CN115304512A - Amide compound and preparation method and application thereof - Google Patents
Amide compound and preparation method and application thereof Download PDFInfo
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- CN115304512A CN115304512A CN202210488711.2A CN202210488711A CN115304512A CN 115304512 A CN115304512 A CN 115304512A CN 202210488711 A CN202210488711 A CN 202210488711A CN 115304512 A CN115304512 A CN 115304512A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
- C07C255/29—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton containing cyano groups and acylated amino groups bound to the carbon skeleton
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
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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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
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- Agronomy & Crop Science (AREA)
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Abstract
The invention provides an amide compound and a preparation method and application thereof, wherein the amide compound has a structure shown in a formula I. The amide compound disclosed by the invention has high insecticidal activity and good quick-acting property under low dosage; and because the effect is good under low dosage, the dosage of the medicine is reduced, the environment is protected, and the application prospect is wide.
Description
Technical Field
The invention belongs to the field of pesticides, and relates to an amide compound, and a preparation method and application thereof.
Background
In the production of crops such as agriculture and horticulture, damage by pests and the like is still remarkable. Because pests have resistance to the existing pesticides and the existing pesticides are not environment-friendly, and the like, development of new pesticides with better activity, lower dosage and more environment-friendly is always needed.
The insecticidal activity of amide compounds has been reported. For example, CN110194726A discloses compound KC1 (compound 9.321 in the patent) and CN110194726A discloses compound KC2 (compound 128 in CN 105873901A) and its pesticidal activity. These disclosed compounds have insecticidal activity, however, at low doses they have poor insecticidal or fast-acting properties.
There is still a need in the art to actively develop new insecticides with high insecticidal activity that can be fast-acting at low doses to meet the needs of agriculture as well as forestry.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an amide compound and a preparation method and application thereof, in particular to an amide compound containing difluoromethoxy and/or pyridyl, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides an amide compound having a structure represented by formula I below:
in the formula I, the compound is shown in the specification,
q is selected from one of the following Q1, Q2, Q3 or Q4:
Z 1 、Z 2 、Z 3 、Z 4 、Z 5 each independently selected from hydrogen, fluorine, chlorine, bromine, iodine,Cyano, nitro, C 1 -C 6 Alkyl radical, C 1 -C 6 Cycloalkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Halogenocycloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 1 -C 6 Alkylsulfinyl radical, C 1 -C 6 Halogenoalkylsulfinyl, C 1 -C 6 Alkylsulfonyl or C 1 -C 6 A haloalkylsulfonyl group;
r is selected from hydrogen, fluorine or methoxy;
W 1 and W 2 Independently an oxygen atom or a sulfur atom.
The amide compound with the structure shown in the formula I can achieve good insecticidal activity at low dose, has quick response, can exert the insecticidal activity after being applied for one day, can achieve high insecticidal activity within 3 days, and has good quick action; and because the effect is good under the low dose, the harm to plants and human beings caused by overlarge drug concentration is reduced, and the drug residue generated during application is less, thereby being more beneficial to environmental protection.
In the present invention, as a preferable embodiment, in formula I, Z 1 、Z 2 、Z 3 、Z 4 、Z 5 Each independently selected from hydrogen, fluoro, chloro, bromo, iodo, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, tert-butyl, isobutyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2-dimethylpropyl, methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, trifluoromethyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoro-isopropyl, difluoromethoxy, trifluoromethoxy, pentafluoroethoxy, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl or trifluoromethylsulfonyl.
As a further preferable technical scheme of the invention, the amide compound is any one of the compounds shown in the following Table 1 and having the general formula I.
TABLE 1
In addition, "H" represents a hydrogen atom, "F" represents a fluorine atom, "Cl" represents a chlorine atom, "Br" represents a bromine atom, "I" represents an iodine atom, "CN" represents a cyano group, "NO 2 "represents nitro," Me "represents methyl," i-Pr "represents isopropyl," t-Bu "represents tert-butyl," OMe "represents methoxy," O-i-Pr "represents isopropoxy," CH 2 F' represents a monofluoromethyl group, CF 3 "represents trifluoromethyl," CF 2 CF 3 "represents pentafluoroethyl group," CF (CF) 3 ) 2 "represents heptafluoroisopropyl group," OCF 3 "represents trifluoromethoxy group," OCF 2 H 'represents difluoromethoxy,' OCF 2 CF 3 "represents pentafluoroethoxy," c-Pr "represents cyclopropyl," MeS (O) 2 "represents a methanesulfonyl group," CF 3 S(O) 2 "represents trifluoromethanesulfonyl.
In the present invention, as a more preferable embodiment, in formula I, Z 1 、Z 2 、Z 3 、Z 4 、Z 5 Each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro and trifluoromethylA group, difluoromethoxy, trifluoromethoxy, methylsulfonyl or trifluoromethylsulfonyl; r is selected from hydrogen or fluorine W 1 And W 2 Selected from oxygen.
In the present invention, as a particularly preferred embodiment, the amide-based compound is any one selected from the following compounds:
wherein the numbering of the compounds corresponds to the numbering of the compounds in table 1.
The alkyl group in the present invention means a straight chain or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, and the like. Haloalkyl refers to a group in which a hydrogen atom on an alkyl group is replaced with one or more halogen atoms. Alkoxy means a group having an oxygen atom attached to the terminal of an alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, and the like. Haloalkoxy refers to a group in which a hydrogen atom on an alkoxy group is replaced with one or more halogen atoms. Halogen is F, cl, br or I.
