CN114805294A - Heteroaryl-substituted m-diamide compound or salt thereof as pesticide acceptable, composition and application thereof - Google Patents

Heteroaryl-substituted m-diamide compound or salt thereof as pesticide acceptable, composition and application thereof Download PDF

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CN114805294A
CN114805294A CN202210613646.1A CN202210613646A CN114805294A CN 114805294 A CN114805294 A CN 114805294A CN 202210613646 A CN202210613646 A CN 202210613646A CN 114805294 A CN114805294 A CN 114805294A
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substituted
heteroaryl
alkyl
compound
formula
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葛家成
胡堂路
邱佳鹏
邢阳阳
孙鹏
赵伟靖
张永芳
李丽
王均竹
王伟香
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Hailir Pesticides and Chemicals Group Co Ltd
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Hailir Pesticides and Chemicals Group Co Ltd
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    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur 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
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • A—HUMAN NECESSITIES
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    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
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    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
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    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
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    • 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
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • 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
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/02—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
    • C07D275/03—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D277/56—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

Abstract

The invention belongs to the field of pesticides, and particularly relates to a heteroaryl-substituted m-diamide compound or a salt and a composition thereof acceptable as pesticides and application thereof, wherein the compound has a structure shown in a formula (I):

Description

Heteroaryl-substituted m-diamide compound or salt thereof acceptable as pesticide, composition and application thereof
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a m-diamide compound or a salt and a composition thereof acceptable as a pesticide, and application of the compound or the salt and the composition thereof acceptable as the pesticide.
Background
In agricultural production, due to the resistance of pesticides and the fact that the existing pesticides are not friendly to the environment, the development of efficient, low-toxicity and environment-friendly pesticides is always pursued by pesticide developers, and the m-diamide compounds belong to the IRAC 30 group, have the mechanism of gamma-aminobutyric acid (GABA) receptor antagonists, are different from the bisamide compounds which are widely used at present and have obvious resistance problems, and gradually become new concerns in the pesticide market after the neonicotinoid compounds and the bisamide compounds. The insecticidal activity of the m-diamide compounds has been reported, for example, CN102119143B reports a series of m-diamide compounds and the insecticidal activity thereof, compounds CK1 (compound No. 7-1596), CK2 (compound No. 7-1597), CK3 (compound No. 6-1126) and CK4 (compound No. 7-1574) are disclosed, and the insecticidal activity of the compounds is disclosed, wherein CK4(ISO common name is broflanilide, Chinese common name is brofenfluride) is commercialized; in addition, other m-diamide compounds are also disclosed in the prior art, and the specific structure is as follows:
Figure BDA0003673591140000011
at present, the number of the m-diamide compounds on the market is infinite, but the accompanying resistance problem needs to be solved urgently.
Technical problem
In order to solve the above problems in the prior art, the present invention provides a heteroaryl-substituted isophthalamide compound or a pesticidally acceptable salt thereof, a composition and use thereof, which have excellent persistence and fast-acting properties for killing pests and are not easily cross-resistant with the existing isophthalamide compound.
Technical solution
The technical scheme adopted by the invention for realizing the purpose is as follows: a heteroaryl-substituted m-diamide compound or a salt thereof which is acceptable as a pesticide has a structural formula shown in a formula (I):
Figure BDA0003673591140000021
in the formula (I), R 1 、R 2 、R 3 Each independently selected from H, halogen, CN, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl or C 3 -C 6 A cycloalkyl group;
R 4 selected from H, C 1 -C 6 Alkyl radical, C 3 -C 6 Cycloalkyl, CN substituted C 1 -C 6 Alkyl or C 3 -C 6 Cycloalkyl-substituted C 1 -C 6 An alkyl group;
g is selected from O or S;
q is selected from five-membered heteroaryl substituted or unsubstituted by a substituent.
Further, in the formula (I), R 1 、R 2 Each independently selected from H, halogen, CN, C 1 -C 4 Alkyl, halo C 1 -C 4 Alkyl or C 3 -C 6 A cycloalkyl group;
still further, R 1 、R 2 Are respectively and independently selected from H, F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu and CF 3 、CHF 2 、CH 2 F、CCl 3 、CHCl 2 、CH 2 Cl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Further, in the formula (I), R 3 Is halo C 3 -C 6 An alkyl group;
still further, R 3 Is halo C 3 -C 4 An alkyl group; still further, R 3 Is heptafluoroisopropyl or nonafluoro-2-butyl.
Further, in the formula (I), R 4 Selected from H, C 1 -C 6 Alkyl, CN substituted C 1 -C 6 Alkyl or C 3 -C 6 Cycloalkyl-substituted C 1 -C 6 An alkyl group;
still further, R 4 Selected from H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CN-substituted methyl, CN-CH 2 -CH 2 -a cyclopropyl substituted methyl group or a cyclopropyl substituted ethyl group.
Further, in the formula (I), G is O.
Further, in formula (I), Q is selected from thiophene, thiazole, isothiazole, thiadiazole, pyrazole, pyrrole, furan, imidazole or oxazole which is substituted or unsubstituted by 1-3 substituents;
still further, the substituent is selected from the group consisting of F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, n-Pr, n-Bu, n-B, n-B, and n-B, and C, n-B, and C, n-B, and C, n-B, n-B, n-,t-Bu、CF 3 、CHF 2 、CH 2 F、CCl 3 、CHCl 2 、CH 2 Cl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Further, formula (I) is:
Figure BDA0003673591140000031
Figure BDA0003673591140000041
Figure BDA0003673591140000051
the salt acceptable as the pesticide can be a salt prepared by reacting the heteroaryl-substituted m-diamide compound of the invention with a chemically acceptable acid, wherein the chemically acceptable acid can be an inorganic acid (such as hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid) or an organic acid (such as oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid or benzoic acid); the pesticide acceptable salt can also be a salt prepared by reacting the heteroaryl-substituted m-diamide compound with a chemically acceptable base, wherein the chemically acceptable base can be an inorganic base (such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate) or an organic base (such as trimethylamine, triethylamine and the like).
Further, the salt acceptable as a pesticide may be a potassium salt, a sodium salt, an ammonium salt, a calcium salt, a pyridinium salt, a choline salt, a hydrochloride salt, a phosphate salt, an acetate salt, a benzenesulfonate salt or an oxalate salt.
The invention also discloses an insecticidal composition, which comprises an insecticidal effective amount of at least one of the heteroaryl-substituted m-diamide compounds or salts thereof acceptable as pesticides; further, the preparation also comprises a preparation carrier or a preparation auxiliary agent.
The present invention also discloses a method for controlling plant pests, which comprises applying an insecticidally effective amount of at least one of the heteroaryl-substituted isophthalamide compounds described above or salts thereof which are acceptable as pesticides or an insecticidal composition as described above to the crop plants or the pests and/or their habitat.
The invention also discloses the application of the heteroaryl-substituted m-diamide compound or at least one of the salts thereof acceptable for pesticides or the insecticidal composition in the field of agriculture and other fields to control plant pests.
