CN110810414B - Pharmaceutical composition containing m-diamide compound and application thereof - Google Patents

Pharmaceutical composition containing m-diamide compound and application thereof Download PDF

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CN110810414B
CN110810414B CN201910704040.7A CN201910704040A CN110810414B CN 110810414 B CN110810414 B CN 110810414B CN 201910704040 A CN201910704040 A CN 201910704040A CN 110810414 B CN110810414 B CN 110810414B
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compound
weight ratio
pharmaceutical composition
active ingredient
combination
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CN110810414A (en
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周丽琪
相君成
吕亮
洪湖
刘吉永
邵佳礼
刘叙杆
倪珏萍
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SUZHOU JIAHUI CHEMICAL CO Ltd
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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
    • A01N37/44—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 at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/46—N-acyl derivatives
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/10—Sulfones; Sulfoxides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • 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
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
    • 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
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic 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
    • A01N57/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds
    • A01N57/28—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds containing acyclic or cycloaliphatic radicals

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention provides a pharmaceutical composition containing a m-diamide compound and application thereof, wherein the pharmaceutical composition comprises an active ingredient A and an active ingredient B, the active ingredient A is the m-diamide compound with a structure shown in a formula I, and the active ingredient B comprises any one or a combination of two of other insecticides. The composition containing the effective component A and the effective component B has the unique effects of synergy, controlling resistant pests, expanding an activity spectrum, controlling toxic insects and the like, and can effectively prevent and control various plant diseases and insect pests in crops such as rice, corn, wheat, vegetables, fruit trees, flowers, oil plants, sugar and the like, and in gardening and forestry.

Description

Pharmaceutical composition containing m-diamide compound and application thereof
Technical Field
The invention belongs to the technical field of preventing and treating pests by using a pharmaceutical composition, and relates to a pharmaceutical composition containing a m-diamide compound and application thereof, in particular to a composition containing the m-diamide compound and pesticides such as chlorantraniliprole, fluorobenzene diamide, cyantraniliprole, tetrachlorantranilide, tetrazolamide, chlorofluorocarbon cyantraniliprole, cyromanilide, flufenoxamide, fipronil, ethiprole, acetoprole, indoxacarb, chlorfenapyr, metaflumizone, tolfenpyrad, methoxyfenozide, lufenuron, pyridalyl and the like and application thereof.
Background
In the production of crops such as agriculture and horticulture, the damage caused by plant diseases and insect pests is still very obvious, and the development of new pesticides or pesticide compositions with better activity, lower dosage and more environment-friendly property is always needed for the reasons that pests have resistance to the existing pesticides and the existing pesticides are not environment-friendly.
For example, CN101208009A discloses that compositions containing m-diamide compounds have insecticidal effects, and insecticides and fungicides of various structural types in the prior art are widely used for various crops. With the continuous use of pesticides, pests and diseases can generate resistance to some existing pesticide products, and the insecticidal activity of the existing pesticide varieties can not always meet the needs of many agricultural practices. The pesticide composition has important functions of improving the control effect of the pesticide, expanding the control spectrum and delaying the generation of resistance. Therefore, in the art, it is still desired to develop more efficient pesticide compositions or pesticidal and bactericidal compositions to meet the needs of agriculture as well as forestry.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a pharmaceutical composition containing a m-diamide compound and application thereof, wherein the pharmaceutical composition has a synergistic effect and can be used for preventing and treating various agricultural and forestry insect pests caused by pests.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a pharmaceutical composition containing a m-diamide compound, which comprises an active ingredient A and an active ingredient B, wherein the active ingredient A is an amide compound with a structure shown in formula I, and the active ingredient B comprises any one or a combination of two of other insecticides;
Figure BDA0002151590810000011
wherein Z is selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, substituted or unsubstituted 3-to 10-membered heterocyclic group, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylsulfinyl radical, C1-C6Haloalkylsulfinyl radical, C1-C6Alkylsulfonyl or C1-C6A haloalkylsulfonyl group; q is selected from C3-C8Cycloalkyl or C3-C8A halocycloalkyl group;
x is selected from hydrogen, fluorine or trifluoromethyl;
Y1selected from fluorine, chlorine, bromine, iodine, cyano, nitro, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Haloalkoxy, C2-C4Alkenyl radical, C2-C4Haloalkenyl, C2-C4Alkynyl, C2-C4Halogenated alkynyl, C3-C8Cycloalkyl radical, C3-C8Halogenocycloalkyl, C1-C6Alkylcarbonyl group, C1-C6Alkylsulfinyl radical, C1-C6Haloalkylsulfinyl radical, C1-C6Alkylsulfonyl or C1-C6A haloalkylsulfonyl group;
Y2selected from bromine, iodine, cyano, nitro, C1-C6Haloalkyl, C1-C6Haloalkoxy, C2-C4Alkenyl radical, C2-C4Haloalkenyl, C2-C4Alkynyl, C2-C4Halogenated alkynyl, C3-C8Cycloalkyl radical, C3-C8Halogenocycloalkyl, C1-C6Alkylcarbonyl group, C1-C6Alkylsulfinyl radical, C1-C6Haloalkylsulfinyl radical, C1-C6Alkylsulfonyl or C1-C6A haloalkylsulfonyl group;
R1selected from hydrogen, fluoro or methoxy; r2Selected from fluoro or trifluoromethyl; r3And R4Each independently selected from hydrogen, halogen, cyano, nitro, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C8Cycloalkyl or C3-C8A halocycloalkyl group;
m represents an integer of 0 to 5 (e.g., 0, 1,2,3, 4, or 5); n represents an integer of 0 to 3 (for example, 0, 1,2 or 3); w1And W2Independently an oxygen atom or a sulfur atom.
The m-diamide compound with the structure shown in the formula I is used as an effective component A and is matched with an effective component B, and due to the synergistic interaction between the effective component A and the effective component B, on one hand, the using amount of a single active component can be reduced, and on the other hand, the prevention and treatment effect is remarkably improved.
Preferably, the invention provides a pharmaceutical composition containing a compound in which the 3-position of the m-diamide is substituted by an N-cyclopropylmethyl derivative, the pharmaceutical composition comprises an effective component A and an effective component B, the effective component A is a m-diamide compound with a structure shown in formula II, and the effective component B comprises any one or a combination of two of other bactericides, insecticides or acaricides;
Figure BDA0002151590810000021
in the formula II, the reaction mixture is shown in the specification,
z is selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, C1-C6Haloalkyl, C1-C6Haloalkoxy, C1-C6Alkylsulfonyl or C1-C6A haloalkylsulfonyl group;
y is selected from C1-C6Haloalkyl or C1-C6A haloalkoxy group;
r is selected from hydrogen or methyl.
In the invention, the m-diamide compound with the structure shown in the formula II is further preferably selected to be matched with the effective component B as the effective component of the pharmaceutical composition, the m-diamide compound and the effective component B have synergistic interaction, the onset of action is fast, the quick-acting property is good, the good effect can be achieved under the condition of low dosage, the drug residue is less, and the environmental protection is facilitated.
In the present invention, as a preferred embodiment, in formula I, Z is selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, trifluoromethoxy, trifluoromethyl, methylsulfonyl or trifluoromethylsulfonyl; y is selected from trifluoromethyl or trifluoromethoxy; r is selected from hydrogen or methyl.
In a further preferred embodiment of the present invention, the m-diamide compound is any one of compounds represented by the following table 1 having the general formula II.
TABLE 1 active ingredient A
Figure BDA0002151590810000022
In Table 1, 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, CF3Is trifluoromethyl, OCF3Is trifluoromethoxy, MeS (O)2Represents methylsulfonyl, CF3S(O)2Represents trifluoromethanesulfonyl.
In the present invention, as a particularly preferred embodiment, the m-diamide compound is any one or a combination of at least two selected from the following compounds 1 to 14:
Figure BDA0002151590810000031
Figure BDA0002151590810000041
the term "C" as used in the present invention1-C6Alkyl "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, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, and the like. The term "C1-C6Alkoxy "refers to a straight or branched chain alkoxy group having 1 to 6 carbon atoms, including without limitation methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, and the like. The term "C1-C6Haloalkyl "refers to an alkyl group of 1 to 6 carbon atoms having halogen substitution, including without limitation chloromethyl, 1-chloroethyl, 2-bromo-n-propyl, and the like. The term "C1-C6Haloalkoxy "refers to alkoxy groups of 1 to 6 carbon atoms having halogen substitution; the same term "C3-C8Cycloalkyl "refers to a cyclic alkyl group having 3 to 8 carbon atoms in the ring, including without limitation cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like; as used herein, the term "C3-C8 halocycloalkyl" refers to a cyclic alkyl group of 3 to 8 carbon atoms having halogen substitution in the ring, including, without limitation, 1-chlorocyclopropyl, 1-fluorocyclopropyl, perfluorocyclopropyl, 1-chlorocyclobutyl, 1-chlorocyclopentyl, and the like.
In the present invention, C before the specific group1-C6、C3-C8Etc. represent the number of carbon atoms contained in the radical, e.g. C1-C6Represents a group having 1,2,3, 4, 5 or 6 carbon atoms, C3-C8Represents a group in which the number of carbon atoms may be 3, 4, 5, 6, 7 or 8, and so on.
The effective component B is selected in the invention, the known effective components of the pesticide have more than 680, the commonly used effective components have more than 100, most of the effective components have different degrees of drug resistance, and the dosage has to be increased in the actual production for use. The active ingredient B is selected from any one or the combination of two of insecticides or acaricides in the prior art.
Preferably, the active ingredient B is selected from one or a combination of two of Chlorantraniliprole (Chlorantraniliprole), fluorobenzene bisamide (flubendiamide), cyantraniliprole (cyaniliprole), tetrachloro-cyantraniliprole (tetrachlortraniliprole), tetrazolium amide (tetranililiprole), chlorofluoro-cyantraniliprole, cyclic bromodiamide (cycloaniliprole), fluxafluxamide (fluxamide), Fipronil (Fipronil), Ethiprole (Ethiprole), Acetoprole (Acetoprole), Indoxacarb (Indoxacarb), Metaflumizone (Metaflumizone), Chlorfenapyr (chlofenpyrar), Tolfenpyrad (Tolfenpyrad), Lufenuron (lunuron), Methoxyfenozide (Methoxyfenozide), Pyridalyl (pyridall).