The term "C" as used in the present invention 1 -C 6 Alkyl "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 "C 1 -C 6 Alkoxy "means a straight or branched chain alkoxy group having 1 to 6 carbon atoms, including, but not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, and the like. "C 1 -C 6 Haloalkyl "refers to a straight or branched chain alkyl group of 1 to 6 carbon atoms substituted with a halogen atom, including without limitation trifluoromethyl, difluoromethyl, 1-trifluoroethyl, pentafluoroethylHeptafluoro-n-propyl, heptafluoro-isopropyl, and the like. "C 1 -C 6 Haloalkoxy "means a straight or branched chain alkoxy group of 1 to 6 carbon atoms substituted with a halogen atom, and includes, without limitation, trifluoromethoxy, difluoromethoxy, 2-trifluoroethoxy, pentafluoroethoxy, heptafluoro-n-propoxy, heptafluoro-isopropoxy, and the like. The term "C" as used in the present invention 3 -C 8 Cycloalkyl "refers to a cyclic alkyl group having 3 to 8 carbon atoms and includes, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. The term "C" as used herein 3 -C 8 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 group 1 -C 6 、C 3 -C 8 Etc. represent the number of carbon atoms contained in the radical, e.g. C 1 -C 6 Represents a group having 1,2,3, 4, 5 or 6 carbon atoms, C 3 -C 8 Represents a group having 3, 4, 5, 6, 7 or 8 carbon atoms, C 2 -C 4 Represents a group in which the number of carbon atoms may be 2,3 or 4, and so on.
In the present invention, it is to be noted that "i-" represents iso, "s-" represents sec, "t-" represents tert, "Me" represents methyl, "Et" represents ethyl, "i-Pr" represents isopropyl, "c-Pr" represents cyclopropyl, "c-Bu" represents cyclopropyl, "c-Pent" represents cyclopentyl, "c-Hex" represents cyclohexyl, "t-Bu" represents tert-butyl, "CF 3 "represents a trifluoromethyl group and" OCF 3 "represents trifluoromethoxy group," methylsulfonyl group "represents difluoromethoxy group," H "represents hydrogen atom," F "represents fluorine atom," Cl "represents chlorine atom," Br "represents bromine atom," I "represents iodine atom," O "represents oxygen atom," S "represents sulfur atom," Ac "represents acetyl group," OMe "represents methoxy group," OEt "represents ethoxy group," O- (I-Pr) "represents isopropoxy group," OCF "represents methoxy group 3 "means toTrifluoromethoxy group, OCF 2 H' represents difluoromethoxy, OCF 2 CF 3 "represents pentafluoroethoxy group," -CN "represents cyano group," -NO "represents cyano group 2 "represents a nitro group.
The compounds of the general formula I according to the invention can be prepared by the following processes, in which the radicals are as defined above, unless otherwise indicated.
The compound of the general formula I has the following structure and can be prepared by the following method:
wherein R, W 1 、W 2 And Q is as defined above
And reacting the compound in the general formula II with the compound in the general formula III to obtain the compound in the general formula I.
Preferably, the molar ratio of the compound of formula II to the compound of formula III is from 0.5 to 2, such as 0.5.
In the present invention, the reaction is carried out in the presence of a basic substance, which is an organic base and/or an inorganic base.
Preferably, the organic base is any one or a combination of at least two of triethylamine, N-diisopropylethylamine, N-dimethylaniline, pyridine, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, sodium tert-butoxide or potassium tert-butoxide.
Preferably, the inorganic base is any one of sodium hydroxide, potassium hydroxide or sodium hydride or a combination of at least two thereof.
Preferably, the solvent of the reaction is selected from any one of dichloromethane, chloroform, toluene, ethyl acetate, acetone, acetonitrile, tetrahydrofuran, dioxane, N-dimethylformamide, dimethylsulfoxide or hexamethylphosphoric triamide or a combination of at least two thereof.
Preferably, the reaction temperature is not less than room temperature and not more than the boiling point of the reaction solvent, such as 25 ℃, 30 ℃, 35 ℃, 40 ℃,45 ℃, 50 ℃, 60 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ or the like, or in the solvent boiling point, i.e. the reflux state.
Preferably, the time of the reaction is 0.5 to 48 hours, such as 0.5 hour, 1 hour, 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 23 hours, 25 hours, 28 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 44 hours, or 48 hours.
In another aspect, the present invention provides a tautomer, enantiomer, diastereomer or salt thereof of the amide-based compound as described above.
In the invention, the tautomer, enantiomer, diastereomer or salt of the amide compound can also exert the same action effect as the amide compound, and the amide compound has good insecticidal effect and quick action at low dosage.
On the other hand, the invention provides the application of the amide compound in the fields of agriculture, forestry and horticulture to control insect pests and nematodes.
The amide compound is suitable for preventing and treating various agricultural and forestry and horticultural insect pests, sanitary pests and nematodes which are harmful to rice, corn, wheat, potatoes, fruit trees, vegetables, other crops, flowers and the like.
In the present invention, the pests include lepidoptera, coleoptera, hemiptera, thysanoptera, diptera, orthoptera, homoptera, isoptera, hymenoptera, spider mite pests, and nematode, mosquito, fly, ant, 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, spodoptera frugiperda, rice leaf roller, rice thrips, western thrips, melon thrips, spring thrips, ginger thrips, mango thrips, green peach aphid, cotton aphid, alfalfa aphid, apple yellow aphid, wheat aphid, flea beetle, stink bug, gray plant hopper, brown plant hopper, sogatella furcifera, termite, mosquito fly, carminespider mite and citrus red spider.
The compound of the invention has wide application range, and the applied plants or the applied range mainly comprises the following types: melons and vegetables, cucumber, towel gourd, watermelon, melon, pumpkin, trichosanthes kirilowii maxim, spinach, celery, cabbage, chinese cabbage, gourd, hot pepper, eggplant, tomato, shallot, ginger, garlic, leek, asparagus lettuce, kidney bean, cowpea, broad bean, radish, carrot, potato and Chinese yam; cereals, wheat, barley, corn, rice, sorghum; fruit trees, apples, pears, bananas, oranges, grapes, litchis and mangoes; flowers, peony, chinese rose, huohan crane; oil crops, peanuts, soybeans, rape, sunflowers, sesame; sugar crops, sugar beets, sugar cane; other crops, such as strawberry, potato, sweet potato, tobacco and tea; horticulture, forestry, home health, public health areas, and the like; the plants or ranges listed above have no limiting effect on the scope of use of the amides of the invention.
In another aspect, the present invention provides a pesticide composition, which comprises an active ingredient and an agriculturally pharmaceutically acceptable carrier, wherein the active ingredient is the amide compound described above.
The compositions of the invention may be applied in the form of formulations in which the compounds of formula I are dissolved or dispersed as active ingredients in carriers or formulated so as to be more easily dispersed for use as insecticides.