In the definitions of the structural formulae of the compounds mentioned above, the terms used have the following meanings:
halogen or halogen: refers to fluorine, chlorine, bromine, iodine.
C 1 -C 6 Alkyl groups: straight-chain or branched alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like.
Halogen substituted C 1 -C 6 Alkyl groups: straight-chain or branched alkyl groups having 1 to 6 carbon atoms, wherein hydrogen atoms in the alkyl groups may be partially or completely substituted with halogen, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl and the like.
The compounds of formula I according to the invention can be prepared by the following processes, in which the radicals are as defined above, unless otherwise indicated.
Figure BDA0003673591140000061
Further, the reaction may be carried out under normal pressure or high pressure, preferably under atmospheric pressure, and the post-treatment may be carried out according to a conventional method.
Further, the synthesis method of II is exemplified as follows:
Figure BDA0003673591140000062
further, II' is at R 4 If H is equal to II, then II' can omit this step.
Further, an example of the synthesis method of II' "is as follows:
Figure BDA0003673591140000071
further, III can be obtained by a commercially available method.
An insecticide comprising a compound represented by the formula (I) or a salt thereof as an active ingredient is suitable for controlling pests in soil in the field of fruit trees, vegetables, other crops and ornamental plants.
Examples of pests to which the insecticides of the present invention can be applied include, but are not limited to, Lepidoptera (Lepidoptera), such as black cutworms (Agrotis ypsilon), yellow cutworms (Agrotis segetum), cotton bollworms (Alabama argillacea), velvet bean moths (Anticarsia mmatalis), Argyresthia conjuella, cross-grain armyworms (Autographa gama), Ectropis obliqua (Bupalusifolia), Cacoecia murrina, Capua retta, Chemobia brumata, spruce cabbage loopers (Choristoneura furaria), Choristoneura occidentata, Chinesota octophylla occidentata, Chinesia ostrinia, Chilo chilo punctata, Chilo chilo chilies, Chilo suppressalis (Cihia punctifera), apple cabbage worms (Cydia pomona), Didia pomonella punctata (Dendrorella), Spirorella pinus pinipes, Heliothis virescens, Graphola, Grapholiota (Graphola), Grapholiota (Grapholiota), and Grapholitha puncta), corn borers (Grapholiota), corn borers (Grapholitura), corn borer, Grapholiota), corn borer (Grapholitha) and corn borer, corn borer (Grapholiota), corn borer, rice, corn borer, rice, corn borer, rice borer, rice, corn borer, Corn earworm (Heliothis zea), Plutella xylostella (Hellulaudalis), Hibernia defoliaria, fall webworm (Hypophria cunea), apple moth (Hypomeutaminales), tomato moth (Keifila lycopersilica), Lambda fischereria, beet armyworm (Laphygma exigua), coffee leaf moth (Leucoptera coffeella), leaf miner (Leucoptera cochlegma), leaf miner (Leucoptera nutans), fruit moth (Lobesia borreria), beet webworm (cabbage webworm), cabbage moth (Lymantria dispar), cabbage moth (Lymantria) trichoplusia, orange fruit moth (Lyocephala), cabbage moth (cabbage caterpillar), cabbage caterpillar (cabbage), cabbage caterpillar (cabbage caterpillar, cabbage caterpillar (cabbage), cabbage caterpillar (cabbage caterpillar, cabbage caterpillar (cabbage caterpillar, cabbage caterpillar (cabbage caterpillar, cabbage caterpillar (cabbage caterpillar, cabbage caterpillar (cabbage caterpillar, cabbage caterpillar (cabbage caterpillar, moth (cabbage caterpillar, moth (cabbage caterpillar, soybean loopers (pseudopluviancirus), rycanidia fructicola, sclerobiopalla absoluta, wheat moth (sitotroganella), grapevine leafworm (sparganothris pileriana), Spodoptera frugiperda (Spodoptera fructicola), Spodoptera littoralis (Spodoptera littoralis), prodenia litura (Spodoptera litura), thamatopoa pitycoampa, green oak moth (torrix viridana), trichoplusia pulosa (trichoplusia), and zeirapuamanseni;
beetles (Coleoptera), such as narrow-leaved beetles (Agrilus cornuta), straight-stripped click beetles (Agriotes lineatus), dark-colored click beetles (Agriotes obscurus), Amphimurius solstitialis, Anaandrus dispar, Gossypium mexicanum (Anthonomus grandis), European flower image (Anthonomus pomorum), Aphthona eholidae, Athous hamemoroilis, Cryptodium betaine (Atomaria tenella), bark beetles (Brutopia mossambucifolia), bark beetles (Dicotyphus), European red beetles (Brutotus), bark beetles (Bhaticus), bark beetles (Castaneta), bark beetles (Brassica juncea), European cabbage beetles (bark beetles), bark beetles (bark beetles), bark beetles (cornflower), bark beetles (cornflower), bark beetles, cornflower), bark beetles (cornflower), cornflower), cornflower, Coccinella varivestis (Epilachna varivestis), tabebuia tabacum (Epitrix hirtennis), cotton gray elephant variety (euthiobotrys brasiliensis), european pine bark elephant (hyperbius abietica), egyplanthus manihot (hyperbius), alfalfa leaf elephant (hyperuricemia pomica), spruce bark beetle (ipsypoglyphora), tobacco mud worm (Lema billinata), black horn mud worm (lemma lanopus), potato leaf beetle (leptinctoria decemlineata), limosus californica (limonium californicum), rice water beetle (lissorophytum californicus), rice water beetle (lissorophytum falcatula (phytophthora), strawberry (phytophthora falcatula falcata), rice rape (lilies), rice plant rape (lilies) rape (phytophthora japonica), rice vine black rice vine (phytophthora rosea), rice vine yellow rice vine (phytophthora rosea), rice vine root (phytophthora rosea), rice yellow rice vine (phytophthora rosea), rice vine, rice stem borer (yellow rice stem, rice stem borer, rice stem, rice stem, rice stem, rice stem, rice stem, rice stem, rice stem, rice stem, rice stem, rice stem, rice stem, rice stem, Pisiform elephants (Sitona linear) and Valley elephants (Sitophilus granaria);