As a further preferred embodiment of the present invention, the pharmaceutical composition containing the m-diamide compound is a pharmaceutical composition containing the m-diamide compound (active ingredient a) and the active ingredient B shown in table 2 below, but not limited to the combinations listed in the table.
TABLE 2
Figure BDA0002151590810000042
Figure BDA0002151590810000051
Figure BDA0002151590810000061
Figure BDA0002151590810000071
Figure BDA0002151590810000081
In a preferred embodiment of the present invention, the pharmaceutical composition containing the m-diamide compound is a pharmaceutical composition containing the active ingredient a shown in table 1 and the active ingredient B shown in the present invention, and the active ingredient B is not limited to the specific examples of the insecticide of the present invention.
The invention adopts pests such as diamondback moth, armyworm, chilo suppressalis, beet armyworm, brown planthopper, prodenia litura and the like to test the combined action of the pharmaceutical composition, and discovers the composition with synergistic action.
The weight ratio of the active ingredient A to the active ingredient B is 200: 1-1: 200, such as 200:1, 180:1, 150:1, 130:1, 100:1, 80:1, 60:1, 40:1, 20:1, 10:1, 1:10, 1:30, 1:50, 1:80, 1:100, 1:120, 1:140, 1:160, 1:180 or 1: 200.
In the present invention, the preferable weight ratio of the pharmaceutical composition containing the m-diamide compound is different according to the effective component a and the effective component B contained therein, and as a preferable embodiment of the present invention, when the effective component a and the effective component B are selected from the components shown in table 3, the preferable weight ratio and the particularly preferable weight ratio are shown in table 3.
TABLE 3
Figure BDA0002151590810000082
More preferably, the m-diamide compound shown in the formula I of the effective component A in the table 3 is replaced by the m-diamide compound shown in the formula II, and the preferable weight ratio in the table 3 is also met.
In the present invention, the m-diamide compounds may also be replaced with tautomers, enantiomers, diastereomers, or salts thereof.
In the invention, the pharmaceutical composition containing the tautomer, enantiomer, diastereomer or salt of the m-diamide compound can also exert the same action and effect as the pharmaceutical composition containing the m-diamide compound, and has good insecticidal effect and quick action at low dosage.
In another aspect, the present invention provides a pharmaceutical preparation, which comprises the pharmaceutical composition containing the m-diamide compound as described above, and an agriculturally and pharmaceutically acceptable adjuvant and/or carrier.
Preferably, the pharmaceutical composition containing the m-diamide compound is contained in the pharmaceutical preparation in an amount of 0.01-99% by weight, 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 0.5-95%.
Preferably, the agriculturally pharmaceutically acceptable auxiliary agent includes any one of a dispersant, a wetting agent, an emulsifier, an antifreeze agent, a thickener, an antifoaming agent, a preservative, a stabilizer or a coloring agent or a combination of at least two thereof.
Preferably, the dispersant comprises lignosulfonate, alkylphenol polyoxyethylene ether, sodium salt of naphthalene sulfonic acid formaldehyde condensate, fatty amine polyoxyethylene ether, fatty acid polyoxyethylene ester, glycerol fatty acid ester polyoxyethylene ether, polycarboxylate, formaldehyde condensate, calcium salt of alkylbenzene sulfonic acid, and alkylphenol polyoxyethylene ether. The wetting agent is selected from sodium dodecyl sulfate, alkyl naphthalene sulfonate, nekal BX, polyoxyethylene ether, EO/PO block polyether, fatty alcohol-polyoxyethylene ether sulfate, sodium alkyl phosphate, alkyl naphthalene sulfonate and alkylphenol polyoxyethylene sodium sulfate. The emulsifier is selected from dodecyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfonate, alkylphenol polyoxyethylene, benzyl phenol polyoxyethylene, phenethyl phenol polyoxyethylene and fatty amine polyoxyethylene. The antifreeze is selected from ethylene glycol, propylene glycol and glycerol. The thickener is selected from xanthan gum, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl starch, methyl cellulose, sodium starch phosphate, magnesium aluminum silicate and polyvinyl alcohol. The defoaming agent is selected from silicone oil, silicone compounds, tributyl phosphate, C10-20 saturated fatty acid compounds and polyether defoaming agents. The preservative is selected from formaldehyde, phenyl salicylate, butyl p-hydroxybenzoate and potassium sorbate, the stabilizer is selected from triphenyl phosphite, epoxy chloroalkane, epoxy soybean oil and magnesium aluminum silicate, and the coloring agent is selected from azo pigment, titanium oxide and iron oxide.
Preferably, the carrier comprises a filler and/or a solvent;
preferably, the agriculturally pharmaceutically acceptable carrier includes a solid carrier and/or a liquid carrier.
Preferably, the solid support 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, montmorillonite and mica; white carbon black, calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; amine salts such as ammonium sulfate, hexamethylene diamine. Liquid carriers include water and organic solvents including aromatic hydrocarbons such as trimethylbenzene, benzene, xylene, toluene, and the like; chlorinated hydrocarbons such as chlorobenzene, vinyl chloride, chloroform, dichloromethane, etc.; aliphatic hydrocarbons such as petroleum fractions, cyclohexane, light mineral oil; alcohols such as isopropanol, butanol, ethylene glycol, propylene glycol, glycerol and cyclohexanol and ethers and esters thereof; ketones such as acetone, cyclohexanone, and dimethylformamide and N-methyl-pyrrolidone.
The active ingredient may be mixed with a liquid carrier and/or a solid carrier during the formulation of the pesticidal composition (i.e., the pharmaceutical preparation), while adding adjuvants such as emulsifiers, dispersants, stabilizers, wetting agents, binders, antifoaming agents, antioxidants, and the like.
Preferably, the dosage form of the pharmaceutical preparation is soluble solution, soluble powder, soluble granule, missible oil, wettable powder, aqueous emulsion, suspending agent, dispersible oil suspending agent, water dispersible granule, microcapsule suspending agent, granule, microemulsion, suspoemulsion, microcapsule suspension-suspending agent, ultra-low volume liquid, hot fogging concentrate, film-spreading oil agent, suspended seed coating agent, seed treatment dry powder, seed treatment suspending agent, seed treatment soluble powder, seed treatment dispersible powder, seed treatment emulsion or seed treatment liquid.
Preferably, the dosage form of the pharmaceutical preparation is soluble agent, soluble granule, suspending agent, missible oil, wettable powder, aqueous emulsion, water dispersible granule, dispersible oil suspending agent, microcapsule suspending agent, ultra-low volume liquid, hot fogging concentrate, suspended seed coating agent or seed treatment dispersible powder.
In another aspect, the invention provides the application of the pharmaceutical composition or the pharmaceutical preparation containing the m-diamide compound in the prevention and treatment of plant diseases or insect pests in agriculture, forestry and horticulture.
The pharmaceutical composition or pharmaceutical preparation containing the m-diamide compound is suitable for preventing and treating various agricultural and forestry and horticultural insect pests and sanitary pests and diseases harmful to rice, corn, wheat, potatoes, fruit trees, vegetables, other crops, flowers and the like.
The composition has wide application range, and the applied plants or crops mainly comprise the following types: vegetables, cucumber, luffa, watermelon, melon, pumpkin, snake gourd, spinach, celery, cabbage, gourd, pepper, eggplant, tomato, shallot, ginger, garlic, leek, strawberry, asparagus lettuce, kidney bean, cowpea, broad bean, radish, carrot, potato, yam; cereals, wheat, barley, corn, rice, sorghum; fruit trees, apples, pears, bananas, oranges, grapes, litchis and mangoes; flowers, peony, rose, and crane; oil crops, peanuts, soybeans, rape, sunflowers, sesame; sugar crops, sugar beets, sugar cane; other crops, such as potato, sweet potato, tobacco and tea; horticulture, forestry, home health, public health areas, and the like; the above list of plant or crop ranges has no limiting effect on the range of use of the pharmaceutical composition.
In the present invention, the pests include lepidoptera, coleoptera, hemiptera, thysanoptera, diptera, orthoptera, homoptera, isoptera, hymenoptera, spider mite pests, and the diseases include diseases caused by deuteromycetes, ascomycetes, basidiomycetes, and the like.
Preferably, the pests include, but are not limited to: cotton bollworm, plutella xylostella, asparagus caterpillar, prodenia litura, cabbage caterpillar, chilo suppressalis, tryporyza incertulas, sesamia inferens, fall armyworm, rice leaf roller, rice thrips, western flower thrips, melon thrips, spring onion thrips, ginger thrips, mango thrips, peach aphid, cotton aphid, alfalfa aphid, apple yellow aphid, wheat aphid, flea beetle, stinkbug, gray planthopper, brown planthopper, white back planthopper, termite, mosquito fly, carmine spider mite and citrus red spider. The diseases include but are not limited to wheat scab, rice sheath blight, rice blast and the like.
In the present invention, the pharmaceutical composition or pharmaceutical preparation is used by spraying, soil treatment, seed treatment, and the like.
In another aspect, the invention provides the use of a pharmaceutical composition comprising a isophthalamide compound, as described above, in the seed treatment of plants, crops or flowers.
In another aspect, the present invention provides a method for controlling plant diseases and insect pests, the method comprising: applying an effective dose of the pharmaceutical composition or the pharmaceutical preparation containing the m-diamide compound to a medium needing to control plant diseases or the growth of the plant diseases.
Preferably, the effective dose is from 10 to 1000g per hectare, for example 10g, 20g, 50g, 80g, 100g, 120g, 150g, 180g, 200g, 250g, 300g, 350g, 400g, 450g, 500g, 600g, 700g, 800g, 900g or 1000g, preferably from 15 to 900g per hectare.