In the invention, the pesticide composition can be prepared into dosage forms such as wettable powder, suspending agent, aqueous emulsion or missible oil.
The pesticide composition can be used in the fields of agriculture, forestry, sanitation and the like.
Preferably, the weight percentage of the active ingredient in the pesticide composition is 1-99%, such as 1%, 3%, 5%, 8%, 10%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 99%.
Preferably, the agriculturally pharmaceutically acceptable carrier includes a surfactant.
In the present invention, the surfactant is an ionic surfactant or a nonionic surfactant.
The surfactant includes an emulsifier, dispersant or wetting agent. The emulsifier can be polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol ether, polyoxyethylene fatty ammonia and commercially available emulsifier (Nongru 2201B, nongru 0203B, nongru 100#, nongru 500#, nongru 600-2#, nongru 1601, nongru 2201, nongru NP-10, nongru NP-15, nongru 507#, nongru OX-635, nongru OX-622, nongru OX-653, nongru OX-667, ningru 36#, etc.). The dispersant comprises sodium lignosulfonate, nekal, calcium lignosulfonate, methyl naphthalene sulfonic acid formaldehyde condensate and the like. The wetting agent includes sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, etc.
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, which can also be used as adjuvants or antifreeze additives when water is used as a solvent or diluent. Suitable organic solvents include aromatic hydrocarbons such as benzene, xylene, toluene, and the like; chlorinated hydrocarbons such as chlorobenzene, vinyl chloride, chloroform, dichloromethane, and the like; aliphatic hydrocarbons such as petroleum fractions, cyclohexane, light mineral oil; alcohols such as isopropyl alcohol, butyl alcohol, ethylene glycol, glycerin, cyclohexanol, and the like; and ethers and esters thereof; and also ketones, such as acetone, cyclohexanone, and dimethylformamide and N-methylpyrrolidone.
The active ingredient may be mixed with liquid and/or solid carriers during the formulation of the pesticidal composition, with the addition of surfactants (e.g., emulsifiers, dispersants, stabilizers, wetting agents), and with the addition of other adjuvants (e.g., binders, defoamers, oxidizers, etc.).
In another aspect, the present invention provides a method for controlling pests, the method comprising: applying an effective dose of the amide compound or the pesticide composition to a medium needing to control pests or the growth of the pests.
Preferably, the effective dose is 7.5-1000g per hectare, for example 7.5g, 10g, 20g, 50g, 80g, 100g, 120g, 150g, 180g, 200g, 250g, 300g, 350g, 400g, 450g, 500g, 600g, 700g, 800g, 900g or 1000g, preferably 15-600g per hectare.
The compositions of the present invention may be applied to the pests or their growth medium in the form of a formulation. The compounds of formula I as active ingredients are dissolved or dispersed in a carrier or formulated so as to be more easily dispersed when used as insecticides. For example: the chemical preparation can be prepared into various liquid preparations, missible oil, suspending agents, water suspending agents, micro-emulsions, aqueous emulsions, powders, wettable powders, soluble powders, granules, water dispersible granules or capsules.
For certain applications, for example in agriculture, one or more other insecticides, fungicides, herbicides, plant growth regulators or fertilizers and the like may be added to the pesticidal compositions of the present invention, thereby providing additional advantages and effects.
Compared with the prior art, the invention has the following beneficial effects:
the amide compound has obvious effects on preventing and treating diseases and insect pests, nematodes and pests in the sanitary field in agriculture and forestry, can achieve good insecticidal effect at low dose, has quick response, can exert insecticidal activity after being applied for one day, can achieve high insecticidal activity within 3 days, has good quick-acting property, can be applied at low dose, reduces the damage of overlarge drug concentration to plants and human beings, generates less drug residue in application, is more beneficial to environmental protection, has simple and efficient preparation method, is easy for large-scale production, and has wide application prospect.
Detailed Description
The technical solution of the present invention is further described below by way of specific 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 limitation of the present invention.
Synthetic examples
Synthesis example 1
Preparation of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -3- [ N- (acetonitrile) -benzamido ] -2-fluorobenzamide (compound No. 1):
(1) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -2-fluoro-3-nitrobenzamide
2-fluoro-3-nitrobenzoic acid (3.15g, 17.07mmol), toluene (10 mL) and thionyl chloride (8.1g, 68.28mmol) are added into a reaction bottle in sequence, stirred and reacted for 2h under the reflux condition, and concentrated under reduced pressure to obtain 2-fluoro-3-nitrobenzoyl chloride. 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6-difluoromethoxyaniline (6.3 g, 15.52mmol) and 4-N, N-lutidine (0.38g, 3.1 mmol) were added to 2-fluoro-3-nitrobenzoyl chloride, the mixture was heated to 110 ℃ to react, after 8 hours, the reaction mixture was cooled to room temperature, 100mL of ethyl acetate and 50mL of water were added, liquid separation and extraction were performed, the organic layer was taken, washed with saturated saline, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent was petroleum ether: ethyl acetate volume ratio = 5) to obtain the objective product as a yellow solid, 6.6g.
1 H NMR(400MHz,DMSO-d6)δ10.79(s,1H),8.36(t,J＝8.0Hz,1H),8.02(t,J＝8.0Hz,1H),7.93(s,1H),7.62(t,J＝8.0Hz,2H),7.40(t,J＝72Hz,1H).
(2) Synthesis of 3-amino-N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -2-fluorobenzamide
N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -2-fluoro-3-nitrobenzamide (6.6 g, 11.51mmol) was dissolved in ethanol (30 mL), and stannous chloride dihydrate (10.5g, 46.07mmol) was added to the solution and reacted for 3 hours under reflux. The reaction was terminated by TLC monitoring until the reaction did not proceed any more. The reaction solution was evaporated to dryness under reduced pressure, the pH of the solution was adjusted to 12 with 10% aqueous sodium hydroxide solution, extracted with ethyl acetate (100 mL), 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 volume ratio = 5).
