acidic substance is an organic acid and/or an inorganic acid.
  • the organic acid is any one or a combination of at least two of p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid and acetic acid.
  • the organic acid is any one or a combination of at least two of hydrochloric acid, hydrobromic acid, sulfuric acid, zinc chloride, ammonium chloride, ferric chloride.
  • no solvent may be added during the preparation of the compound represented by formula III.
  • the reaction in the preparation of the compound shown in formula III, can be carried out in a suitable solvent, the solvent of the reaction is dichloromethane, chloroform, ethyl acetate, toluene, acetonitrile, tetrahydrofuran, 1,4 dioxane Any one or a combination of at least two of rings, methanol, ethanol, isopropanol, n-butanol, water, N,N-dimethylformamide or dimethyl sulfoxide.
  • the solvent of the reaction is dichloromethane, chloroform, ethyl acetate, toluene, acetonitrile, tetrahydrofuran, 1,4 dioxane Any one or a combination of at least two of rings, methanol, ethanol, isopropanol, n-butanol, water, N,N-dimethylformamide or dimethyl sulfoxide.
  • the reaction temperature is greater than or equal to 0°C and less than or equal to the boiling point of the reaction solvent, such as 0°C, 3°C, 5°C, 8°C, 10°C, 15°C, 20°C °C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 60°C, 70°C, 75°C, 80°C, 85°C, 90°C, etc., or react at the boiling point of the solvent, that is, under reflux.
  • the reaction solvent such as 0°C, 3°C, 5°C, 8°C, 10°C, 15°C, 20°C °C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 60°C, 70°C, 75°C, 80°C, 85°C, 90°C, etc.
  • the reaction time is 0.5-48 hours, such as 0.5 hours, 1 hour, 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours Hours, 20 hours, 23 hours, 25 hours, 28 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 44 hours, or 48 hours.
  • the compound shown in formula IV is prepared by the following method: the compound shown in formula VI is reduced in the presence of a reducing agent to obtain the compound shown in formula IV, and the reaction formula is as follows:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are as described above, and will not be repeated here.
  • the reducing agent is any one or a combination of at least two of hydrogen, hydrazine hydrate, iron powder, zinc powder, stannous chloride or sodium dithionite.
  • the reaction is carried out in the presence of a catalyst, and the catalyst is preferably any one of palladium carbon, palladium dioxide, Raney nickel, iron trichloride or basic iron oxide one or a combination of at least two.
  • the catalyst is preferably any one of palladium carbon, palladium dioxide, Raney nickel, iron trichloride or basic iron oxide one or a combination of at least two.
  • the solvent for the reaction is dichloromethane, chloroform, ethyl acetate, toluene, acetonitrile, tetrahydrofuran, dioxane, ethanol, methanol, N,N-dimethyl Any one or a combination of at least two of methyl formamide, saturated ammonium chloride aqueous solution, acetic acid, hydrochloric acid, water or dimethyl sulfoxide.
  • the reaction temperature is greater than or equal to 0°C and less than or equal to the boiling point of the reaction solvent, such as 0°C, 3°C, 5°C, 8°C, 10°C, 15°C, 20°C °C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 60°C, 70°C, 75°C, 80°C, 85°C, 90°C, etc., or react at the boiling point of the solvent, that is, under reflux.
  • the boiling point of the reaction solvent such as 0°C, 3°C, 5°C, 8°C, 10°C, 15°C, 20°C °C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 60°C, 70°C, 75°C, 80°C, 85°C, 90°C, etc.
  • the reaction time is 0.5-48 hours, such as 0.5 hours, 1 hour, 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours Hours, 20 hours, 23 hours, 25 hours, 28 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 44 hours, or 48 hours.
  • the compound shown in formula VI is prepared by the following method: the compound shown in formula VII is reacted with the compound shown in formula VIII to obtain the compound shown in formula VI, and the reaction formula is as follows:
  • L is fluorine or chlorine.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are as described above and will not be repeated here.