The composition of the present invention may be applied in the form of a formulation on the disease or its growth medium. The compounds of formula I (especially compounds of formula II) are dissolved or dispersed as active ingredients in carriers or formulated so as to be more easily dispersed when used as fungicides. For example: the chemical preparations can be prepared into soluble agents, missible oil, wettable powder, aqueous emulsion, suspending agents, dispersible oil suspending agents, water dispersible granules, seed treatment agents, microcapsule suspending agents, granules, microemulsions, suspension emulsions, suspension-microcapsule suspending agents and the like.
Compared with the prior art, the invention has the following beneficial effects:
compared with the traditional insecticide, the pharmaceutical composition has the following advantages in use:
(1) the composition of the effective component A and the effective component B has a synergistic effect, the usage amount of the composition is greatly reduced compared with that of the composition using a single active component alone, and the prevention and treatment effect is obviously improved; due to the obvious activity of the effective component A to resistant pests, the prevention and control medicine for the important crop diseases and insect pests such as resistant chilo suppressalis, diamond back moth and the like is also solved.
(2) Because of different action mechanisms of the effective component A and the effective component B, the drug resistance of the medicament can be delayed after the composition is compounded, and the composition is an effective resistance risk management tool and prolongs the life cycle of the medicament.
(3) The effective component A is compounded and combined with the effective component B of different control objects, so that the control spectrum is expanded, the labor cost of the pesticide is saved, the pesticide composition can be applied to crops such as vegetables, fruit trees, flowers, cereals, oil plants, sugar materials and the like, and various diseases and insect pests in gardening, forestry and sanitation, and in addition, the pesticide composition has extremely high activity for emerging Spodoptera frugiperda, can be used for emergency control, and is favorable for maintaining the ecological safety of the environment and social stability.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Synthetic examples
Synthesis example 1
Preparation of N- [ 2-bromo-4- (1,1,1,2,3,3, 3-heptafluoropropan-2-yl) -6- (trifluoromethyl) phenyl ] -3- [ N- (cyclopropylmethyl) -benzamido ] -2-fluorobenzamide (compound No. 1):
(1) synthesis of methyl 2-fluoro- [3- (cyclopropylmethyl) amino ] benzoate
Figure BDA0002151590810000101
Methyl 2-fluoro-3-aminobenzoate (20g, 118.23mmol), bromomethylcyclopropane (20.75g, 153.70mmol), potassium carbonate (21.24g, 153.70mmol) and N, N-dimethylformamide (200mL) were added to the reaction flask in this order, stirred under reflux for 16h, and the heating was turned off to terminate the reaction when TLC monitored that the reaction did not progress. After the reaction solution was cooled to room temperature, water (200mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100mL), the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: petroleum ether: ethyl acetate: 10: 1) to give 2-fluoro- [3- (cyclopropylmethyl) amino [ methyl benzoate (13g, yield 49.39%) as a pale yellow liquid product.
(2) Synthesis of methyl 2-fluoro-3- [ N- (cyclopropylmethyl) benzamido ] benzoate
Figure BDA0002151590810000102
Benzoic acid (6.67g, 53.78mmol), toluene (50mL) and thionyl chloride (31.99g, 268.9mmol) were added sequentially to a reaction flask, reacted under reflux for 2h, toluene was concentrated under reduced pressure, and the concentrated residue was dissolved in tetrahydrofuran (30mL) until use. Methyl 2-fluoro-3- (N-cyclopropylmethylamino) benzoate (10.00g, 44.82mmol) was dissolved in tetrahydrofuran (100mL), pyridine (4.25g, 53.78mmol) was added thereto, the resulting benzoyl chloride tetrahydrofuran solution was added dropwise, and the mixture was stirred at room temperature for 4 hours. The reaction was terminated by TLC monitoring until the reaction did not proceed any more. The reaction mixture was dissolved in ethyl acetate (50mL), and the organic layer was washed with 2M hydrochloric acid and saturated sodium bicarbonate in this order, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: petroleum ether: ethyl acetate: 8: 1) to give methyl 2-fluoro-3- (N- (cyclopropylmethyl) benzamide) benzoate (13.00g, yield 88.70%) as a colorless liquid.
(3) Synthesis of 2-fluoro-3- [ N- (cyclopropylmethyl) benzamido ] benzoic acid
Figure BDA0002151590810000111
Methyl 2-fluoro-3- (N- (cyclopropylmethyl) benzamide) benzoate (13.00g, 40.88mmol) was dissolved in methanol (100mL), and 10% aqueous sodium hydroxide (6.54g, 163.52mmol, 65.4mL) was added thereto, and after stirring at room temperature for 2 hours, the reaction was monitored by TLC for completion. After removing methanol by concentration under reduced pressure, the concentrated residue was dissolved in water (100mL), extracted with ethyl acetate (50mL), the organic phase was discarded, the pH of the aqueous phase was adjusted to 7 with 2M aqueous hydrochloric acid solution, extraction was continued with ethyl acetate (100mL), the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give a colorless solution product, 2-fluoro-3- [ N- (cyclopropylmethyl) benzamide ] benzoic acid (12.00g, yield 93.82%), which was left overnight to stand as a white solid.
(4) Synthesis of N- [ 2-bromo-4- (1,1,1,2,3,3, 3-heptafluoropropan-2-yl) -6- (trifluoromethyl) phenyl ] -3- [ N- (cyclopropylmethyl) benzamido ] -2-fluorobenzamide
Figure BDA0002151590810000112
2-fluoro-3- (N- (cyclopropylmethyl) benzamido) benzoic acid (0.40g, 1.28mmol), toluene (6mL), thionyl chloride (0.75g, 6.40mmol) were added to a reaction flask in this order, and the reaction was stirred at 140 ℃ for 2 hours, concentrated under reduced pressure, and the concentrated residue was dissolved in tetrahydrofuran (3mL) for further use.
Dissolving 2-bromo-6-trifluoromethyl-4-heptafluoroisopropylaniline (0.52g, 1.28mmol) in tetrahydrofuran (4mL), dropwise adding lithium diisopropylamide (0.77mL, 1.54mmol) at-70 ℃, dropwise adding the tetrahydrofuran solution of the 2-fluoro-3- [ N- (cyclopropylmethyl) benzamido ] benzoyl chloride synthesized in the previous step after 5min, stirring at-70 ℃ for 30min, raising the temperature to room temperature, and continuing to stir for 30 min. The reaction was terminated by TLC monitoring until the reaction did not proceed any more. Water (20mL) was added to the reaction mixture, and the mixture was extracted with ethyl acetate (20mL), the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure, and the residue was purified by column chromatography (eluent was petroleum ether: ethyl acetate ═ 3:1) to give N- [ 2-bromo-4- (1,1,1,2,3,3, 3-heptafluoropropan-2-yl) -6- (trifluoromethyl) phenyl ] -3- [ N- (cyclopropylmethyl) -benzoylamino ] -2-fluorobenzamide (0.25g, yield 27.84%).
Process for preparation of Compound 11H NMR(400MHz,CDCl3-d),δ[ppm]：8.15(d,J＝2.1Hz,1H),8.03(br s,2H),7.92(d,J＝2.1Hz,1H),7.55(br s,1H),7.35-7.21(m,5H),3.84(d,J＝93.6Hz,2H),1.14(br s,1H),0.59-0.40(m,2H),0.20(d,J＝42.2Hz,2H)。
Synthesis example 2
Synthesis of N- [ 2-bromo-4- (1,1,1,2,3,3, 3-heptafluoropropan-2-yl) -6-trifluoromethoxyphenyl ] -3- [ N- (cyclopropylmethyl) benzamido ] -2-fluorobenzamide (Compound No. 3)
Figure BDA0002151590810000113
2-fluoro-3- (N- (cyclopropylmethyl) benzamide) benzoic acid (0.50g, 1.60mmol), toluene (6mL), and thionyl chloride (1.07g, 9.00mmol) were added to a reaction flask in this order, and the reaction was stirred under reflux for 2 hours, toluene was concentrated under reduced pressure, and the concentrated residue was dissolved in tetrahydrofuran (3mL) for further use.
Dissolving 2-bromo-4-heptafluoroisopropyl-6-trifluoromethoxyaniline (0.68g, 1.60mmol) in tetrahydrofuran (4mL), dropwise adding 2M lithium diisopropylamide tetrahydrofuran solution (0.96mL, 1.93mmol) at-70 ℃, dropwise adding the tetrahydrofuran solution for later use after 5min, stirring at-70 ℃ for 30min, heating to room temperature, and continuing stirring for 30 min. The reaction was terminated when the reaction was no longer proceeding as monitored by Thin Layer Chromatography (TLC). Water (20mL) was added to the reaction mixture, and extraction was performed with ethyl acetate (20mL), and the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent was petroleum ether: ethyl acetate 5: 1) to obtain the objective product (0.24g, yield 20.50%) as a white solid.
Process for preparation of Compound 31H NMR(400MHz,CDCl3-d) data as follows (δ)[ppm])：8.01-7.81(m,2H),7.58–7.51(m,3H),7.35-7.21(m,6H),3.85(d,J＝64.0Hz,2H),1.20-1.13(m,1H),0.50(d,J＝7.8Hz,2H),0.20(d,J＝32.0Hz,2H).
Synthesis example 3
Preparation of N- [ 2-bromo-4- (1,1,1,2,3,3, 3-heptafluoropropan-2-yl) -6- (trifluoromethyl) phenyl ] -3- [ N- (cyclopropylmethyl) -4-cyanobenzamido ] -2-fluorobenzamide (compound No. 4):
(1) synthesis of methyl 2-fluoro-3- [ N- (cyclopropylmethyl) -4-cyanobenzamido ] benzoate
Figure BDA0002151590810000121
4-Cyanobenzoic acid (0.80g, 5.38mmol), toluene (6mL), and thionyl chloride (3.2g, 26.9mmol) were added to a reaction flask in this order, and the mixture was stirred under reflux for 2 hours, toluene was concentrated under reduced pressure, and the concentrated residue was dissolved in tetrahydrofuran (3mL) for further use. Methyl 2-fluoro- [3- (cyclopropylmethyl) amino ] benzoate (1.0g, 4.48mmol) was dissolved in tetrahydrofuran (6mL), triethylamine (0.74g, 5.38mmol) was added, a solution of 4-cyanobenzoyl chloride in tetrahydrofuran was added dropwise, and the mixture was stirred at room temperature for 4 hours. The reaction was terminated by TLC monitoring until the reaction did not proceed any more. Water (20mL) was added to the reaction mixture, and the mixture was extracted with ethyl acetate (20mL), the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: petroleum ether: ethyl acetate: 3:1) to give methyl 2-fluoro-3- [ N- (cyclopropylmethyl) -4-cyanobenzamide ] benzoate (1.40g, yield 88.83%) as a colorless liquid product.