1 H NMR(400MHz,DMSO-d6)δ10.20(s,1H),7.89(s,1H),7.53(s,1H),7.32(t,J＝72.0Hz,1H),7.03–6.89(m,2H),6.80(t,J＝6.7Hz,1H),5.39(s,2H)。
(3) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6- (difluoromethoxy) phenyl ] -3- (benzamido) -2-fluorobenzamide
To a solution of 3-amino-N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6-difluoromethoxyphenyl ] -2-fluorobenzamide (800mg, 1.47mmol) in tetrahydrofuran (10 mL) were added pyridine (470mg, 5.89mmol), benzoyl chloride (248mg, 1.76mmol) in this order, and the reaction was carried out at room temperature for 2 hours. After 50mL of ethyl acetate was added, the mixture was washed once with 2M hydrochloric acid (10 mL) and a saturated aqueous sodium bicarbonate solution (30 mL) in this order, the organic layer was taken out, 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 volume ratio = 10) to obtain 858mg of the objective product.
(4) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6- (difluoromethoxy) phenyl ] -3- [ N- (acetonitrile) -benzamido ] -2-fluorobenzamide
To a solution of N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6- (difluoromethoxy) phenyl ] -3- (benzamido) -2-fluorobenzamide (0.40g, 0.62mmol) in tetrahydrofuran (10 mL) was added 60wt% sodium hydride (248mg, 6.2mmol), and the reaction was carried out at room temperature for 1 hour. Bromoacetonitrile (369mg, 3.1 mmol) was added and the reaction was continued at room temperature for 1 hour. After quenching with 10ml of water, 40ml of ethyl acetate was added, the organic layer was collected, 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 volume ratio = 8).
Process for preparation of Compound 1 1 H NMR (400MHz, DMSO-d 6) data was as follows (delta [ ppm ], (])：10.42(s,1H),7.91(d,J＝2.0,1H),7.62–7.59(m,2H),7.54(br s,1H),7.40-7.28(m,7H),4.92(s,2H)。
Synthesis example 2
Preparation of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -3- [ N- (acetonitrile) -4- (trifluoromethyl) benzamido ] -2-fluorobenzamide (Compound No. 14):
(1) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6- (difluoromethoxy) phenyl ] -3- [4- (trifluoromethyl) benzamido ] -2-fluorobenzamide
To a solution of 3-amino-N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6-difluoromethoxyphenyl ] -2-fluorobenzamide (500mg, 0.92mmol) in tetrahydrofuran (10 mL) were added pyridine (290mg, 3.68mmol), 4- (trifluoromethyl) benzoyl chloride (210mg, 1.10 mmol) in this order, and the reaction was carried out at room temperature for 2 hours. After 50mL of ethyl acetate was added, the mixture was washed once with 2M hydrochloric acid (10 mL) and a saturated aqueous solution of sodium hydrogencarbonate (30 mL) in this order, the organic layer was taken out, 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 volume ratio = 10) to obtain 600mg of the objective product.
(2) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -3- [ N- (acetonitrile) -4- (trifluoromethyl) benzamido ] -2-fluorobenzamide
To a solution of N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6- (difluoromethoxy) phenyl ] -3- [4- (trifluoromethyl) benzamido ] -2-fluorobenzamide (0.30g, 0.42mmol) in tetrahydrofuran (10 mL) was added 60wt% sodium hydride (168mg, 4.2mmol) and the reaction was carried out at room temperature for 1 hour. Bromoacetonitrile (250mg, 2.1 mmol) was added and the reaction was continued at room temperature for 1 hour. After the reaction was quenched with 10ml of water, 40ml of ethyl acetate was added, and an organic layer was taken out, 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 volume ratio = 8).
Process for preparation of Compound 14 1 H NMR (400MHz, DMSO-d 6) data was as follows (delta [ ppm ], (])：10.39(s,1H),7.90(d,J＝2.0,1H),7.71-7.58(m,6H),7.54(d,J＝2.0,1H),7.37(t,J＝8.0,1H),7.39(t,J＝72.8Hz,1H),4.98(s,2H)。
Synthesis example 3
Preparation of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -3- [ N- (acetonitrile) -4-fluorobenzamido ] -2-fluorobenzamide (Compound No. 17):
(1) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6- (difluoromethoxy) phenyl ] -3- (4-fluorobenzamido) -2-fluorobenzamide
To a solution of 3-amino-N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6-difluoromethoxyphenyl ] -2-fluorobenzamide (500mg, 0.92mmol) in tetrahydrofuran (10 mL) were added pyridine (290mg, 3.68mmol), 4-fluorobenzoyl chloride (175mg, 1.10mmol) in this order, and the mixture was reacted at room temperature for 2 hours. After 50mL of ethyl acetate was added, the mixture was washed once with 2M hydrochloric acid (10 mL) and saturated aqueous sodium bicarbonate (30 mL) in this order, the organic layer was taken out, 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 in a volume ratio = 10) to obtain 554mg of the objective product.
1 H NMR (400MHz, DMSO-d 6) data was as follows (delta [ ppm ], (])：10.49(s,1H),10.33(s,1H),8.10-8.07(m,2H),7.92(d,J＝2.0Hz,1H),7.83-7.79(td,J＝1.6,7.6,1H),7.59-7.55(m,2H),7.43-7.41(m,1H),7.39(m,3H)。
(2) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -3- [ N- (acetonitrile) -4-fluorobenzamido ] -2-fluorobenzamide
To a solution of N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6- (difluoromethoxy) phenyl ] -3- (4-fluorobenzamido) -2-fluorobenzamide (0.30g, 0.45mmol) in tetrahydrofuran (10 mL) was added 60wt% sodium hydride (180mg, 4.5 mmol), and the reaction was carried out at room temperature for 1 hour. Bromoacetonitrile (268mg, 2.25mmol) was added, and the reaction was continued at room temperature for 1 hour. The reaction mixture was quenched with 10mL of water, 40mL of ethyl acetate was added, the organic layer was taken out, 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 volume ratio = 8).