flies, mosquitoes (Diptera)), such as Aedes aegypti (Aedes aegypti), Aedes albopictus (Aedes albopictus), Aedes spinosa (Aedes vexans), Drosophila pallidum (Anastrephaluens), Anopheles quinquefolius (Anopheles maculipennis), Anopheles cruzi, Anopheles leucotrichum (Anopheles albomasum), Anopheles giganteus (Anopheles albi), Anopheles freeboni, Anopheles anka (Anopheles leucotrichum), Anopheles minimus (Anopheles minimus), Anopheles quadratus (Anopheles quadratus), Rhododendron virens (Calyphora vicina), Chrysopheles (Ceratopteria nipponica), Chrysopheles labris (Ceratopteria), Chrysopheles procollis pallidus, Chrysopheles lutea, Chrysopheles sinensis, Chrysopheles, Chrysophyta, Chrysophytalis, Chrysophyta, and Chrysophyta, or Phaeophilus, Chrysophyta, or Phaeophilus, Chrysophyta, or Phaeophila, or Chrysophyta, or Phaeophila, Chrysophyta, or Phaeophila, or Pha, The leaf gall of rape (Dasineura brassicae), the flies of Allium fistulosum (Delia indica), the species of Meloidogyrus (Delia coarctata), the species of Gelidium griseus (Delia platura), the species of Brassica oleracea (Delia radiata), the species of dermatia hominis (Dermatobia hominis), the species of Musca microphylla (Fannia caniculularis), the species of Geomya triphylla, the species of Musca domestica (Gasterophilus intestinalis), the species of Glossilalis (Glossina morsella pallida), the species of Glossina fusca, the species of Glossina tachia, the species of Haematobia iritans, the species of Haplopsis equestris, the species of Hippels, the species of peanut gray scale (Hypoplasia), the species of Meloidea splendensa (Hygrophyta), the species of Musca domestica, the species of Osmanthus ovatus (Ostoria), the species of Luciliaris, the species of Ostoria (Luciliaris), the species of Osteus domestica (Luciliaris), the species of Ostoria (Luciliaris), the species of Osteus domestica indica), the species of, Phorbia antia, radish fly (Phorbia brassicae), Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixum, cherry fruit fly (Rhagoletis cerasi), apple fruit fly (Rhagoletis pomonella), Sarcophaga rubra (Sarcophaga haematodes), Sarcophaga (Sarcophaga), Simulium vitatum, Davida stabulans (Stomoxystalisrans), Tabanus bovis (Tabanus bovinus), Tabanus atus, Tabanus rubra lineola, Tabanus sinesis, Tipula and European panda mosa (Tilapulo);
thrips (Thysanoptera), such as Thrips orchid (dichlorthrips corbeti), dichlorthrips ssp, Thrips tabaci (Frankliniella fusca), Thrips lucernifolia (Frankliniella occidentalis), Thrips orientalis (Frankliniella tritici), Thrips platycodi (Scirtothrips citri), Thrips oryzae (Thrips oryzae), Thrips palmi (Thrips palmi) and Thrips tabaci (Thrips tabaci);
termites (Isoptera), such as Calotermes flaviolis, leucotermes flavipes, hetermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Euroticus Termes lucifugus, Blastoma virginica (Reticulitermes santonensis), Reticulitermes grassei, Termes natalensis, and Coptotermes formosanus;
cockroaches (Blattaria) -Blattodea, such as german cockroach (Blattaria germanica), Blattaria ashianae, american cockroach (Periplaneta americana), japanese cockroach (Periplaneta japonica), brown cockroach (Periplaneta rubra), Periplaneta fuligrina, Blattaria australis (Blattaria orientalis), and Blattaria orientalis (Blattaria orientalis);
bed bugs, aphids, leafhoppers, whiteflies, scale insects, cicadas (Hemiptera), e.g. Lygus lucorum (Acrosternum hirae), corn bugs (Blissus leucopterus), blind black spot bugs (Cyrtopteris sutatus), cotton red bugs (Dysdercus cingulatus), Dysdercus intermedius, Lygus applanatus (Eurygaster integriceps), tobacco bugs (Euschistus impiestigotris), red bell bugs (Leptophytylopus), American grass bugs (Lygus lineolaris), Lygus pratensis (Lygus), Lygus pratensis (Apphaleria), aphids (Aphis), aphid (Aphyllum), Aphis viridis (Aphis viridula, Aphis viridis), Aphis japonica (Aphis gossypium, Aphis japonica), Aphis japonica, Aphis, Pleurophycus eryngii (Brachycaulus helicopterys), Brachyurophycus persicae, Brachyurophycus pruricola, cabbage aphid (Brevicoryne brassicae), Capitophorus horni, Cerosiphas gossypii, Chaetophyn fragilis, Cryptomyces ribacter, Dreyphysa nodemanniana, Dophycus spretus (Dreyphysa piriaceae), Phyllophycus giganteus (Dasyphilia), Phyllophycus giganteus (Daphnia viridis), Phyllophycus giganteus (Daphniphyllus major), Phyllophycus giganteus (Daphniphycus carota), Phyllophycus carota major (Daphniphycus), Phyllophycus caris major (Daphus major), Phyllophycus carina, Phyllophycus caris, Phyllophycus carina indica (Phyllophycus caris), Phyllophycus caris niloticus indica), Phyllophycus carica grandis major (Phyllophora, Phyllophycus carina indica, Phyllophora major), Phyllophora major (Phyllophora grandis, Phyllophora grandis (Mycerosa), Phyllophora grandis (Mycerosa), Phyllophora nipulus, Phyllophora nipulus (Mycerosa), Phyllophora nipulus major, Phyllophora nipulus (Mycerosa, Phyllophora nipulus, Phyllophora nipulus, Phyllophora nipulus, Phyllophora nipulus (Mycerosa, Phyllophora nipulus, Phyllophora nipulus, Phyllophora, Mycerosa, Phyllophora nipulus (Mycerosa, Phyllophora nipulus, Myzus, Mycerosa, Myzus, (ii) the species Phosphaerella viridis (Rhopalomyces ascalonicius), Zea mays (Rhopalosiphum maidis), Aphis graminicola (Rhopalosiphum padi), Rhopalosiphum insertum, Sappaaphis mala, Sappaaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Aphis graminis (Sitobion avenae), Trialeurodes vaporariorum, Toxoptera aurantia nd, Rhizopus viticola (Viteusvitifolii), Cimex tulalemma, Cimex hemipterus, Reduvius sensis, Triatoma spp. and Arilus citritus;
ants, bees, wasps, leaf bees (Hymenoptera), such as Sinkiang apis cerana (Athaliarosae), incised leaf ants (Atta cephalotes), Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Ant belladonna (Crematogater), Hoplocapamina, Hoplocapa testudinea, Black ants (Lasius niger), yellow family ants (Monomorpharonis), Tropical fire ants (Solenopsis geminiensis), Red fire ants (Solenopsis invincina), Black fire ants (Solenopsis trices), southern fire ants (Solenopsis nigra), Red fire ants (Ponomyces), yellow jacket wasps, Vespera, Vespertiliota, Vespera, Vespertiliota, Vesperica, Vetiveria sticta, Vesperica, Vetiveria penniscus, Vetiveria;
cricket, grasshopper, locust (Orthoptera), such as cricket (Acheta domestica), mole cricket (gryllopa Gryllotalpa), Locusta migratoria (Locusta migoritia), black Locusta bifida (melanopus bivittatus), red-foot black Locusta (melanopus femurirbum), black mezopus (melanopus nigricans), black Locusta migratoria (melanopus sanguinipes), black Locusta (melanopus spicatus), red stripe red (nodakermacoper fasciata), desert Locusta (schistococcus caligenes), schoecium maculata (schoecium, Locusta), grasshopper (hypopharyopsis maculata), Locusta (hypopharyanus flavus), Locusta (hypopharyanus pacificus), Locusta (hypopharyophyllus maculatus), Locusta (hypopharyoides), Locusta pacificus (hypopharyophyllus maculatus), Locusta (hypopharyanus pacificus) (hypopharyanus), Locusta (hypopharyophyllus), Locusta pacificus (hypopharya), Locusta pacificus) (hypopharya), Locusta pacificus) (hypopharya), Locusta (hypopharyophyllus), Locusta pacificus) (hypopharya pacifica (hypopharya), Locusta pacifica (hypopharya), Locusta pacifica (hypopharyophyllus), Locusta pacifica (hypopharyophyllus (hypopharya), Locusta pacifica (hypopharya), Locusta pacifica (hypopharya), Locusta pacifica (hypopharya pacifica (hypopharya), Locusta pacifica (hypopharya pacific Locusta), Locusta pacific Locusta), Locusta (pacific Locusta), Locusta pacific Locusta (pacific Locusta), Locusta (pacific Locusta), Locusta (pacific Locusta), Locusta (pacific Locusta), Locusta (pacific Locusta), Locusta (aca;
