CN113582987A - Substituted benzamide isoxazoline derivative or salt and composition thereof acceptable as pesticide and application thereof - Google Patents
Substituted benzamide isoxazoline derivative or salt and composition thereof acceptable as pesticide and application thereof Download PDFInfo
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- CN113582987A CN113582987A CN202111028546.4A CN202111028546A CN113582987A CN 113582987 A CN113582987 A CN 113582987A CN 202111028546 A CN202111028546 A CN 202111028546A CN 113582987 A CN113582987 A CN 113582987A
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- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
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- 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
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Abstract
The invention belongs to the field of pesticides, and particularly relates to a substituted benzamide isoxazoline derivative 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
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to substituted benzamide isoxazoline derivatives or salts and compositions thereof which are acceptable as pesticides, and application of the compounds or the salts and compositions thereof which are acceptable as pesticides as acaricides.
Background
Substituted benzamide isoxazoline derivatives having insecticidal activity are described in patents JP2008239611A, CN1930136A, CN111909143A, etc., but their insecticidal or acaricidal activity is still insufficient in practical applications, and the activity against other target organisms other than whiteflies is not satisfactory. The invention provides a novel substituted benzamide isoxazoline derivative with insecticidal or acaricidal activity, a preparation method thereof, and application of the compounds in the aspects of insecticidal or acaricidal activity, particularly excellent activity in the aspect of killing lepidoptera pests, and still having better biological activity at an extremely low dosage.
Technical problem
In order to solve the above problems in the prior art, the present invention provides a substituted benzamide isoxazoline derivative or a salt thereof acceptable as a pesticide, a composition and a use thereof, which surprisingly has excellent biological activity, can effectively kill pests, has sufficient safety to crops, is not easy to generate resistance, and still has excellent biological activity at an extremely low dosage.
Technical solution
The technical scheme adopted by the invention for realizing the purpose is as follows: a substituted benzamide isoxazoline derivative or a pesticidally acceptable salt thereof, having the structural formula shown in formula (I):
in the formula (I), the compound is shown in the specification,
X1、X2、X3the same or different, are respectively selected from F or Cl;
R1selected from halogen, CN, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl radical, C1-C6Alkoxy or C3-C6A cycloalkyl group;
R2、R3each independently selected from H, halogen, CN, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl radical, C1-C6Alkoxy or C3-C6A cycloalkyl group;
G1is S, G2Is N;
n is an integer from 1 to 5.
Further, in the formula (I),
X1、X3the same or different, are respectively selected from F or Cl;
X2is F;
R1is selected from C1-C4Alkyl, halo C1-C4Alkyl radical, C2-C4Alkenyl radical, C1-C4Alkoxy or C3-C6A cycloalkyl group;
R2、R3each independently selected from H, halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl or C3-C6A cycloalkyl group;
G1in the form of S, the content of the S,G2is N;
n represents 1,2 or 3.
Further, in the formula (I),
X1、X3the same or different, are respectively selected from F or Cl;
X2is F;
R1selected from Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3、CH2Br、CHBr2、CBr3、CH2CF3、CH2CH2Cl, OMe, OEt, n-PrO, i-PrO, n-BuO, i-BuO, s-BuO, t-BuO, cyclopropane, cyclobutane, cyclopentane or cyclohexane;
R2、R3are respectively and independently selected from H, F, Cl, Br, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu and CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3、CH2Br、CHBr2、CBr3、CH2CF3、CH2CH2Cl；
G1Is S, G2Is N;
n represents 1,2 or 3.
Further, in the formula (I),
X1、X3the same or different, are respectively selected from F or Cl;
X2is F;
R1selected from Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3A cyclopropyl, cyclopentyl or cyclohexyl group;
R2、R3each independently selected from H, F, Cl, Br, CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3；
G1Is S, G2Is N;
n represents 1 or 2.
Further, in the formula (I),
X1、X2、X3is also F, or X1、X3X when both are Cl2Is F;
R1selected from Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, cyclopropane or cyclopentane;
R2、R3each independently selected from H or Cl;
G1is S, G2Is N;
n is 1 or 2.
Further, in the formula (I),
X1、X2、X3is also F, or X1、X3X when both are Cl2Is F;
R1selected from Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu or cyclopropane;
R2is Cl;
R3is H;
G1is S, G2Is N;
n is 1.
Further, the compound of formula (I) is selected from:
the salt acceptable as a pesticide can be a salt prepared by reacting the substituted benzamide isoxazoline derivative 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 pesticidally acceptable salt may also be a salt obtained by reacting the substituted benzamide isoxazoline derivative of the present invention with a chemically acceptable base, wherein the chemically acceptable base may 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, etc.).
