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CN118125938B - Amide compound and application thereof - Google Patents

Amide compound and application thereof Download PDF

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Publication number
CN118125938B
CN118125938B CN202410559377.4A CN202410559377A CN118125938B CN 118125938 B CN118125938 B CN 118125938B CN 202410559377 A CN202410559377 A CN 202410559377A CN 118125938 B CN118125938 B CN 118125938B
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formula
compound
optionally substituted
halogen
alkyl
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CN118125938A (en
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Hangzhou Qinong Biotechnology Co ltd
Kai Nong Biotechnology Beijing Co ltd
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Hangzhou Qinong Biotechnology Co ltd
Kai Nong Biotechnology Beijing Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
    • C07C237/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having nitrogen atoms of amino groups bound to the carbon skeleton of the acid part, further acylated
    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/04—Insecticides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/14—Preparation of carboxylic acid amides by formation of carboxamide groups together with reactions not involving the carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C07C381/10—Compounds containing sulfur atoms doubly-bound to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Zoology (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Agronomy & Crop Science (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Insects & Arthropods (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention provides an amide compound shown as a formula (I), which has an excellent insecticidal effect on pests (such as peach aphids) in the agricultural and horticultural field.

Description

Amide compound and application thereof
Technical Field
The invention belongs to the field of agricultural pesticides, and particularly relates to an amide compound and application thereof.
Background
In crop production in agriculture, gardening, and the like, losses caused by pests and the like are still large, and pests having resistance to existing drugs are liable to occur. From the viewpoints of environmental biological influence, labor saving and the like, development of an agricultural and horticultural insecticide which has a novel action, has little influence on natural enemy beneficial insects, has osmotic transfer activity and the like is of great significance.
The amide compound is used for sterilization, inhibits mitochondrial respiration mainly by blocking electron transfer of succinic dehydrogenase in respiratory chain, and has the characteristics of broad sterilization spectrum and good sterilization effect. Meanwhile, the amide compounds are reported in the prior art to have better insecticidal effect, and are widely applied to agriculture, forestry and residential pest control.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides an amide compound represented by the following formula (I), a nitrogen oxide, a stereoisomer, a tautomer, an isotopic label, a solvate, a polymorph, a metabolite, an ester, a prodrug or a pesticidally acceptable salt thereof;
Wherein R 1 is selected from H, halogen, C 1-10 alkyl optionally substituted with one, two or more R a, C 1-10 alkoxy optionally substituted with one, two or more R a, C 3-10 cycloalkyl optionally substituted with one, two or more R a, 3-10 membered heterocyclyl optionally substituted with one, two or more R a, C 1-10 alkylene-C 3-10 cycloalkyl optionally substituted with one, two or more R a, C 1-10 alkylene-3-10 membered heterocyclyl optionally substituted with one, two or more R a;
R 2 is selected from H, halogen, C 1-10 alkyl optionally substituted with one, two or more R a, C 1-10 alkoxy optionally substituted with one, two or more R a;
R 3 is selected from H, halogen, C 1-10 alkyl optionally substituted with one, two or more R a, C 1-10 alkoxy optionally substituted with one, two or more R a;
R 4 is selected from H, halogen, C 1-10 alkyl optionally substituted with one, two or more R a, C 1-10 alkoxy optionally substituted with one, two or more R a;
R 5 is selected from the group consisting of-C 2-10 alkynyl-C 3-10 cycloalkyl, -C 2-10 alkynyl-C 3-10 heterocycloalkyl, ; The-C 2-10 alkynyl-C 3-10 cycloalkyl, -C 2-10 alkynyl-C 3-10 heterocycloalkyl is optionally substituted with one, two or more R a;
Y 1、Y2、Y3、Y4、Y5, which are identical or different, are independently of one another selected from H, halogen, C 1-10 alkyl optionally substituted by one, two or more R a, C 1-10 alkoxy optionally substituted by one, two or more R a;
a 1、A2、A3、A4 are identical or different and are independently selected from CH and N;
m, n are the same or different and are independently selected from natural numbers of 0 to 4 (e.g., 0, 1,2, 3, 4);
r a is selected from H, halogen, C 1-10 alkyl optionally substituted with one, two or more R b, C 1-10 alkoxy optionally substituted with one, two or more R b;
R b is selected from H, halogen;
r s is selected from H, halogen, C 1-10 alkyl optionally substituted with one, two or more R b;
R t is selected from H, halogen, C 1-10 alkyl optionally substituted with one, two or more R a, C 1-10 alkoxy optionally substituted with one, two or more R a; representing a linking group.
According to an embodiment of the invention, R 1 is selected from H, halogen, C 1-6 alkyl optionally substituted with one, two or more R a, C 1-6 alkoxy optionally substituted with one, two or more R a, C 3-8 cycloalkyl optionally substituted with one, two or more R a, 3-8 membered heterocyclyl optionally substituted with one, two or more R a, C 1-6 alkylene-C 3-8 cycloalkyl optionally substituted with one, two or more R a, C 1-6 alkylene-3-8 membered heterocyclyl optionally substituted with one, two or more R a; Preferably, R 1 is selected from H, halogen, C 1-4 alkyl optionally substituted with one, two or more R a, C 1-4 alkoxy optionally substituted with one, two or more R a, C 3-6 cycloalkyl optionally substituted with one, two or more R a, 3-6 membered heterocyclyl optionally substituted with one, two or more R a, C 1-4 alkylene-C 3-6 cycloalkyl optionally substituted with one, two or more R a, C 1-4 alkylene-3-6 membered heterocyclyl optionally substituted with one, two or more R a; illustratively, R 1 is selected from methyl, ethyl, propyl, -methylene-cyclopropyl, -ethylene-cyclopropyl, -methylene-ethylene oxide, -ethylene oxide.
According to an embodiment of the invention, R 2 is selected from H, halogen, C 1-6 alkyl optionally substituted with one, two or more R a, C 1-6 alkoxy optionally substituted with one, two or more R a; preferably, R 2 is selected from H, halogen, C 1-4 alkyl optionally substituted with one, two or more R a, C 1-4 alkoxy optionally substituted with one, two or more R a; illustratively, R 2 is selected from H, fluoro, chloro, bromo, iodo, methyl, ethyl, propyl.
According to an embodiment of the invention, R 3 is selected from H, halogen, C 1-6 alkyl optionally substituted with one, two or more R a, C 1-6 alkoxy optionally substituted with one, two or more R a; preferably, R 3 is selected from H, halogen, C 1-4 alkyl optionally substituted with one, two or more R a, C 1-4 alkoxy optionally substituted with one, two or more R a; illustratively, R 3 is selected from H, fluoro, chloro, bromo, iodo, methyl, ethyl, propyl.