arachnida (Arachnoidea), such as spiders (Acarina), for example, the soft tick family (Argasidae), the hard tick family (Ixodidae) and the scabies family (Sarcoptidae), such as Amblyomma longum (Amblyomma americanum), the tropical flower tick (Amblyomma variegatum), the Ambryomma masum, the Periploca americana (Argas persicus), the Boophilus annuus (Boophilus annuatus), the Boophilus decorticatus, the Boophilus microplus (Boophilus microplus), the German siderurlus, the Dermacentor nigrum, the Dermacentor andersoni, the Dermacentella americana (Dermacentoruifolia), the Hyaltrunum, the Holothuropus (Ixodes), the scleroderma), the Rhynchophora (Acanthomonas campestris), the Gracilaria officinalis (Orchionades purpurea), the sclerotium (Orthophycus), the sclerotinia sclerotiorhodorus (Orchis), the Gracilaria), the sclerotiorhinus (Orchis), the sarcophagoides), the sclerotium (Orchidionalis), the Rhynchophyllus (Orchis, the Rhynchophyllus), the Rhynchophyllus (Orchis), the Gracilus), the sclerotium), the Rhynchophyllus (Orchis), the Gracilus), the Rhynchophyllus (Orchis), the Rhynchophyllus), the Rhynchophus (Oryza), the Roteus (Orchis (Oryza), the Rhynchophus (Orchii), the Roteus), the Rhynchophus (Oryza), the Rhynchophyllus (Oryza), the Rhynchophus (Oryza), the Roteus (Orchii), the Roteus (Oryza), the Roteus (Orchii), the Roteus (Orchirophus, the Roteus), the Roteopilus (Orchirophus, the Roteopyridis), the Roteopyrodes), the Roteopyridis), the Roteopyrodes), the Roteus), the Roteophilus), the Roteus), the Roteopyridis), the Roteopyri (Orchirophus (Orchis), the Roteus), the Roteopyri (Orchirophus (Orchirophus, the, Phyllocoptataroleivora and Eriophyes sheldoni; dermatophagoides (Tarsonemidae), such as Phytonemus pallidus and Tarsonemus laterosus (Polyphagotarsonemus latus); spider mites (tenuipipida), such as red spider mite (brevipus phoenicis); tetranychus (Tetranyhidae), such as Tetranychus cinnabarinus (Tetranychus cinnabarinus), Tetranychus cinnabarinus (Tetranychus kanzawai), Tetranychus pacificus (Tetranychus pacificus), Tetranychus gossypii (Tetranychus Tetranychus tetranyicus) and Tetranychus urticae (Tetranychus urticae), Tetranychus pomi (Pannychus ulmi), Tetranychus ulmi (Pannychus citri) and Oligonychus pratenses; araneida (Araneida), such as the Black widow spider (Latrodectus macrants) and the Brown spider (Loxosceles reclusia);
fleas (Siphonaptera), such as cat fleas (Ctenococcus felis), dog fleas (Ctenococcus canis), rat fleas (Xenopsylla cheopis), prurigo (Pulex irutans), dermatia penetrans (Tunga pendans) and sick fleas (Nosopsyllus fasciatus);
chlamydomonas, cheilfish (Thysanura), such as chlamydomonas occidentalis (Lepisma saccharana) and chlamydomonas maculata (Thermobia domestica), copepods (Chilopoda), such as scutiger colortrata, millipedes (Diplopoda), such as narcoleus spp., [0491] earoca (Dermaptera), such as compactula auricularia, louse (Phthiraptera), such as trichum auricularia, louse (Phthiraptera), such as Pediculus humanus capitis (pediococcus), Pediculus humanus (pediluus gorius), pubis (pthorusus), blood louse (haemapulirus), cattle blood louse (trichoderma), pig trichoderma (trichoderma), cattle trichoderma, cattle trichoderma and cattle trichoderma;
from the order of the Collelmbola (springtail), for example, the genus Onychiurus (Onychiurus).
They are also suitable for controlling nematodes: plant parasitic nematodes such as root-knot nematodes, northern root-knot nematodes (melodogyne hapla), southern root-knot nematodes (melodogyne incognita), Meloidogyne javanica (melodogyne japonica) and other root-knot nematodes (melodogyne); cyst-forming nematodes, potato gold thread (Globodera roseochiensis) and other globulospora (Globodera); heterodera avenae (Heterodera avenae), Heterodera glycines (Heterodera glycines), Heterodera betanae (Heterodera schachtii), trefoil cyst nematode (Heterodera trifolii) and other cyst nematodes (Heterodera); seed gall nematode, granulomatosis (Anguina); nematode stem and leaf, Aphelenchoides (Aphelenchoides); nematoda, weed nematoda (belonolaima longicaudatus) and other nematoda (belonolaimas); pine nematodes, pine wood nematodes (Bursaphelenchus xylophilus) and other species of Gliocladium spp (Bursaphelenchus); roundworm, Trichinella circinata (Criconema), Trichinella ringgoldiana (Criconema), Strychnos (Criconemoides), Trichinella intermedia (Mesocroniema); globodera, putrescent stem nematode (Ditylenchus destructor), sweet potato stem nematode (Ditylenchus dipsaci) and other phylogenetic species (Ditylenchus); conus, Conus spp (Dolichodorus); helicoid nematodes, the genera heliotylenchus and other heliotylenchus; coleoptera and coleoptera, coleoptera (Hemiclilopora) and Hemicconemoides (Hemicconomoides); latent root nematodes (Hirshmanniella); coronaries, rifles spp (hopolaimus); pseudoroot knot nematode, pearl nematode (Nacobbus); nematodes, longilineans transversa (Longidorus elengatus) and other longetidae (Longidorus); root-rot nematodes, Praylenchus negectus, Praylenchus punctatus (Praylenchus penetrrans), Praylenchus curvitatus, Pratylenchus geodenus (Praylenchus) and other species of root-rot nematodes (Praylenchus); periploca, Radopholus similis (Radopholus simlis) and other species of Periploca (Radopholus); reniform nematodes, discoid nematodes (Rotylenchus robustus) and other species of reniform nematodes (Rotylenchus); scutellonema; residual root nematodes, primitive ragworms (Trichodorus primativus) and other trichodera species (Trichodorus); genus pseudospiders (parathichodours); nematodes of the resistant species, purslane dwarf (Tylenchus clavoni), cis-trans dwarf (Tylenchus dubius) and other species of the dwarf species (Tylenchus); citrus nematodes, heminematoda (Tylenchulus); sword nematode, sword nematode (xiphilinema); and other plant parasitic nematodes.
