CN114394912A - Metadiamide compound or salt acceptable as pesticide, composition and application thereof - Google Patents

Metadiamide compound or salt acceptable as pesticide, composition and application thereof Download PDF

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CN114394912A
CN114394912A CN202210081326.6A CN202210081326A CN114394912A CN 114394912 A CN114394912 A CN 114394912A CN 202210081326 A CN202210081326 A CN 202210081326A CN 114394912 A CN114394912 A CN 114394912A
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compound
alkyl
cycloalkyl
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CN114394912B (en
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葛家成
胡堂路
李丽
邢阳阳
孙鹏
吕心童
邱佳鹏
杨春河
张永芳
王均竹
董成武
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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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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/66—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
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  • Engineering & Computer Science (AREA)
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Abstract

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

Description

Metadiamide compound or salt 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 pesticides, and application of the compound or the salt and the composition acceptable as pesticides.
Background
The m-diamide compounds have attracted global attention due to their insecticidal activities, and are becoming a new focus of attention in the insecticide market after neonicotinoid compounds and bisamide compounds. The m-diamide compound belongs to IRAC 30 group, and the mechanism is gamma-aminobutyric acid (GABA) receptor antagonist, which is different from the bisamide compound which is widely used at present and has obvious resistance problem.
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 brofenflurane bisamide) is commercialized; in addition, other m-diamide compounds are also disclosed in the prior art, and the specific structure is as follows:
Figure BDA0003486027200000011
Figure BDA0003486027200000021
although the m-diamide compounds on the market at present solve the resistance problem of the bisamide compounds, with the increasing use requirement of the pesticide in reality, the development of more efficient pesticide is still a problem to be solved.
Technical problem
In order to solve the problems in the prior art, the invention provides a m-diamide compound or a salt thereof acceptable as a pesticide, a composition and a use thereof, which can effectively kill pests, have better safety to crops and have excellent persistence and quick action.
Technical solution
The technical scheme adopted by the invention for realizing the purpose is as follows: a m-diamide compound or a salt thereof acceptable as a pesticide, which has a structural formula shown in formula (I):
Figure BDA0003486027200000022
in the formula (I), the compound is shown in the specification,
X1、X2、X3、X4each independently selected from H, halogen, CN, C1-C6Alkyl, halo C1-C6Alkyl or C3-C6Cycloalkyl radical, X1、X2、X3、X4Not H at the same time;
R1、R2each independently selected from H, halogen, CN, C1-C6Alkyl, halo C1-C6Alkyl or C3-C6A cycloalkyl group;
R3selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C6Cycloalkyl or C3-C6Cycloalkyl radicalsSubstituted C1-C6An alkyl group;
Y1selected from halogen, CN, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C6Cycloalkyl or C3-C6Cycloalkyl-substituted C1-C6An alkyl group.
Further, in the formula (I), R1、R2Each independently selected from H, F, Cl, Br, CN; still further, R1、R2And is F, Cl or Br; still further, R1、R2And is also F.
Further, in the formula (I), Y1Selected from halogen or halogeno C1-C4An alkyl group.
Further, in the formula (I), R3Selected from H, C1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl or C3-C6Cycloalkyl-substituted C1-C4An alkyl group;
further, R3Selected from H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, vinyl, allyl, ethynyl, propargyl, cyclopropylalkyl, cyclobutylalkyl, cyclopentylalkyl, cyclohexylalkyl, cyclopropylmethyl or cyclobutylmethyl;
still more preferably, R3Selected from H, Me or Et.
Further, in the formula (I), X1、X2、X3、X4Each independently selected from H, F, Cl, CF3And X1、X2、X3、X4Not H at the same time;
still further, X1、X2Are simultaneously F and X3、X4While being H, or X1、X2Is simultaneously H and X3、X4Simultaneously being F, or X1、X2Are respectively provided withIs H and F and X3、X4Are each H and F, or X1、X2Is simultaneously H and X3、X4Are H and CF, respectively3Or X1、X2Is simultaneously H and X3、X4Are each H and F, or X1、X2While being Cl and X3、X4While being H, or X1、X2、X3、X4And F at the same time.