According to an embodiment of the invention, R 4 is selected from H, halogen, C 1-6 alkyl optionally substituted with one, two or more R a, C 1-6 alkoxy optionally substituted with one, two or more R a; preferably, R 4 is selected from H, halogen, C 1-4 alkyl optionally substituted with one, two or more R a, C 1-4 alkoxy optionally substituted with one, two or more R a; illustratively, R 4 is selected from H, fluoro, chloro, bromo, iodo, methyl, ethyl, propyl.
According to an embodiment of the invention, R 5 is selected from the group consisting of-C 2-8 alkynyl-C 3-8 cycloalkyl, -C 2-8 alkynyl-C 3-8 heterocycloalkyl,; Preferably, R 5 is selected from the group consisting of-C 2-6 alkynyl-C 3-6 cycloalkyl, -C 2-6 alkynyl-C 3-6 heterocycloalkyl,; Further preferably, R 5 is selected from the group consisting of-C 2-4 alkynyl-C 3-5 cycloalkyl, -C 2-4 alkynyl-C 3-5 heterocycloalkyl,; By way of example only, and in an illustrative, R 5 is selected from-C 2 alkynyl-C 3 cycloalkyl (-ethynyl-cyclopropenyl), -C 2 alkynyl-C 3 heterocycloalkyl (-ethynyl-glycidylyl),。
According to an embodiment of the invention, R s is selected from H, halogen, C 1-6 alkyl optionally substituted by one, two or more R b; preferably, R s is selected from H, halogen, C 1-4 alkyl optionally substituted with one, two or more R b; illustratively, R s is selected from H, fluoro, chloro, bromo, iodo, methyl, ethyl, propyl.
According to an embodiment of the invention, R t is selected from H, halogen, C 1-6 alkyl optionally substituted with one, two or more R b, C 1-6 alkoxy optionally substituted with one, two or more R b; preferably, R t is selected from H, halogen, C 1-4 alkyl optionally substituted with one, two or more R b, C 1-4 alkoxy optionally substituted with one, two or more R b; illustratively, R t is selected from methyl, ethyl, propyl, trifluoromethyl, trifluoroethyl.
According to an embodiment of the invention, at least one of A 1、A2、A3、A4 is selected from N; preferably, a 1、A4 is selected from CH, and at least one of a 2、A3 is selected from N; illustratively, a 1、A2、A4 is selected from CH and a 3 is selected from N.
According to an embodiment of the invention, a 1、A2、A3、A4 is each selected from CH.
According to an embodiment of the invention, Y 1、Y2、Y3、Y4、Y5, equal to or different from each other, are selected from H, halogen, C 1-6 alkyl optionally substituted by one, two or more R a, C 1-6 alkoxy optionally substituted by one, two or more R a; Preferably, Y 1、Y2、Y3、Y4、Y5, equal to or different from each other, are selected from H, halogen, C 1-4 alkyl optionally substituted with one, two or more R a, C 1-4 alkoxy optionally substituted with one, two or more R a; Illustratively, Y 1、Y2、Y3、Y4、Y5, the same or different, are independently selected from H, fluoro, chloro, bromo, iodo, methyl, ethyl, propyl, trifluoromethyl, trifluoroethyl, butyl (or isobutyl) substituted with one, two or more R a, propyl substituted with one, two or more R a; Illustratively, Y 1 is selected from trifluoromethyl; illustratively, Y 2 is selected from H; illustratively, Y 3 is selected from the group consisting of-CHF-CH (CF 3)2、-CHF(CF3)-CF3、-CF(CF3)2; Illustratively, Y 4 is selected from H; illustratively, Y 5 is selected from Br.
According to an embodiment of the invention, R a is selected from H, halogen, C 1-6 alkyl optionally substituted with one, two or more R b, C 1-6 alkoxy optionally substituted with one, two or more R b; preferably, R a is selected from H, halogen, C 1-4 alkyl optionally substituted with one, two or more R b, C 1-4 alkoxy optionally substituted with one, two or more R b; illustratively, R a is selected from H, fluoro, chloro, bromo, iodo, methyl, ethyl, propyl.
According to an embodiment of the invention, R b is selected from H, fluoro, chloro, bromo, iodo.
According to an embodiment of the present invention, the amide compound represented by the above formula (I) is selected from compounds represented by the following formula (II):
Wherein ,R1、R2、R3、R4、Y1、Y2、Y3、Y4、Y5、m、n has the above definition.
According to an embodiment of the present invention, the amide compound represented by the above formula (I) is selected from compounds represented by the following formula (III):
Wherein ,R1、R2、R3、R4、Y1、Y2、Y3、Y4、Y5、m、n、Rt has the above definition.
According to an embodiment of the present invention, the amide compound represented by formula (I) is selected from the following specific compounds:
。
The invention also provides a preparation method of the amide compound shown in the formula (I), which comprises the following steps:
Reacting a compound shown in a formula (IV) with a compound shown in a formula (V) under the conditions of alkali and a condensing agent to prepare a compound shown in a formula (I);
The reaction formula is as follows:
；
Wherein ,R1、R2、R3、R4、R5、Y1、Y2、Y3、Y4、Y5、A1、A2、A3、A4、m、n has the foregoing definition;
x is selected from OH or halogen (e.g., fluorine, chlorine, bromine, iodine).
According to an embodiment of the present invention, the condensing agent is selected from any one, two or more of HATU (2- (7-azabenzotriazol) -N, N' -tetramethyluronium hexafluorophosphate), HOBT (1-hydroxybenzotriazole), pyBOP (benzotriazol-1-yl-oxy-tripyrrolidinylphosphorus hexafluorophosphate), EDCI (carbodiimide).
According to an embodiment of the present invention, the base is selected from organic or inorganic bases, exemplified by triethylamine, pyridine, potassium carbonate, sodium carbonate, and the like.
According to an embodiment of the invention, the reaction temperature is 20-30 ℃.
According to an embodiment of the invention, the reaction is carried out in a solvent; preferably, the solvent is selected from tetrahydrofuran.
The invention also provides application of an intermediate compound shown in the following formula (IV) in preparation of the compound shown in the formula (I):
；
Wherein R 1、R2、R3、Y1、Y2、Y3、Y4、Y5, m have the above definition.
The invention also provides application of the intermediate compound shown in the following formula (III) in preparing the compound shown in the formula (I):
；
Wherein R 4、R5、A1、A2、A3、A4, n have the foregoing definition;
x is selected from OH or halogen (e.g., fluorine, chlorine, bromine, iodine).