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 or acaricidal composition comprising an insecticidally or acaricidally effective amount of at least one of the substituted benzamide isoxazoline derivatives as described previously or as a pesticidally acceptable salt thereof;
further, the preparation also comprises a preparation carrier or a preparation auxiliary agent.
Also disclosed is a method for controlling pests or mites which comprises applying an insecticidally or acaricidally effective amount of at least one of the substituted benzamide isoxazoline derivatives as described above or as a pesticidally acceptable salt thereof or an insecticidal or acaricidal composition as described above to the pests or mites and/or their habitat.
The invention also discloses the use of the substituted benzamide isoxazoline derivative or at least one of its salts acceptable as pesticides or the insecticidal or acaricidal composition as described above in controlling pests or mites in agriculture and other fields.
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.
Halogen substituted C1-C6Alkoxy groups: straight or branched alkoxy having 1 to 6 carbon atoms, wherein hydrogen atoms in the alkoxy groups may be partially or wholly replaced by halogen, for example, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, etc.
A method for synthesizing the compound shown in the formula I is characterized in that the compound shown in the formula II is reacted with a compound shown in the formula III (in the chemical formula shown in the specification, the substituent and the symbol have the same meanings as those of the substituent and the symbol defined in the formula I if the substituent and the symbol are not defined otherwise) to obtain the target product, namely the compound shown in the formula I.
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.
The active compounds of the formula (I) according to the invention are suitable for controlling pests or mites, i.e. for controlling pests or mites, which mean harmful or unwanted insects or mites, in particular those encountered in agriculture, forestry, in the protection of stored goods and in the protection of materials and in the hygiene sector, which are active against sensitive and resistant species in general and are effective at all stages of their development; the present invention also relates to a method of inhibiting pests or mites which comprises applying to the locus of the insect, habitat of the pest, area to be protected, or directly on the insect to be controlled, a biologically effective amount of a compound of formula (I). The compounds of the present invention may also be used to control other invertebrate pests or organisms.
The insect habitat, the pest habitat or the pest mite habitat refers to an environment where insects, pests or pest mites live or eggs of the insects, the pests or the pest mites exist, including air around the environment, food for eating or objects in contact with the environment. For example, by applying the active compounds to the seed of the plant (before planting), to the seedling, or to the planted cuttings, leaves, stems, fruits, grains and/or roots, or to the soil or other growth medium (before or after planting of the crop), it is possible to control insects or pest mites which eat, destroy or come into contact with edible agricultural products, ornamentals, turf, pasture plants or other plants of economic value, it is also possible to achieve protection of these plants against diseases caused by viruses, fungi or bacteria by controlling sap-feeding pests such as whitefly, planthopper, aphid and the like or pest mites such as tetranychus urticae, tetranychus cinnabarinus and the like; such plants include those propagated by conventional means, as well as those plants with insect or pest mite resistance, herbicide resistance, high yield, and/or other beneficial properties resulting from the genetic modification by modern biotechnology. It is contemplated that these compounds will be useful for protecting fabrics, paper, stored grain, seeds and other food, housing, buildings and the like items and/or locations by applying the compounds of the present invention to or near such objects.
The term controlling pests or mites, inhibiting pests or mites refers to reducing the number of live insects, pests or mites, or reducing the number of eggs on which live insects, pests or mites can reside. The degree of reduction achieved by the compound will depend on the rate of application of the compound, the particular compound used and the target insect, pest or pest mite species, at least in amounts that will produce an effect.
