WO2020030094A1 - Composition pharmaceutique comprenant un composé méta-diamide et utilisation de celle-ci - Google Patents

Composition pharmaceutique comprenant un composé méta-diamide et utilisation de celle-ci Download PDF

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Publication number
WO2020030094A1
WO2020030094A1 PCT/CN2019/099950 CN2019099950W WO2020030094A1 WO 2020030094 A1 WO2020030094 A1 WO 2020030094A1 CN 2019099950 W CN2019099950 W CN 2019099950W WO 2020030094 A1 WO2020030094 A1 WO 2020030094A1
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Prior art keywords
compound
active ingredient
pharmaceutical composition
composition containing
hydrogen
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PCT/CN2019/099950
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English (en)
Chinese (zh)
Inventor
周丽琪
相君成
吕亮
洪湖
刘吉永
邵佳礼
刘叙杆
倪珏萍
Original Assignee
上海泰禾国际贸易有限公司
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Priority claimed from CN201910704040.7A external-priority patent/CN110810414B/zh
Application filed by 上海泰禾国际贸易有限公司 filed Critical 上海泰禾国际贸易有限公司
Publication of WO2020030094A1 publication Critical patent/WO2020030094A1/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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/34—Nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
    • C07C237/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having nitrogen atoms of amino groups bound to the carbon skeleton of the acid part, further acylated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles

Definitions

  • the present application belongs to the technical field of prevention and control of pests by pharmaceutical compositions, and relates to a pharmaceutical composition containing metadiamide compounds and its application, and in particular, to a compound containing metadiamide compounds, chlorantraniliprole and flubendiamide.
  • CN101208009A discloses that a composition containing a metadiamide compound has an insecticidal effect.
  • insecticides and fungicides of various structural types are widely used in various crops. With the continuous use of pesticides, pests and diseases will become resistant to some existing pesticide products, and the insecticidal activity of existing pesticide varieties may not always meet the needs of many agricultural practices. Insecticide compositions have an important role in improving the effectiveness of insecticides, expanding the spectrum of control, and delaying the development of resistance. Therefore, in the art, it is still desired to develop more efficient insecticide compositions or insecticidal bactericidal compositions to meet the needs of agriculture and the forestry industry.
  • the object of the present application is to provide a pharmaceutical composition containing a metadiamide compound and its application.
  • the pharmaceutical composition has a synergistic effect and can prevent and control various agricultural diseases caused by pests. , Forestry pests.
  • the present application provides a pharmaceutical composition containing an m-diamide compound.
  • the pharmaceutical composition includes an active ingredient A and an active ingredient B.
  • the active ingredient A is an amide compound having a structure represented by Formula I.
  • the active ingredient B includes any one or a combination of two other pesticides;
  • Z is selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, substituted or unsubstituted 3-10 membered heterocyclic group, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl or C 1 -C 6 haloalkylsulfonyl;
  • Q is selected from C 3 -C 8 cycloalkyl or C 3 -C 8 halocycloalkyl;
  • X is selected from hydrogen, fluorine or trifluoromethyl
  • Y 1 is selected from fluorine, chlorine, bromine, iodine, cyano, nitro, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkoxy, C 2 -C 4 alkenyl , C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 2 -C 4 haloalkynyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 1- C 6 alkylcarbonyl, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl or C 1 -C 6 haloalkylsulfonyl;
  • Y 2 is selected from bromine, iodine, cyano, nitro, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkoxy, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 2 -C 4 haloalkynyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl or C 1 -C 6 haloalkylsulfonyl;
  • R 1 is selected from hydrogen, fluorine or methoxy
  • R 2 is selected from fluorine or trifluoromethyl
  • R 3 and R 4 are each independently selected from hydrogen, halogen, cyano, nitro, C 1 -C 6 alkyl , C 1 -C 6 haloalkyl, C 3 -C 8 cycloalkyl or C 3 -C 8 halocycloalkyl;
  • n represents an integer of 0 to 3 (for example, 0, 1, 2 or 3); W 1 and W 2 are independently an oxygen atom Or sulfur atom.
  • the pharmaceutical composition using the m-bisamide compound having the structure shown by the formula I as described in the present application as the active ingredient A and blended with the active ingredient B has a synergistic effect between the active ingredient A and the active ingredient B.
  • the present application provides a pharmaceutical composition containing a compound substituted at the 3-position of m-diamide with an N-cyclopropylmethyl derivative.
  • the pharmaceutical composition includes active ingredient A and active ingredient B.
  • the active ingredient A It is an m-bisamide compound having a structure represented by Formula II, and the active ingredient B includes any one or a combination of other fungicides, insecticides, or acaricides;
  • Z is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, cyano, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylsulfonyl, or C 1 -C 6 haloalkyl Sulfonyl
  • Y is selected from C 1 -C 6 haloalkyl or C 1 -C 6 haloalkoxy;
  • R is selected from hydrogen or methyl.