The invention also provides a composition comprising an amide compound represented by the above formula (I), a nitrogen oxide, a stereoisomer, a tautomer, an isotopic label, a solvate, a polymorph, a metabolite, an ester, a prodrug or a pesticidally acceptable salt thereof, and at least one auxiliary agent.
According to an embodiment of the invention, the auxiliary agent is selected from one, two or more of a surfactant, a solid diluent and a liquid diluent.
The present invention also provides an agricultural/horticultural insecticide comprising an amide compound represented by the above formula (I), a nitrogen oxide, a stereoisomer, a tautomer, an isotopic label, a solvate, a polymorph, a metabolite, an ester, a prodrug or a pesticidally acceptable salt thereof as an active ingredient.
According to an embodiment of the present invention, the composition or agro-horticultural insecticide comprises the following components: amide compounds shown in the formula (I) or salts acceptable in pesticides, toluene, MDF and fast T;
Preferably, 10 parts of amide compounds shown in the formula (I) or pesticide acceptable salts thereof, 75 parts of toluene, 10 parts of DMF and 5 parts of fast T;
Preferably, the composition or agrohorticultural insecticide is a emulsifiable concentrate.
The invention also provides an application of the amide compound shown in the formula (I), nitrogen oxides, stereoisomers, tautomers, isotopic labels, solvates, polymorphs, metabolites, esters, prodrugs or pesticide acceptable salts thereof or the composition in controlling plant pests.
The invention also provides a use method of the agricultural and horticultural insecticide, which comprises treating plants or soil with an effective amount of the amide compound shown in the formula (I), nitrogen oxides, stereoisomers, tautomers, isotopic labels, solvates, polymorphs, metabolites, esters, prodrugs or pesticidally acceptable salts thereof.
The present invention also provides a method for treating plant propagation material, which comprises applying an amide compound represented by the above formula (I), a nitrogen oxide, a stereoisomer, a tautomer, an isotopic label, a solvate, a polymorph, a metabolite, an ester, a prodrug or a pesticidally acceptable salt thereof, or a composition or an insecticide thereof to a plant propagation material.
The invention also provides a method for the therapeutic or prophylactic control of plant or crop pests, which comprises applying an amide compound of formula (I), a nitrogen oxide, a stereoisomer, a tautomer, an isotopic label, a solvate, a polymorph, a metabolite, an ester, a prodrug or a pesticidally acceptable salt or a composition or an insecticide to seeds, plants or plant fruits or to soil in which plants are growing or are in need of growing.
The amide compounds shown in the formula (I), nitrogen oxides, stereoisomers, tautomers, isotopic labels, solvates, polymorphs, metabolites, esters, prodrugs or pesticidally acceptable salts thereof provided by the invention can be generally used as active ingredients in compositions (i.e. preparations), and generally comprise a pharmaceutically acceptable surfactant and a carrier. The carrier may be a solid carrier or a liquid carrier.
Suitable solid carriers include natural or synthetic clays and silicates, such as natural silica and diatomaceous earth; magnesium silicate, such as talc; magnesium aluminum silicate such as kaolinite, kaolin, montmorillonite and mica; white carbon black, calcium carbonate and light calcium carbonate; calcium sulfate; limestone; sodium sulfate; ammonium salts such as ammonium sulfate, hexamethylenediamine, urea, and the like.
The liquid carrier includes water and an organic solvent, which can also be used as an adjuvant or an anti-freezing additive when water is used as a solvent or diluent. Useful liquefied gaseous fillers or carriers are those liquids which are gaseous at standard temperature and standard pressure, for example aerosol propellants such as halogenated hydrocarbons, and butane, propane, nitrogen, carbon dioxide and the like.
Suitable organic solvents include aromatic hydrocarbons such as benzene, xylene, toluene, and the like; chlorinated hydrocarbons such as chlorobenzene, vinyl chloride, chloroform, methylene chloride, etc.; aliphatic hydrocarbons such as petroleum fractions, cyclohexane, light mineral oils; alcohols such as isopropanol, butanol, ethylene glycol, propylene glycol, cyclohexanol, and the like; and their ethers and esters; ketones, such as acetone, cyclohexanone, dimethylformamide and N-methyl-pyrrolidone; vegetable oils such as soybean oil, rapeseed oil, and cottonseed oil, among others.
Suitable surfactants (adjuvants, emulsifiers, dispersants, protective colloids, wetting agents and binders) include all customary ionic and nonionic substances, for example ethoxylated nonylphenols, polyalkylene glycol ethers of straight-chain or branched alcohols, reaction products of alkylphenols with ethylene oxide and/or propylene oxide, reaction products of fatty acid amines with ethylene oxide and/or propylene oxide, and also fatty acid esters, alkyl sulfonates, alkyl sulfates, alkyl ether phosphates, aryl sulfates, ethoxylated arylalkyl phenols (such as tristyryl-phenol-ethoxylates), and ethoxylated and propoxylated arylalkyl phenols, sulfated and phosphated arylalkyl phenol-ethoxylates and-ethoxy and-propoxy oxides. Other examples are natural and synthetic water-soluble polymers, such as lignosulfonates, gelatin, gum arabic, phospholipids, starches, hydrophobically modified starches and cellulose derivatives, in particular cellulose esters and cellulose ethers, and also polyvinyl alcohol, polyvinyl acetate, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid and copolymers of (meth) acrylic acid and (meth) acrylic esters, and copolymers of methacrylic acid and methacrylic esters neutralized by alkali metal hydroxides, and optionally substituted naphthalenesulfonates condensed with formaldehyde. The presence of a surfactant is necessary if one of the active ingredients and/or one of the inert carriers is insoluble in water and the application takes place in water.
The composition or agricultural or horticultural insecticide of the present invention may be prepared by a general method. For example, the active substances are mixed with liquid solvents and/or solid carriers, while surfactants such as emulsifiers, dispersants, stabilizers, wetting agents, and also other auxiliaries such as binders, defoamers, foaming agents, antioxidants, crystallization inhibitors, viscosity regulators, suspending agents, spray droplet regulators, pigments, neutralizing agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, permeation aids, micronutrients, dispersants, thickeners, freezing point depressants, biocides, etc. are added.
The compositions of the present invention or agrohorticultural pesticides may be applied in the form of their formulations or in the form of use prepared therefrom, such as aerosols, capsule suspensions, cold mist concentrates (cold-fogging concentrate), hot mist concentrates, encapsulated granules, fine granules, flowable concentrates for seed treatment (flowable concentrate), ready-to-use solutions, dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, large granules, microparticles, oil-dispersible powders, oil-miscible flowable concentrates, oil-miscible liquids, aerosols (under pressure), gas-generating products, foams, pastes, suspension concentrates, soluble concentrates, suspension concentrates, wettable powders, soluble powders, dusts and granules, water-soluble and water-dispersible granules, water-soluble or water-dispersible powders for seed treatment, wettable powders, active substance-impregnated natural and synthetic substances, and microcapsules in polymers and seed coating materials, and hot mist ULV (ultra low volume).