By "mortality" is meant an amount sufficient to measurably reduce the number of insects, pests or mites being treated. Typically, 1 to 1000ppm (by weight) of active compound are used. For example, insects or other pests, mites that may be inhibited include, but are not limited to:
lepidoptera: heliothis armigera (Heliothis spp.), Heliothis armigera (Heliotropha spp.), Spodoptera spp.), Mythistle (Mythimna unipunctum), Agrotis japonicas (Agrotis ipsilon), Diamond-Diamond (Earias spp.), Trichoplusia ni (Trichoplusia ni), Heliothis punctatus (Anticarsia gemmatalis), Grapholitha minuensis (Rachipusanu), Plutella xylostella (Plutella xylostella), Chilo suppressalis (Chilo spp), Sclerotiopsis triforida (Sciopsis hamiltoniana), Sesamia incertulas (Sesamia incognita), Cnaphalocrocis medinalis (Cnaphalocrocis medinalis), Ostrinia Ostrinia (Ostrinia), Spodopteris pomona (Cydia pomona), Spodopteria punctifera punctata (Plutella xylostellata), Plutella xylostella (Ostrinia, Plutella xylostella), Plutella xylostella (Ostrinalis), Plutella xylostella (Ostrinia uniflora), Plutella xylostella (Ostrinalis), Plutella niponaria), Plutella xylostella (Ostrinalis), Plutella (Plutella niponaria), Plutella xylostella (Plutella) and Bombycis (Plutella niponaria) Ostrinalis), Plumbum) Piercalis (Plumbum) Pierca niponaria), Plumbum niponaria) Pierca niponaria (Plumbum) Ostrinia) Sphaemaphila (Plumbum, Plumbum niponaria) and Bombycis (Plumbum, Sphaemaphila (Plumbum niponaria) Farfa (Plumbum niponaria) A (Plumbum, Sporina niponaria) and Bombycis (Plumbum niponaria) No (Plumbum, Sphaepress (Plumbum niponaria) No (Plumbum, Plumbum (Plumbum niponaria) and Bombycis (Plumbum niponaria) No. niponaria) No (Plumbum, Plumbum niponaria) No (Plumbum niponaria) Farfa (Plumbum nigeria) Sphae (Plumbum niponaria) Farfa (Plumbum, Plumbum niponia) Sprensis) and Bombycis (Plumbum, Spia (Plumbum, Sporina) Pilata (Plumbum, Plumbum niponaria) Pilata (Plumbum, Sporina) Pilata (Plumbum niponia (Plumbum, Plumbum nigeria (Plumbum, Sporina, Plumbum, Sporina, Sprensis (Plumbum, Sporina, Plumbum, Phyllonorycter spp, Spodoptera spirifera (Leucoptera malinella), Phyllocnidae (Phyllocnitia citrella), Spodoptera exigua (Podoptera exigua Hubner);
coleoptera order: diabrotica (Diabrotica spp.), Leptinotarsa decemlineata (Leptinotarsa decemlineata), rice weevil (Oulema oryzae), cotton boll weevil (anthomonomgrandis), rice weevil (Lissorhoptrus oryzae), wireworms (Agriotes spp.), melantotus communis, japanese bean beetle (Popillia japonica), chafer species (cytochalella spp.), and pseudogrishell (Tribolium spp.);
from the order of homoptera: aphids (Aphis spp.), Myzus Persicae (Myzus Persicae), Rhopalosiphum spp., plantago asiatica (Dysaphis plantaginea), citrus aphids (toxiptera spp.), alfalfa aphids (Aphis craccivora Koch), euphorbia magna (macrophylla), solanum torvum (auorthum solani), physalis graminis (Sitobion avena), physalis graminis (opodium digerum), trichomonas oryzae (schizophyllum graminum), phoma graminis (branchoides), leafhopper nigra (Nephotettix spp.), brown planthopper (nilavarvalueva), white fly (botrytis furaria), green fly (vegetative louse), red fly (vegetative louse), green fly (green fly), green fly (green grass grub);
hemiptera: lygus spp, Eurygaster maura, Lygus lucorum (Nezaravidula), Pizodorum guilidi, Rhagotarda (Leptosporidia varicornis), Cimex lectularius, Tropical bed bug (Cimex eminentius), and Tropical bed bug (Cimex hemipterus);
from the order of thysanoptera: frankliniella occidentalis (Frankliniella occidentalis), Thrips (Thrips spp.), Thrips tabaci (Sciroththrips dorsalis);
from the order of the Isoptera: termites luteinis (termites flavipes), Coptotermes formosanus (Coptotermes formosanus), southern white termites vitroneucicus (Reticulitermes virginicus), hettotermes saururus, western white termites (Reticulitermes heperucus), Coptotermes francchi, shedporphitermes spp, morindothex sanguinea (Reticulitermes santonensis), Reticulitermes batyuensis, morindothex lutescens (Reticulitermes speratus), morindothex sanguinea (Reticulitermes spp), morindothex chinensis (Reticulitermes spp), termites (Reticulitermes spp), spertiliosis chinensis, termites spectabilis spp (Reticulitermes spp), termites spp (termites spp);