They can also be used for controlling arachnids (arachnids), such as acarids (order acarina), for example the families of the soft, hard and sarcoptic acaridae, such as the long-star-shaped ticks (Amblyomma americanum), the tropical flower ticks (Amblyomma variegatum), the Persian tick (Argas persicus), the cowlice (Boophilus annuatus), the Boophilus decorticatus, the Boophilus microplus (Boophilus microplus), the German silverareum, the Hyalomma truncatum, the Ricinum hard tick (Ixodesricinus), the Ixodes rubicundus, the Ornithiodorus mouubulus, the Otobius megrini, the Dermanyssus gallina, the sheep scabies (Psoropteris), the Rhiocephalus pendula, the aphidicola, the Epicoccus apercha, the Rhynchophyllus purpureus phaea, the Rhynchophyllus mange (Acacia), and the acarina, such as mange (Acanthopanax mange, and Acacia; dermatophagoides (Tarsonemidae), such as Phytonemus pallidus and Tarsonemus laterosus (Polyphagotarsonemulatus); spider mites (tenuipiladae), such as red spider mite (brevipus phoenicis); tetranychus (Tetranyhidae), such as Tetranychus cinnabarinus (Tetranychus cinabarinus), Tetranychus cinnabarinus (Tetranychus kanzawai), Tetranychus pacificus (Tetranychus pacificus), Tetranychus gossypii (Tetranychus Tetranychus), and Tetranychus urticae (Tetranychus urticae), Tetranychus pomi (Pannychus ulmi), Tetranychus ulmi (Pannychus urtri), Phyllostachys citroensis (Pannychus urtri), and oligoychus pratensis.
The plant object used for the pesticide of the present invention is not particularly limited; there may be mentioned, for example, cereals (e.g., rice, barley, wheat, rye, oat, corn, sorghum, etc.), beans (soybean, adzuki bean, broad bean, pea, groundnut, etc.), fruit trees/fruits (apple, citrus, pear, grape, peach, japanese apricot, cherry, walnut, apricot, banana, strawberry, etc.), vegetables (cabbage, tomato, spinach, broccoli, lettuce, onion, welsh onion, green pepper, etc.), root vegetables (carrot, potato, sweet potato, radish, lotus root, turnip, etc.), industrial crops (cotton, hemp, broussonetia papyrifera, rape, beet, hop, sugarcane, sugar beet, olive, rubber, coffee, tobacco, tea, etc.), berry fruits (pumpkin, cucumber, watermelon, melon, etc.), pasture grasses (orchard grass, milo, timothy, alfalfa, etc.), turf grasses (korean chickweed, grass, etc.), grasses (korean chickweed, rye, sorghum, etc.), alfalfa, etc, Bentgrass, etc.), crops for spices (lavender, rosemary, thyme, parsley, pepper, ginger, etc.), and flowers (chrysanthemum, rose, orchid, etc.).
Advantageous effects
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
by carrying out chemical modification and molecular design on the compound with the m-diamide structure, a five-membered aromatic heterocycle is introduced and/or a substituent group is introduced on N of an amide group, so that a series of compounds which are more efficient and can be used for agriculture or forestry insecticidal use and have excellent activity are obtained, particularly, the compounds have quick-acting and lasting insecticidal activity under low dosage and do not generate cross resistance with the existing m-diamide insecticide.
Modes for carrying out the invention
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
By taking into account the economics, diversity and biological activity of the synthesized compounds, it is preferred that some of the compounds are listed in the following table. Specific compound structures are shown in table 1, and specific physical property data of the compounds are shown in table 2. The compounds in tables 1-2 are only for better illustration of the invention and are not intended to be limiting, and those skilled in the art will not understand that the scope of the above subject matter of the invention is limited to the following compounds.
Figure BDA0003673591140000121
TABLE 1 Structure of Compounds of formula I
Figure BDA0003673591140000122
Figure BDA0003673591140000131
Figure BDA0003673591140000141
Figure BDA0003673591140000151
Figure BDA0003673591140000161
Figure BDA0003673591140000171
Figure BDA0003673591140000181
TABLE 2 1 H NMR data
Figure BDA0003673591140000182
Figure BDA0003673591140000191
Figure BDA0003673591140000201
The methods for preparing the compounds of the present invention are illustrated in the following schemes and examples. The starting materials are commercially available or can be prepared by methods known in the literature or as shown in detail. It will be appreciated by those skilled in the art that other synthetic routes may also be utilized to synthesize the compounds of the present invention. Although specific starting materials and conditions for the synthetic routes are described below, they can be readily substituted with other similar starting materials and conditions, and variations or modifications of the preparation process of the present invention, such as various isomers of the compounds, are included in the scope of the present invention. In addition, the preparation methods described below may be further modified in accordance with the present disclosure using conventional chemical methods well known to those skilled in the art. For example, protecting the appropriate groups during the reaction, and the like.
Example 1
Preparation of Compound I-1:
(1) preparation of 2-bromo-4- (heptafluoropropan-2-yl) -6- (trifluoromethyl) aniline:
Figure BDA0003673591140000211
FeSO was added to a dry 500mL single neck flask 4 ·7H 2 Dissolving O (14.60g, 0.052mol) in 30mL of water, adding 300mL of DMSO, O-trifluoromethylaniline (24.16g, 0.15mol) and 2-heptafluoroiodopropane (53.27g, 0.18mol) in sequence, slowly adding 30mL of hydrogen peroxide in an ice water bath, stirring at room temperature, monitoring the reaction by LC-MS, adding 75mL of 5% hydrochloric acid aqueous solution and 300mL of ethyl acetate after the reaction is finished, extracting the organic phase once, washing with 200mL of saturated saline water for 3 times, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, dissolving in 250mL of DMF, adding NBS (29.37g, 0.16mol), stirring at 60 ℃ for 1h, monitoring the reaction by LC-MS, adding 200mL of saturated sodium chloride aqueous solution after the reaction is finished, extracting with 200mL of dichloromethane for three times, combining the organic phases, drying with anhydrous sodium sulfate, concentrating under reduced pressure, separating the product by column chromatography (eluent is petroleum ether: ethyl acetate 50:1), the desired product (49.52g, 81.11% yield) was obtained as a yellow oily liquid.