The compositions or agrohorticultural insecticides of the present invention may also contain other components, for example other bactericides, insecticides, herbicides, plant growth regulators, attractants, acaricides, nematicides, fertilizers, safeners and the like, which can be formulated with liquid fertilizers or solid, granular fertilizer carriers (such as ammonium nitrate, urea and the like) or mixed with fine sand or soil.
The treatment of plants and plant parts with compositions comprising the compounds according to the invention or agrohorticultural pesticides can be carried out directly or by customary treatment methods, for example by dipping, spraying, atomizing, irrigating, evaporating, dusting, atomizing, broadcasting, foaming, painting, coating, watering (pouring), instilling. For plant propagation material, in particular for seeds, it is also possible to treat the seed by dry seed treatment, wet seed treatment, slurry treatment, crusting, coating with one or more coatings, etc. The active substance can also be effectively utilized by an ultra low volume method or injection of a composition comprising the compound of the present invention or an agrohorticultural insecticide or the compound of the present invention itself into the soil.
The agricultural/horticultural insecticide containing the amide compound represented by the formula (I) of the present invention as an active ingredient is suitable for controlling various agricultural/forestry, horticultural, grain-storing pests, sanitary pests or nematodes which cause disasters to rice, fruit trees, vegetables, other crops and flowers. Non-limiting examples of pests that control or prevent attack by useful plants or beneficial plants include:
Examples of lepidopteran pests include, for example, a green thorn moth, a citrus butterfly, a red bean moth, a sedge armyworm, a fall webworm, an asian corn borer, a yellow cutworm, a sugarcane yellow borer, huang Fengdie, a yellow borer, and the like;
Examples of the hemipteran pests include rice green Chinese toon, mealy bugs, pea aphids (Acyrthosiphon pisum), oak leafhoppers, citrus scale insects, inula chrysanthemi, yellow green swan, soybean aphids, bemisia tabaci, corn aphids, omnipotent leafhoppers, pine-like leafhoppers, peach aphids, apple wood louses, apple She Mangchun (Heterocordylusflavipes), apple tumor aphids (Myzus malisuctus), apple aphids, apple leafhoppers, apple aphids, cotton aphids, and the like;
Examples of the coleopteran pests include green bean weevil, green weevil, yellow leaf beetle, huang Xing longhorned, yellow longhorn beetle, corn weevil, red larch, rice weevil, potato leaf beetle, beet flea beetle, dahlia beetle, cucumber flea beetle, and pine beetle;
Examples of the dipteran pest include culex, leaf miner, house fly, melon fly, cherry fruit fly, anopheles sinensis, apple fruit fly, and the like;
examples of Hymenoptera pests include wasps, galls, black-back white wasps, rose wasps, japanese turnip wasps, leaf cutting ants, fire ants, and the like;
Examples of the orthoptera (Orthoptera) pests include southern straw general name for grass hoppers and crickets, small rice locust, small wing rice locust, migratory locust, short wing rice locust, and the like;
examples of the thysanoptera pests include thrips oryzae, thrips oryzae Huang Jima, thrips citri, thrips lilii, and the like;
examples of the acarina pests include spider mites such as hawkthorn, spider mites, citrus mites, and apple mites;
examples of the isoptera pests include termites such as termites from the family, wet carpentry termites from the japan, termites from the genus termitid (Reticulitermes speratus) from the species termitid;
Examples of the blattaria pests include periplaneta americana, german cockroach, oriental cockroach, japanese cockroach, american cockroach, and the like;
examples of the order of the fleas include human fleas, cat-head fleas, and chicken fleas;
Examples of nematodes include strawberry-bud nematodes, rice-stem nematodes, northern root-knot nematodes, southern root-knot nematodes, soybean cyst nematodes, and the like;
examples of mollusks include ampullaria gigas, snails Huangyu, and snails.
Since the compound of the present invention has a remarkable control effect on the pests that cause disasters in paddy field crops, upland field crops, fruit trees, vegetables, other crops, flowers, etc., the desired effect of the agricultural and horticultural insecticide of the present invention can be exhibited by applying the compound to a cultivation carrier or the like such as seeds, paddy field water, stems and leaves, soil of seedling raising facilities, paddy fields, upland fields, fruit trees, vegetables, other crops, flowers, etc., before or when the pest generation is confirmed according to the period in which the pest generation is predicted. The preferred mode of use is: the application method of the compound of the present invention, that is, the application method utilizing systemic property, is absorbed by roots via or without soil by applying to seedling raising soil of crops, flowers and the like, planting pit soil at the time of transplanting, plant roots, irrigation water, cultivation water in hydroponics and the like.
The useful plants for which the composition of the present invention or agricultural and horticultural insecticide can be used are not particularly limited, and examples thereof include cereals (for example, rice, barley, wheat, rye, oat, corn, etc.), beans (soybean, red bean, broad bean, pea, kidney bean, peanut, etc.), fruit trees, fruits (apple, citrus, pear, grape, peach, plum, cherry, walnut, chestnut, almond, banana, etc.), she vegetables and fruits (cabbage, tomato, spinach, broccoli, lettuce, onion (shallot, winter onion, etc.), green pepper, eggplant, strawberry, pepper, okra, leek, etc.), root vegetables (carrot, potato, sweet potato, taro, radish, turnip, lotus root, burdock, garlic, hot leek, etc.), processed crops (cotton, hemp, lotus root, burdock, garlic, hot leek, etc sugar radish, hop, sugarcane, beet, olive, rubber, coffee, tobacco, tea, etc.), melons (pumpkin, cucumber, watermelon, melon, etc.), grasses (cogongrass, sorghum, timothy, clover, alfalfa, etc.), grasses (korea grass, bentgrass, etc.), spices, etc. ornamental crops (lavender, rosemary, thyme, parsley, pepper, ginger, etc.), flowers (chrysanthemum, rose, carnation, orchid, tulip, lily, etc.), garden trees (ginkgo, cherry, coral, etc.), woods (fir, spruce, pine, cypress, fir, juniper, eucalyptus, etc.), etc.