the order of Diptera: liriomyza spp, Musca domestica (Musca domestica), Aedes spp, Anopheles spp, commonwia spp, Fannia spp, and disuse fly (Stomoxys spp);
hymenoptera: red ants (Iridomyrmex humilis), fire ants (Solenopsis spp.), old fagopyrum ants (monoomorium pharaonis), Atta spp., harvested ants (pogomomycex spp.), bowlder ants (Camponotus spp.), little family ants (monoomorium spp.), stink family ants (taprooma sessile.), paving ants (Tetramorium spp.), xylococcus spp., xylocarpa spp., xylococcus spp., wasp (vespela spp.), and hornet (Polistes spp.);
trichophaga (feather lice);
lice (sucking lice)): pubic pubis (Pthirus pubis), lice (pediulus spp.);
orthoptera (locusts, crickets): black locusts (Melanoplus spp.), Locusta migratoria (Locusta migratoria), desert locusts (schistoserca gregaria), mole cricket (gryllotalpidata) (mole crickets);
from the order of the blattaria (cockroaches)): blattella orientalis (Blatta orientalis), Blattella germanica (Blattella germanica), Periplaneta americana (Periplaneta americana), Blattella longipedunculata (Supella longipalea), Blattella australis (Periplaneta australiana), Blattella fusca (Periplaneta brunnea), Periplanea pennyana (Parablata pennyvanensis), Blattella fuliginosa (Periplaneta fuliginosa), Blattella henryana (Pycnochelus surriniae);
siphonaptera: fleas (Ctenophilides spp.), human fleas (Pulex irritans);
from the order Acarina: including Tetranychus (Tetranychus), Pediodaceae (Eupodidae), Gephyridae (Eriophyiade), Phytoseiidae (Phytoseiidae), Amycoridae (Acaridae), including but not limited to Tetranychus (Tetranychus spp.), spider mites (Panocyhus spp.), Tetranychus cinnabarinus (Tetranychus cinabarinus), Tetranychus orientalis (Eotetranychus carpini), Tetranychus urticae (Tetranychus urticae Koch.), Citrus aurantii (Phylocirus flavus) Citrus aurantia (Phytocoptera olyoides), Aculus pelekassis, Brevibacterium parvus (Brevibacterium flavus), Boophilus spyrifos (Boophilus spp.), Dermatophus varia (Dermacera variorum), Amethorhyemaphytes (Amethorhyemaphycus), Tetranychus mangiferus (Ambrotica mangiferus), Tetranychus mangiferus (Ambrotus) or Amblyofos (Acanthophytes mangiferus);
nematoda (Nematoda): dirofilaria immitis, root-knot nematode (Meloidogyne spp.), cyst nematode (Heterodera spp.), crown nematode (Hoplolimus columba.), needlestick nematode (Belonolaimus spp.), root-rot nematode (Pratylenchus spp.), reniform nematode (Rotylenchus reniformis), rosette nematode (Criconella ornata), stem nematode (Ditylenchus spp.), leaf bud nematode (Aphelenchus besseyi), and rice field root-knot nematode (Hirschnella spp.).
The compound of formula I of the present invention shows excellent control of various pests or harmful mites when used at low concentrations, has insecticidal or acaricidal activity at every stage of the life cycle of pests or harmful mites (e.g., eggs, larvae (nymphs), pupae, adults), and also shows excellent control of pests or harmful mites that have developed resistance to conventional insecticides or acaricides. The compounds of formula I can be formulated in a variety of ways depending on the usual biological and/or chemical physical parameters. Examples of suitable formulation choices are: wettable Powders (WP), wettable liquids (SL), Soluble Powders (SP), dispersible liquids (DC), Aqueous Solutions (AS), Microemulsions (ME), Emulsifiable Concentrates (EC), aqueous Emulsions (EW), sprayable solutions, Suspensions (SC), dispersible oil suspensions (OD), powders (DP), microcapsule suspensions (CS), water dispersible granules (WG), water Soluble Granules (SG), macrogranules (GG), granules for spreading and soil application (GR), Aerosols (AE), ultra low volume agents (ULV) and wax products. Necessary formulation auxiliaries, such as inert substances, surfactants, solvents and other additives.