(2) Synthesis of 2-fluoro-3- [ N- (cyclopropylmethyl) -4-cyanobenzamido ] benzoic acid
Figure BDA0002151590810000122
Methyl 2-fluoro-3- [ N- (cyclopropylmethyl) -4-cyanobenzamido ] benzoate (1.40g,3.96mmol) was dissolved in methanol (20mL), 10% aqueous sodium hydroxide (0.63g,15.86mmol,6.3mL) was added, the mixture was stirred at room temperature for 2h, and the reaction was monitored by TLC for completion. After removing methanol by concentration under reduced pressure, the concentrated residue was dissolved in water (20mL), extracted with ethyl acetate (10mL), the organic phase was discarded, the pH of the aqueous phase was adjusted to 7 with 2M aqueous hydrochloric acid solution, and further extracted with ethyl acetate (10mL), and the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give 2-fluoro-3- [ N- (cyclopropylmethyl) -4-cyanobenzoylamino ] benzoic acid (1.30g, yield 96.79%) as a white solid.
(3) Synthesis of N- [ 2-bromo-4- (1,1,1,2,3,3, 3-heptafluoropropan-2-yl) -6- (trifluoromethyl) phenyl ] -3- [ N- (cyclopropylmethyl) -4-cyanobenzamido ] -2-fluorobenzamide:
Figure BDA0002151590810000131
2-fluoro-3- [ N- (cyclopropylmethyl) -4-cyanobenzamide ] benzoic acid (0.75g, 2.22mmol), toluene (6mL) and thionyl chloride (1.31g, 11.10mmol) were added to a reaction flask in this order, the reaction was stirred under reflux for 2h, concentrated under reduced pressure, and the concentrated residue was dissolved in tetrahydrofuran (3mL) for use.
Dissolving 2-bromo-6-trifluoromethyl-4-heptafluoroisopropylaniline (0.90g, 2.22mmol) in tetrahydrofuran (4mL), dropwise adding lithium diisopropylamide (1.30mL, 2.66mmol) at-70 ℃, dropwise adding the 2-fluoro-3- [ N- (cyclopropylmethyl) -4-cyanobenzamide ] benzoyl chloride tetrahydrofuran solution prepared in the previous step after 5min, stirring at-70 ℃ for 30min, heating to room temperature, and continuing to stir for 30 min. The reaction was terminated by TLC monitoring until the reaction did not proceed any more. To the reaction mixture was added a saturated aqueous ammonium chloride solution (20mL), extracted with ethyl acetate (20mL), the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure, and the residue was purified by column chromatography (eluent was petroleum ether: ethyl acetate ═ 3:1) to give N- [ 2-bromo-4- (1,1,1,2,3,3, 3-heptafluoropropan-2-yl) -6- (trifluoromethyl) phenyl ] -3- [ N- (cyclopropylmethyl) -4-cyanobenzoylamino ] -2-fluorobenzamide (0.24g, yield 14.91%).
Process for preparation of Compound 41H NMR(400MHz,CDCl3-d),δ[ppm]：8.14(d,J＝2.0Hz,1H),8.12-7.94(m,2H),7.91(t,J＝1.4Hz,1H),7.58-7.39(m,4H),7.32(t,J＝7.9Hz,1H),3.81(dd,J＝76.0,18.8Hz,2H),1.11(br s,1H),0.5(br s,2H),0.20(d,J＝36.7Hz,2H)。
Synthesis example 4
Preparation of N- [ 2-bromo-4- (1,1,1,2,3,3, 3-heptafluoropropan-2-yl) -6- (trifluoromethyl) phenyl ] -3- [ N- (cyclopropylmethyl) -4- (trifluoromethyl) benzamido ] -2-fluorobenzamide (compound No. 7):
Figure BDA0002151590810000132
(1) 2-fluoro-3- [ N- (cyclopropylmethyl) -4-trifluoromethylbenzamide ] benzoic acid (0.45g, 1.12mmol), toluene (6mL), and thionyl chloride (0.67g, 5.60mmol) were added to a reaction flask in this order, and the reaction was stirred under reflux for 2 hours, toluene was concentrated under reduced pressure, and the concentrated residue was dissolved in tetrahydrofuran (3mL) for further use.
(2) Dissolving 2-bromo-6-trifluoromethyl-4-heptafluoroisopropylaniline (0.46g, 1.12mmol) in tetrahydrofuran (4mL), dropwise adding lithium diisopropylamide (0.70mL, 1.42mmol) at-70 ℃, dropwise adding the tetrahydrofuran solution for later use in the previous step after 5min, stirring at-70 ℃ for 30min, heating to room temperature, and continuing stirring for 30 min. The reaction was terminated by TLC monitoring until the reaction did not proceed any more. Water (20mL) was added to the reaction mixture, and extraction was performed with ethyl acetate (20mL), and the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent was petroleum ether: ethyl acetate ═ 3:1) to obtain the objective product (0.11g, yield 13.75%).
Process for preparation of Compound 71H NMR(400MHz,CDCl3-d)δ[ppm]：8.21-7.79(m,4H),7.66-7.28(m,5H),3.85(d,J＝104.7Hz,2H),1.12(br s,1H),0.51(br s,2H),0.20(d,J＝42.7Hz,1H)。
Synthesis example 5
Preparation of N- [ 2-bromo-4- (1,1,1,2,3,3, 3-heptafluoropropan-2-yl) -6- (trifluoromethyl) phenyl ] -3- [ N- (cyclopropylmethyl) -4-fluorobenzamido ] -2-fluorobenzamide (Compound No. 8) as follows:
Figure BDA0002151590810000141
2-fluoro-3- [ N- (cyclopropylmethyl) -4-fluoro-benzamide ] benzoic acid (2.20g, 6.67mmol), toluene (20mL), thionyl chloride (3.97g, 33.35mmol) were added to the reaction flask in this order, stirred under reflux for 2h and concentrated under reduced pressure to give 2-fluoro-3- [ N- (cyclopropylmethyl) -4-fluorobenzamide ] benzoyl chloride. 2-bromo-6-trifluoromethyl-4-heptafluoroisopropylaniline (3.26g, 7.99mmol), N-diisopropylethylamine (1.72g, 13.30mmol) and 4-N, N-dimethylaminopyridine (0.33g, 2.69mmol) were added to 2-fluoro-3- [ N- (cyclopropylmethyl) -4-fluorobenzamide ] benzoyl chloride, respectively, and the mixture was stirred at 120 ℃ for 2 hours, after which time heating was stopped. Water (20mL) was added to the reaction mixture, and extraction was performed with ethyl acetate (20mL), and the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: PE: EA ═ 3:1) to obtain the objective product (1.80g, yield 37.5%).
Process for preparation of Compound 81H NMR(400MHz,DMSO-d6)δ[ppm]：10.56(s,1H),8.41(s,1H),7.95(s,1H),7.70-7.56(m,2H),7.38-7.32(m,3H),7.09(br s,2H),3.69(br s,2H),1.03-1.01(m,1H),0.41-0.39(m,2H),0.08-0.06(m,2H)。
Synthesis example 6
Preparation of N- [ 2-bromo-4- (1,1,1,2,3,3, 3-heptafluoropropan-2-yl) -6- (trifluoromethyl) phenyl ] -3- [ N- (cyclopropylmethyl) -4-chlorobenzamido ] -2-fluorobenzamide (Compound No. 10) as follows:
Figure BDA0002151590810000142
(1) 2-fluoro-3- [ N- (cyclopropylmethyl) -4-chlorobenzamide ] benzoic acid (0.60g, 1.76mmol), toluene (6mL), and thionyl chloride (1.04g, 8.80mmol) were added to a reaction flask in this order, and the reaction was stirred under reflux for 2 hours, toluene was concentrated under reduced pressure, and the concentrated residue was dissolved in tetrahydrofuran (3mL) for further use.
(2) Dissolving 2-bromo-6-trifluoromethyl-4-heptafluoroisopropylaniline (0.72g, 1.76mmol) in tetrahydrofuran (4mL), dropwise adding lithium diisopropylamide (1.05mL, 2.11mmol) at-70 ℃, dropwise adding the tetrahydrofuran solution for later use in the previous step after 5min, stirring at-70 ℃ for 30min, heating to room temperature, and continuing stirring for 30 min. The reaction was terminated by TLC monitoring until the reaction did not proceed any more. Water (20mL) was added to the reaction mixture, and extraction was performed with ethyl acetate (20mL), and the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent was petroleum ether: ethyl acetate ═ 3:1) to obtain the objective product (0.15g, yield 11.63%).
Process for preparation of Compound 101H NMR(400MHz,CDCl3-d)δ[ppm]：8.18-7.84(m,4H),7.53(t,J＝7.7Hz,1H),7.37-7.07(m,4H),3.81(d,J＝85.0Hz,2H),1.11(br s,1H),0.49(br s,2H),0.17(d,J＝32.1Hz,2H)。
Synthesis example 7
Preparation of N- [ 2-bromo-4- (1,1,1,2,3,3, 3-heptafluoropropan-2-yl) -6- (trifluoromethyl) phenyl ] -3- [ N- (1-cyclopropyl-ethyl) -benzamido ] -2-fluorobenzamide (compound No. 2) by the following method:
Figure BDA0002151590810000143
(1) synthesis of methyl 3- [ N- (1-cyclopropylethyl) amino ] -2-fluorobenzoate
Methyl 2-fluoro-3-aminobenzoate (2.00g, 11.82mmol) was dissolved in 1, 2-dichloroethane (65mL), and cyclopropylmethyl ketone (2.98g, 35.47mmol), trifluoroacetic acid (8.08g, 70.92mmol) and sodium triacetoxyborohydride (7.51g, 35.47mmol) were added in this order at room temperature, and the reaction was heated to 45 ℃ for 1 h. The reaction was terminated by TLC monitoring until the reaction did not proceed any more. Adding saturated NaHCO into the reaction solution3The solution (50mL) was extracted with dichloromethane (80mL), the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: petroleum ether: ethyl acetate 10: 1) to obtain a crude productThe title product (1.50g, 53.5% yield) was obtained as a colorless oil.