Within the scope of the present invention, useful plants include the following plant species: grains (wheat, barley, rye, oats, rice, corn, sorghum and related species); beet (sugar beet); pome, stone fruit, and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, and blackberries); leguminous plants (lentils, bingo, peas, soybeans); oil crops (rape, mustard, olives, sunflowers, coconuts, castor oil plants, cocoa beans, groundnuts or soybeans); melon plants (pumpkin, cucumber, melon); fiber plants (cotton, flax, hemp, jute); citrus fruits (orange, lemon, grapefruit, mandarin); vegetables (spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato, red pepper); laures (avocado, camphor) or plants, such as tobacco, nuts, coffee, eggplant, sugar cane, tea, pepper, grape vine, hops, bananas and natural rubber plants, as well as turf, ornamental and forest plants, such as flowers, shrubs, broad-leaved trees or evergreen trees, such as conifers, and plant propagation material.
The composition comprising the compound of the present invention or the agricultural or horticultural insecticide is simple to use and the composition comprising the compound of the present invention is applied to the pest or a growing medium thereof. The dosage of the composition of the present invention to be applied varies depending on weather conditions, dosage forms, application timing, application method, application area, target insect pest, target crop, etc.
Advantageous effects
The invention provides an amide compound shown as a formula (I), which has an excellent insecticidal effect on pests (such as peach aphids) in the agricultural and horticultural field.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated elements or steps without excluding other material elements or steps.
In addition, numerous specific details are set forth in the following description in order to provide a better illustration of the invention.
It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In some embodiments, materials, methods, means, etc. well known to those skilled in the art are not described in detail in order to highlight the gist of the present invention.
The numerical ranges recited in the specification and claims are equivalent to at least each specific integer number recited therein unless otherwise stated. For example, the numerical range "1 to 40" corresponds to each of the integer numbers 1, 2, 3, 4, 5,6,7,8, 9, 10 in the numerical range "1 to 10", and each of the integer numbers 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40 in the numerical range "11 to 40". It is to be understood that "more" in one, two or more as used herein in describing substituents shall mean an integer of ≡3, such as 3, 4, 5,6,7,8, 9 or 10.
In general, the term "substituted" means that one or more hydrogen atoms in a given structure are replaced with a specific substituent. Further, when the group is substituted with 1 or more of the substituents, the substituents are independent of each other, that is, the 1 or more substituents may be different from each other or the same. Unless otherwise indicated, a substituent group may be substituted at each substitutable position of the substituted group. When more than one position in a given formula can be substituted with one or more substituents selected from a particular group, then the substituents may be the same or different at each position.
In addition, unless explicitly indicated otherwise, the expression "… is independently selected" as used in the present invention is to be understood broadly to mean that the individual entities described are independent of each other and may be independently selected from the same or different specific groups. In more detail, the description that "… is independently selected" may mean that specific options expressed between the same symbols in different groups do not affect each other; it may also be expressed that specific options expressed between the same symbols in the same group do not affect each other.
In the various parts of the present specification, substituents of the presently disclosed compounds are disclosed in terms of the type or scope of groups. It is specifically noted that the present invention includes each individual subcombination of the individual members of these group classes and ranges. For example, the term "C 1-6 alkyl" particularly refers to independently disclosed C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, or C 6 alkyl.
In the various parts of the invention, linking substituents are described. When the structure clearly requires a linking group, the markush variables recited for that group are understood to be linking groups. For example, if the structure requires a linking group and the markush group definition for that variable enumerates an "alkyl" or "aryl" group, it will be understood that the "alkyl" or "aryl" represents a linked alkylene group or arylene group, respectively.
If the compounds of formula (I) according to the invention are capable of forming geometric isomers, for example E/Z isomers, both pure isomers and mixtures thereof can be applied in the compositions according to the invention.
If the compounds of the formula (I) according to the invention have one or more chiral centers and are therefore present as enantiomers or diastereomers, pure enantiomers, racemates, diastereomers may be used in the compositions according to the invention.
When the compounds of the invention can exist in tautomeric forms, the compounds mentioned above and below are to be understood as also including the corresponding tautomeric forms, where applicable, even if these tautomeric forms are not explicitly mentioned in each case.
Any asymmetric atom (e.g., carbon, etc.) of the disclosed compounds may exist in racemic or enantiomerically enriched form, such as in the (R) -, (S) -or (R, S) -configuration.
"Stereoisomers" refer to compounds having the same chemical structure but different arrangements of atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformational isomers (rotamers), geometric isomers (cis/trans), atropisomers, and the like.
"Enantiomer" refers to two isomers of a compound that do not overlap but are in mirror image relationship to each other.
"Diastereoisomers" refers to stereoisomers which have two or more chiral centers and whose molecules are not mirror images of each other. Diastereomers have different physical properties, such as melting point, boiling point, spectral properties, and reactivity. The diastereomeric mixture may be separated by high resolution analytical procedures such as electrophoresis and chromatography, e.g., HPLC.
Any asymmetric atom (e.g., carbon, etc.) of the disclosed compounds may exist in racemic or enantiomerically enriched form, such as in the (R) -, (S) -or (R, S) -configuration. In certain embodiments, each asymmetric atom has at least 0% enantiomeric excess, at least 60% enantiomeric excess, at least 70% enantiomeric excess, at least 80% enantiomeric excess, at least 90% enantiomeric excess, at least 95% enantiomeric excess, or at least 99% enantiomeric excess in the (R) -or (S) -configuration.
The resulting mixture of any stereoisomers may be separated into pure or substantially pure geometric isomers, enantiomers, diastereomers, e.g., by chromatography and/or fractional crystallization, depending on the differences in the physicochemical properties of the components.
The term "tautomer" refers to structural isomers having different energies that can be interconverted by a low energy barrier (low energy barrier). If tautomerism is possible (e.g., in solution), chemical equilibrium of the tautomers can be achieved. For example, proton tautomer (proton tautomer) (also known as proton transfer tautomer (prototro pictautomer)) includes interconversions by proton transfer, such as keto-enol isomerisation and imine-enamine isomerisation. Valence tautomers (valen cetautomer) include interconversions by recombination of some of the bond-forming electrons. Specific examples of keto-enol tautomerism are tautomerism of pentane-2, 4-dione and 4-hydroxypent-3-en-2-one tautomer. Another example of tautomerism is phenol-ketone tautomerism. One specific example of phenol-ketone tautomerism is the interconversion of pyridin-4-ol and pyridin-4 (1H) -one tautomers. Unless otherwise indicated, all tautomeric forms of the compounds of the invention are within the scope of the invention.
"Nitroxide" in the present invention means that when a compound contains several amine functions, 1 or more than 1 nitrogen atom can be oxidized to form an N-oxide. Specific examples of N-oxides are N-oxides of tertiary amines or N-oxides of nitrogen atoms of nitrogen-containing heterocycles. The corresponding amine may be treated with an oxidizing agent such as hydrogen peroxide or a peracid (e.g., peroxycarboxylic acid) to form an N-oxide (see Advanced Organic Chemistry, WILEY INTERSCIENCE, 4 th edition, jerry March, pages). In particular, the N-oxides can be prepared by the method L.W.Deady (Syn.Comm.1977, 7, 509-514) in which an amine compound is reacted with m-chloroperoxybenzoic acid (MCPBA), for example in an inert solvent such as methylene chloride.