  • an m-bisamide compound having a structure represented by Formula II is further preferred, and it is compounded with active ingredient B as an active ingredient of a pharmaceutical composition. Good results can be achieved at low doses, resulting in less drug residues and more environmental protection.
  • Z is selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, trifluoromethoxy, trifluoromethyl, methanesulfonyl, or trifluoromethanesulfonyl.
  • Y is selected from trifluoromethyl or trifluoromethoxy
  • R is selected from hydrogen or methyl.
  • the m-bisamide compound is any one of the compounds shown in Table 1 below having the general formula II.
  • H is a hydrogen atom
  • F is a fluorine atom
  • Cl is a chlorine atom
  • Br is a bromine atom
  • I is an iodine atom
  • CN is a cyano group
  • CF 3 is a trifluoromethyl group
  • OCF 3 is a trifluoromethoxy group
  • MeS (O) 2 represents methanesulfonyl
  • CF 3 S (O) 2 represents trifluoromethanesulfonyl.
  • the m-diamide compound is any one or a combination of at least two selected from the following compounds 1-14:
  • C 1 -C 6 alkyl refers to a straight or branched chain alkyl group having 1 to 6 carbon atoms, and includes, without limitation, methyl, ethyl, n-propyl, isopropyl, N-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, n-hexyl and the like.
  • C 1 -C 6 alkoxy refers to a straight or branched chain alkoxy group having 1 to 6 carbon atoms, including without limitation methoxy, ethoxy, n-propoxy, isopropyl Oxy, t-butoxy and the like.
  • C 1 -C 6 haloalkyl refers to an alkyl group having 1 to 6 carbon atoms substituted with a halogen, and includes, without limitation, chloromethyl, 1-chloroethyl, 2-bromo-n-propyl, and the like.
  • C 1 -C 6 haloalkoxy refers to an alkoxy group having 1 to 6 carbon atoms substituted with halogen; similarly the term “C 3 -C 8 cycloalkyl” refers to having 3 to 8 on the ring A cyclic alkyl group with a carbon atom, including but not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc .; the term “C3-C8 halocycloalkane” used in this application "Group” refers to a cyclic alkyl group having 3 to 8 carbon atoms substituted with a halogen on the ring, and includes, without limitation, 1-chlorocyclopropyl, 1-fluorocyclopropyl, perfluorocyclopropyl , 1-chlorocyclobutyl, 1-chlorocyclopentyl and the like.
  • C 1 -C 6 , C 3 -C 8, etc. before the specific group indicate the number of carbon atoms contained in the group, for example, C 1 -C 6 indicates that the number of carbon atoms can be 1, 2 , 3, 4, 5, or 6 groups, C 3 -C 8 represent groups having 3 , 4, 5, 6, 7, or 8 carbon atoms, and so on.
  • the active ingredient B was selected. There are more than 680 known active ingredients of pesticides and more than 100 commonly used active ingredients. Most of them have developed different degrees of resistance. In actual production, the dosage must be increased. To use.
  • the active ingredient B is selected from any one or a combination of two pesticides or acaricides in the prior art.
  • the active ingredient B is selected from the group consisting of Chlorantraniliprole, flubendiamide, cyantraniliprole, tetrachlorantraniliprole, and Tetraniliprole. , Cyflufenamid, Cyclaniliprole, Fluxametamide, Fipronil, Ethiprole, Acetoprole, Indoxacarb , Metaflumizone, Chlorfenapyr, Tolfenpyrad, Lufenuron, Methoxyfenozide, Pyridalyl Species or a combination of both.
  • the pharmaceutical composition containing the metadiamide compound is a pharmaceutical composition containing the metadiamide compound (active ingredient A) and the active ingredient B described in Table 2 below, but not Limited to the combinations listed in the table.
  • the medicinal composition containing a metadiamide compound is a pharmaceutical composition containing the active ingredient A described in Table 1 and the active ingredient B described in the present application, and the active ingredient B is not limited to the present application Specific pesticide species listed.
  • the combined action of the pharmaceutical composition was tested using harmful organisms such as diamondback moth, armyworm, diploid pupae, Spodoptera exigua, brown planthopper, Spodoptera litura, and a composition having a synergistic effect was found.
  • the weight ratio of the active ingredient A and the active ingredient B described herein is 200: 1 to 1: 200, for example, 200: 1, 180: 1, 150: 1, 130: 1, 100: 1, 80: 1, and 60: 1, 40: 1, 20: 1, 10: 1, 1: 1, 1:10, 1:30, 1:50, 1:80, 1: 100, 1: 120, 1: 140, 1: 160, 1: 180 or 1: 200, etc.
  • the pharmaceutical composition containing the metadiamide compound has different preferred weight ratios according to the difference between the active ingredient A and the active ingredient B.