(2) Synthesis of methyl 3- [ N- (1-cyclopropyl) ethyl) benzamido ] -2-fluorobenzoate
Benzoic acid (1.54g, 12.64mmol), toluene (15mL) and thionyl chloride (6.27g, 52.68mmol) were added to a reaction flask in this order, the reaction was stirred under reflux for 2h, toluene was concentrated under reduced pressure, and the concentrated residue was dissolved in tetrahydrofuran (5mL) for use.
Methyl 3- [ N- (1-cyclopropyl) ethyl) amino ] -2-fluorobenzoate (2.50g, 10.54mmol) was dissolved in tetrahydrofuran (15mL), triethylamine (1.60g, 15.80mmol) and a tetrahydrofuran solution of the acid chloride prepared in the previous step were added in this order, and the reaction was stirred at 80 ℃ for 6 h. The reaction was terminated by TLC monitoring until the reaction did not proceed any more. Water (50mL) was added to the reaction mixture, and extraction was performed with ethyl acetate (60mL), and the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent was petroleum ether: ethyl acetate 10: 1) to obtain the objective product (1.03g, yield 28.6%) as a yellow solid.
(3)3- [ N- (1-cyclopropyl) ethyl) benzamido ] -2-fluorobenzoic acid
Methyl 3- [ (1-cyclopropyl-ethyl) benzamido ] -2-fluorobenzoate (1.00g, 2.93mmol) was dissolved in methanol (10mL), 10% aqueous sodium hydroxide (0.46g, 11.72mmol, 4.6mL) was added, stirring was carried out at room temperature for 2h, and the reaction was monitored by TLC for completion. After removing methanol by concentration under reduced pressure, the concentrated residue was dissolved in water (20mL), extracted with ethyl acetate (10mL), the organic phase was discarded, the pH of the aqueous phase was adjusted to 3 with 2M aqueous hydrochloric acid solution, extraction was continued with ethyl acetate (10mL), the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain the objective product (0.60g, yield 62.6%).
(4) Synthesis of N- [ 2-bromo-4- (1,1,1,2,3,3, 3-heptafluoropropan-2-yl) -6- (trifluoromethyl) phenyl ] -3- [ N- (1-cyclopropyl-ethyl) benzamido ] -2-fluorobenzamide
To a reaction flask were added 3- (N- (1-cyclopropyl) -ethyl) benzamido) -2-fluorobenzoic acid (0.60g, 1.83mmol), toluene (6mL) and thionyl chloride (1.09g, 9.16mmol) in this order, and the reaction was stirred at 140 ℃ for 2h, the toluene was concentrated under reduced pressure, and the concentrated residue was dissolved in tetrahydrofuran (2mL) for further use.
Dissolving 2-bromo-6-trifluoromethyl-4-heptafluoroisopropylaniline (0.75g, 1.83mmol) in tetrahydrofuran (6mL), dropwise adding lithium diisopropylamide (1.10mL, 2.20mmol) at-70 ℃, dropwise adding the tetrahydrofuran solution for later use in the previous step after 5min, stirring at-70 ℃ for 30min, heating to room temperature, and continuing stirring for 30 min. The reaction was terminated by TLC monitoring until the reaction did not proceed any more. Water (20mL) was added to the reaction mixture, and extraction was performed with ethyl acetate (20mL), and the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent was petroleum ether: ethyl acetate ═ 5: 1) to obtain the objective product (0.23g, yield 17.5%) as a yellow solid.
Process for preparation of Compound 21H NMR(400MHz,CDCl3-d),δ[ppm]：8.19(s,1H),8.05-7.95(m,1H),7.89(s,1H),7.77-7.73(m,1H),7.56-7.52(m,1H),7.28-7.11(m,6H),4.26-4.23(m,1H),1.63(br s,2H),1.51(br s,1H),0.89–0.40(m,5H)。
In addition to the above-described compounds, some of the compounds in Table 1 were prepared or preparable by a method similar to that in Synthesis examples 1 to 7, and nuclear magnetic data of some of the compounds synthesized by reference to Synthesis examples 1 to 7 are given in Table 4 below.
TABLE 4
Figure BDA0002151590810000151
Figure BDA0002151590810000161
Other compounds of formula I of the present invention may be synthesized by reference to the methods described above.
Formulation examples
The following examples are provided to illustrate the composition ratios and preparation of the present invention:
formulation example 1:40% of compound 8-lufenuron emulsifiable concentrate (the concentration is 40)% means the sum of the concentrations of Compound 8 and lufenuron in the cream formulation)
The composition of the 40% compound 8 lufenuron emulsifiable concentrate is shown in table 5:
TABLE 5
Name (R) Pleated (W/W,%) Remarks for note
Compound 8 12 Active ingredient A
Lufenuron 28 An active ingredient B
Calcium dodecyl benzene sulfonate 8 Emulsifier
Castor oil polyoxyethylene ether 8 Emulsifier
No. 200 solvent oil Complement 100 Solvent(s)
The preparation method comprises the following steps: calculating the amount of each material according to the formula, adding No. 200 solvent oil into a material preparation kettle, adding the compound 8 and lufenuron into the kettle for complete dissolution, adding the calcium dodecyl benzene sulfonate and the castor oil polyoxyethylene ether, stirring the mixture for 1.5 hours at the temperature of 40-50 ℃, and filtering the mixture to obtain the 40% compound 8 lufenuron emulsifiable solution.
Formulation example 2:30% of compound 4. fipronil suspension seed coating agent
The composition of the 30% compound 4. fipronil suspension seed coating is shown in table 6:
TABLE 6
Figure BDA0002151590810000162
Figure BDA0002151590810000171
The preparation method comprises the following steps: adding deionized water, the compound 4, fipronil, FS3000, TER4894, kasong, SAG1522 and propylene glycol into a blending kettle according to the material proportion, shearing, sanding, controlling the particle size to be about 905 micrometers, transferring into the blending kettle, adding a 2% xanthan gum solution and a pigment F2R, mixing and stirring for 1 hour to obtain the 30% compound 4. fipronil suspension seed coating agent.
Formulation example 3:25% compound 6-chlorantraniliprole water dispersible granule
The composition of 25% compound 6. chlorantraniliprole water dispersible granules is shown in table 7:
TABLE 7
Name (R) Pleated (W/W,%) Remarks for note
Compound 6 10 Active ingredient A
Chlorantraniliprole 15 An active ingredient B
Sodium dodecyl sulfate 1.5 Wetting agent
Lignosulfonic acid sodium salt 6 Dispersing agent
Naphthalenedicarbaldehyde polymer sodium sulfonate 2 Dispersing agent
Ammonium sulfate 5 Disintegrating agent
Corn starch 20 Filler material
Kaolin clay Complement 100 Filler material
The preparation method comprises the following steps: calculating the amount of each material according to the formula, uniformly mixing the compound 6, chlorantraniliprole, sodium dodecyl sulfate, sodium lignosulfonate, sodium naphthalene formaldehyde polymer sulfonate, ammonium sulfate, corn starch and kaolin, crushing the mixture to an average particle size of 10-15 microns by using an airflow crusher, adding water accounting for 17% of the powder amount, kneading the mixture, performing rotary extrusion granulation, drying the mixture for 3 hours at 50 ℃, and screening the dried mixture to obtain the 25% compound 6-chlorantraniliprole water dispersible granule.
Formulation example 4:24% of compound 8. cyantraniliprole suspending agent
The composition of the 24% compound 8. cyantraniliprole suspension is shown in table 8:
TABLE 8
Figure BDA0002151590810000172
Figure BDA0002151590810000181
The preparation method comprises the following steps: calculating the amount of each material according to the formula, uniformly stirring and dissolving deionized water, propylene glycol, tristyrylphenol polyoxyethylene ether phosphate, sodium lignosulphonate, kathon and a defoaming agent, adding cyantraniliprole and a compound 8, uniformly shearing, grinding by a sand mill until the average particle size is 2 microns, adding 10 parts of 1% xanthan gum solution, and stirring for 30 minutes to obtain the 24% compound 8. cyantraniliprole suspending agent.
Formulation example 5:30% of compound 7 methoxyfenozide water dispersible granule
The composition of 30% compound 7 methoxyfenozide water dispersible granules is shown in table 9:
TABLE 9
Name (R) Pleated (W/W,%) Remarks for note
Compound 7 6 Active ingredient A
Methoxyfenozide 24 An active ingredient B
Sodium dodecyl sulfate 1.5 Wetting agent
Lignosulfonic acid sodium salt 6 Dispersing agent
Naphthalenedicarbaldehyde polymer sodium sulfonate 2 Dispersing agent
Ammonium sulfate 5 Disintegrating agent
Corn starch 20 Filler material
Kaolin clay Complement 100 Filler material
The preparation method comprises the following steps: calculating the amount of each material according to the formula, uniformly mixing the compound 7, methoxyfenozide, sodium dodecyl sulfate, sodium lignosulfonate, sodium naphthalene formaldehyde polymer sulfonate, ammonium sulfate, corn starch and kaolin, crushing the mixture to an average particle size of 10-15 microns by using an airflow crusher, adding water accounting for 17% of the powder amount, kneading the mixture, performing rotary extrusion granulation, drying the mixture for 3 hours at 50 ℃, and screening the dried mixture to obtain the 30% compound 7 methoxyfenozide water dispersible granule.