Process for preparation of compound 17 1 H NMR (400MHz, DMSO-d 6) data was as follows (delta [ ppm ], (])：10.41(s,1H),7.92(d,J＝2.0,1H),7.66–7.64(m,2H),7.54(br s,1H),7.46-7.43(m,2H),7.37(d,J＝8.0,1H),7.34(t,J＝72.8Hz,1H),7.17-7.12(m,2H),4.92(s,2H)。
Synthesis example 4
Preparation of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -3- [ N- (acetonitrile) -4-chlorobenzamido ] -2-fluorobenzamide (Compound No. 23):
(1) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6- (difluoromethoxy) phenyl ] -3- (4-chlorobenzoylamino) -2-fluorobenzamide
To a solution of 3-amino-N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6-difluoromethoxyphenyl ] -2-fluorobenzamide (200mg, 0.37mmol) in tetrahydrofuran (10 mL) were added pyridine (117mg, 1.47mmol), 4-chlorobenzoyl chloride (78mg, 0.444mmol) in this order, and the reaction was carried out at room temperature for 2 hours. After 50mL of ethyl acetate was added, the mixture was washed once with 2M hydrochloric acid (10 mL) and a saturated aqueous solution of sodium hydrogencarbonate (30 mL) in this order, the organic layer was taken out, 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 volume ratio = 10) to obtain 250mg of the objective product.
1 H NMR (400MHz, DMSO-d 6) data was as follows (delta [ ppm ], (])：10.50(s,1H),10.39(s,1H),8.04(d,J＝8.0Hz,2H),7.91(br s,1H),7.85-7.81(m,1H),7.64(d,J＝8.0Hz,2H),7.58-7.56(m,2H),7.41-7.19(m,2H)。
(2) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -3- [ N- (acetonitrile) -4-chlorobenzamido ] -2-fluorobenzamide
To a solution of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6- (difluoromethoxy) phenyl ] -3- (4-chlorobenzoylamino) -2-fluorobenzamide (250mg, 0.37mmol) in tetrahydrofuran (10 mL) was added 60% by weight sodium hydride (147mg, 3.7 mmol), and the reaction was carried out at room temperature for 1 hour. Bromoacetonitrile (220mg, 1.85mmol) was added and the reaction was continued at room temperature for 1 hour. The reaction mixture was quenched with 10ml of water, 40ml of ethyl acetate was added, the organic layer was taken out, 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 volume ratio = 8).
Process for preparation of compound 23 1 H NMR(400MHz, DMSO-d 6) data are as follows (delta [ ppm ], (])：10.41(s,1H),7.91(d,J＝2.0Hz,1H),7.68–7.62(m,2H),7.54(d,J＝2.0Hz,1H),,7.38-7.37(m,5H),7.34(t,J＝72.8Hz,1H)4.92(s,2H)。
Synthesis example 5
Preparation of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -3- [ N- (acetonitrile) -4-bromobenzamide ] -2-fluorobenzamide (Compound No. 24):
(1) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6- (difluoromethoxy) phenyl ] -3- (4-bromobenzamide) -2-fluorobenzamide
To a solution of 3-amino-N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -2-fluorobenzamide (500mg, 0.92mmol) in tetrahydrofuran (10 mL) were added pyridine (290mg, 3.68mmol), 4-chlorobenzoyl chloride (242mg, 1.1 mmol) in this order, and the reaction was carried out at room temperature for 2 hours. After 50mL of ethyl acetate was added, the mixture was washed once with 2M hydrochloric acid (10 mL) and a saturated aqueous solution of sodium hydrogencarbonate (30 mL) in this order, the organic layer was taken out, 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 volume ratio = 10) to obtain 600mg of the objective product.
1 H NMR (400MHz, DMSO-d 6) data were as follows (delta [ ppm ], [])：10.50(s,1H),10.41(s,1H),7.92(d,J＝2.0Hz,1H),7.68–7.62(m,2H),7.54(s,1H),7.38-7.14(m,6H)。
(2) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -3- [ N- (acetonitrile) -4-bromobenzamide ] -2-fluorobenzamide
To a solution of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6- (difluoromethoxy) phenyl ] -3- (4-bromobenzamide) -2-fluorobenzamide (300mg, 0.41mmol) in tetrahydrofuran (10 mL) was added 60wt% sodium hydride (165mg, 4.1 mmol), and the mixture was reacted at room temperature for 1 hour. Bromoacetonitrile (244mg, 2.05mmol) was added and the reaction was continued at room temperature for 1 hour. After the reaction was quenched with 10mL of water, 40mL of ethyl acetate was added, and an organic layer was taken out, 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 volume ratio = 8).
Process for preparation of compound 24 1 H NMR (400MHz, DMSO-d 6) data were as follows (delta [ ppm ], [])：10.42(s,1H),(d,J＝2.0,1H),7.70-7.63(m,2H),7.55(br s,1H),7.52(d,J＝8.0,2H),7.38-7.16(m,4H),4.92(s,2H)。
Synthesis example 6
Preparation of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -3- [ N- (acetonitrile) -4-iodobenzamido ] -2-fluorobenzamide (Compound No. 25):
(1) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6- (difluoromethoxy) phenyl ] -3- (4-iodobenzamido) -2-fluorobenzamide
To a solution of 3-amino-N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6-difluoromethoxyphenyl ] -2-fluorobenzamide (800mg, 1.47mmol) in tetrahydrofuran (10 mL) were added pyridine (466 mg, 5.89mmol), 4-iodobenzoyl chloride (470mg, 1.76mmol) in this order, and the reaction was carried out at room temperature for 2 hours. After 50mL of ethyl acetate was added, the mixture was washed once with 2M hydrochloric acid (10 mL) and saturated aqueous sodium bicarbonate solution (30 mL) in this order, the organic layer was taken out, 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 in a volume ratio = 10) to obtain 991mg of the objective product.