  • the molar ratio of the compound shown in formula VII to the compound shown in formula VIII is 1-3:1, such as 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.3:1, 2.5 :1, 2.8:1 or 3:1.
  • the reaction is carried out in the presence of a basic substance, and the basic substance is an organic base and/or an inorganic base.
  • the organic base is any one or a combination of at least two of triethylamine, N,N-dimethylaniline, pyridine, sodium methoxide, sodium ethoxide, sodium tert-butoxide or potassium tert-butoxide.
  • the inorganic base is any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium hydride.
  • the solvent for the reaction is dichloromethane, chloroform, acetone, toluene, acetonitrile, tetrahydrofuran, dioxane, methanol, ethanol, N,N-dimethylform Any one or a combination of at least two of amide, dimethylsulfoxide or hexamethylphosphoric triamide.
  • the temperature of the reaction is greater than or equal to 0°C and less than or equal to the boiling point of the reaction solvent, such as 0°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C °C, 50 °C, 60 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, etc., or the reaction is carried out at the boiling point of the solvent, that is, under reflux.
  • the boiling point of the reaction solvent such as 0°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C °C, 50 °C, 60 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, etc.
  • the reaction time is 0.5-48 hours, such as 0.5 hours, 1 hour, 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours Hours, 20 hours, 23 hours, 25 hours, 28 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 44 hours, or 48 hours.
  • the present application provides the use of the above-mentioned pyrazole ether compounds in the prevention and treatment of plant diseases.
  • the pyrazole ether compound described in the application has unexpectedly high fungicidal activity and has a good control effect on plant diseases.
  • the plant diseases include Oomycetes, Ascomycetes, Basidiomycetes or Deuteromycetes diseases.
  • the plant diseases include, but are not limited to: wheat rust, wheat powdery mildew, wheat head blight, wheat root rot, wheat sheath blight, wheat take-all, wheat glume blight, cucumber downy mildew, cucumber Powdery mildew, melon powdery mildew, bitter melon powdery mildew, cucumber anthracnose, cucumber wilt, cucumber gray mold, grape downy mildew, tomato early blight, tomato late blight, rice sheath blight, rice blast, watermelon blight , Peanut scab, Peanut black spot, Citrus scab, Capsicum root rot, Cotton Verticillium wilt, Cotton wilt, Rapeseed black stem, Rapeseed sclerotinia, Pear scab, Ginseng rust rot, Corn rust , Corn Curvularia, Corn Spot, Mango Stem Rot, Apple Ringworm, Apple Rot, Banana Leaf Spot, Soybean
  • the plant diseases include wheat rust, wheat powdery mildew, wheat scab, cucumber powdery mildew, cucumber downy mildew or soybean rust.
  • the present application provides a fungicide composition, which includes an active component and a pesticide acceptable carrier, and the active component is the above-mentioned pyrazole ether compound.
  • the bactericide composition described in this application can be used in fields such as agriculture, forestry, and sanitation.
  • the weight percentage of the active ingredient is 1-99%, such as 1%, 3%, 5%, 8%, 10%, 15%, 18%, 20% , 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99%.
  • the pesticidally acceptable carrier includes a surfactant.
  • the surfactant is an ionic surfactant or a nonionic surfactant.
  • the surfactants include emulsifiers, dispersants or wetting agents.
  • Emulsifier can be polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol ether, polyoxyethylene fatty ammonia and commercially available emulsifier (Nong milk 2201B, Nong milk 0203B, Nong milk 100#, Nong milk 500#, Nong milk 600 #, Agricultural Milk 600-2#, Agricultural Milk 1601, Agricultural Milk 2201, Agricultural Milk NP-10, Agricultural Milk NP-15, Agricultural Milk 507#, Agricultural Milk OX-635, Agricultural Milk OX-622, Agricultural Milk OX- 653, Nongru OX-667, Ningru 36#).