Formulation example 6:27% of compound 10. metaflumizone microcapsule suspending agent
The composition of the 27% compound 10. metaflumizone microcapsule suspension is shown in table 10:
watch 10
Figure BDA0002151590810000182
Figure BDA0002151590810000191
The preparation method comprises the following steps: calculating the material amount according to the formula, and uniformly dissolving the compound 10, metaflumizone, polyarylpolymethylene polyisocyanate and trimethylbenzene at 40-50 ℃ to obtain an A phase; dissolving deionized water, D-800 and propylene glycol uniformly to obtain phase B; slowly adding the phase A into the phase B under high shear, shearing to an average particle size of 2-3 microns, then adding the materials into a three-neck flask, adding hexamethylene diamine, stirring and reacting for 10 hours at 50-60 ℃, adding tristyrylphenol polyoxyethylene ether phosphate, carbazone, a defoaming agent and 1% xanthan gum solution, and stirring for 1 hour to obtain the 27% compound 10. metaflumizone microcapsule suspending agent.
Formulation example 7:25% compound 6 tolfenpyrad wettable powder
The composition of the 25% compound 6 tolfenpyrad wettable powder is shown in table 11:
TABLE 11
Name (R) Pleated (W/W,%) Remarks for note
Compound 6 5 Active ingredient A
Tolfenpyrad 20 An active ingredient B
Sodium dodecyl sulfate 1.5 Wetting agent
Lignosulfonic acid sodium salt 6 Dispersing agent
Kaolin clay Complement 100 Carrier
The preparation method comprises the following steps: calculating the material amount according to the formula, adding the compound 6, tolfenpyrad, sodium dodecyl sulfate, sodium lignin sulfonate and kaolin into a material preparation kettle, uniformly mixing, and crushing by using an airflow crusher to obtain the 25% compound 6-tolfenpyrad wettable powder with the average particle size of 10 microns.
Formulation example 8:15% of compound 7-fluxapyroxamide dispersible agent
The composition of the 15% compound 7-fluxafluxaflutole dispersible formulation is shown in table 12:
TABLE 12
Name (R) Pleated (W/W,%) Remarks for note
Compound 5 5 Active ingredient A
Fluorooxazolamides 10 An active ingredient B
No. 100 solvent oil 15 Solvent(s)
Cyclohexanone 10 Solvent(s)
Castor oil polyoxyethylene ether (EL40) 5 Dispersing agent
Fatty alcohol polyoxyethylene ether 10 Wetting agent
Polydimethylsiloxane emulsion (SAG1522) 0.2 Defoaming agent
Deionized water Complement 100 Carrier
The preparation method comprises the following steps: adding No. 100 solvent oil and cyclohexanone into a batching kettle according to a process proportion, adding the compound 7 and the fluorine oxazole amide under stirring, heating to 50 ℃ until the solvent is completely dissolved, adding EL40, fatty alcohol-polyoxyethylene ether and SAG1522, continuing stirring for 10 minutes, cooling, and adding deionized water to obtain the 15% compound 7-fluorine oxazole amide dispersible agent.
Formulation embodiment 9: 28% compound 1-ethiprole emulsion in water
The composition of the 28% compound 1 ethiprole emulsion in water is shown in table 13:
watch 13
Figure BDA0002151590810000192
Figure BDA0002151590810000201
The preparation method comprises the following steps: adding No. 150 solvent oil into a batching kettle, starting stirring, adding the compound 1, stirring for dissolving, adding ethiprole and an emulsifier TERMUL5030 after complete dissolution, continuing stirring for 20 minutes, and uniformly mixing to obtain an oil phase for later use; adding deionized water, a defoaming agent and an antifreezing agent into a shearing kettle, starting a shearing device, slowly adding an oil phase material after 5 minutes, and shearing for 10 minutes after the addition to obtain the 28% compound 1-ethiprole emulsion in water.
Bioassay examples
The following examples are intended to illustrate some of the practice of the present invention and the present invention is not limited to the following examples.
Bioassay example 1:when the active ingredient A is a compound of a formula II, the compound has obvious insecticidal activity on various pests
Target: the 3 rd larva of diamondback moth, the 3 rd larva of armyworm and the 3 rd larva of chilo suppressalis are all raised indoors.
The method comprises the following steps: a diamondback moth and leaf soaking feeding method, a armyworm and leaf soaking feeding method, and a chilo suppressalis and rice stem soaking method.
Diamondback moth and leaf soaking feeding method. With reference to NY/1154.14-2008, the main operations are described as follows: soaking clean bracteatum leaf dishes in the liquid medicine for 10s, airing, placing in culture dishes with 4 dishes in each dish, and placing filter paper in the culture dishes for moisture preservation. Each dish was inoculated with 10 plutella xylostella test insects, and the procedure was repeated 3 times. Placing in a light incubator at 25 deg.C under 14hL:10hD for culture. And (5) investigating the number of dead and live plutella xylostella insects 3 days after the application of the composition, and calculating the mortality.
Feeding method with armyworm and soaked leaves. With reference to NY/1154.14-2008, the main operations are described as follows: soaking clean corn leaf segments in the medicinal liquid for 10s, air drying, placing in culture dish with 4 pieces per dish, and placing filter paper in the culture dish for keeping moisture. Each dish was inoculated with 10 test insects of armyworm, and the procedure was repeated 3 times. Placing in a light incubator at 25 deg.C under 14hL:10hD for culture. The number of dead and live armyworms of armyworms is investigated 3 days after the drug administration, and the death rate is calculated.
Chilo suppressalis and rice stem soaking method. Referring to NY/T1154.11-2008, the main operations are as follows: soaking clean rice stem in the medicinal liquid for 10s, taking out, air drying in shade, placing into finger tube, inoculating 10 Chilo suppressalis larva of 3 years old, repeating for 3 times, sealing the tube with cotton black cloth, fastening with rubber band, and culturing in light incubator at 28 deg.C in dark. The number of dead and live chilo suppressalis insects is investigated 3 days after the drug administration, and the mortality rate of each drug treatment is calculated.
The results are shown in table 14, and it can be seen from the results that compounds 1 to 14 all have very significant insecticidal activity against diamond back moth, armyworm and chilo suppressalis.
TABLE 14 insecticidal Activity of Compounds 1-14 against Plutella xylostella, armyworm, Chilo suppressalis
Figure BDA0002151590810000202
Figure BDA0002151590810000211
Bioassay example 2:the active ingredient A is a compound of a formula II and the active ingredient B is a composition of chlorantraniliprole, flubendiamide, cyantraniliprole and the like, and the activity test of the diamondback moth is carried out
Target: vegetable diamondback moth, 3 instar larva
The method comprises the following steps: leaf-dipping dish feeding method, the operation is described in the same way as in the bioassay example 1.
The evaluation methods and criteria were as follows:
the synergistic effect is the percent of actual mortality to the percent of theoretical mortality
Theoretical mortality ═ 1-the mortality of active ingredient a at this dose (1-the mortality of active ingredient B at this dose)
The synergistic effect is more than or equal to 20, and the obvious synergistic effect is shown; the synergistic effect is more than or equal to 10 and less than 20, which represents the synergy; -10. ltoreq. synergistic effects < 10, indicating addition; the synergistic effect is less than-10, which represents antagonism, and the larger the negative value is, the greater the antagonism degree is.
The results are shown in table 15, and it can be seen from the results that the effective ingredient a, compound 1, compound 4, compound 8, had excellent activity against plutella xylostella; when the effective component B is chlorantraniliprole, flubendiamide, cyantraniliprole and tebuconazole, the composition has excellent activity on diamondback moths; when a is combined with B, the combined effect appears to be synergistic or significant synergistic.
TABLE 15 insecticidal Activity of test Agents against Plutella xylostella
Test agent or combination name Dosage mg/L 3d mortality% Theoretical mortality% Synergistic effect Mode of combined action
Compound 1 0.01 36.67 / / /
Compound 4 0.01 43.33 / / /
Compound 8 0.02 53.33 / / /
Chlorantraniliprole 0.5 60.00 / / /
Flubendiamide 0.4 70.00 / / /
Cyantraniliprole bromide 0.25 66.67 / / /
Compound 1+ chlorantraniliprole 0.01+0.5 100 74.67 25.33 Significant synergy
Compound 4+ flubendiamide 0.01+0.4 100 60.33 39.67 Significant synergy
Compound 8+ cyantraniliprole 0.02+0.25 100 84.44 15.56 Efficiency enhancement
Bioassay example 3:the composition of the compound with the effective component A as the formula II and the cyantraniliprole, the tetrachloro-insect amide, the cyromantraniliprole and the like as the effective component B has a synergistic effect on rice stem borers
Target: and (4) feeding chilo suppressalis 3-instar larvae indoors.
The method comprises the following steps: soaking rice stem. The main operational description is in contemporaneous assay implementation 1. Evaluation method example 2 was evaluated in the same manner as the standard.
As shown in table 16, it can be seen from the results that compound 4, compound 5, compound 6, compound 7, compound 8, compound 9, compound 10, compound 11, compound 12 and compound 13 as the active ingredient a had excellent activity against chilo suppressalis; when the effective components B are cyantraniliprole, tetrachloro-insect amide and cyclic bromotraniliprole, the active ingredients have excellent activity on chilo suppressalis; when a is combined with B, the combined effect appears to be synergistic or significant synergistic.
TABLE 16 insecticidal Activity of test Agents against Chilo suppressalis
Figure BDA0002151590810000212
Figure BDA0002151590810000221
Bioassay example 4:the active ingredient A is a compound of a formula II and the active ingredient B is a composition of fipronil, ethiprole, acetoprole and the like, and the activity test on brown planthopper is carried out
Target: brown planthopper, 3-year-old nymph.
The method comprises the following steps: soaking rice seedling. Reference is made to NY/T1154.11-2008.