1 H NMR (400MHz, DMSO-d 6) data were as follows (delta [ ppm ], [])：10.51(s,1H),10.38(s,1H),7.96(d,J＝8.8Hz,2H),7.92(d,J＝2.0,1H),7.84(dd,J＝2.0,7.6,1H),7.80(d,J＝8.8Hz,2H),7.59(dd,J＝2.0,7.6,1H),7.56(br s,2H),7.41(d,J＝7.6Hz,1H),7.20(t,J＝72.8Hz,1H)。
(2) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -3- [ N- (acetonitrile) -4-iodobenzamido ] -2-fluorobenzamide
To a solution of N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6- (difluoromethoxy) phenyl ] -3- (4-iodobenzamido) -2-fluorobenzamide (0.5 g, 0.65mmol) in tetrahydrofuran (10 mL) was added 60wt% sodium hydride (259mg, 6.5mmol) and the reaction was carried out at room temperature for 1 hour. Bromoacetonitrile (387mg, 3.25mmol) was added and the reaction was continued at room temperature for 1 hour. After quenching the reaction with 10ml of water and adding 40ml of ethyl acetate, the organic layer was taken, washed with saturated brine and dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent was petroleum ether: ethyl acetate in a volume ratio = 8).
Process for preparation of Compound 25 1 H NMR (400MHz, DMSO-d 6) data was as follows (delta [ ppm ], (])：10.41(s,1H),7.91(br s,1H),7.69(d,J＝8.8Hz,2H),7.64(d,J＝7.8Hz,2H),7.54(br s,1H),7.37(d,J＝8.8Hz,1H),7.38(t,J＝72.8Hz,1H),7.15(d,J＝8.8Hz,2H),4.92(s,2H)。
Synthesis example 7
Preparation of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -3- [ N- (acetonitrile) -4- (trifluoromethoxy) benzamido ] -2-fluorobenzamide (Compound No. 39):
(1) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6- (difluoromethoxy) phenyl ] -3- [4- (trifluoromethoxy) benzamido ] -2-fluorobenzamide
To a solution of 3-amino-N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6-difluoromethoxyphenyl ] -2-fluorobenzamide (0.80g, 1.47mmol) in tetrahydrofuran (10 mL) were added pyridine (466 mg, 5.89mmol) and 4- (trifluoromethoxy) benzoyl chloride (396mg, 1.76mmol) in this order, and the reaction was carried out at room temperature for 2 hours. After 50mL of ethyl acetate was added, the mixture was washed once with 2M hydrochloric acid (10 mL) and saturated aqueous sodium bicarbonate solution (30 mL) in this order, the organic layer was taken out, 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 in a volume ratio = 10) to obtain the objective product (0.90 g, yield 83.72%).
1 H NMR (400MHz, DMSO-d 6) data was as follows (delta [ ppm ], (])：10.51(s,1H),10.43(s,1H),8.14(d,J＝8.8Hz,2H),7.92(d,J＝2.0Hz,1H),7.83(td,J＝2.0Hz,8.8Hz,1H),7.59-7.56(m,4H),7.41(d,J＝8.0Hz,1H),7.38(t,J＝72.8Hz,1H)。
(2) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -3- [ N- (acetonitrile) -4- (trifluoromethoxy) benzamido ] -2-fluorobenzamide
To a solution of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6- (difluoromethoxy) phenyl ] -3- [4- (trifluoromethoxy) benzamido ] -2-fluorobenzamide (0.50g, 0.68mmol) in tetrahydrofuran (10 mL) was added 60% by weight sodium hydride (273mg, 6.8mmol) and the reaction was carried out at room temperature for 1 hour. Bromoacetonitrile (405mg, 3.4 mmol) was added, and the reaction was continued at room temperature for 1 hour. The reaction mixture was quenched with 10mL of water, 40mL of ethyl acetate was added, the organic layer was taken, 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 in a volume ratio =8 = 1) to obtain the objective product 177mg.
Process for preparation of Compound 39 1 H NMR (400MHz, DMSO-d 6) data were as follows (delta [ ppm ], [])：10.39(s,1H),7.91(s,1H),7.68-7.65(m,2H),7.54-7.38(m,4H),7.37-7.15(m,3H),4.94(s,2H)。
Synthesis example 8
Preparation of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -3- [ N- (acetonitrile) -2-fluoroisonicotinamide ] -2-fluorobenzamide (Compound No. 78):
(1) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6- (difluoromethoxy) phenyl ] -3- (2-fluoroisonicotinamido) -2-fluorobenzamide
Pyridine (175mg, 2.2 mmol) and 2-fluoroisonicotinoyl chloride (105mg, 0.66mmol) were sequentially added to a solution of 3-amino-N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6-difluoromethoxyphenyl ] -2-fluorobenzamide (0.30g, 0.55mmol) in tetrahydrofuran (10 mL) and reacted at room temperature for 2 hours. After 50mL of ethyl acetate was added, the mixture was washed once with 2M hydrochloric acid (10 mL) and a saturated aqueous sodium bicarbonate solution (30 mL) in this order, the organic layer was taken out, 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 volume ratio = 10) to obtain 300mg of the objective product.
(2) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -3- [ N- (acetonitrile) -2-fluoroisonicotinamide ] -2-fluorobenzamide
To a solution of N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6- (difluoromethoxy) phenyl ] -3- (2-fluoroisonicotinamido) -2-fluorobenzamide (300mg, 0.45mmol) in tetrahydrofuran (10 mL) was added 60wt% sodium hydride (180mg, 4.5 mmol), and the mixture was reacted at room temperature for 1 hour. Bromoacetonitrile (268mg, 2.25mmol) was added, and the reaction was continued at room temperature for 1 hour. The reaction mixture was quenched with 10mL of water, 40mL of ethyl acetate was added, the organic layer was taken out, 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 volume ratio = 8).
Process for preparation of Compound 78 1 H NMR (400MHz, DMSO-d 6) data were as follows (delta [ ppm ], [])：10.44(s,1H),8.19(br s,1H),7.91(s,1H),7.79(t,J＝7.2Hz,1H),7.66(m,1H),7.54(s,1H),7.40(t,J＝7.8Hz,1H),7.34(t,J＝72.8Hz,1H),7.27(br s,2H),7.21(br s,1H),4.99(s，2H)。
Synthesis example 9
Preparation of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -3- [ N- (acetonitrile) -2-chloroisonicotinamide ] -2-fluorobenzamide (compound No. 79):
(1) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6- (difluoromethoxy) phenyl ] -3- (2-chloroisonicotinamido) -2-fluorobenzamide
Pyridine (175mg, 2.2mmol) and 2-chloroisonicotinoyl chloride (116mg, 0.66mmol) were added in this order to a solution of 3-amino-N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6-difluoromethoxyphenyl ] -2-fluorobenzamide (0.30g, 0.55mmol) in tetrahydrofuran (10 mL) and reacted at room temperature for 2 hours. After 50mL of ethyl acetate was added, the mixture was washed once with 2M hydrochloric acid (10 mL) and a saturated aqueous sodium bicarbonate solution (30 mL) in this order, the organic layer was taken out, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: petroleum ether: ethyl acetate volume ratio = 10).