The term "isotopic label" includes, but is not limited to, compounds of the present invention labeled with isotopes of hydrogen, carbon, nitrogen, oxygen, fluorine, sulfur, and chlorine (e.g., 2H,3H,13C,14C,15N,18O,17O,18F,35 S and 36 Cl). Isotopically-labeled compounds of the present invention are useful in the determination of the tissue distribution of a compound, prodrug thereof, and metabolite thereof; preferred isotopes for use in such assays include 3 H and 14 C. Furthermore, in some cases, substitution with heavier isotopes, such as deuterium (2H or D), may afford increased metabolic stability, which may afford therapeutic advantages such as increased in vivo half-life or reduced dosage requirements. Isotopically-labeled compounds of the present invention can generally be prepared according to the methods described herein by substituting an isotopically-labeled reagent for a non-isotopically-labeled reagent.
The term "prodrug" as used herein means a compound that is converted in vivo to a compound of formula (I). Such conversion is effected by hydrolysis of the prodrug in the blood or enzymatic conversion to the parent structure in the blood or tissue. The prodrug of the invention can be esters, and in the prior invention, the esters can be phenyl esters, aliphatic (C 1-24) esters, acyloxymethyl esters, carbonic esters, carbamates and amino acid esters as the prodrugs. For example, one compound of the invention may contain a hydroxyl group, i.e., it may be acylated to provide the compound in a prodrug form. Other prodrug forms include phosphates, such as those obtained by phosphorylation of a hydroxyl group on the parent. For a complete discussion of prodrugs, reference may be made to the following documents ：T. Higuchiand V. Stella, Pro-drugsas Novel Delivery Systems, Vol.14 of the A.C.S. Symposium Series, Edward B. Roche, ed., Bioreversible Carriersin Drug Design, American Pharmaceutical Associationand Pergamon Press, 1987, J. Rautioetal., Prodrugs: Designand Clinical Applications, Nature Review Drug Discovery, 2008, 7, 255-270, and S. J. Heckeretal., Prodrugs of Phosphatesand Phosphonates, Journal of Medicinal Chemistry, 2008, 51, 2328-2345.
The term "metabolite" as used herein refers to a product obtained by metabolizing a specific compound or salt thereof in vivo. The metabolites of a compound may be identified by techniques well known in the art and their activity may be characterized by employing the assay methods as described herein. Such products may be obtained by oxidation, reduction, hydrolysis, amidization, deamination, esterification, degreasing, enzymatic cleavage, etc. of the administered compound. Accordingly, the present invention includes metabolites of compounds, including metabolites produced by contacting a compound of the present invention with a mammal for a period of time sufficient.
"Solvate" according to the present invention refers to an association of one or more solvent molecules with a compound according to the present invention. Solvents that form solvates include, but are not limited to, water, isopropanol, ethanol, methanol, dimethylsulfoxide, ethyl acetate, acetic acid, and aminoethanol. The term "hydrate" refers to an association of solvent molecules that are water.
The term "ester" as used herein refers to an in vivo hydrolysable ester formed from a compound containing a hydroxyl or carboxyl group. Such esters are, for example, pharmaceutically acceptable esters which hydrolyze in the human or animal body to produce the parent alcohol or acid. The compounds of formula (I) of the present invention contain a carboxyl group which may form an in vivo hydrolysable ester with suitable groups including, but not limited to, alkyl, arylalkyl and the like.
If the compounds of the formula I according to the invention have functional groups which can be ionized, they can also be used in the form of their agriculturally acceptable salts or mixtures thereof.
Suitable are generally salts of those cations whose cations do not adversely affect the action of the active compound ("agriculturally acceptable"). Preferred cations are ions of alkali metals, preferably lithium, sodium and potassium ions, alkaline earth metals, preferably calcium and magnesium ions, and transition metals, preferably manganese, copper, zinc and iron ions.
Anions of useful acid addition salts are mainly chloride, bromide, fluoride, iodide, hydrogen sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate.
The subscripts n and m in C n-m of the invention in each case denote the number of carbon atoms in the group. For example, C 1-10 represents a group containing 1 to 10 carbon atoms. The alkyl groups present in the definition of substituents may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl. Alkoxy groups are derived from the alkyl groups mentioned.
Halogen in the present invention is typically fluorine, chlorine, bromine or iodine, preferably fluorine, bromine or chlorine. Accordingly, this also applies to halogens, such as haloalkyl, which are bonded to other structures. The haloalkyl group preferably has a chain length of 1 to 6 carbon atoms, more preferably a chain length of 1 to 4 carbon atoms. Examples of the alkyl groups of the haloalkyl group, such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-trifluoroethyl, 2-fluoroethyl 2-chloroethyl, pentafluoroethyl, 1-difluoro-2, 2-trichloroethyl, 2, 3-tetrafluoroethyl and 2, 2-trichloroethyl; preferred are fluoromethyl, difluoromethyl, trifluoromethyl, trichloromethyl, difluoromethyl and dichlorofluoromethyl.
The term "C 1-10 alkyl" denotes a straight or branched saturated monovalent hydrocarbon radical having 1 to 10 carbon atoms. For example, "C 1-6 alkyl" means straight and branched alkyl groups having 1,2,3, 4, 5, or 6 carbon atoms. Wherein the alkyl group may be optionally substituted with one or more substituents described herein. In some embodiments, the alkyl group contains 1 to 12 carbon atoms; in other embodiments, the alkyl group contains 1 to 6 carbon atoms; in still other embodiments, the alkyl group contains 1 to 4 carbon atoms. Examples of such alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3-dimethylbutyl, 2-dimethylbutyl, 1-dimethylbutyl, 2, 3-dimethylbutyl, 1, 3-dimethylbutyl, or 1, 2-dimethylbutyl, and the like, or isomers thereof. The same definition applies to C 2-10 alkynyl.
The term "C 3-10 cycloalkyl" is understood to mean a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cycloalkane having 3 to 10 carbon atoms, preferably "C 3-8 cycloalkyl". The term "C 3-10 cycloalkyl" is understood to mean a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cycloalkane having 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. The C 3-10 cycloalkyl group may be a monocyclic hydrocarbon group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or a bicyclic hydrocarbon group such as a decalin ring.