  • the active ingredient is When A and active ingredient B are selected from the components described in Table 3, their preferred weight ratios and particularly preferred weight ratios are shown in Table 3.
  • the isodiamide compound represented by Formula I shown in Table 3 as the active ingredient A is replaced with the isodiamide compound represented by Formula II, which also satisfies the preferred weight ratio in Table 3.
  • the m-diamide compound may also be replaced with a tautomer, an enantiomer, a diastereomer or a salt thereof.
  • a pharmaceutical composition containing the tautomer, enantiomer, diastereomer, or a salt of the m-diamide compound can also exert the same properties as the m-diamide-containing compound described in the present application.
  • the pharmaceutical composition has the same action effect, good insecticidal effect and fast-acting effect at a low dose.
  • the present application provides a pharmaceutical formulation comprising a pharmaceutical composition containing a metadiamide compound as described above and an agrochemically acceptable adjuvant and / or carrier as described above.
  • the weight percentage content of the mesodiamide compound-containing pharmaceutical composition is 0.01-99%, such as 0.01%, 0.1%, 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%, preferably 0.5 to 95%.
  • the agrochemically acceptable adjuvant includes any one or at least one of a dispersant, a wetting agent, an emulsifier, an antifreeze, a thickener, a defoamer, a preservative, a stabilizer, or a colorant. A combination of the two.
  • the dispersant includes lignin sulfonate, alkylphenol polyoxyethylene ether, naphthalenesulfonic acid formaldehyde condensate sodium salt, fatty amine polyoxyethylene ether, fatty acid polyoxyethylene ester, glycerin fatty acid ester polyoxylate Vinyl ether, polycarboxylate, formaldehyde condensate, calcium alkylbenzenesulfonate, alkylphenol polyoxyethylene ether.
  • the wetting agent is selected from the group consisting of sodium lauryl sulfate, alkyl naphthalene sulfonate, pulverized powder BX, polyoxyethylene ether, EO / PO block polyether, fatty alcohol polyoxyethylene ether, and fatty alcohol polyoxylate.
  • the emulsifier is selected from dodecylbenzenesulfonate, alkylnaphthalenesulfonate, alkylsulfonate, alkylphenol polyoxyethylene ether, benzylphenol polyoxyethylene, phenethylphenol polyoxyethylene Ether, fatty amine polyoxyethylene ether.
  • the antifreeze is selected from ethylene glycol, propylene glycol, and glycerol.
  • the thickener is selected from the group consisting of xanthan gum, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl starch, methyl cellulose, sodium starch phosphate, magnesium aluminum silicate, and polyvinyl alcohol.
  • the defoamer is selected from the group consisting of silicone oil, silicone compounds, tributyl phosphate, C10-20 saturated fatty acid compounds, and polyether defoamers.
  • the preservative is selected from the group consisting of formaldehyde, phenyl salicylate, butyl parahydroxybenzoate, and potassium sorbate
  • the stabilizer is selected from triphenyl phosphite, epichlorohydrin, epoxy soybean oil, and silicic acid.
  • Magnesium aluminum, the colorant is selected from the group consisting of azo pigments, titanium oxide, and iron oxide.
  • the carrier includes a filler and / or a solvent
  • the agrochemically acceptable carrier includes a solid carrier and / or a liquid carrier.
  • the solid support includes 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 and hexamethylene diamine.
  • Liquid carriers include water and organic solvents.
  • Organic solvents include aromatic hydrocarbons such as xylene, benzene, xylene, toluene, etc .; chlorinated hydrocarbons such as chlorobenzene, vinyl chloride, trichloromethane, dichloromethane, etc .; aliphatic hydrocarbons such as petroleum distillates, Cyclohexane, light mineral oil; alcohols such as isopropanol, butanol, ethylene glycol, propylene glycol, glycerol, and cyclohexanol and their ethers and esters; ketones such as acetone, cyclohexanone, and dimethyl Formamide and N-methyl-pyrrolidone.
  • aromatic hydrocarbons such as xylene, benzene, xylene, toluene, etc .
  • chlorinated hydrocarbons such as chlorobenzene, vinyl chloride, trichloromethane, dichloromethane, etc .
  • the active ingredient may be mixed with a liquid carrier and / or a solid carrier, and auxiliary agents such as emulsifiers, dispersants, stabilizers, wetting agents, adhesives Mixtures, defoamers, antioxidants, etc.
  • auxiliary agents such as emulsifiers, dispersants, stabilizers, wetting agents, adhesives Mixtures, defoamers, antioxidants, etc.
  • the dosage form of the pharmaceutical preparation is a solution, a soluble powder, a soluble granule, an emulsifiable concentrate, a wettable powder, an aqueous emulsion, a suspending agent, a dispersible oil suspending agent, a water-dispersible granule, and a microcapsule suspending agent.