The method operation is described as follows: preparation of the medicament: according to the proportion and dosage of experimental design, a certain amount of original drug is weighed, dissolved by N, N-Dimethylformamide (DMF), and then 0.05% of Tween 80 water is added to prepare mother liquor with a certain concentration. 5-7 doses are set in each proportion, and the mother liquor is sequentially diluted to the test dose according to the test design. Medicament treatment: soaking rice seedlings in the liquid medicine for 10s, then placing the rice seedlings into disposable cups, inoculating 15 insects to each cup, sealing the cups by using a preservative film, and treating 45 test insects each time. During medicine soaking, the same medicines are sequentially soaked from low concentration to high concentration, and a blank control and a solvent control are arranged. After the treatment, the mixture is placed in an illumination incubator at the temperature of 28 +/-1 ℃ and the light-dark ratio of 15h to 9 h. And (4) investigating a result: the number of dead insects was investigated 3d after the administration. And (5) counting the mortality.
Evaluation method example 2 was evaluated in the same manner as the standard.
The results are shown in table 17, and it can be seen from the results that the active ingredient a, compound 6, compound 8, compound 10, had good activity against brown planthopper; when the effective components B are fipronil, ethiprole and acetoprole, the composition has good activity on brown planthopper; when a is combined with B, the combined effect appears to be synergistic.
TABLE 17 insecticidal Activity of test Agents against Nilaparvata lugens
Figure BDA0002151590810000222
Figure BDA0002151590810000231
Bioassay example 5:the active ingredient A is a compound shown in the formula II, and the active ingredient B is indoxacarb, chlorfenapyr, metaflumizone, tolfenpyrad and the like, and the activity test on armyworm is carried out
The method comprises the following steps: and (4) an insect soaking method. The operation is described as follows: with reference to NY/1154.6-2006, the main operations are described as follows: soaking 10 test insects into the liquid medicine for 10s, airing, placing into culture dishes, placing 4 clean corn leaf segments into each dish, and placing filter paper in each culture dish for moisture preservation. 3 replicates. Placing in a light incubator at 25 deg.C under 14hL:10hD for culture. The number of the armyworm dead insects is investigated 3 days after the drug administration, and the death rate is calculated.
Evaluation method in the same manner as in production example 2.
The results are shown in table 18, and it can be seen from the results that the active ingredient a, when it was compound 2, compound 3, compound 5, compound 10, compound 12, compound 14, had excellent activity against armyworm; when the effective component B is indoxacarb, chlorfenapyr, metaflumizone and tolfenpyrad, the composition has good activity on armyworms; when a is combined with B, the combined effect appears to be synergistic or significant synergistic.
TABLE 18 insecticidal Activity of test Agents against armyworm indoors
Test agent or combination name Dosage mg/L 3d mortality% Theoretical mortality% Synergistic effect Mode of combined action
Compound 2 0.04 53.33 / / /
Compound 3 0.04 60 / / /
Compound 5 0.04 75 / / /
Compound 10 0.04 80 / / /
Compound 12 0.04 65 / / /
Compound 14 0.04 60 / / /
Indoxacarb 0.8 50 / / /
Chlorfenapyr 2.0 56.67 / / /
Metaflumizone 4.0 43.33 /
Tolfenpyrad 2.5 50 / / /
Compound 2+ indoxacarb 0.04+0.8 100 76.66 23.34 Significant synergy
Compound 3+ indoxacarb 0.04+0.8 100 80.00 20.00 Significant synergy
Compound 3+ chlorfenapyr 0.04+2.0 100 82.67 17.33 Efficiency enhancement
Compound 5+ indoxacarb 0.04+0.8 100 87.50 12.5 Efficiency enhancement
Compound 10+ metaflumizone 0.04+4.0 100 88.67 11.33 Efficiency enhancement
Compound 10+ tolfenpyrad 0.04+2.5 100 90.00 10.00 Efficiency enhancement
Compound 12+ metaflumizone 0.04+4.0 100 80.17 19.83 Efficiency enhancement
Compound 14+ metaflumizone 0.04+4.0 100 77.32 22.68 Significant synergy
Bioassay example 6:and when the effective component A is the compound shown in the formula I and the effective component B is methoxyfenozide, lufenuron and pyridalyl, the activity of the compound on prodenia litura is tested.
The method comprises the following steps: leaf soaking method, 3 instar larva. The operation is described as follows: soaking clean bract cabbage leaf disks in the medicinal liquid for 10s, airing, placing in a 24-hole plate, and inoculating 1 test insect of prodenia litura in each hole, and treating 24 test insects each time. Placing in a light incubator at 25 deg.C under 14hL:10hD for culture. The number of dead insects was investigated 3 days after the administration, and the mortality was calculated.
The results are shown in table 19, and it can be seen from the results that when the active ingredient a is compound 1, compound 4, compound 6, it has excellent activity against prodenia litura; when the effective component B is methoxyfenozide, lufenuron and pyridalyl, the compound has good activity on prodenia litura; when a is combined with B, the combined effect appears to be synergistic or significant synergistic.
TABLE 19 insecticidal Activity Table for Prodenia litura in test agent room
Test agent or combination name Dosage formmg/L 5d mortality% Theoretical mortality% Synergistic effect Mode of combined 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 / / /
Pyridalyl 20 46.67 / / /
Compound 1+ methoxyfenozide 1.0+4.0 100 84.00 16.00 Efficiency enhancement
Compound 4+ lufenuron 0.4+0.8 100 80.00 20.00 Significant synergy
Compound 6+ pyridalyl 1.0+20 100 73.33 26.67 Significant synergy
Bioassay example 7:activity test of compound 8 and tebuconazole amide composition on chilo suppressalis
Insect sources: and (4) feeding chilo suppressalis 3-instar larvae indoors.
The method comprises the following steps: stem dipping method, the procedure is as described in bioassay example 1, and evaluation is made by co-toxicity coefficient with reference to NY/T1154.7-2006.
The co-toxicity coefficient (CTC value) of the mixture is calculated according to the formula (1), the formula (2) and the formula (3):
Figure BDA0002151590810000241
in the formula: ATI-measured toxicity index of mixed agent;
S-LC of Standard insecticide50In milligrams per liter (mg/L);
LC of M-mixtures50In milligrams per liter (mg/L).
TTI＝A×PA+B×PB····················(2)
In the formula: TTI-theoretical virulence index of the mixture;
A-A agent virulence index;
the percentage of the PA-A agent in the mixture is expressed as percentage (%);
B-B agent virulence index;
the percentage of the PB-B medicament in the mixture is given as percentage (%).
Figure BDA0002151590810000242
In the formula: CTC-co-toxicity coefficient; ATI-measured toxicity index of mixed agent; TTI-theoretical virulence index of the mixture.
The co-toxicity coefficient (CTC) of the compound agent is more than or equal to 120, which shows a synergistic effect; CTC is less than or equal to 80 and shows antagonism; 80 < CTC < 120 showed additive effects.
The results are shown in table 20, and it can be seen from the results that both compound 8 and tebuconazole amide have better activity against chilo suppressalis; the compound 8 and the tebuconazole amide are compounded, the co-toxicity coefficient is 101.97-163.88 when the mixture ratio is 160:1-1: 160, and the effect is additive or synergistic; when the ratio is 80: 1-1: 80, the co-toxicity coefficient is more than 120, and the effect is enhanced.
TABLE 20 Co-toxicity coefficient of combination of Compound 8 and Tebuconazole on Chilo suppressalis
Figure BDA0002151590810000251
Bioassay example 8:activity test of composition of compound 9 and fluxapyroxad against plutella xylostella
Insect sources: and breeding 3-instar larvae of the plutella xylostella indoors.
Soaking leaves and feeding. Description of the operation the in-situ test example 1 and the statistical evaluation in-situ test example 7 were carried out.
The results are shown in table 21, and it can be seen from the results that both compound 9 and fluxapyroxad have good activity against plutella xylostella; the compound 9 and the fluxapyroxamide are compounded, the co-toxicity coefficient of each mixture ratio is 111.07-173.06 in the ratio of 120: 1-1: 120, and the co-toxicity coefficient are added or enhanced; the ratio of the active ingredients to the active ingredients is 80: 1-1: 80.
TABLE 21 Co-toxicity factor of combination of Compound 9 and Fluroxazole amide against Plutella xylostella
Figure BDA0002151590810000252
Figure BDA0002151590810000261
Bioassay example 9:activity test of composition of compound 3 and metaflumizone on beet armyworm
Insect sources: and (4) breeding 3-instar beet armyworm larvae indoors.
The method comprises the following steps: a leaf soaking dish feeding method. The operation is described as follows: soaking clean bract vegetable leaf disks in the medicinal liquid for 10s, air-drying, placing in a 24-hole plate, inoculating 1 test insect of beet armyworm in each hole, and treating 24 test insects each time. Placing in a light incubator at 25 deg.C under 14hL:10hD for culture. The number of dead insects was investigated 3 days after the administration, and the mortality was calculated.
Evaluation same test example 7.
The results are shown in table 22, and it can be seen from the results that both compound 3 and metaflumizone have better activity against spodoptera exigua; the compound 3 and metaflumizone are compounded, wherein the cotoxicity coefficient of 100: 1-1:100 in each proportion is 94.11-189.71, and the cotoxicity coefficients are additive or synergistic; the ratio of the active ingredients to the active ingredients is 50:1-1: 50.
TABLE 22 Cotoxicity coefficient of composition of Compound 3 and metaflumizone against beet armyworm
Figure BDA0002151590810000262
Bioassay example 10:activity test of a combination of Compound 7 and ethiprole against Nilaparvata lugens
Target: brown planthopper, 3-year-old nymph.
The method comprises the following steps: soaking rice seedling. Description of the operation the in-situ test example 4 and the statistical evaluation in-situ test example 7 were carried out.
The results are shown in table 23, from which it can be seen that compound 7 and ethiprole have better activity against brown planthopper; the compound 7 and the ethiprole are compounded, the co-toxicity coefficient of each mixture ratio of 100: 1-1:100 is 121.27-162.37, and the synergistic effect is achieved.
TABLE 23 Co-toxicity of combination of Compound 7 and ethiprole against Nilaparvata lugens (post-application 3d)
Figure BDA0002151590810000263
Figure BDA0002151590810000271
Bioassay example 11:activity test of combination of Compound 12 and lufenuron against Plutella xylostella
Insect sources: and breeding 3-instar larvae of the plutella xylostella indoors.