Further, in the formula (I), X1、X2、X3、X4Each independently selected from H, F, Cl, CF3And X1、X2、X3、X4Not H at the same time;
R1、R2and is simultaneously F;
R3selected from H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, vinyl, ethynyl, cyclopropylalkyl, cyclobutylalkyl, cyclopentylalkyl, cyclohexylalkyl, cyclopropylmethyl or cyclobutylmethyl;
Y1selected from Br or CF3。
Still further, the structure of formula (I) is specified below,
Figure BDA0003486027200000031
Figure BDA0003486027200000041
the salt acceptable as the pesticide can be a salt prepared by reacting the m-diamide compound 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 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 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 above-mentioned isophthalamide compounds or salts thereof acceptable as pesticides or an insecticidal composition as described hereinbefore to the crops or the pests and/or their habitat.
The invention also discloses the application of at least one of the m-diamide compounds or the salts thereof acceptable as pesticides or the insecticidal composition in the 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.
C1-C6Alkyl 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 C1-C6Alkyl 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.
C1-C6Alkoxy groups: a linear or branched alkyl group having 1 to 6 carbon atoms bonded to the structure via an oxygen atom bond.
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 BDA0003486027200000051
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 BDA0003486027200000052
further, II' is at R3If H is equal to II, then II' can omit this step.
Further, the synthesis of II "is exemplified as follows:
Figure BDA0003486027200000053
further, an example of the synthesis method of II' "is as follows:
Figure BDA0003486027200000054
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, lepidopteran insects (Lepidoptera), such as black cutworms (Agrotis ypsilon), yellow cutworms (Agrotis segetum), cotton bollworms (Alabama argillacea), velvet armyworms (Anticarsia mmatalis), Argyresthia conjuella, Spodoptera litura (Autographa gamma), Echinacea (Bupalustaflavicularis), Cacoecia murrina, Pucaea reiculata, Chemobia brumata, Sporidia elata (Choristoneura hamella fumaria), Choristoneura coccinella occidentata (Choristoneura cocca), Choristoneura occidentalis (Choristoneura cocca), Euglena occidentalis (Grapholiota), Ostrinia punctifera (Graphole), Ostrinia punctifera, Sphacea grandis (Grapholidia punctifera), Sphacea grandis (Grapholitura), Grapholitura heterodera (Grapholiota), Sphacea grandis (Grapholitura), Grapholitura heterochaeta (Grapholitha calis), and Grapholitha calis (Grapholitha calis), Grapholitura) and Grapholitura heterochaeta (Grapholiota), Grapholitha calis (Grapholitha californica) and Grapholiota), Grapholiota, Sphacea) including corn borers (corn borers), corn borers (corn borers), corn borers (corn borers ), corn borers (corn borers, corn borers (corn borers), corn borers), corn borers (corn borers ), corn borers (corn borers, corn borers, 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 hirpentis), cotton gray elephant variety (euthiobotrys brasiliensis), european pine bark elephant (hyperbius abietica), egyplanthus manihot (hyperbius), alfalfa leaf elephant (hyperuricemia prostrate), spruce bark beetle (ipsypoglypharophus), tobacco mud worm (Lema billinata), black horn mud worm (lemma lanopus), potato leaf beetle (leptinctoria decemlineata), limonium californicum (lemongrasta), rice water beetle (lissorthophyllophiuni), cabbage mud worm (phytophthora falcatula falcata), rice