  • Granules, microemulsions, suspension emulsions, microcapsule suspension-suspensions ultra-low-volume liquids, hot aerosols, film-spreading oils, suspended seed coatings, dry powders for seeds, suspensions for seeds, and seeds for Powder dissolving agent, seed treatment dispersible powder, seed treatment emulsion or seed treatment liquid.
  • the dosage form of the pharmaceutical preparation is a solution, a soluble granule, a suspension, an emulsifiable concentrate, a wettable powder, an aqueous emulsion, a water-dispersible granule, a dispersible oil suspension, a microcapsule suspension, and an ultra-low capacity.
  • Liquid, hot aerosol, suspension seed coating or seed treatment dispersible powder is a solution, a soluble granule, a suspension, an emulsifiable concentrate, a wettable powder, an aqueous emulsion, a water-dispersible granule, a dispersible oil suspension, a microcapsule suspension, and an ultra-low capacity.
  • the present application provides the application of the pharmaceutical composition or pharmaceutical preparation containing the metadiamide compound as described above in the prevention, control of plant diseases or insect pests in agriculture, forestry, and horticulture.
  • the medicinal composition or medicinal preparation containing the metadiamide compound described in the present application is suitable for controlling various agricultural, forestry, horticultural pests and sanitary pests that harm rice, corn, wheat, potato, fruit trees, vegetables, other crops and flowers, and Disease.
  • the composition of the present application has a wide range of applications, and the scope of plants or crops to be applied mainly includes the following categories: vegetables, cucumbers, loofahs, watermelons, melon, pumpkins, hanging melon, spinach, celery, cabbage, cabbage, gourd, pepper, eggplant , Tomato, shallot, ginger, garlic, leek, strawberry, lettuce, kidney bean, cowpea, broad bean, radish, carrot, potato, yam; cereal, wheat, barley, corn, rice, sorghum; fruit tree, apple, pear, banana , Citrus, grape, lychee, mango; flowers, peony, rose, flamingo; oil crops, peanuts, soybeans, rape, sunflower, sesame; sugar crops, sugar beets, sugar cane; other crops, such as potatoes, sweet potatoes, tobacco and Tea; horticulture, forestry, home health, public health areas, etc .; the above-listed plants or crops have no limiting effect on the scope of use of the pharmaceutical
  • the pests include lepidoptera, coleoptera, hemiptera, tarptera, diptera, orthoptera, homoptera, isoptera, hymenoptera, and spider mite
  • said Diseases include diseases caused by semi-known bacteria, ascomycetes, basidiomycetes, and the like.
  • the pests include but are not limited to: cotton bollworm, diamondback moth, Spodoptera exigua, Spodoptera litura, Pieris rapae, diploid pupae, pupae trichoderma, big pupae, Spodoptera frugipera, rice leaf roller, rice Thrips, western flower thrips, melon thrips, onion thrips, ginger thrips, mango thrips, peach aphid, cotton aphid, alfalfa aphid, apple yellow aphid, wheat aphid, jumping beetle, stink bug, gray planthopper, Brown planthopper, white-backed planthopper, termite, mosquito fly, spider mite, citrus red spider.
  • the diseases include, but are not limited to, wheat scab, rice sheath blight, rice blast and the like.
  • the method of using the pharmaceutical composition or pharmaceutical preparation is spraying, soil treatment, seed treatment, or the like.
  • the present application provides the use of a pharmaceutical composition containing an m-bisamide compound as described above in seed treatment of plants, crops, or flowers.
  • the present application provides a method for controlling plant diseases and insect pests, which method is: applying an effective dose of the above-mentioned pharmaceutical composition containing metadiamide compounds to a plant disease to be controlled or a growth medium thereof Or pharmaceutical preparations.
  • 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 15-900g per hectare.
  • composition of the present application may be applied to the disease or its growth medium in the form of a formulation.
  • the compound of the general formula I (especially the compound of the general formula II) is dissolved or dispersed in a carrier as an active ingredient or formulated into a formulation for easier dispersion when used as a fungicide.
  • these chemical preparations can be formulated as solution, emulsifiable concentrate, wettable powder, water emulsion, suspension, dispersible oil suspension, water-dispersible granule, seed treatment, microcapsule suspension, granule, microemulsion , Suspension emulsion, suspension-microcapsule suspension and so on.
  • the pharmaceutical composition of the present application has the following advantages in use:
  • composition of active ingredient A and active ingredient B in this application has a synergistic effect.
  • the amount of the composition used is greatly reduced compared with the single active ingredient alone, and the control effect is significantly improved; due to the significant resistance of active ingredient A to resistant pests
  • the activity also solves the diseases and insect pests of important crops such as pupae, diamondback moth and other important crops.
  • the drug resistance can be delayed after compounding, which is an effective resistance risk management tool and extends the life cycle of the drug.