(2) Preparation of N- (2-bromo-4- (heptafluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -2-fluoro-3-nitrobenzamide:
Figure BDA0003673591140000212
in a dry 500mL single neck flask was added 2-fluoro-3-nitrobenzoic acid (33.76g, 0.18mol), dissolved with 300mL of dichloromethane and 4 drops of DMF were added dropwise, oxalyl chloride (27.81.g, 0.22mol) was added slowly dropwise over an ice water bath, stirred at room temperature for 3h, the reaction was monitored by LC-MS and after completion, concentrated under reduced pressure and dissolved in 30mL of acetonitrile for use. The product of the first step was added to a dry 500mL single-neck flask, dissolved in 250mL of acetonitrile, KI (6.06g, 0.036mol) was added, an acetonitrile solution of 2-fluoro-3-nitrobenzoyl chloride was slowly added dropwise to the reaction system with stirring at room temperature, stirred at 85 ℃ for 20 hours, the reaction was monitored by LC-MS, after the reaction was completed, concentrated under reduced pressure, and the product was isolated by column chromatography (eluent was petroleum ether: ethyl acetate: 5:1) to obtain the desired product (39.33g, yield 56.32%) as a pale yellow solid.
(3) Preparation of 3-amino-N- (2-bromo-4- (heptafluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -2-fluorobenzamide:
Figure BDA0003673591140000213
in a dry 500mL single neck flask was added stannous chloride dihydrate (46.38g, 0.21mol), dissolved with concentrated hydrochloric acid, and the second step product was dissolved in 80mL of methanol and added dropwise to the reaction system. Heating the reaction mixture to 60 ℃, reacting for 3h, monitoring the reaction by LC-MS, after the reaction is finished, adjusting the pH to 8-9 by using a sodium hydroxide aqueous solution, separating out a large amount of solid, performing suction filtration, concentrating under reduced pressure, extracting by ethyl acetate, drying, and separating the product by column chromatography (eluent is petroleum ether: ethyl acetate 4:1) to obtain a target product (34.62g, the yield is 91.2%) which is a yellow solid.
(4) Preparation of Compound I-1:
Figure BDA0003673591140000221
compound intermediate III-1(3.21g, 0.022mol), toluene (35mL) were added to a dry 100mL single-neck flask, compound intermediate II-1(10.88g, 0.02mol) was added with stirring at room temperature, the reaction mixture was heated to 90 ℃, reacted for 5 hours, LC-MS monitored the reaction, after the reaction was completed, concentrated under reduced pressure, and the product was separated by column chromatography (eluent was petroleum ether: ethyl acetate 5:1) to obtain the target product I-1(3.99g, 61.05%).
Example 2
Preparation of Compound I-27:
(1) preparation of 2, 6-dibromo-4- (heptafluoropropane-2-yl) aniline:
Figure BDA0003673591140000222
FeSO was added to a dry 500mL single neck flask 4 ·7H 2 Dissolving O (14.60g, 0.052mol) in 20mL of water, sequentially adding 200mL of DMSO, 2, 6-dibromoaniline (37.64g, 0.15mol) and 2-heptafluoroiodopropane (66.58g, 0.22mol), slowly and dropwise adding hydrogen peroxide under ice water bath to obtain 30mL, stirring at room temperature, monitoring the reaction by LC-MS, adding 60mL of 5% hydrochloric acid aqueous solution and 300mL of ethyl acetate to extract once after the reaction is finished, collecting an organic phase, washing with 200mL of saturated saline water for 3 times, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, and separating the product by column chromatography (the eluent is petroleum ether: ethyl acetate ═ 50:1) to obtain the target product (50.10g, the yield is 80.1%) which is a yellow solid.
(2) Preparation of N- (2, 6-dibromo-4- (perfluoropropyl-2-yl) phenyl) -2-fluoro-3-nitrobenzamide:
Figure BDA0003673591140000223
in a dry 500mL single neck flask was added 2-fluoro-3-nitrobenzoic acid (33.34g, 0.18mol), dissolved with 200mL of dichloromethane and 4 drops of DMF were added dropwise, oxalyl chloride (27.43g, 0.22mol) was slowly added dropwise under an ice water bath, stirred at room temperature for 3h, the reaction was monitored by LC-MS and after completion of the reaction, concentrated under reduced pressure, dissolved in 30mL of acetonitrile for use. The product of the first step was added to a dry 500mL single-neck flask, dissolved in 250mL of acetonitrile, KI (6.98g, 0.042mol) was added, an acetonitrile solution of 2-fluoro-3-nitrobenzoyl chloride was slowly added dropwise to the reaction system with stirring at room temperature, stirred at 85 ℃ for 20 hours, the reaction was monitored by LC-MS, after the reaction was completed, concentrated under reduced pressure, and the product was isolated by column chromatography (eluent was petroleum ether: ethyl acetate: 5:1) to obtain the desired product (69.12g, yield 93.2%) as a yellow solid.
(3) Preparation of 3-amino-N- (2, 6-dibromo-4- (heptafluoropropan-2-yl) phenyl) -2-fluorobenzamide:
Figure BDA0003673591140000224
in a dry 500mL single neck flask was added stannous chloride dihydrate (75.82g, 0.336mol), dissolved with concentrated hydrochloric acid, and the second step product was dissolved in 90mL of methanol and added dropwise to the reaction system. Heating the reaction mixture to 60 ℃, reacting for 3h, monitoring the reaction by LC-MS, after the reaction is finished, adjusting the pH to 8-9 by using a sodium hydroxide aqueous solution, separating out a large amount of solid, performing suction filtration, concentrating under reduced pressure, extracting by ethyl acetate, drying, and separating the product by column chromatography (eluent is petroleum ether: ethyl acetate 4:1) to obtain a target product (55.89g, the yield is 90.2%) which is a yellow solid.
(4) Preparation of Compound I-27:
Figure BDA0003673591140000231
compound intermediate III-27(2.86g, 0.022mol), toluene (40mL) was added to a dry 100mL single-neck flask, compound intermediate II-27(11.08g, 0.02mol) was added with stirring at room temperature, the reaction mixture was heated to 90 ℃ to react for 5h, LC-MS monitored, after the reaction was completed, concentrated under reduced pressure, and the product was isolated by column chromatography (eluent was petroleum ether: ethyl acetate: 5:1) to give the target product I-27(8.97g, 69.2%).
Example 3
Preparation of Compound I-50:
(1) preparation of 2, 6-dibromo-4- (heptafluoropropane-2-yl) aniline:
Figure BDA0003673591140000232
in a dry 500mL single-neck flask, FeSO4 · 7H2O (14.60g, 0.052mol) is dissolved in 20mL of water, 200mL of DMSO, 2, 6-dibromoaniline (37.64g, 0.15mol), 2-heptafluoro iodopropane (66.58g, 0.22mol) are added in sequence, 30mL of hydrogen peroxide is slowly added dropwise in an ice water bath, stirring is carried out at room temperature, LC-MS monitors the reaction, after the reaction is finished, 60mL of 5% hydrochloric acid aqueous solution and 300mL of ethyl acetate are added for extraction once, an organic phase is collected, 200mL of saturated saline is washed 3 times, anhydrous sodium sulfate is dried, filtration is carried out, concentration under reduced pressure is carried out, and the product is separated by column chromatography (eluent is petroleum ether: ethyl acetate: 50:1) to obtain the target product (50.10g, yield is 80.1%) as a yellow solid.