plant louse (phytophthora falcatula falcata), rice plant (phytophthora japonica), rice plant (phytophthora falva sylvestis), rice plant (phytophthora falva sylvestis, rice plant (phytophthora), rice plant (rice plant melothrina), rice plant stem, rice stem fungus, rice stem plant stem, rice stem grass stem plant stem, rice stem grass stem, rice stem, rice stem, rice stem, rice stem, rice stem, rice stem, rice stem, rice stem, rice stem, rice stem, rice stem, 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 lucorum (Nezara), aphid (Aphibiscus), aphid (Apphaleria aphid), aphid (Aphis), aphid (Aphis japonica), aphid (Aphis japonica), aphid (aphid), aphid (aphid), aphid (aphid), aphid (aphid), aphid (aphid), aphid (aphid), aphid (aphid), aphid), aphid (aphid), aphid (aphid), aphid (aphid), aphid (aphid), aphid (aphid), aphid (aphid), aphid (aphid), aphid), etc. plant, aphid (aphid), etc. plant (aphid), etc. grass flower, aphid (aphid), etc. plant, aphid), etc. plant stem, aphid), etc. plant (aphid), etc. of plant, aphid), etc. of rice green plant, etc. of rice green plant, etc. of rice plant, etc. of rice, 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 nilotis major), Phyllophycus caris major (Phyllophora, Phyllophora major), Phyllophora major (Phyllophora grandis, Phyllophora major, Phyllophora grandis (Mycerosa, Phyllophora nipulus major), Phyllophora major, Phyllophora grandis (Mycerulophycus carina, Phyllophora nipulus (Mycerosa, Phyllophora nipulus, Phyllophora nipulus major, Phyllophora nipulus (Mycerosa, Phyllophora nipulus, Phyllophora nipulus, Phyllophora, Mycerosa, Mysium grandis, Mycerosa, Mysium grandis, 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 house ants (Monomorium pharaonis), Tropical fire ants (Solenopsis geminium), Red fire ants (Solenopsis invincina), Black fire ants (Solenopsis nigricans), southern fire ants (Solenopsis xylaria), Red fire ants (Ponomyces), Paralichia, Vespertiliota, Vespera, Vespertiliota, Vesperica, Vetiveria penniscus, Vetiveria sticta, 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 (schoecium), grassland Locusta (hypopharyanus), Locusta (hypopharyanus flavus), Locusta (hypopharyanus pacificus), Locusta (hypopharyophyllus), Locusta (hypopharyanus pacificus) (hypopharynx), Locusta (hypopharynx pacificus) (hypopharyanus) and Locusta (hypopharynx);
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 (tenuipiladae), 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, chlamydomonas (Thysanura), such as chlamydomonas occidentalis (Lepisma saccharana) and chlamydomonas maculans (Thermobia domestica), copepods (Chilopoda), such as scutiger colortrata, millipedes (Diplopoda), such as narcoleus spp, earbud octopus (Dermaptera), such as continenta auricularia, lice (trichpira), such as human capitulum auricularia, human Pediculus trichopterus, bovine hemorrhinus (trichoderma), porcine hemorrhinus (trichoderma), bovine hemorrhinus purpurus, porcine hemorrhinus (trichoderma), bovine hemorrhinus vitis, bovine hemorrhinus leucoderma, and bovine hemorrhinula grandis (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); coronaria, rifle nematode (hopolaimaus); 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, introducing a substituent on N of an amide group and/or additionally arranging at least one substituent which is not H on a fluorine-substituted phenyl group, a series of compounds which are more efficient and have excellent activity and can be used for agriculture or forestry insecticide are obtained, and particularly, the compounds have quick-acting and durable insecticidal activity at low dosage.