  • the active ingredient A described in this application is compounded with the active ingredient B of different control objects, which expands the spectrum of control and saves labor costs of medication, and can be applied to vegetables, fruit trees, flowers, cereals, oil, sugar, etc. Crops, horticulture, forestry, health and various diseases and insect pests. In addition, it has extremely high activity against newly emerged Spodoptera frugiperda, which can be used for emergency prevention and control, which is conducive to maintaining environmental ecological security and social stability.
  • Methyl 2-fluoro-3- (N- (cyclopropylmethyl) benzamide) benzoate (13.00 g, 40.88 mmol) was dissolved in methanol (100 mL), and a 10% aqueous sodium hydroxide solution (6.54 g) was added. , 163.52 mmol, 65.4 mL), after stirring at room temperature for 2 h, the reaction was monitored by TLC for completion. The methanol was concentrated and removed under reduced pressure. The concentrated residue was dissolved in water (100 mL) and extracted with ethyl acetate (50 mL). The organic phase was discarded, and the pH of the aqueous phase was adjusted to 7 with a 2M aqueous hydrochloric acid solution.
  • 2-Bromo-6-trifluoromethyl-4-heptafluoroisopropylaniline (0.52 g, 1.28 mmol) was dissolved in tetrahydrofuran (4 mL), and lithium diisopropylaminoamide (0.77 mL) was added dropwise at -70 ° C. , 1.54 mmol), 5 minutes later, a tetrafluorofuran solution of 2-fluoro-3- [N- (cyclopropylmethyl) benzamido] benzoyl chloride synthesized in one step was added dropwise, stirred at -70 ° C for 30 minutes, and raised to Stirring was continued for 30 min at room temperature.
  • a saturated ammonium chloride aqueous solution (20 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (20 mL). The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure.
  • Methyl 2-fluoro-3-aminobenzoate (2.00 g, 11.82 mmol) was dissolved in 1,2-dichloroethane (65 mL), and cyclopropylmethyl ketone (2.98 g, 35.47 mmol) was sequentially added at room temperature. ), Trifluoroacetic acid (8.08 g, 70.92 mmol) and sodium triacetoxyborohydride (7.51 g, 35.47 mmol). The reaction was heated to 45 ° C. for 1 h. When TLC monitored that the reaction was no longer in progress, the reaction was terminated. A saturated NaHCO 3 solution (50 mL) was added to the reaction solution, and extracted with dichloromethane (80 mL).
  • composition of 40% compound 8 lice mite urea cream is shown in Table 5:
  • Preparation method Calculate the amount of each material according to the formula, add 200 # solvent oil to the batching kettle, and then add compound 8 and lufenuron to dissolve completely, then add calcium dodecylbenzenesulfonate and castor oil polyoxyethylene Ether was added, and the mixture was stirred at 40 to 50 ° C. for 1.5 hours, and filtered to obtain 40% compound 8 ⁇ carnitur cream.
  • composition of 30% Compound 4 ⁇ Fipronil Suspension Seed Coating is shown in Table 6:
  • Preparation method In a batching kettle, according to the material ratio, deionized water, compound 4, fipronil, FS3000, TER4894, Casson, SAG1522, and propylene glycol are sanded after shearing to control the particle size of D90 and about 5 microns, and then Transfer to a blending kettle, add 2% xanthan gum solution, pigment F2R, and stir for 1 hour to obtain 30% Compound 4 ⁇ Fipronil seed coating.
  • Chlorantraniliprole Water-Dispersible Granules is shown in Table 7:
  • Preparation method Calculate the amount of each material according to the formula, and mix compound 6, chlorantraniliprole, sodium lauryl sulfate, sodium lignin sulfonate, sodium naphthalene formaldehyde polymer sulfonate, ammonium sulfate, corn starch, and kaolin Homogeneous, pulverized to an average particle size of 10 to 15 microns by a jet mill, kneaded with 17% of the powder, and then granulated by rotary extrusion, dried at 50 ° C for 3 hours, and sieved to obtain 25% of the compound 6. Chlorantraniliprole water dispersible granules.
  • Active ingredient A Bromocyanide 14
  • Active ingredient B Fatty alcohol polyoxyethylene ether 1.5 moisturizer Tristyryl phenol polyoxyethylene ether phosphate 2
  • Dispersant Propylene glycol 4 antifreeze 1% xanthan gum solution 10
  • Thickener Casson 0.1 preservative Polydimethylsiloxane 0.2 Silicone defoamer Deionized water make up 100 Carrier
  • Preparation method Calculate the amount of each material according to the formula, stir and dissolve the deionized water, propylene glycol, tristyryl phenol polyoxyethylene ether phosphate, sodium lignin sulfonate, carson, and defoamer, and add bromocyanide Amide and compound 8 were sheared uniformly, and then ground to an average particle diameter of 2 microns by a sand mill, and 10 parts of a 1% xanthan gum solution was added and stirred for 30 minutes to obtain 24% compound 8 ⁇ bromocyanide suspension.