(2) Preparation of N- (2, 6-dibromo-4- (perfluoropropyl-2-yl) phenyl) -2-fluoro-3-nitrobenzamide:
Figure BDA0003673591140000233
in a dry 500mL single neck flask was added 2-fluoro-3-nitrobenzoic acid (33.34g, 0.18mol), dissolved with 200mL of dichloromethane and 4 drops of DMF were added dropwise, oxalyl chloride (27.43g, 0.22mol) was slowly added dropwise under an ice water bath, stirred at room temperature for 3h, the reaction was monitored by LC-MS and after completion of the reaction, concentrated under reduced pressure, dissolved in 30mL of acetonitrile for use. The product of the first step was added to a dry 500mL single-neck flask, dissolved in 250mL of acetonitrile, KI (6.98g, 0.042mol) was added, an acetonitrile solution of 2-fluoro-3-nitrobenzoyl chloride was slowly added dropwise to the reaction system with stirring at room temperature, stirred at 85 ℃ for 20 hours, the reaction was monitored by LC-MS, after the reaction was completed, concentrated under reduced pressure, and the product was isolated by column chromatography (eluent was petroleum ether: ethyl acetate: 5:1) to obtain the desired product (69.12g, yield 93.2%) as a yellow solid.
(3) Preparation of 3-amino-N- (2, 6-dibromo-4- (heptafluoropropan-2-yl) phenyl) -2-fluorobenzamide:
Figure BDA0003673591140000241
in a dry 500mL single neck flask was added stannous chloride dihydrate (75.82g, 0.336mol), dissolved with concentrated hydrochloric acid, and the second step product was dissolved in 90mL of methanol and added dropwise to the reaction system. Heating the reaction mixture to 60 ℃, reacting for 3h, monitoring the reaction by LC-MS, after the reaction is finished, adjusting the pH to 8-9 by using a sodium hydroxide aqueous solution, separating out a large amount of solid, performing suction filtration, concentrating under reduced pressure, extracting by ethyl acetate, drying, and separating the product by column chromatography (eluent is petroleum ether: ethyl acetate 4:1) to obtain a target product (55.89g, the yield is 90.2%) which is a yellow solid.
(4) Preparation of N- (2, 6-dibromo-4- (heptafluoropropan-2-yl) phenyl) -2-fluoro-3- (methylamino) benzamide:
Figure BDA0003673591140000242
200mL of tetrahydrofuran, NaH (8.95g, 60%, 0.372mol) and 3-amino-N- (2, 6-dibromo-4- (heptafluoropropane-2-yl) phenyl) -2-fluorobenzamide are sequentially added into a dry 500mL single-neck flask, methyl iodide (15.76g, 0.111mol) is dropwise added under stirring at room temperature, the mixture is heated to 60 ℃ after completion of dropwise addition to react for 3 hours, LC-MS monitors the reaction, the reaction is cooled to room temperature after the completion of the reaction, 5mL of water is added to quench, the mixture is concentrated under reduced pressure, ethyl acetate is extracted and dried, and the product is separated by column chromatography (eluent is petroleum ether: ethyl acetate ═ 5:1) to obtain the target product (39.30g, yield is 68.5%).
(5) Preparation of Compound I-50:
Figure BDA0003673591140000243
compound intermediate III-5(3.21g, 0.022mol), toluene (40mL) was added to a dry 100mL single-neck flask, compound intermediate II-50(11.36g, 0.02mol) was added with stirring at room temperature, the reaction mixture was heated to 90 ℃ to react for 5h, LC-MS monitored the reaction, after the reaction was completed, concentrated under reduced pressure, and the product was isolated by column chromatography (eluent was petroleum ether: ethyl acetate: 5:1) to give the target product I-50(8.81g, 65.01%).
Example 4
Preparation of the preparation:
1. soluble liquid agent: dissolving 10-50% of the compound of formula (I) and 5-20% of wetting agent in water and/or water-soluble solvent added to 100% to obtain the product.
2. And (3) missible oil: dissolving 15-70% of the compound of formula (I) and 5-10% of emulsifier in 100% of water-insoluble organic solvent to obtain the product.
3. Emulsion in water: dissolving 5-40% of the compound of formula (I) and 1-10% of an emulsifier in 20-40% of a water-insoluble organic solvent. The mixture was introduced into water added to 100% by means of an emulsifying machine and made into a homogeneous emulsion to obtain the product.
4. Suspending agent: in a stirred ball mill, 20-60% of the compound of formula (I) is ground in the presence of 2-10% of a dispersant, 1-5% of a wetting agent, 0.1-5% of a thickener and 100% of water to form an active substance suspension.
5. Water dispersible granules: grinding 50-80% of the compound of formula (I) with the addition of 100% of dispersing and wetting agents and shaping it into water-dispersible granules with the aid of industrial production equipment to give the product.
The above are all weight percentages.
Example 5
Evaluation of biological Activity: diamondback moth (Plutella xylostella)
After dissolving the test compound in N, N-dimethylformamide, the solution was diluted with water containing 0.1% Tween-80 to the desired concentration.
The indoor bioassay adopts a leaf soaking method. Selecting 3-instar diamondback moth larvae with uniform healthy size for testing, placing cabbage leaves in liquid medicine to be tested for 10 seconds, taking out, naturally airing, placing in culture dishes, inoculating 20 larvae into each dish, repeating each concentration treatment for 4 times, and setting solvent treatment containing the same content of no medicament as blank control. The breeding is carried out in an artificial climate chamber with a photoperiod of 16h to 8h (light: dark) at 25 +/-1 ℃. The number of dead diamondback moth insects was investigated 2 days after the administration, and the mortality rate (retention of integer) was calculated.
The activity was as follows:
at a concentration of 10ppm, the control effect of CK1-18 is more than 90 percent: CK4, CK5, CK10 and CK 14.
The above compounds and a part of the compounds of the present invention were subjected to low concentration activity assay, and the results were as follows:
Figure BDA0003673591140000251
Figure BDA0003673591140000261
example 6
Evaluation of biological Activity: chilo suppersalis (Chilo suppersalis)
After dissolving the test compound in N, N-dimethylformamide, the solution was diluted with water containing 0.1% Tween-80 to the desired concentration. The indoor bioassay adopts a leaf soaking method. Selecting healthy and consistent chilo suppressalis 3-instar larvae, putting fresh water bamboo slices into liquid medicine by using tweezers, soaking for 10 seconds, taking out, naturally airing the liquid medicine, putting the water bamboo slices into culture dishes padded with moisturizing filter paper, and repeating the treatment for 4 times for each of 20 chilo suppressalis 3-instar larvae in each dish, wherein blank treatment is used as a control. The treated test insects are placed in an artificial intelligent culture room with the temperature of 25 +/-1 ℃, the illumination time L: D: 16h:8h and the relative humidity of 60 percent for feeding. The number of dead chilo suppressalis was investigated 2 days after drug administration, and the mortality rate (retention integer) was calculated.