The term "3-10 membered heterocyclic group" is understood to mean a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cycloalkane comprising 1 to 5 non-aromatic cyclic groups having 3 to 10 (e.g. 3,4, 5,6, 7, 8,9, 10, etc. atoms) of total ring atoms independently selected from the group consisting of N, O and S heteroatoms, preferably a "3-8 membered heterocyclic group". The term "3-10 membered heterocyclyl" means a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cycloalkane comprising 1-5, preferably 1-3 heteroatoms independently selected from N, O and S, for example 1,2, 3 heteroatoms independently selected from N, O and S. The heterocyclic group may be attached to the remainder of the molecule through any of the carbon atoms or a nitrogen atom, if present. In particular, the heterocyclic groups may include, but are not limited to: 4-membered rings such as azetidinyl, oxetanyl; a 5-membered ring such as tetrahydrofuranyl, dioxolyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or a6 membered ring such as tetrahydropyranyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl or trithianyl; or a 7-membered ring such as diazepanyl. Optionally, the heterocyclyl may be benzo-fused. The heterocyclyl may be bicyclic, such as, but not limited to, a5, 5 membered ring, such as hexahydrocyclopenta [ c ] pyrrol-2 (1H) -yl ring, or a5, 6 membered bicyclic ring, such as hexahydropyrrolo [1,2-a ] pyrazin-2 (1H) -yl ring. The ring containing nitrogen atoms may be partially unsaturated, i.e. it may contain one or more double bonds, such as but not limited to 2, 5-dihydro-1H-pyrrolyl, 4H- [1,3,4] thiadiazinyl, 4, 5-dihydro-oxazolyl or 4H- [1,4] thiazinyl, or it may be benzo-fused, such as but not limited to dihydroisoquinolinyl. According to the invention, the heterocyclic group is non-aromatic.
The term "plant propagation material" is understood to mean reproductive parts of plants, such as seeds, which can be used for plant propagation, as well as plant material, such as cuttings or tubers, for example potatoes. Mention may be made, for example, of seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and plant parts. Mention may also be made of germinated plants and seedlings to be transplanted after germination or after emergence from the soil. These seedlings may be protected by a whole or partial dipping treatment prior to transplantation. Preferably "plant propagation material" is understood to mean seeds.
In general, the compounds of the present invention may be prepared by the methods described herein, and unless otherwise indicated, the starting materials, reagents, and the like used to prepare the compounds of the present invention are commercially available or may be prepared by methods conventional in the art.
Example 1 preparation of Compound 1
The preparation process comprises the following steps:
(1) A500 mL reaction flask equipped with a stirrer reflux condenser and a thermometer was charged with 21.5g of methyl p-bromobenzoate and 100mL of DMF, and triphenylphosphine (2 mmol) and palladium chloride (2 mmol), triethylamine (0.015 mol) and cyclopropylacetylene (0.02 mol) were added under nitrogen protection to react at 90℃for 3 hours. Cooling to room temperature, adding water and ethyl acetate for extraction, washing the organic phase with saturated saline solution, drying the organic phase with anhydrous sodium sulfate, carrying out suction filtration, concentrating the filtrate under reduced pressure, and separating and purifying the obtained product by column chromatography to obtain 18g of 4- (cyclopropylethynyl) methyl benzoate.
(2) 18G of methyl 4- (cyclopropylethynyl) benzoate and 160g of ten percent sodium hydroxide aqueous solution are added into a 250mL reaction bottle provided with a reflux condenser of a stirrer and a thermometer, the temperature is raised to 60 ℃ for reaction for 3 hours, diluted hydrochloric acid is used for regulating strong acidity after the temperature is reduced, and a filter cake is dried after suction filtration to obtain 15g of 4- (cyclopropylethynyl) benzoic acid.
(3) 21G of 2-bromo-4- (1, 3-tetrafluoro-2- (trifluoromethyl) propyl) -6- (trifluoromethyl) aniline, 100mL of tetrahydrofuran, 10g of EDCI and 9.5g of 2-fluoro-3-nitrobenzoic acid are added into a 250mL reaction bottle with a reflux condenser and a thermometer, 30g of pyridine is dropwise added at room temperature, the reaction is stopped for 0.5h, most of tetrahydrofuran is removed, water is added, ethyl acetate is added for extraction, and the organic phase is desolventized, thus 22g of compound N- (2-bromo-4- (1, 3-tetrafluoro-2- (trifluoromethyl) propyl) -6- (trifluoromethyl) phenyl) -2-fluoro-3-nitrobenzamide is obtained.
(4) A250 mL reaction flask equipped with a stirrer reflux condenser and thermometer was charged with 22g of the compound N- (2-bromo-4- (1, 3-tetrafluoro-2- (trifluoromethyl) propyl) -6- (trifluoromethyl) phenyl) -2-fluoro-3-nitrobenzamide, 23g of stannous chloride (anhydrous), 220mL of ethanol, and then 22mL (9.78 mmol) of concentrated hydrochloric acid was added and stirred at 60℃for 4 hours. The reaction mixture was adjusted to pH 10 by adding an aqueous sodium hydroxide solution, and insoluble matter separated out was removed by filtration using celite. The filtered collection on celite was washed with ethyl acetate. The filtrate was extracted with ethyl acetate, and the organic layer was washed with a 20% aqueous sodium hydroxide solution and a saturated brine, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was subjected to silica gel column chromatography to thereby prepare 19g of 3-amino-N- (2-bromo-4- (1, 3-tetrafluoro-2- (trifluoromethyl) propyl) -6- (trifluoromethyl) phenyl) -2-fluorobenzamide.
(5) A250 mL reaction flask equipped with a stirrer reflux condenser and a thermometer was charged with 19g of 3-amino-N- (2-bromo-4- (1, 3-tetrafluoro-2- (trifluoromethyl) propyl) -6- (trifluoromethyl) phenyl) -2-fluorobenzamide, 95mL of concentrated sulfuric acid, and 190mL of 37% aqueous formaldehyde solution was added dropwise at 40 ℃. The reaction solution was poured into ice water, the pH was adjusted to 10 with an aqueous sodium hydroxide solution, and then ethyl acetate was added thereto for extraction. The organic layer was washed with a 20% aqueous sodium hydroxide solution and a saturated brine, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to give 18g N- (2-bromo-4- (1, 3-tetrafluoro-2- (trifluoromethyl) propyl) -6- (trifluoromethyl) phenyl) -2-fluoro-3- (methylamino) benzamide.