  • Preparation method Calculate the amount of each material according to the formula, and mix compound 7, methoxyfenozide, sodium lauryl sulfate, sodium lignin sulfonate, sodium naphthalene formaldehyde polymer sulfonate, ammonium sulfate, corn starch, and kaolin Evenly, pulverize to an average particle size of 10 to 15 microns with a jet mill, knead with 17% of the powder, and then granulate by rotary extrusion, dry at 50 ° C for 3 hours, and sieving to obtain 30% of the compound. 7. Water-dispersible granules of methoxyfenozide.
  • Preparation method Calculate the amount of each material according to the formula. Dissolve compound 10, cyanfludizone, polyaryl polymethylene polyisocyanate, and xylene uniformly at 40-50 degrees as Phase A; take deionized water separately.
  • phase B D-800, propylene glycol, dissolve uniformly, as phase B; under high shear, slowly add phase A to phase B, cut to an average particle size of 2 to 3 microns, then add the material to a three-necked flask, add hexane Diamine, stirred and reacted at 50-60 ° C for 10 hours, and added tristyrenol phenol polyoxyethylene ether phosphate, carson, defoamer, 1% xanthan gum solution, and stirred for 1 hour to obtain 27% compound 10 ⁇ Cyflufenazone microcapsule suspension.
  • composition of the 25% compound 6, pyraclostrobin wettable powder is shown in Table 11:
  • Preparation method Calculate the amount of each material according to the formula. Put compound 6, pyraclostrobin, sodium dodecyl sulfate, sodium lignin sulfonate, and kaolin in the batching kettle. After mixing well, use a jet mill to pulverize to the average particle size. With a diameter of 10 micrometers, 25% of the compound 6. azoxystrobin wettable powder is obtained. .
  • composition of the 15% compound 7 ⁇ fluorooxazole amide dispersible liquid agent is shown in Table 12:
  • Active ingredient A Fluoxamide 10 Active ingredient B 100 solvent oil 15 Solvent Cyclohexanone 10 Solvent Castor oil polyoxyethylene ether (EL40) 5 Dispersant Fatty alcohol polyoxyethylene ether 10 moisturizer Polydimethylsiloxane emulsion (SAG1522) 0.2 Defoamer Deionized water Make up 100 Carrier
  • Preparation method In a batching kettle, according to the process ratio, add No. 100 solvent oil and cyclohexanone, add compound 7, fluorooxazole amide with stirring, and heat to 50 ° C. After the solvent is completely added, add EL40 and fatty alcohol polyoxyethylene. After the ether and SAG1522 were stirred for 10 minutes, deionized water was added after the temperature was reduced to obtain 15% compound 7 ⁇ fluorooxazole amide dispersible liquid agent.
  • Formulation agent 9 28% Compound 1 ⁇ Ethionil water emulsion
  • Preparation method In a batching kettle, first add solvent oil No. 150, then start stirring, add compound 1 and stir to dissolve. After the dissolution is complete, add acetonitrile and emulsifier TERMUL5030, continue stirring for 20 minutes, and mix evenly as the oil phase Put in deionized water, defoamer and antifreeze in the shear kettle, turn on the shearing device, and slowly add the oil phase materials after 5 minutes, and then shear for 10 minutes after adding, to obtain 28% compound 1 ⁇ Ethyl nitrile water emulsion.
  • Bioassay Example 1 When the active ingredient A is a compound of formula II, it has significant insecticidal activity against a variety of pests
  • Targets Plutella xylostella 3rd instar larvae, armyworm 3rd instar larvae, diploid pupae 3rd instar larvae, all reared indoors.
  • Plutella xylostella + leaf soaking feeding method With reference to NY / 1154.14-2008, the main operation description is as follows: immerse the clean bract leaf dish in the medicinal solution for 10s, dry it and place it in petri dishes, 4 dishes per dish, put filter paper in the petri dish to moisturize. Ten dishes of Plutella xylostella were received in each dish and repeated three times. It was placed in a light incubator at a temperature of 25 ° C under 14hL: 10hD and cultured. The number of dead and live insects of Plutella xylostella was investigated 3 days after the administration, and the mortality was calculated.
  • Feeding on slime + dipping leaf With reference to NY / 1154.14-2008, the main operation description is as follows: immerse the clean corn leaf section in the medicinal solution for 10s, dry it and place it in petri dishes, 4 pieces per dish, put filter paper in the petri dish to moisturize. Ten dishes of slimeworms were received in each dish, and 3 replicates were performed. It was placed in a light incubator at a temperature of 25 ° C under 14hL: 10hD and cultured. The number of dead and live insects of the armyworm was investigated 3 days after the administration, and the mortality was calculated.