(2) Synthesis of N- [ 2-bromo-4- (1, 2, 3-heptafluoropropan-2-yl) -6-difluoromethoxyphenyl ] -3- [ N- (acetonitrile) -2-chloroisonicotinamide ] -2-fluorobenzamide
To a solution of N- [ 2-bromo-4- (1, 2, 3-heptafluoroprop-2-yl) -6- (difluoromethoxy) phenyl ] -3- (2-chloroisonicotinamido) -2-fluorobenzamide (320mg, 0.45mmol) in tetrahydrofuran (10 mL) was added 60wt% sodium hydride (180mg, 4.5mmol), and the reaction was carried out at room temperature for 1 hour. Bromoacetonitrile (268mg, 2.25mmol) was added, and the reaction was continued at room temperature for 1 hour. The reaction mixture was quenched with 10mL of water, 40mL of ethyl acetate was added, the organic layer was taken out, 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 volume ratio = 8).
Process for preparation of compound 79 1 H NMR (400MHz, DMSO-d 6) data was as follows (delta [ ppm ], (])：10.44(s,1H),8.36(br s,1H),7.91(br s,1H),7.80(t,J＝7.2Hz,1H),7.68(m,1H),7.55-7.52(m,2H),7.41(t,J＝8.4Hz,1H),7.33(t,J＝72.8Hz,1H),7.31(br s,1H),4.98(s,2H)。
Other compounds of formula I of the present invention may be synthesized by reference to the methods described above.
Formulation example 1
In this example, a formulation was prepared using compound 1 of the present invention as a representative compound, as follows:
30 parts by weight of Compound 1 of the present invention, 15 parts by weight of polyoxyethylene styrylphenyl ether, 10 parts by weight of phosphorous acid, and 45 parts by weight of xylene were uniformly mixed to obtain a 30% concentration emulsifiable concentrate of Compound 1 of the present invention.
Formulation example 2
In this example, a formulation was prepared using compound 17 of the present invention as a representative compound, as follows:
20 parts by weight of Compound 27 of the present invention, 2 parts by weight of sodium lauryl sulfate, 2 parts by weight of a dialkyl sulfosuccinate, 1 part by weight of a sodium salt of a formaldehyde condensate of β -naphthalenesulfonic acid, and 75 parts by weight of diatomaceous earth were uniformly mixed with stirring to obtain a 20% wettable powder of Compound 17 of the present invention.
Formulation example 3
In this example, a formulation was prepared using compound 78 of the present invention as a representative compound, as follows:
30 parts by weight of the compound of the present invention 5, 10 parts by weight of ethylene glycol, 6 parts by weight of nonylphenol polyethylene glycol ether, 10 parts by weight of sodium lignosulfonate, 10 parts by weight of carboxymethylcellulose, 1 part by weight of a silicone oil aqueous solution, and water were supplemented to 100 parts by weight to obtain a 30% suspending agent of the compound of the present invention 78.
Examples of biological Activity test
Various pests were tested with the above-obtained compounds of the present invention. Unless specifically indicated in the examples and in the present invention: the sample preparation method comprises weighing 10mg of original drug of a sample to be tested, dissolving with 1mL of DMF, preparing 10000ppm of mother liquor, and diluting the mother liquor to the required concentration with 0.05% of Tween-80 water for activity test. Mortality is the mortality that leads to death of the pest at the tested concentration of the compound, calculated by the formula mortality (%) = number of dead insects/total number of insects 100.
The compounds of example 1 were tested for indoor biological activity against armyworm
The activity test is carried out by adopting a corn dipping seedling feeding method. And (3) shearing the overground part of the fresh indoor planted corn seedling by about 10cm for later use. Soaking the corn seedlings in the liquid medicine for 10s, airing in the shade, cutting into 3-5 cm leaf sections, placing in culture dishes, and placing 3 corn seedlings in each dish. 10 mythimna separata larvae of 4 th instar were inoculated into each well and repeated 3 times. Placing in a light incubator at 25 deg.C, and culturing in dark. Reaction symptoms were investigated 1,2,3 days after the administration, and the mortality was counted.
At a concentration of 0.04ppm, part of the compounds of the present invention have a mortality rate to armyworm (i.e., a mortality rate that leads to death of pests at the test concentration of the compound) of 100% 3 days after application, and the compound numbers are: 1. 17, 23.
Test example 2Indoor biological activity of compound on aphis medicaginis
In this example, the insecticidal activity of aphis medicaginis was tested by the following method:
3 day old myzus persicae preparation: broad bean with stem and single leaf was cut and inserted into a penicillin bottle (capacity 20 mL) filled with clear water. Each single leaf is inoculated with 5 heads of alfalfa aphids to form aphids, and a plastic cup with a hole is covered. And removing adult aphids after 24 hours. Base number investigation is carried out before the test, and if the aphid number is more than 15, single leaves are selected for the test.
An insect soaking method: soaking single leaf of semen Viciae Fabae (with Myzus persicae) in the medicinal liquid for 10s, taking out, air drying, and repeating for 3 times. Placing on a culture shelf in an observation room, and covering with a perforated plastic cup. The number of dead and live insects was investigated after 3 days.
The following compounds have the concentration of 100ppm, have good insecticidal effect 3 days after the application, and have the insect mortality rate of 100 percent: 1. 17.
According to the above method, compounds 1 and 17 were selected and compared with KC1 for insecticidal activity of Myzus medicae to compare the insecticidal activity. The test results are shown in Table 2.