  • Dispersants include sodium lignosulfonate, pull-off powder, calcium lignosulfonate, methylnaphthalenesulfonic acid formaldehyde condensate, etc.
  • Wetting agents include sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, and the like.
  • the pesticide acceptable carrier includes a solid carrier and/or a liquid carrier.
  • the solid carrier comprises natural or synthetic clays and silicates, such as natural silica and diatomaceous earth; magnesium silicates such as talc; magnesium aluminum silicates such as kaolinite, kaolin, montmorillonite and mica; White carbon black, calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; amine salts such as ammonium sulfate, hexamethylenediamine.
  • Liquid carriers include water and organic solvents. When water is used as a solvent or diluent, organic solvents can also be used as auxiliary agents or antifreeze additives.
  • Suitable organic solvents include aromatic hydrocarbons such as benzene, xylene, toluene, etc.; chlorinated hydrocarbons, such as chlorobenzene, vinyl chloride, chloroform, methylene chloride, etc.; aliphatic hydrocarbons, such as petroleum fractions, cyclohexane, light minerals oils; alcohols such as isopropanol, butanol, ethylene glycol, glycerol, and cyclohexanol; and their ethers and esters; and ketones such as acetone, cyclohexanone, and dimethylformamide and N-methyl-pyrrolidone.
  • aromatic hydrocarbons such as benzene, xylene, toluene, etc.
  • chlorinated hydrocarbons such as chlorobenzene, vinyl chloride, chloroform, methylene chloride, etc.
  • aliphatic hydrocarbons such as petroleum fractions, cyclohexane, light minerals oils
  • the active components can be mixed with the liquid carrier and/or solid carrier, while adding surfactants (such as emulsifiers, dispersants, stabilizers, wetting agents), and other auxiliary agents can also be added (such as adhesives, defoamers, oxidizing agents, etc.).
  • surfactants such as emulsifiers, dispersants, stabilizers, wetting agents
  • auxiliary agents such as adhesives, defoamers, oxidizing agents, etc.
  • the present application provides a method for controlling plant diseases, the method comprising: applying an effective dose of the above-mentioned fungicide composition to the plant disease to be controlled or the growth medium thereof.
  • the effective dose is 10-1000g per hectare, such as 10g, 20g, 50g, 80g, 100g, 120g, 150g, 180g, 200g, 250g, 300g, 350g, 400g, 450g, 500g, 600g, 700g, 800g , 900g or 1000g, preferably 20-500g per hectare.
  • compositions of the present application may be applied to the disease or its growth medium in the form of a formulation.
  • the compound of general formula I is dissolved or dispersed in the carrier as an active component or formulated into a preparation so that it is easier to disperse when used as a fungicide.
  • these chemical preparations can be formulated into various liquids, emulsifiable concentrates, suspensions, aqueous suspensions, microemulsions, emulsions, emulsions in water, powders, wettable powders, soluble powders, granules, water-dispersible granules or capsules agent.
  • one or more other fungicides, insecticides, herbicides, plant growth regulators or fertilizers, etc. can be added in the fungicidal composition of the present application in agriculture, which can produce additional advantages and effects.
  • the pyrazole ether compounds having the structure shown in formula I in the examples of the present application have significant effects on the prevention and control of diseases in agriculture and forestry, especially for cucumber powdery mildew, cucumber downy mildew, soybean rust, and wheat head blight.
  • Control effect when the concentration of pyrazole ether compounds is 10ppm, the control effect on cucumber powdery mildew is ⁇ 90%, and when the concentration of pyrazole ether compounds is 10ppm, the control effect on cucumber downy mildew is ⁇ 90%;
  • the control effect of rust is more than 90%; when the concentration of pyrazole ether compounds is 100ppm, the inhibition rate of germination of wheat scab spores is more than 90%, and the preparation method is simple and efficient, easy for large-scale production, and has wide application prospects.