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 compound physical property data 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 BDA0003486027200000111
TABLE 1 Structure of Compounds of formula I
Figure BDA0003486027200000112
Figure BDA0003486027200000121
TABLE 21H NMR data
Figure BDA0003486027200000122
Figure BDA0003486027200000131
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 BDA0003486027200000132
FeSO was added to a dry 500mL single neck flask4·7H2Dissolving O (9.73g, 0.035mol) in 20mL of water, adding 200mL of DMSO, O-trifluoromethylaniline (16.11g, 0.1mol) and 2-heptafluoro iodopropane (44.39g, 0.15mol) in turn, slowly adding 20mL of hydrogen peroxide under ice-water bath, stirring at room temperature, monitoring the reaction by LC-MS, adding 50mL of 5% hydrochloric acid aqueous solution and 200mL of ethyl acetate after the reaction is finished, extracting the organic phase, washing with 150mL of saturated sodium chloride water for 3 times, drying with anhydrous sodium sulfate, filtering, concentrating under reduced pressure, dissolving in 200mL of DMF, adding NBS (19.58g, 0.11mol), stirring at 60 ℃ for 1h, monitoring the reaction by LC-MS, adding 100mL of saturated sodium chloride aqueous solution after the reaction is finished, extracting with 150mL of dichloromethane for three times, combining the organic phases, drying with anhydrous sodium sulfate, concentrating under reduced pressure, separating the product by column chromatography (the eluent is petroleum ether: ethyl acetate 50:1), the objective product (32.23g, yield 79.2%) 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 BDA0003486027200000141
in a dry 500mL single neck flask was added 2-fluoro-3-nitrobenzoic acid (18.5g, 0.1mol), dissolved with 200mL of dichloromethane and 4 drops of DMF were added dropwise, oxalyl chloride (14.22g, 0.112mol) 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 20mL of acetonitrile for use. Adding the product of the first step into a dry 500mL single-neck flask, dissolving with 200mL acetonitrile, adding KI (3.98g, 0.024mol), slowly dropwise adding a 2-fluoro-3-nitrobenzoyl chloride acetonitrile solution into the reaction system under stirring at room temperature, stirring for 20h at 85 ℃, monitoring the reaction by LC-MS, concentrating under reduced pressure after the reaction is finished, and separating the product by column chromatography (eluent is petroleum ether: ethyl acetate: 5:1) to obtain the target product (31.50g, the yield is 69.3%) which is yellow oily liquid.
(3) Preparation of 3-amino-N- (2-bromo-4- (heptafluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -2-fluorobenzamide:
Figure BDA0003486027200000142
in a dry 500mL single neck flask was added stannous chloride dihydrate (37.53g, 0.166mol), 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 (27.02g, yield is 90.5%) which is a yellow solid.
(4) Preparation of Compound I-1:
Figure BDA0003486027200000143
compound intermediate III-1(2.13g, 0.011mol), toluene (30mL) was added to a dry 100mL single neck flask, compound intermediate II-1(5.44g, 0.01mol) was added with stirring at room temperature, the reaction mixture was heated to 90 ℃ and reacted 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-1(2.82g, yield 40.2%).
Example 2
Preparation of Compound I-4:
(1) preparation of 2, 6-dibromo-4- (heptafluoropropane-2-yl) aniline:
Figure BDA0003486027200000151
FeSO was added to a dry 500mL single neck flask4·7H2Dissolving O (9.73g and 0.035mol) in 20mL of water, sequentially adding 200mL of DMSO, 2, 6-dibromoaniline (25.09g and 0.1mol) and 2-heptafluoro iodopropane (44.39g and 0.15mol), slowly adding 20mL of hydrogen peroxide in an ice water bath, stirring at room temperature, monitoring the reaction by LC-MS, after the reaction is finished, adding 50mL of 5% hydrochloric acid solution and 200mL of ethyl acetate for extraction, collecting an organic phase, washing with 150mL 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 (35.53g, the yield is 85.2%) which is a yellow solid.