The activity was as follows:
at a concentration of 20pppm, the control in CK1-18 was greater than 90%: CK2, CK4, CK10 and CK 14.
The above compounds and a part of the compounds of the present invention were subjected to low concentration activity assay, and the results were as follows:
Figure BDA0003673591140000271
example 7
And (3) evaluating the biological activity: beet armyworm (Laphygma exigua)
After dissolving the test compound in N, N-dimethylformamide, the solution was diluted with water containing 0.1% Tween-80 to the desired concentration.
The indoor bioassay adopts a leaf soaking method. Selecting healthy and uniform-size 3-instar larvae of spodoptera exigua for testing, placing cabbage leaves in liquid medicine to be tested for 10 seconds, taking out, naturally airing, placing in culture dishes, inoculating 20 larvae into each dish, repeating for 4 times for each concentration treatment, and setting solvent treatment without medicament and with the same content as blank control. The breeding is carried out in an artificial climate chamber with a photoperiod of 16h to 8h (light: dark) at 25 +/-1 ℃. The number of dead beet armyworm was investigated 2 days after the drug administration, and the mortality rate (integral number retained) was calculated.
The activity was as follows:
at the concentration of 20ppm, the control effect of CK1-18 is more than 90 percent: CK5, CK10 and CK 14.
The above compounds and a part of the compounds of the present invention were subjected to low concentration activity assay, and the results were as follows:
Figure BDA0003673591140000281
Figure BDA0003673591140000291
the above embodiments are only for illustrating the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention accordingly, and not to limit the protection scope of the present invention accordingly. All equivalent changes or modifications made in accordance with the spirit of the present disclosure are intended to be covered by the scope of the present disclosure.

Claims (10)

1. A heteroaryl-substituted m-diamide compound or a salt thereof which is acceptable as a pesticide has a structural formula shown in a formula (I):
Figure FDA0003673591130000011
in the formula (I), R 1 、R 2 、R 3 Each independently selected from H, halogen, CN, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl or C 3 -C 6 A cycloalkyl group;
R 4 selected from H, C 1 -C 6 Alkyl radical, C 3 -C 6 Cycloalkyl, CN substituted C 1 -C 6 Alkyl or C 3 -C 6 Cycloalkyl-substituted C 1 -C 6 An alkyl group;
g is selected from O or S;
q is selected from five-membered heteroaryl substituted or unsubstituted by a substituent.
2. A heteroaryl-substituted isophthalamide compound or a pesticidally acceptable salt thereof as defined in claim 1, wherein, in the formula (I), R is 1 、R 2 Each independently selected from H, halogen, CN, C 1 -C 4 Alkyl, halo C 1 -C 4 Alkyl or C 3 -C 6 A cycloalkyl group;
preferably, R 1 、R 2 Are respectively and independently selected from H, F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu and CF 3 、CHF 2 、CH 2 F、CCl 3 、CHCl 2 、CH 2 Cl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
3. A heteroaryl-substituted isophthalamide compound or a pesticidally acceptable salt thereof as defined in claim 1, wherein, in the formula (I), R is 3 Is halo C 3 -C 6 An alkyl group;
preferably, R 3 Is halo C 3 -C 4 An alkyl group;
still more preferably, R 3 Is heptafluoroisopropyl or nonafluoro-2-butyl.
4. A heteroaryl-substituted isophthalamide compound or a pesticidally acceptable salt thereof as defined in claim 1, wherein, in the formula (I), R is 4 Selected from H, C 1 -C 6 Alkyl, CN substituted C 1 -C 6 Alkyl or C 3 -C 6 Cycloalkyl-substituted C 1 -C 6 An alkyl group;
still more preferably, R 4 Selected from H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CN-substituted methyl, CN-CH 2 -CH 2 -a cyclopropyl substituted methyl group or a cyclopropyl substituted ethyl group.
5. A heteroaryl substituted isophthalamide compound or a pesticidally acceptable salt thereof as claimed in claim 1, wherein, in formula (I), G is O.
6. The heteroaryl-substituted isophthalamide compound or a pesticidally acceptable salt thereof according to claim 1, wherein in formula (I), Q is selected from thiophene, thiazole, isothiazole, thiadiazole, pyrazole, pyrrole, furan, imidazole, or oxazole, which is substituted or unsubstituted with 1 to 3 substituents;
preferably, the substituents are selected from F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CF 3 、CHF 2 、CH 2 F、CCl 3 、CHCl 2 、CH 2 Cl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
7. A heteroaryl substituted isophthalamide compound or a pesticidally acceptable salt thereof as claimed in claim 1, wherein formula (I) is:
Figure FDA0003673591130000021
Figure FDA0003673591130000031
Figure FDA0003673591130000041
8. an insecticidal composition comprising an insecticidally effective amount of at least one of a heteroaryl-substituted isophthalamide compound or a pesticidally acceptable salt thereof as described in any one of claims 1-7; preferably, the composition also comprises a preparation carrier or a preparation auxiliary agent.
9. A method for controlling plant pests, which comprises applying an insecticidally effective amount of at least one of the heteroaryl-substituted isophthalamide compounds or salts thereof as claimed in any one of claims 1 to 7 or an insecticidal composition as claimed in claim 8 to the crop plants or the pests and/or their habitat.
10. Use of a heteroaryl-substituted isophthalamide compound or at least one of its salts as a pesticidally acceptable salt, as defined in any one of claims 1 to 7, or of a pesticidal composition as defined in claim 8, for controlling plant pests in agriculture and in other fields.
CN202210613646.1A 2022-06-01 2022-06-01 Heteroaryl-substituted m-diamide compound or salt thereof as pesticide acceptable, composition and application thereof Pending CN114805294A (en)

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Citations (3)

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CN101273009A (en) * 2005-07-29 2008-09-24 拜尔农作物科学股份公司 Insecticidal 3-acylaminobenzanilides
CN102119143A (en) * 2008-08-13 2011-07-06 三井化学Agro株式会社 Amide derivative, pest control agent containing the amide derivative and use of the pest control agent
CN114573547A (en) * 2020-12-01 2022-06-03 东莞市东阳光农药研发有限公司 Amide derivative, preparation method and application thereof

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CN101273009A (en) * 2005-07-29 2008-09-24 拜尔农作物科学股份公司 Insecticidal 3-acylaminobenzanilides
CN102119143A (en) * 2008-08-13 2011-07-06 三井化学Agro株式会社 Amide derivative, pest control agent containing the amide derivative and use of the pest control agent
CN114573547A (en) * 2020-12-01 2022-06-03 东莞市东阳光农药研发有限公司 Amide derivative, preparation method and application thereof

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