  • Bioassay Example 2 Composition of active ingredient A being a compound of formula II and active ingredient B being chlorantraniliprole, flubendiamide, bromocyanidin, etc., tested against Plutella xylostella
  • Target Plutella xylostella, 3rd instar larva
  • Theoretical mortality 1-(1-mortality of active ingredient A at this dose) (1-mortality of active ingredient B at this dose)
  • Synergistic effect ⁇ 20 means significant synergy; 10 ⁇ synergistic effect ⁇ 20, synergistic effect; -10 ⁇ synergistic effect ⁇ 10, synergistic effect; synergistic effect ⁇ -10, antagonistic, negative value The greater the degree of antagonism.
  • Test agent or combination name Dose mg / L 3d mortality% Theoretical mortality% Synergy effect Joint mode of action Compound 1 0.01 36.67 / / / Compound 4 0.01 43.33 / / / Compound 8 0.02 53.33 / / /
  • Bioassay Example 3 A composition in which the effective ingredient A is a compound of formula II and the effective ingredient B is bromocrifamide, tetracloprid, cycloprofenil and the like, and has a synergistic effect on rice diploid
  • Target 3rd instar larvae of pupae, indoor breeding.
  • Test agent or combination name Dose mg / L 3d mortality% Theoretical mortality% Synergy effect Joint mode of action Compound 4 0.4 53.33 / / / Compound 5 1.0 63.33 Zh Zh Zh Compound 6 1.00 56.67 / / / Compound 7 0.5 50 / / / Compound 8 0.5 56.67 / / / Compound 9 1.0 66.67 / / / Compound 10 0.5 33.33 / / / Compound 11 1.25 76.67 / / / Compound 12 1.00 56.67 / / / Compound 13 0.5 33.33 / / Bromocyanide 4.0 53.33 / / / Tetrachloropyramid 2.5 70 / / / Cypromethoxam 1.0 66.67 / / / Compound 4 + Bromocyanid 0.4 + 4.0 100 78.22 21.78 Significant synergy Compound 5 +
  • Bioassay Example 4 The composition of active ingredient A is a compound of formula II and active ingredient B is fipronil, ethiprole, acetapronil, etc., and its activity is tested against brown planthopper
  • Target Brown planthopper, 3rd instar nymph.
  • the evaluation method is the same as the standard test example 2.
  • Test agent or combination name Dose mg / L 3d mortality% Theoretical mortality% Synergy effect Joint mode of action Compound 6 10 60.00 / / / Compound 8 5 71.55 / / / Compound 10 10 78.29 / / / Fipronil 2.5 53.22 / / / Ethiprole 80 61.86 / / / Acetofen 100 45.35 / / / Compound 6+ fipronil 10 + 2.5 100 81.33 18.67 Synergy Compound 8 + ethiprole 10 + 80 100 89.15 10.85 Synergy Compound 10+ Acetonitrile 10 + 100 100 88.14 11.86 Synergy
  • Bioassay Example 5 When the active ingredient A is a compound of formula II and the active ingredient B is indoxacarb, fenprofen, fenflubenzuron, acetamiprid, etc., the activity test on the armyworm
  • Soaking method The operation description is as follows: With reference to NY / 1154.6-2006, the main operation description is as follows: immerse 10 test insects in the medicinal solution for 10s, dry them and place them in petri dishes, put 4 clean corn leaf sections in each dish, and petri dishes Put filter paper inside to moisturize. 3 repetitions. It was placed in a light incubator at a temperature of 25 ° C under 14hL: 10hD and cultured. The number of dead insects of the armyworm was investigated 3 days after the administration, and the mortality was calculated.
  • the evaluation method was the same as that in Example 2.
  • Test agent or combination name Dose mg / L 3d mortality% Theoretical mortality% Synergy effect Joint mode of action Compound 2 0.04 53.33 / / / Compound 3 0.04 60 / / / Compound 5 0.04 75 / / / /
  • Bioassay Example 6 Tests on the activity of Spodoptera litura when the active ingredient A is a compound of formula I and the active ingredient B is methoxyfenozide, lufenuron, and acetamiprid.
  • Leaf soaking method 3rd instar larva.
  • the operation description is as follows: immerse the clean bract leaf dish in the medicinal solution for 10s, dry it, and place it in a 24-well plate. Each hole is connected with one Spodoptera litura test insect and each handles 24. It was placed in a light incubator at a temperature of 25 ° C under 14hL: 10hD and cultured. The number of dead insects was investigated 3 days after the treatment, and the mortality was calculated.