(2) Preparation of N- (2, 6-dibromo-4- (heptafluoropropyl-2-yl) phenyl) -2-fluoro-3-nitrobenzamide
Figure BDA0003486027200000152
In a dry 500mL single neck flask was added 2-fluoro-3-nitrobenzoic acid (19.70g, 0.106mol), dissolved with 200mL of dichloromethane and 4 drops of DMF were added dropwise, oxalyl chloride (15.15g, 0.119mol) 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, concentrated under reduced pressure and dissolved in 20mL of acetonitrile for use. Adding the product of the first step into a dry 500mL single-neck flask, dissolving with 200mL acetonitrile, adding KI (4.24g, 0.026mol), slowly dropwise adding the 2-fluoro-3-nitrobenzoyl chloride acetonitrile solution into the reaction system under stirring at room temperature, stirring for 20h at 85 ℃, monitoring the reaction by LC-MS, concentrating under reduced pressure after the reaction is finished, and separating the product by column chromatography (eluent is petroleum ether: ethyl acetate: 5:1) to obtain the target product (45.97g, yield 92.4%) as a yellow solid.
(3) Preparation of 3-amino-N- (2, 6-dibromo-4- (heptafluoropropan-2-yl) phenyl) -2-fluorobenzamide:
Figure BDA0003486027200000153
in a dry 500mL single neck flask was added stannous chloride dihydrate (53.28g, 0.236mol), 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 (40.16g, the yield is 92.1%) which is a yellow solid.
(4) Preparation of N- (2, 6-dibromo-4- (heptafluoropropan-2-yl) phenyl) -2-fluoro-3- (methylamino) benzamide:
Figure BDA0003486027200000161
150mL of tetrahydrofuran, NaH (9.68g, 60%, 0.242mol), and 3-amino-N- (2, 6-dibromo-4- (heptafluoropropane-2-yl) phenyl) -2-fluorobenzamide were sequentially added to a dry 500mL single-neck flask, methyl iodide (15.43g, 0.108mol) was added dropwise with stirring at room temperature, the mixture was heated to 60 ℃ after completion of the dropwise addition, and the reaction was monitored by LC-MS, cooled to room temperature after completion of the reaction, quenched with 5mL of water, concentrated under reduced pressure, extracted with ethyl acetate, dried, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate ═ 5:1) to obtain the desired product (28.91g, yield 70.2%).
(5) Preparation of Compound I-4:
Figure BDA0003486027200000162
compound intermediate III-1(2.13g, 0.011mol), toluene (30mL) was added to a dry 100mL single neck flask, compound intermediate II-4(5.68g, 0.01mol) was added with stirring at room temperature, the reaction mixture was heated to 90 ℃ and reacted 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-4(2.74g, yield 37.7%).
Example 3
Preparation of Compound I-23:
(1) preparation of 2, 6-dibromo-4- (heptafluoropropane-2-yl) aniline:
Figure BDA0003486027200000163
FeSO was added to a dry 500mL single neck flask4·7H2Dissolving O (9.73g and 0.035mol) in 20mL of water, sequentially adding 200mL of DMSO, 2, 6-dibromoaniline (25.09g and 0.1mol) and 2-heptafluoro iodopropane (44.39g and 0.15mol), slowly adding 20mL of hydrogen peroxide under an ice water bath, stirring at room temperature, monitoring the reaction by LC-MS, after the reaction is finished, adding 50mL of 5% hydrochloric acid solution and 200mL of ethyl acetate for extraction, collecting an organic phase, washing with 150mL 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 (35.53g, the yield is 85.2%) which is a yellow solid.
(2) Preparation of N- (2, 6-dibromo-4- (heptafluoropropyl-2-yl) phenyl) -2-fluoro-3-nitrobenzamide:
Figure BDA0003486027200000171
in a dry 500mL single neck flask was added 2-fluoro-3-nitrobenzoic acid (19.70g, 0.106mol), dissolved with 200mL of dichloromethane and 4 drops of DMF were added dropwise, oxalyl chloride (15.15g, 0.119mol) 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, concentrated under reduced pressure and dissolved in 20mL of acetonitrile for use. Adding the product of the first step into a dry 500mL single-neck flask, dissolving with 200mL acetonitrile, adding KI (4.24g, 0.026mol), slowly dropwise adding the 2-fluoro-3-nitrobenzoyl chloride acetonitrile solution into the reaction system under stirring at room temperature, stirring for 20h at 85 ℃, monitoring the reaction by LC-MS, concentrating under reduced pressure after the reaction is finished, and separating the product by column chromatography (eluent is petroleum ether: ethyl acetate: 5:1) to obtain the target product (45.97g, yield 92.4%) as a yellow solid.