(6) To a 250mL reaction flask equipped with a reflux condenser and a thermometer, 18g N- (2-bromo-4- (1, 3-tetrafluoro-2- (trifluoromethyl) propyl) -6- (trifluoromethyl) phenyl) -2-fluoro-3- (methylamino) benzamide, 100mL of tetrahydrofuran, 10gEDCI, 6g of 4- (cyclopropylethynyl) benzoic acid, 30g of pyridine were added dropwise at room temperature, the reaction was stopped after the dropwise addition of 0.5 hour, most of the tetrahydrofuran was removed, water was added to extract with ethyl acetate, the organic phase was desolventized, and the obtained residue was purified by silica gel column chromatography to give 11g N- (2-bromo-4- (1, 3-tetrafluoro-2- (trifluoromethyl) propyl) -6- (trifluoromethyl) phenyl) -3- (4- (cyclopropylethynyl) -N-methylbenzamide) -2-fluorobenzamide (compound 1) in 47.2% yield.
1 H NMR data of Compound 1 were as follows ：δ 0.88 (m, 4H, H-1,2), 0.88 (m, 4H, H-1`,2`), 1.80 m, 1H, H-3), 3.04 (s, H-8), 6.80 (d, J = 1.2 Hz, 1H, H-13), 7.00 (d, J = 1.2 Hz, 1H, H-14), 7.40 (t, J = 7.8 Hz, 1H, H-10), 7.44 (m,1H, H-11), 7.50 (m, 1H, H-9), 7.69 (m, 2H, H-4,6), 7.91 (m, 2H, H-5,7).
Referring to the above method for preparing compound 1, compounds 2-6 were prepared.
Example 2 pesticide Activity assay
(1) Insecticidal Activity test against Myzus persicae (Myzus persicae)
10 Parts of the compound (compound 1-6) produced in example 1, 75 parts of toluene, 10 parts of DMF and 5 parts of fast T (available from Beijing coupling technology Co., ltd.) were mixed to prepare an emulsifiable concentrate. The prepared emulsion is dispersed in water and diluted into the liquid medicine with the concentration of 250ppm for standby.
Cabbage is planted in a plastic pot with the diameter of 10cm and the height of 8cm, so that the green peach aphids are propagated on the cabbage, and the number of the green peach aphids in the pot is investigated.
The prepared medicinal liquid is applied to stems and leaves of Chinese cabbage in a pot, the pot is placed in a greenhouse after air drying, the number of green peach aphids on the Chinese cabbage is investigated after the 6 th day of the administration, and water is used as a blank control. The control rate of the green peach aphids is calculated by the following equation:
control rate=100- { (t×ca)/(ta×c) } 100
Wherein,
Ta represents the number of green peach aphids before treatment in the application area
T represents the number of the green peach aphids after the treatment of the pesticide application area
Ca represents the number of green peach aphids before water application in a blank control area
C represents the number of green peach aphids investigated after day 6 of the blank control zone.
The results show that the compounds 1 to 6 prepared in example 1 of the present invention have excellent insecticidal effect at 250ppm, and the control rate is 100%.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

1. An amide compound represented by the following formula (I) or a pesticidally acceptable salt thereof;
（I）;
Wherein,
R 1 is selected from H, C 1-6 alkyl, C 1 alkylene-C 3 cycloalkyl;
R 2 is selected from H, halogen;
r 3 is selected from H, halogen;
r 4 is selected from H, halogen;
R 5 is selected from the group consisting of-C 2 alkynyl-C 3 cycloalkyl, ;
Y 1、Y2、Y3、Y4、Y5, which are identical or different, are independently of one another selected from H, halogen, C 1-6 alkyl, C 1-6 alkyl substituted by one, two or more halogens, C 1-6 alkoxy;
a 1、A2、A3、A4 is CH;
m and n are the same or different and are independently selected from natural numbers of 0 to 4;
R s is selected from H;
R t is selected from C 1-6 alkyl, C 1-6 alkyl substituted with one, two or more halogens;
representing a linking group.
2. The compound according to claim 1, wherein the amide compound represented by formula (I) is selected from compounds represented by the following formula (II):
（II）;
Wherein ,R1、R2、R3、R4、Y1、Y2、Y3、Y4、Y5、m、n has the definition of claim 1.
3. The compound according to claim 1, wherein the amide compound represented by formula (I) is selected from compounds represented by the following formula (III):
（III）;
Wherein ,R1、R2、R3、R4、Y1、Y2、Y3、Y4、Y5、m、n、Rt has the definition of claim 1.
4. A compound according to any one of claims 1 to 3, wherein the amide compound of formula (I) is selected from the following specific compounds:
；；
；；
；。
5. A process for producing an amide-based compound represented by the formula (I) as claimed in any one of claims 1 to 4, comprising the steps of:
Reacting a compound shown in a formula (IV) with a compound shown in a formula (V) under the conditions of alkali and a condensing agent to prepare a compound shown in a formula (I);
The reaction formula is as follows:
；
wherein ,R1、R2、R3、R4、R5、Y1、Y2、Y3、Y4、Y5、A1、A2、A3、A4、m、n has the definition as defined in any one of claims 1 to 4;
X is selected from OH or halogen.
6. A composition or agricultural or horticultural insecticide comprising an amide compound of formula (I) as defined in any one of claims 1 to 4 or a pesticidally acceptable salt and at least one adjuvant.
7. Use of an amide compound of formula (I) or a pesticidally acceptable salt as defined in any of claims 1 to 4, or of a composition as defined in claim 6 or an agrohorticultural pesticide for controlling plant pests.
8. A method of treating plant propagation material by applying an amide compound of formula (I) or a pesticidally acceptable salt thereof, or a composition or an agrohorticultural pesticide according to claim 6, according to any one of claims 1 to 4, to plant propagation material.
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Citations (2)

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Publication number Priority date Publication date Assignee Title
CN101098864A (en) * 2004-12-09 2008-01-02 辛根塔参与股份公司 Anthranilamide derivatives as insecticides
CN102112437A (en) * 2008-08-01 2011-06-29 三井化学Agro株式会社 Amide derivative, pest control agent containing amide derivative and pest controlling method

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CN111132549B (en) * 2017-09-20 2022-04-12 三井化学Agro株式会社 Long-acting control agent for ectoparasites of animals
CN115304510B (en) * 2022-09-13 2024-01-02 海利尔药业集团股份有限公司 Aryl substituted meta-diamide compound or salt and composition thereof acceptable as pesticides and application thereof
WO2024069632A2 (en) * 2022-09-30 2024-04-04 Adama Makhteshim Ltd. Novaluron mixtures for efficient insecticidal controls

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Publication number Priority date Publication date Assignee Title
CN101098864A (en) * 2004-12-09 2008-01-02 辛根塔参与股份公司 Anthranilamide derivatives as insecticides
CN102112437A (en) * 2008-08-01 2011-06-29 三井化学Agro株式会社 Amide derivative, pest control agent containing amide derivative and pest controlling method

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