  • Step 5 Synthesis of (E)-N-(4-((1-phenyl-1H-pyrazol-3-yl)oxy)-2,5-dimethylphenyl)formamidine ethyl ether:
  • Step 6 (E)-N'-(4-((1-Phenyl-1H-pyrazol-3-yl)oxy)-2,5-dimethylphenyl)-N-ethyl-N -Synthesis of methyl formamidine:
  • Step 4 Synthesis of 2,5-dimethyl-4-((1-(4-fluorophenyl)-1H-pyrazol-3-yl)oxy)aniline:
  • Step 6 E)-N'-(4-((1-(4-fluorophenyl)-1H-pyrazol-3-yl)oxy)-2,5-dimethylphenyl)-N- Synthesis of ethyl-N-methylformamidine:
  • Step 1 Synthesis of 1-(4-chlorophenyl)-3-(2,5-dimethyl-4-nitrophenoxy)-1H-pyrazole:
  • Step 4 E)-N'-(4-((1-(4-chlorophenyl)-1H-pyrazol-3-yl)oxy)-2,5-dimethylphenyl)-N- Synthesis of ethyl-N-methylformamidine:
  • 3,4-Dichlorophenylhydrazine hydrochloride (10g, 60.39mmol) was dissolved in 50ml of ethanol, the temperature was raised to 40°C, sodium methoxide (9.8g, 181.17mmol) was added, the solution changed from light yellow turbidity to purple red, After 30 minutes, methyl acrylate (7.8g, 90.59mmol) was added dropwise, and the temperature was raised to reflux reaction.
  • Step 4 Synthesis of 2,5-dimethyl-4-((1-(3,4-dichlorophenyl)-1H-pyrazol-3-yl)oxy)aniline:
  • Step 6 (E)-N'-(4-((1-(3,4-dichlorophenyl)-1H-pyrazol-3-yl)oxy)-2,5-dimethylphenyl )-N-ethyl-N-methyl formamidine synthesis:
  • 4-cyanophenylhydrazine hydrochloride (15g, 88.44mmol) was added to 50ml of tetrahydrofuran, methyl acrylate (6.45g, 73.41mmol) was added, potassium tert-butoxide (16.47g, 146.82mmol) was added, and the solution changed from light The yellow turbidity turned into orange, and the temperature was raised to reflux for reaction.
  • Step 4 Synthesis of 2,5-dimethyl-4-((1-(4-cyanophenyl)-1H-pyrazol-3-yl)oxy)aniline:
  • Step 6 E)-N'-(4-((1-(4-cyanophenyl)-1H-pyrazol-3-yl)oxy)-2,5-dimethylphenyl)-N -Synthesis of Propylformamidine:
  • Step 4 Synthesis of 2,5-dimethyl-4-((1-(4-methoxyphenyl)-1H-pyrazol-3-yl)oxy)aniline:
  • Step 6 E)-N'-(4-((1-(4-methoxyphenyl)-1H-pyrazol-3-yl)oxy)-2,5-dimethylphenyl)- Synthesis of N-methyl-N-ethylformamidine:
  • the fungicide preparation was prepared from the prepared pyrazole ether compounds, and the compound 2 was formulated according to the mass ratio to obtain a suspension concentrate with a concentration of 30%.
  • the preparation method is as follows: fully mix compound 2 and other components to obtain a 30% suspension concentrate. And diluting the resulting suspension with water can give a dilution of the desired concentration.
  • the sample preparation method is to take 10 mg of the original drug of the sample to be tested, dissolve it with 1 mL DMF, and prepare a 10000 ppm mother solution, and dilute the mother solution to the required concentration with 0.05% Tween-80 water. Activity test.
  • test embodiment 1 The bactericidal activity of test embodiment 1 compound to cucumber powdery mildew
  • the effect of the prepared pyrazole ether compounds on the prevention and treatment of cucumber powdery mildew is determined, the method is as follows:
  • Screening adopts the living potted assay method, that is, the sample of the compound to be tested is mixed with a small amount of solvent (the type of solvent such as acetone, methanol, DMF, etc., is selected according to its dissolving ability for the sample, and the volume ratio of the amount of solvent to the amount of spray liquid is equal to or less than 0.05 ) was dissolved, diluted with water containing 0.1% Tween 80, and prepared into a test solution of required concentration.