(3) Preparation of 3-amino-N- (2, 6-dibromo-4- (heptafluoropropan-2-yl) phenyl) -2-fluorobenzamide:
Figure BDA0003486027200000172
in a dry 500mL single neck flask was added stannous chloride dihydrate (53.29g, 0.236mol), 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 (40.16g, the yield is 92.1%) which is a yellow solid.
(4) Preparation of Compound I-23:
Figure BDA0003486027200000173
compound intermediate III-6(2.48g, 0.011mol), toluene (30mL) was added to a dry 100mL single neck flask, compound intermediate II-3(5.54, 0.01mol) was added with stirring at room temperature, the reaction mixture was heated to 90 ℃ and reacted 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 petroleum ether: ethyl acetate: 5:1) to give the target product I-23(3.23g, yield 43.4%).
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, 0.1-2% 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 larvae of the plutella xylostella which are healthy and uniform in size for testing, placing cabbage leaves in liquid medicine to be tested for 10 seconds, taking out, placing the cabbage leaves in culture dishes after the cabbage leaves are naturally dried, inoculating 30 larvae into each dish, repeating the concentration treatment for 4 times, 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 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 the compounds 1 to 36 and CK1 to 16 is more than 90 percent: compounds 1-33, CK4, CK 5.
The activity of the above compounds was measured at low concentrations, and the results were as follows:
Figure BDA0003486027200000181
Figure BDA0003486027200000191
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 20ppm, the control effect of the compounds 1-36 and CK1-16 is more than 90%: compounds 1-33, CK2, CK 4.
The activity of the above compounds was measured at low concentrations, and the results were as follows:
Figure BDA0003486027200000192
Figure BDA0003486027200000201
example 7
Evaluation of 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 30 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 a concentration of 20ppm, the control effect of the compounds 1-36 and CK1-16 is more than 90%: compounds 1-33, CK4, CK 5.
The activity of the above compounds was measured at low concentrations, and the results were as follows:
Figure BDA0003486027200000202
Figure BDA0003486027200000211
example 8
Evaluation of biological Activity: prodenia litura (Spodoptera litura)
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 larvae of prodenia litura 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 30 larvae into each dish, setting 4 times of repetition for each concentration treatment, and setting solvent treatment without medicament and with the same content as blank control. Placing at (25 +/-1) DEG C, wherein the photoperiod is 16h: feeding in an artificial climate chamber for 8h (light: dark). The number of dead prodenia litura was investigated 3 days after the application, and the mortality (integral retention) was calculated.
The activity was as follows:
at a concentration of 20ppm, the control effect of the compounds 1-36 and CK1-16 is more than 90%: compound 1-33, CK 4.
The activity of the above compounds was measured at low concentrations, and the results were as follows:
Figure BDA0003486027200000212
Figure BDA0003486027200000221
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 m-diamide compound or a salt thereof acceptable as a pesticide, which has a structural formula shown in formula (I):
Figure FDA0003486027190000011
in the formula (I), X1、X2、X3、X4Each independently selected from H, halogen, CN, C1-C6Alkyl, halo C1-C6Alkyl or C3-C6Cycloalkyl radical, X1、X2、X3、X4Not H at the same time;
R1、R2each independently selected from H,Halogen, CN, C1-C6Alkyl, halo C1-C6Alkyl or C3-C6A cycloalkyl group;
R3selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C6Cycloalkyl or C3-C6Cycloalkyl-substituted C1-C6An alkyl group;
Y1selected from halogen, CN, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C6Cycloalkyl or C3-C6Cycloalkyl-substituted C1-C6An alkyl group.