The method comprises the following steps: soaking leaves and feeding. Description of the operation the in-situ test example 1 and the statistical evaluation in-situ test example 7 were carried out.
The results are shown in table 24, from which it can be seen that both compound 12 and lufenuron have better activity against plutella xylostella; the compound 12 and the lufenuron are compounded, the co-toxicity coefficient of each proportion is 89.09-224.74 in the proportion of 150: 1-1: 150, and the compounds have additive or synergistic effect; the ratio of the active ingredients to the active ingredients is 50:1-1: 50.
TABLE 24 Co-toxicity factor of combinations of Compound 12 and lufenuron against Plutella xylostella
Figure BDA0002151590810000272
The applicant states that the present invention is illustrated by the above examples to the pharmaceutical composition containing the isophthalamide and the application thereof, but the present invention is not limited by the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (22)

1. The pharmaceutical composition containing the m-diamide compound is characterized by comprising an effective component A and an effective component B, wherein the effective component A is an amide compound with a structure shown in a formula I, and the effective component B comprises any one of chlorantraniliprole, methoxyfenozide, indoxacarb, chlorfenapyr, metaflumizone, flubendiamide, lufenuron, cyantraniliprole, fipronil, pyridalyl, tetrachlorantranil, ethiprole, cyromanilide, teflufenoxanide, acetafenoxanide, metaflumizone or tolfenpyrad;
Figure FDA0003164525540000011
in the formula I, Z isFrom hydrogen, fluoro, chloro, bromo, iodo, cyano, C1-C3 haloalkyl, C1-C3 haloalkoxy or C1-C3 alkylsulfonyl, Q is selected from cyclopropyl; x is selected from hydrogen; y is1Is selected from bromine; y is2Selected from trifluoromethyl or trifluoromethoxy; r1Selected from fluorine; r2Selected from fluorine; r3And R4Each independently selected from hydrogen or C1-C3An alkyl group; m represents an integer of 0 to 5; n is 3; w1And W2Independently an oxygen atom;
the weight ratio of the effective component A to the effective component B is 160:1-1: 100.
2. The pharmaceutical composition containing the m-diamide compound as claimed in claim 1, wherein the active ingredient A is the m-diamide compound having the structure shown in formula II:
Figure FDA0003164525540000012
in the formula II, the reaction mixture is shown in the specification,
z is selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano-C1-C3 haloalkyl, C1-C3 haloalkoxy or C1-C3 alkylsulfonyl;
y is selected from trifluoromethyl or trifluoromethoxy;
r is selected from hydrogen or methyl.
3. The pharmaceutical composition containing the m-diamide compound according to claim 2, wherein in formula II,
z is selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, trifluoromethoxy, trifluoromethyl, methylsulfonyl or trifluoromethylsulfonyl;
y is selected from trifluoromethyl or trifluoromethoxy;
r is selected from hydrogen or methyl.
4. The pharmaceutical composition containing the m-diamide compound according to claim 1, wherein the m-diamide compound is any one or a combination of at least two of the following compounds 1-14:
Figure FDA0003164525540000013
Figure FDA0003164525540000021
Figure FDA0003164525540000031
5. the pharmaceutical composition containing the m-diamide compound as claimed in claim 1, wherein when the active ingredient B in the pharmaceutical composition containing the m-diamide compound is chlorantraniliprole, fluorobenzene bisamide, cyantraniliprole, tetrachloro-cyantraniliprole, tetrazolium amide, chlorofluoro-cyantraniliprole or cyclic bromotraniliprole, the weight ratio of the active ingredient A to the active ingredient B is 80: 1-1: 80.
6. The pharmaceutical composition containing the m-diamide compound as claimed in claim 1, wherein when the active ingredient B in the pharmaceutical composition containing the m-diamide compound is fluxapyroxamide, the weight ratio of the active ingredient A to the active ingredient B is 80: 1-1: 80.
7. The pharmaceutical composition containing the m-diamide compound as claimed in claim 1, wherein when the active ingredient B in the pharmaceutical composition containing the m-diamide compound is fipronil, ethiprole or acetoprole, the weight ratio of the active ingredient A to the active ingredient B is 60:1-1: 60.
8. The pharmaceutical composition containing the m-diamide compound as claimed in claim 1, wherein when the active ingredient B in the pharmaceutical composition containing the m-diamide compound is indoxacarb, metaflumizone, chlorfenapyr or tolfenpyrad, the weight ratio of the active ingredient A to the active ingredient B is 50:1-1: 50.
9. The pharmaceutical composition containing the m-diamide compound as claimed in claim 1, wherein when the active ingredient B in the pharmaceutical composition containing the m-diamide compound is lufenuron, methoxyfenozide or pyridalyl, the weight ratio of the active ingredient A to the active ingredient B is 50:1-1: 50.
10. The pharmaceutical composition containing the m-diamide compound according to claim 4, which comprises the following combinations;
the combination of the compound 1 and chlorantraniliprole in a weight ratio of 1:50, the combination of the compound 1 and methoxyfenozide in a weight ratio of 1:4,
the compound 2+ indoxacarb is combined according to the weight ratio of 1:20,
the combination of a compound 3+ indoxacarb in a weight ratio of 1:20, the combination of a compound 3+ chlorfenapyr in a weight ratio of 1:50, the combination of a compound 3 and metaflumizone in a weight ratio of 50:1-1:50,
the combination of a compound 4 and flubendiamide in a weight ratio of 1:40, the combination of a compound 4 and lufenuron in a weight ratio of 1:2, the combination of a compound 4 and cyantraniliprole in a weight ratio of 1:10,
the combination of a compound 5 and indoxacarb in a weight ratio of 1:20, the combination of a compound 5 and cyantraniliprole in a weight ratio of 1:4,
the combination of a compound 6 and cyantraniliprole in a weight ratio of 1:4, the combination of a compound 6 and fipronil in a weight ratio of 4:1, the combination of a compound 6 and pyridalyl in a weight ratio of 1:20,
the compound 7 and the tetrachloro-insect amide are combined in a weight ratio of 1:5, and the compound 7 and the ethiprole are combined in a weight ratio of 100: 1-1: 100;
the combination of a compound 8 and cyantraniliprole in a weight ratio of 1:12.5, the combination of the compound 8 and the cyclic cyantraniliprole in a weight ratio of 1:2, the combination of the compound 8 and the ethiprole in a weight ratio of 1:16, the combination of the compound 8 and the tebuconazole in a weight ratio of 1:80-160:1,
the compound 9 and the cyclic bromantraniliprole are combined in a weight ratio of 1:1, the compound 10 and the cyantraniliprole are combined in a weight ratio of 1:8, and the compound 9 and the fluxapyroxamide are combined in a weight ratio of 80: 1-1: 80;
the combination of a compound 10 and acetylfipronil in a weight ratio of 1:10, the combination of the compound 10 and metaflumizone in a weight ratio of 1:100, the combination of the compound 10 and tolfenpyrad in a weight ratio of 1:62.5,
the compound 11+ cyantraniliprole is combined according to the weight ratio of 1:3.2,
the compound 12+ cyclic bromoantraniliprole is combined in a weight ratio of 1:1, the compound 12+ metaflumizone is combined in a weight ratio of 1:100, and the compound 12 and lufenuron are combined in a weight ratio of 50:1-1: 50;
the compound 13+ cyantraniliprole is combined according to the weight ratio of 1:8,
the compound 14+ metaflumizone is combined in a weight ratio of 1: 100.
11. A pharmaceutical preparation, which comprises the pharmaceutical composition containing the m-diamide compound as claimed in any one of claims 1 to 10 and an agriculturally pharmaceutically acceptable adjuvant and/or carrier.
12. The pharmaceutical formulation of claim 11, wherein the agriculturally acceptable auxiliary comprises any one or a combination of at least two of a dispersing agent, a wetting agent, an emulsifying agent, a freezing point depressant, a thickening agent, a defoaming agent, a preservative, a stabilizing agent, or a coloring agent.
13. The pharmaceutical formulation of claim 11, wherein the carrier comprises a filler and/or a solvent.
14. The pharmaceutical formulation of claim 11, wherein the pharmaceutical formulation is in the form of a soluble solution, a soluble powder, a soluble granule, an emulsifiable concentrate, a wettable powder, an aqueous emulsion, a suspension, a dispersible oil suspension, a water dispersible granule, a microcapsule suspension, a granule, a microemulsion, a suspoemulsion, a microcapsule suspension-suspension, an ultra-low volume liquid formulation, a hot fogging concentrate, a spreading oil formulation, a suspended seed coating formulation, a dry seed treatment formulation, a suspension seed treatment formulation, a soluble seed treatment powder, a dispersible seed treatment powder, a seed treatment emulsion, or a liquid seed treatment formulation.
15. The pharmaceutical preparation according to claim 11, wherein the pharmaceutical preparation is in the form of a soluble 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, an ultra-low volume liquid, a hot fogging concentrate, a suspended seed coating or a seed treatment dispersible powder.
16. The pharmaceutical preparation according to claim 11, wherein the pharmaceutical composition comprising the m-diamide compound is contained in an amount of 0.01 to 99% by weight of the pharmaceutical preparation.
17. The pharmaceutical preparation according to claim 11, wherein the content of the pharmaceutical composition containing the m-diamide compound in the pharmaceutical preparation is 0.5-95% by weight.
18. Use of the pharmaceutical composition according to any one of claims 1 to 10 or the pharmaceutical formulation according to any one of claims 11 to 17 for controlling plant diseases or insect pests in agriculture, forestry, horticulture.
19. Use according to claim 18, wherein the application is carried out by spraying, pouring or seed treatment.
20. A method for controlling plant diseases and insect pests, which is characterized by comprising the following steps: applying an effective dose of the pharmaceutical composition containing the m-diamide compound as claimed in any one of claims 1 to 10 or the pharmaceutical preparation as claimed in any one of claims 11 to 17 to a medium in which a plant pest or growth thereof is to be controlled.
21. The method of claim 20, wherein the effective dose is 10-1000g per hectare.
22. The method of claim 20, wherein the effective dose is 15-900g per hectare.
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