TABLE 2 comparison of the Amazonian aphid-killing Activity of the Compounds of the present application with KC1
| Medicament | Concentration of | Mortality (%) |
| Compound 1 | 100ppm | 100 |
| Compound 17 | 100ppm | 100 |
| KC1 | 100ppm | 27.62 |
Test example 3 indoor bioactivity of Compounds on Spodoptera frugiperda
The activity test is carried out by adopting a corn dipping seedling feeding method. And (3) shearing the overground part of the fresh indoor planted corn seedling by about 10cm for later use. Soaking the corn seedlings in the liquid medicine for 10s, airing in the shade, cutting into 3-5 cm leaf sections, placing in culture dishes, and placing 3 corn seedlings in each dish. 10 Spodoptera frugiperda larvae of 4 th instar were inoculated into each well and repeated 3 times. Placing in a light incubator at 25 deg.C, and culturing in dark. Reaction symptoms were investigated 1,2,3 days after the administration, and the mortality was counted.
When the concentration of the following compounds is 0.1ppm, the insecticidal effect on spodoptera frugiperda is better after 3 days of application, and the pest mortality rate is more than 90%: 14. 17, 23, 78.
According to the method, part of the compounds and KC2 are selected to compare the insecticidal activity of Spodoptera frugiperda. The test results are shown in Table 3.
TABLE 3 comparison of insecticidal Activity of Compounds of the present application with KC2 against Spodoptera frugiperda
Test of the indoor biological Activity of the Compound of example 4 against Tetranychus cinnabarinus
Cutting broad bean with stem and single leaf, inserting into penicillin bottle filled with 20mL clear water, and inoculating 20 heads of Tetranychus cinnabarinus to each leaf. After 24h the mite formation was checked and a single leaf above 15 mites was selected for the test. Soaking the single leaves with the adult mites into the liquid medicine for 10s, taking out and airing, placing in an observation room for culture, wherein the temperature is 20-26 ℃, the illumination is 14hL. The number of dead mites was investigated 3d after the application and the mortality was calculated.
The compound 17, 78 and 79 of the invention has a mortality rate of >90% to tetranychus urticae 3 days after application at a concentration of 100 ppm.
The present invention is illustrated by the above examples, but the present invention is not limited to the above examples, i.e., it is not intended that the present invention be implemented by relying on the above examples. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (9)
1. An amide compound, characterized in that the amide compound has a structure shown as the following formula I:
in the formula I, the compound is shown in the specification,
q is selected from one of the following Q1, Q2, Q3 or Q4:
Z 1 、Z 2 、Z 3 、Z 4 、Z 5 each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro and C 1 -C 6 Alkyl radical, C 1 -C 6 Cycloalkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Halogenocycloalkyl, C 1 -C 6 Alkoxy radical, C 1 -C 6 Haloalkoxy, C 1 -C 6 Alkylsulfinyl radical, C 1 -C 6 Haloalkylsulfinyl radical, C 1 -C 6 Alkylsulfonyl or C 1 -C 6 A haloalkylsulfonyl group;
r is selected from hydrogen, fluorine or methoxy;
W 1 and W 2 Independently an oxygen atom or a sulfur atom.
2. Amide-based compound according to claim 1, characterized in that, in formula I,
Z 1 、Z 2 、Z 3 、Z 4 、Z 5 each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, and cycloPropyl, n-butyl, tert-butyl, isobutyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2-dimethylpropyl, methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, trifluoromethyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoro-isopropyl, difluoromethoxy, trifluoromethoxy, pentafluoroethoxy, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl or trifluoromethylsulfonyl.
3. Amide-based compound according to claim 1, characterized in that, in formula I,
Z 1 、Z 2 、Z 3 、Z 4 、Z 5 each independently selected from hydrogen, fluoro, chloro, bromo, iodo, cyano, nitro, methyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, methylsulfonyl or trifluoromethylsulfonyl; r is selected from hydrogen or fluorine W 1 And W 2 Selected from oxygen.
4. Amide-based compound according to any of claims 1 to 3, characterized in that the amide-based compound is any one selected from the following compounds:
5. the tautomer, enantiomer, diastereomer or salt thereof of the amide-based compound according to any one of claims 1 to 4.
6. Use of the amide-based compound according to any one of claims 1 to 4 or the tautomer, enantiomer, diastereomer or salt thereof according to claim 5 for controlling plant pests.
7. A pesticidal composition, which comprises an active ingredient which is the amide-based compound according to any one of claims 1 to 4 or the tautomer, enantiomer, diastereomer or salt thereof according to claim 5, and an agriculturally pharmaceutically acceptable carrier.
8. The insecticidal composition according to claim 7, wherein the weight percentage of the active ingredient in the insecticidal composition is 1-99%.
9. A method of controlling pests, said method comprising: applying an effective dose of an amide-based compound according to any one of claims 1 to 4 or a tautomer, enantiomer, diastereomer or salt thereof according to claim 5 or a pesticidal composition according to claim 7 or 8 to a pest or a medium in which control is desired;
preferably, the effective dose is from 7.5 to 1000g per hectare, preferably from 15 to 600g per hectare.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105873901A (en) * | 2013-12-23 | 2016-08-17 | 先正达参股股份有限公司 | Insecticidal compounds |
| CN110194726A (en) * | 2018-05-11 | 2019-09-03 | 沈阳化工大学 | A kind of benzamide compound and its application |
| CN112430211A (en) * | 2019-08-26 | 2021-03-02 | 沈阳化工大学 | Isophthalamide compound and application thereof |
| CN112661665A (en) * | 2019-10-15 | 2021-04-16 | 南通泰禾化工股份有限公司 | Amide compound and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105873901A (en) * | 2013-12-23 | 2016-08-17 | 先正达参股股份有限公司 | Insecticidal compounds |
| CN110194726A (en) * | 2018-05-11 | 2019-09-03 | 沈阳化工大学 | A kind of benzamide compound and its application |
| WO2019214588A1 (en) * | 2018-05-11 | 2019-11-14 | 沈阳化工大学 | Benzamide compound and application thereof |
| CN112430211A (en) * | 2019-08-26 | 2021-03-02 | 沈阳化工大学 | Isophthalamide compound and application thereof |
| CN112661665A (en) * | 2019-10-15 | 2021-04-16 | 南通泰禾化工股份有限公司 | Amide compound and preparation method and application thereof |
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