  • the two-leaf cucumber seedlings cultivated in the greenhouse were used as experimental host plants for cucumber powdery mildew (Erysiphe cichoracearum). Carry out foliar spray treatment with the application compound according to the designed concentration.
  • a blank control sprayed with water was set up, repeated 3 times, and the bacteria were inoculated 24 hours after the treatment.
  • the plants were placed in an artificial climate chamber for moisturizing cultivation (temperature: 25° C. during the day, 20° C. at night, relative humidity: 95-99%).
  • the test materials were cultivated for 24 hours, they were transferred to the greenhouse for cultivation.
  • the control is fully onset (usually within a week), the disease prevention effect of the compound is evaluated.
  • the results of the investigation were represented by a scale of 100 to 0, with "100" representing no disease and "0" representing the most severe disease.
  • Test embodiment 2 compound is to the bactericidal activity of cucumber downy mildew
  • Screening adopts the living potted assay method, that is, the sample of the compound to be tested is mixed with a small amount of solvent (the type of solvent such as acetone, methanol, DMF, etc., is selected according to its dissolving ability for the sample, and the volume ratio of the amount of solvent to the amount of spray liquid is equal to or less than 0.05 ) was dissolved, diluted with water containing 0.1% Tween 80, and prepared into a test solution of required concentration.
  • Cucumber seedlings at the two-leaf stage cultivated in the greenhouse were used as experimental host plants for cucumber downy mildew (Pseudoperonospora cubensis). Carry out foliar spray treatment with the application compound according to the designed concentration.
  • Test embodiment 3 compound is to the bactericidal activity of soybean rust
  • the effect of the prepared pyrazole ether compounds on the prevention and treatment of soybean rust is determined, the method is as follows:
  • Screening adopts the living potted assay method, that is, the sample of the compound to be tested is mixed with a small amount of solvent (the type of solvent such as acetone, methanol, DMF, etc., is selected according to its dissolving ability for the sample, and the volume ratio of the amount of solvent to the amount of spray liquid is equal to or less than 0.05 ) was dissolved, diluted with water containing 0.1% Tween 80, and prepared into a test solution of required concentration. Soybean at the two-leaf stage was cultivated in the greenhouse as an experimental host plant for soybean rust (Phakopsora pachyrhizi). Carry out foliar spray treatment with the application compound according to the designed concentration.
  • solvent the type of solvent such as acetone, methanol, DMF, etc.
  • test embodiment 4 compound to wheat head blight spore germination
  • the spore germination method is used to test, and an appropriate amount of mother liquor is prepared to make a 1% water agar (WA) drug-containing plate.
  • WA water agar
  • the germination of spores in each treatment was observed under a microscope at 10 times, and the number of ungerminated spores and the total number of spores were recorded, and the inhibition rate of spore germination was calculated.
  • the present application illustrates the pyrazole ether compounds of the present application and their preparation methods and applications through the above examples, but the application is not limited to the above examples, that is, it does not mean that the application must rely on the above examples to be implemented.
  • Those skilled in the art should understand that any improvement to the present application, the equivalent replacement of each raw material of the product of the present application, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present application.

Abstract

La présente invention concerne un composé pyrazole éther, son procédé de préparation et son utilisation. Le composé a une structure telle que représentée par la formule I, a un effet significatif sur la prévention et la lutte contre les maladies en agriculture et en sylviculture, en particulier ayant un bon effet de prévention et de lutte contre l'oïdium du concombre, le mildiou du concombre, la rouille du soja et la brûlure de l'épi du blé, et a de vastes perspectives d'application.
PCT/CN2022/105331 2021-07-13 2022-07-13 Composé pyrazole éther, son procédé de préparation et son utilisation WO2023284761A1 (fr)

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