2. The m-diamide compound of claim 1 or a pesticidally acceptable salt thereof, wherein R in the formula (I)1、R2Each independently selected from H, F, Cl, Br, CN; preferably, R1、R2And is F, Cl or Br; still more preferably, R1、R2And is also F.
3. The m-diamides compound of claim 1 wherein Y in formula (I) is1Selected from halogen or halogeno C1-C4An alkyl group.
4. The m-diamide compound of claim 1 or a pesticidally acceptable salt thereof, wherein R in the formula (I)3Selected from H, C1-C4Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl or C3-C6Cycloalkyl-substituted C1-C4An alkyl group;
preferably, R3Selected from H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, vinyl, allyl, ethynyl, propargyl, cyclopropylalkyl, cyclobutylalkyl, cyclopentylalkyl, cyclohexylalkyl, cyclopropylmethyl or cyclobutylmethyl; still more preferably, R3Selected from H, Me or Et.
5. The m-diamide compound of claim 4, or a pesticidally acceptable salt thereof, which is represented by the formula (I),
X1、X2、X3、X4each independently selected from H, F, Cl, CF3And X1、X2、X3、X4Not H at the same time;
preferably, X1、X2Are simultaneously F and X3、X4While being H, or X1、X2Is simultaneously H and X3、X4Simultaneously being F, or X1、X2Are respectively H and F and X3、X4Are each H and F, or X1、X2Is simultaneously H and X3、X4Are H and CF, respectively3Or X1、X2Is simultaneously H and X3、X4Are each H and F, or X1、X2While being Cl and X3、X4While being H, or X1、X2、X3、X4And F at the same time.
6. The m-diamide compound of claim 1, or a pesticidally acceptable salt thereof, which is represented by the formula (I),
X1、X2、X3、X4each independently selected from H, F, Cl, CF3And X1、X2、X3、X4Not H at the same time;
R1、R2and is simultaneously F;
R3selected from H, MeEt, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, vinyl, ethynyl, cyclopropylalkyl, cyclobutylalkyl, cyclopentylalkyl, cyclohexylalkyl, cyclopropylmethyl or cyclobutylmethyl;
Y1selected from Br or CF3。
7. The compound of the formula (I) as claimed in claim 1, wherein the compound is represented by the formula (I)
Figure FDA0003486027190000021
8. An insecticidal composition comprising an insecticidally effective amount of at least one of the m-diamide compound according to any one of claims 1 to 7 or a pesticidally acceptable salt thereof; 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 isophthalamide compounds described in any one of claims 1 to 7 or as a pesticidally acceptable salt thereof, or an insecticidal composition according to claim 8 to the crop plants or the pests and/or their habitat.
10. Use of at least one of the isophthalamide compounds or salts thereof acceptable as pesticides as set forth in any one of claims 1 to 7 or the pesticidal composition as set forth in claim 8 for controlling plant pests in agriculture and other fields.
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Citations (6)

* Cited by examiner, † Cited by third party
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
CN110810413A (en) * 2018-08-10 2020-02-21 上海泰禾国际贸易有限公司 Pharmaceutical composition containing m-diamide compound and application thereof
CN111132549A (en) * 2017-09-20 2020-05-08 三井化学Agro株式会社 Long-acting control agent for ectoparasites of animals
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
CN113321595A (en) * 2020-02-28 2021-08-31 南通泰禾化工股份有限公司 Metadiamide compound and application thereof
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

Patent Citations (6)

* Cited by examiner, † Cited by third party
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
CN111132549A (en) * 2017-09-20 2020-05-08 三井化学Agro株式会社 Long-acting control agent for ectoparasites of animals
CN110810413A (en) * 2018-08-10 2020-02-21 上海泰禾国际贸易有限公司 Pharmaceutical composition containing m-diamide 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
CN113321595A (en) * 2020-02-28 2021-08-31 南通泰禾化工股份有限公司 Metadiamide compound and application thereof
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"《STN：Rgistry》", pages: 2 - 6 *

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