  • Test agent or combination name Dose mg / L 5d mortality% Theoretical mortality% Synergy effect Joint mode of action Compound 1 1.0 73.33 / / / Compound 4 0.4 60.00 / / / Compound 6 1.0 50.00 / / / Methoxyfenozide 4.0 40.00 / / / Lufenuron 0.8 50.00 / / / Acetamiprid 20 46.67 / / / Compound 1 + Methofenazide 1.0 + 4.0 100 84.00 16.00 Synergy Compound 4+ 0.4 + 0.8 100 80.00 20.00 Significant synergy Compound 6+ acetamiprid 1.0 + 20 100 73.33 26.67 Significant synergy
  • Bioassay Example 7 Test of the activity of a combination of compound 8 and tetrazole on dioxin
  • Insect source 3rd instar larvae of pupae, indoor breeding.
  • Example 1 Rice stalk immersion method, the operation description is described in Example 1.
  • the evaluation method is referred to NY / T1154.7-2006, and the co-toxicity coefficient is used for evaluation.
  • the co-toxicity coefficient (CTC value) of the mixture is calculated according to formula (1), formula (2), and formula (3):
  • LC 50 of M-mixture, unit is milligram per liter (mg / L).
  • the percentage content of PA-A agent in the mixture is percentage (%);
  • the percentage content of PB-B agent in the mixture is percentage (%).
  • CTC co-toxicity coefficient
  • ATI mixed measured virulence index
  • TTI mixed theoretical virulence index
  • the co-toxicity coefficient (CTC) ⁇ 120 of the compounding agent is synergistic; CTC ⁇ 80 is antagonistic; 80 ⁇ CTC ⁇ 120 is additive.
  • Bioassay Example 8 Activity test of a composition of compound 9 and fluoxazole amide on Plutella xylostella
  • Insect source Plutella xylostella 3rd instar larvae, reared indoors.
  • Bioassay Example 9 Activity test of a composition of compound 3 and cyanofazone on Spodoptera exigua
  • Insect source 3rd instar larvae of Spodoptera exigua, reared indoors.
  • Soaked leaf dish feeding method Soaked leaf dish feeding method. The operation description is as follows: immerse the clean bract leaf dish in the medicinal solution for 10s, dry it, and place it in a 24-well plate. Each well receives one test of beet armyworm, and each handles 24. It was placed in a light incubator at a temperature of 25 ° C under 14hL: 10hD and cultured. The number of dead insects was investigated 3 days after the treatment, and the mortality was calculated.
  • Bioassay Example 10 Activity test of a combination of compound 7 and ethiprole against brown planthopper
  • Target Brown planthopper, 3rd instar nymph.
  • Bioassay Example 11 Activity test of a compound 12 and acarid urea on Plutella xylostella
  • Insect source Plutella xylostella 3rd instar larvae, reared indoors.

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  • Life Sciences & Earth Sciences (AREA)
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  • Pest Control & Pesticides (AREA)
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  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
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Abstract

L'invention concerne une composition pharmaceutique comprenant un composé méta-diamide et l'utilisation de celle-ci. La composition pharmaceutique comprend un principe actif A et un principe actif B, le principe actif A étant un composé de méta-diamide ayant une structure telle que représentée dans la formule I, et le principe actif B étant une combinaison d'un ou deux autres insecticides ou fongicides quelconques. La composition comprenant le principe actif A et le principe actif B possède les effets uniques de synergie, de gestion d'organismes nuisibles résistants, d'expansion du spectre d'activité et de lutte contre les insectes nuisibles, ce qui peut efficacement lutter contre une variété de maladies et d'insectes nuisibles au riz, au maïs, au blé, aux légumes, aux arbres fruitiers, aux fleurs, aux plantes oléagineuses, aux cultures sucrières et à d'autres cultures, ainsi que les maladies et les insectes nuisibles en horticulture et en sylviculture.
PCT/CN2019/099950 2018-08-10 2019-08-09 Composition pharmaceutique comprenant un composé méta-diamide et utilisation de celle-ci WO2020030094A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101208009A (zh) * 2005-07-27 2008-06-25 三井化学株式会社 有害生物防除组合物
CN102119143A (zh) * 2008-08-13 2011-07-06 三井化学Agro株式会社 酰胺衍生物、含有该酰胺衍生物的有害生物防除剂及其使用方法
JP2011157294A (ja) * 2010-01-29 2011-08-18 Mitsui Chemicals Agro Inc 有害生物防除組成物
CN108586279A (zh) * 2018-06-26 2018-09-28 上海泰禾国际贸易有限公司 一种间二酰胺类化合物及其制备方法和应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101208009A (zh) * 2005-07-27 2008-06-25 三井化学株式会社 有害生物防除组合物
CN102119143A (zh) * 2008-08-13 2011-07-06 三井化学Agro株式会社 酰胺衍生物、含有该酰胺衍生物的有害生物防除剂及其使用方法
JP2011157294A (ja) * 2010-01-29 2011-08-18 Mitsui Chemicals Agro Inc 有害生物防除組成物
CN108586279A (zh) * 2018-06-26 2018-09-28 上海泰禾国际贸易有限公司 一种间二酰胺类化合物及其制备方法和应用

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