Suitable active substances which can be mixed with the active substances according to the invention in a compound or tank-mix formulation are, for example, the substances known from the handbook of pesticides (Beijing: chemical industry Press, 1 st edition 5.2015). For example, the insecticidal active substances mentioned below can be mixed with compounds of the formula I (remarks: name of the compound, or common name according to the International organization for standardization (ISO), or chemical name, where appropriate with a reference number): antibiotic insecticides (e.g., allosamidin and thuringiensis); macrolide insecticides (e.g., spinosad, spinoetoram, and other spinosyns including 21-butylspinosyn, and derivatives thereof); avermectin insecticides (e.g., abamectin (abamectin), doramectin, emamectin, eprinomectin, ivermectin, and selamectin; milbemycin insecticides (e.g., lepimectin, milbetin, miticidin oxime, and moxidectin), arsenic-containing insecticides (e.g., calcium arsenate, copper acetoarsenite, copper arsenate, lead arsenate, potassium arsenite, and sodium arsenite), biological insecticides (e.g., Bacillus megaterium (Bacilluspidata), Bacillus sphaericus (B.sphaericus), Bacillus thuringiensis subspecies (B.thuringiensis subsp.aizawai), Bacillus thuringiensis subspecies (B.thuringiensis subsp.kurstaki), Bacillus thuringiensis subspecies (B.glutaminesis virus), Spodopterygria bassiana, Spodopteria litura), Spodopterocarpus nivea (B.v), Spodopterocarpus Nivea (NPV), Spodopteria litura), Spodopterocarpus nivea (B., Indian meal moth granulosis virus (Indian meal granulosis virus), Metarhizium anisopliae (Metarhizium anisopliae), Nosema locusta (Nosema locusta), Paecilomyces fumosoroseus (Paecilomyces fumosoroseus), Paecilomyces lilacinus (P. lilacinus), Photorhabdus luminescens (Photorhabdus luminescens), Spodoptera exiguaNPV (Spodoptera exiguaNPV), trypsin-regulating autostatic factors (trypsin modulating fungal factor), Xenorhabdus nematophilus (Xenorhabdus nematophilus), and Xenorhabdus burus boviensis (Xovienii)); plants are added with protective insecticides (e.g., Cry1Ab, Cry1Ac, Cry1F, cry1a.105, Cry2Ab2, Cry3A, mirCry3A, Cry3Bb1, Cry34, Cry35, and VIP 3A); plant insecticides (e.g., neonicotinoid, azadirachtin, d-limonene, nicotine, pyrethrin, guaethrin I, guaethrin II, heliotropin I, heliotropin II, pyrethrin I, pyrethrin II, amaranth (quassia), rotenone, ryania, and veratrine); carbamate insecticides (e.g., bendiocarb and carbaryl; benzofuranyl methyl carbamate insecticides such as benfuracarb, carbofuran and furacarb); dimethyl carbamate insecticides (e.g., dimitan, trichlorfon, hyquincarb, and pirimicarb); oxime carbamate insecticides (e.g., cotton boll-carbofuran, aldicarb, butocarbosulfan, methomyl, carbosulfan, oxamyl, carbosulfan, thiodicarb and monocarb); phenyl methyl carbamate insecticides (e.g., carbofuran, methiocarb, oxamyl, dichlorcarb, dicarb, EMPC, ethiofencarb, fentehacarb, fenobucarb, isoprocarb, methiocarb, metolcarb, tebucarb, lufenuron, propoxur, trimethacarb, XMC, and propoxur); dinitrophenol insecticides (e.g., fenaminophen, nitrophenol, pentol, and DNOC); fluorine type insecticides (e.g., barium hexafluorosilicate, cryolite, sodium fluoride, sodium hexafluorosilicate, and sulfluramid); formamidine insecticides (e.g., amitraz, chlordimeform, varacetam and formanate); fumigant type insecticides (e.g., acrylonitrile, carbon disulfide, carbon tetrachloride, chloroform, chloropicrin, p-dichlorobenzene, 1, 2-dichloropropane, ethyl formate, 1, 2-dichloroethane, ethylene oxide, hydrogen cyanide, methyl iodide, methyl bromide, methyl chloroform, dichloromethane, naphthalene, phosphine, sulfuryl fluoride, and tetrachloroethane); inorganic insecticides (e.g., borax, lime sulphur, copper oleate, mercurous chloride, potassium thiocyanate, and sodium thiocyanate); chitin synthesis inhibitors (e.g., bistrifluron, buprofezin, chlorfluazuron, cyromazine, diflubenzuron, flufenoxuron, hexaflumuron, lufenuron, alachlor (novaluron), noviflumuron, chlorfluazuron, teflubenzuron and triflumuron); juvenile mimetics (e.g., juvenile ether (eponenane), fenoxycarb, methoprene, pyriproxyfen, and methoprene); juvenile hormones (e.g., juvenile hormone I, juvenile hormone II, juvenile hormone III); ecdysone agonists (e.g., chromafenozide, flufenozide, methoxyfenozide, and tebufenozide); ecdysone (e.g., alpha-ecdysone and ecdysteroid); molting suppressant formulas (e.g., benchol ether); precocenes (e.g., precocene I, precocene II, precocene III); non-class insect growth regulators (e.g., dicyclanil); nereistoxin analogue (nereistoxin analogue) insecticides (e.g., dimethion, cartap, thiocyclam, and dimehypo (thiosultap)); a nicotinic pesticide (e.g., flonicamid); nitroguanidine insecticides (e.g., clothianidin, dinotefuran, imidacloprid, and thiamethoxam); nitromethylene (nitromethylene) type pesticides (e.g., nitenpyram and nithiazine); pyridylmethylamine insecticides (e.g., acetamiprid, nitenpyram, and thiacloprid); organochlorine insecticides (e.g., bromo-DDT, toxaphene, DDT, pp' -DDT, ethyl-DDD, HCH, γ -HCH, lindane, methoxychlor, pentachlorophenol, and TDE); cyclodiene insecticides (e.g., aldrin, bromoxyrene, bornbuterol, chlordane, galbanum (chloredione), dieldrin, dilor, endosulfan, endrin, HEOD, heptachlor, HHDN, carbachol, isoethan, crimafen and mirex); organophosphate insecticides (e.g., bromfenvinfos, chlorfenvinphos, bafenphos, dichlorvos, chlormephos, chlorfenvinphos, chlormephos, heptenophos, methocrotophos, methamphos, monocrotophos, naloxon, naphthylenephos, phosphamidon, propaphos, TEPP, and sandfenvinphos); organic thiophosphate insecticides (e.g., acephate, fenthion, and phenthoate); aliphatic organic thiophosphate insecticides (e.g., housefly phosphorus, amiton, cadusafos, phosphorus oxychloride, chlormephos, phosphorus Tianle-O, phosphorus Tianle-S, systemic phosphorus-O, systemic phosphorus-S, methyl systemic phosphorus, O-methyl systemic phosphorus, S-methyl systemic phosphorus, phosphorus sulfone (demeton-S-methyl sullphon), disulfoton, ethion, fenamiphos, IPSP, isofenthion, malathion, chlorfenvinphos, sulfoxaflor, isosulfovinphos, phorate, fenitrothion, terbufos and methyl ethosulfan); aliphatic amide organophosphate insecticides (e.g., phosmet, guobao, dimethoate, phoxim, methidathion, omethoate, fenthion, suthion, and aphifenamiphos); oxime organophosphate insecticides (e.g., chlorophoxim, phoxim, and methyl phoxim); heterocyclic organic thiophosphate insecticides (e.g., methylpyrafen, coumaphos, fosthien, dioxaphos, ifop, methidathion, mafenthion, vothion, pyrazothion, pyridaphenthion and quinothion); thiochromane organophosphate insecticides (e.g., dutichlorofos and thiocorofos); benzotriazine organothiophosphate insecticides (e.g., ethyl-valefos and methyl-valefos); isoindoline organophosphate insecticides (e.g., chloroimidan and phoxim); isoxazole organophosphate insecticides (e.g., oxazaphos and zolaprofos); pyrazolopyrimidine organophosphate insecticides (e.g., chlorprazophos and pyraclostrobin); pyridine organic thiophosphate insecticides (e.g., chlorpyrifos and chlorpyrifos-methyl); pyrimidine organothiophosphate insecticides (e.g., butathiofos, diazinon, etrimfos, lirimfos, ethylpyrimidinophos, pirimiphos-methyl, primidophos, pyrithion, and butamiphos); quinoxaline organophosphate insecticides (e.g., quinalphos and methyl quinalphos); thiadiazole organophosphate insecticides (e.g., athidathion, fosthiazate, methidathion, and ethidathion); triazole organic thiophosphate insecticides (e.g., chlortriazophos and triazophos); phenyl organic thiophosphate insecticides (e.g., azophos, bromophos, ethyl bromophos, thiophosphoryl (carbaphenothion), chlorfenapyr, cyanophos, fenamiphos, isochlorophos, fenamiphos, etaphos, vamephos, pyrathiofos, fenthion, dichlorphos, iodophos, dichlofop, parathion, methyl parathion, fenthion, parathion, profenofos, thioprofos, disulfoton, trichlormetaphos-3, and triclopyr); phosphonate insecticides (e.g., butylphosphine and trichlorfon); thiophosphonate (phosphorothioate) insecticides (e.g., tetramethylphosphonium); phenylethylthiophosphonate insecticides (e.g., bendiumothioate and phosphonite); phenylphenylthiophosphonate insecticides (e.g., cyanophosphine, EPN, and bromophenylphosphine); phosphoramidate (phosphamidoate) type pesticides (e.g., foster phosphine, fenamiphos, thiophosphoryl butane, phosphamidon, thiophosphoryl and pirimepiphos); phosphoroamidite (phosphorothioate) insecticides (e.g., acephate, isocarbophos, isoxaphos, methamidophos, and triafamone); phosphoric diamide (phosphorodiamide) insecticides (e.g., methylphosphonium, triazophos, propaphos, and octamethylphosphonium); oxadiazine insecticides (e.g., indoxacarb); phthalimide insecticides (e.g., chlorfenapyr, phosmet, and tetramethrin); pyrazole insecticides (e.g., acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole, tebufenpyrad, tolfenpyrad, and vaniliprole), pyrethroid insecticides (e.g., fluthrin, allethrin, bioallethrin, barthrin, bifenthrin, bioethanolmethrin, cyhalothrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, Zeta-cypermethrin, cyphenothrin, deltamethrin, transfluthrin, permethrin, prallethrin, penfluthrin, cypermethrin, cyhalothrin, esmethrin, esfenvalerate, fenvalerate, fluvalinate, fluthrin, imidacloprofenprin, sumicidin, prallethrin, prallethri, Metofluthrin, permethrin, biothrin, permethrin, phenothrin, prallethrin, pyrethroid allethrin (profluthrin), pyremethrin, resmethrin, bioremethrin, cismethrin, tefluthrin, cyclopentenoprothrin, tetramethrin, tetrabromthrin, and transfluthrin); pyrethroid ether insecticides (e.g., ethofenprox, trifloxystrobin, hexythrox, protifenbute, and silafluofen); pyrimidinamine (pyrimidinamine) insecticides (e.g., flufenarim and pyriminobac-methyl); pyrrole insecticides (e.g., chlorfenapyr); ketofenamic acid insecticides (e.g., spirodiclofen, spiromesifen); thiourea insecticides (e.g., diafenthiuron); urea insecticides (e.g., flucofuron and sulcofuron); and unclassified insecticides (e.g., AKD-3088, closantel, crotonylmethylamine, cyflutenfen (cyflumetofen), E2Y45, EXD, antiacarid, fenazaquin (fenazaquin), fenoxacrim, fenpyroximate (fenpyroximate), FKI-1033, fluendiamide, HGW86, hydramethylnon, IKI-2002, isoprothiolane, terfenapyr, metaflumizone, xanthone, fluformin, NNI-9850, NNI-0101, pymetrozine, pyridaben, pyridalyl, Qcide, iodoether willow, chlorantranilide (ryxypyr), SYJ-159, fenpyrad, and triazamate, and any combination thereof); and any combination thereof.
Some of the fungicides that can be used in combination with the compounds of the present invention include: 2- (thiocyanomethyl-benzothiazole), 2-phenylphenol, 8-hydroxyquinoline sulfate, parasitospora cichoracearum, quisqualis (quisqualis), epoxiconazole, azoxystrobin, bacillus subtilis, benalaxyl, benomyl, benthiavalicarb, benomyl-sulfonate (BABS) salt, bicarbonate, biphenyl, bismerthiazol, bitertanol, rinoconazole, rinderpest, borax, Borax, Bordeaux, boscalid, bromuconazole, bupirimate, lime sulphur, captan, carbendazim, isoprotundine, clidanum, cyclopropamide, carvone, diclometham (Chloroneb), chlorothalonil, ethiprole, Chimomyces, copper hydroxide, copper octoate, copper royal, copper sulfate basic sulfate (coppersulfate (tribasisic)), cuprous oxide, cyazofamid, flufenamid, cyazofamid, cyproconazole, dazomethyl, chlomethyl, chlomethoate, imicarb (tribenuron (tribasic)), cuprous oxide, cyhalonil, cyhalothrin, cyhalonil, cyhalothrin, prochlorvinum, prochlorvini, prochlorvinum, and the use, etc.) Ethylenebis- (dithiocarbamate) diammonium (diammoniumethylenibis- (dithiocarbamate)), benflufenamide, dichlorophen, diclorocyanide, diclofen, dichlorpyran, diethofencarb, difenoconazole, avenacellene (difenoquat ion), fluomepanid, dimethomorph, dimoxystrobin, diniconazole-M, fenaminostrobin, dinocap, diphenylamine, dithianon, dodine free base, dipheny, epoxiconazole, ethaboxam, ethoxyquin, hymexazol, famoxadone, fenamidone, fenamidol, fenbuconazole, methylfuroamide (nfuram), fenhexamid, fenpropathrin, fenpropidin, fenpropimorph, fenpropitin triphenyl acetate, triphenyl tin hydroxide, ferbam, fenflurazon, flufenamidone, flufenflurazone, fludioxonil, fluopicolide, fenflurazole, fenpropimorph, fenflurazole, fluoxastrobin (fluoxastrobin), fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, fol, formaldehyde, fosetyl acid, fosetyl-aluminum, fuberidazole, furalaxyl, iminoctadine acetate, GY-81, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imipram, iminoctadine acetate, iminoctadine tris (albesilate)), ipconazole, iprobenfos, iprodione, iprovalicarb, kasugamycin hydrochloride (kasugamycin hydrochloride), kresoxim-methyl, mansfungstate, mancozeb, maneb, pyrimethanil, metiram, mercuric chloride, mercuric oxide, metalaxyl oxide, mefenoxam, metam-sodium), metam-sodium, metham (sodium-acre), metham-sodium, sodium benzoate, sodium benzoate, sodium benzoate, sodium benzoate, sodium benzoate, sodium benzoate, sodium benzoate, sodium benzoate, sodium, Metconazole, sulbencarb, methyl iodide, methyl isothiocyanate, metiram, metominostrobin, metrafenone, fenaminocycline, myclobutanil, sodium metiram, peptidyl ester, fluoropyrimidinol, octreox, furosemide, oleic acid (fatty acid), orysastrobin, oxadixyl, oxine-copper, oxpoconazole fumarate, carboxin, pefurazoate, penconazole, pencycuron, pentachlorophenol, pentachlorophenyl laurate, penthiopyrad, phenylmercuric acetate, phosphonic acid, isoprothiolane, picoxystrobin, polyoxin-B, polyoxin, potassium bicarbonate, hydroxyquinoline potassium sulfate, probenazole, prochloraz (prochloraz), procymidone, propamocarb hydrochloride, propiconazole, propineb, propoxymidone, prothioconazole, pyraclostrobin, pyrazophos, pyrifos, pyriproxyfen, pyrimethanil, pymetrozine, pyroxim, fluazinam, quinoxalin, quinoxalone, quinoxyfen, fluazid, fluazinam, cloquindox, clorac, and the like, Quintozene, giant knotweed rhizome (Reynoutria sachalinensis) extract, silthiopham, simeconazole, 2-phenylphenol sodium, sodium bicarbonate, pentachlorophenol sodium, spiroxamine, sulfur, SYP-Z071, tar oil, tebuconazole, tetrachloronitrobenzene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tolclofos-methyl, tolylfluanide, triadimefon, triadimenol, imidazozine, tricyclazole, tridemorph, oxime, triflumizole, triforine, triticonazole, validamycin, vinclozolin, zineb, ziram, zoxamide, (RS) -N- (3, 5-dichlorophenyl) -2- (methoxymethyl) -succinimide, 1, 2-dichloropropane, 1, 3-dichloro-1, 1,3, 3-tetrafluoroacetone hydrate, 1-chloro-2, 4-dinitronaphthalene, 1-chloro-2-nitrobenzane, 2- (2-heptadecyl-2-imidazolin-1-yl) ethanol, 2, 3-dihydro-5-phenyl-1, 4-dithi-inel,1,4, 4-tetraoxide, 2-methoxyethylmercuric acetate, 2-methoxyethylmercuric chloride, 2-methoxyethylmercuric silicate, 3- (4-chlorophenyl) -5-methylrhodanine, 4- (2-nitroprop-1-enyl) phenyl, thiocyanateme, aminopropylphosphonic acid, trichlormate, oxydamethizole, barium polysulfide, Bayer 32394, mexican, quinoxaline, cyclamate, dichlormacril; benzacril-isobutryl, benzamorf, binapacryl, bis (methylmercury) sulfate, bis (tributyltin) oxide, buthionine, cadmium calcium copper zinc chromate sulfate (cadnium copperzinc chromate sulfate), mycophenolate, CECA, chlorobenthiazone, chlororaniforme, 2- (2-chlorophenyl) -1H-benzimidazole (chlorofenazole), tetrachloroquinoxaline, fenamidone, copper bis (3-phenylsalicylate), copper chromate, thiabendazole, cuprous hydrazine sulfate, cuprobromide, cyamectin, esteramine, fenpropidin, decafosetyl, dichloquinocyl, sclerotium, benzchlorotriazol, dimetachlor, fenaminostrobin, nitrooctyl, nitrobutyl, dipyrithione, sterile, triazophos, doxycycline, EBP, metiram, thiflutriafol, dimethomorph, trifloxystrobin, fludioxonil, flubensultap, fludioxonil, flubensultap, fludioxonil, flubenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbensultap, flubenfurbenfurbensultap, flubenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurben, Benfurathiazole, glyodine, griseofulvin, quinolinylacrylate, Hercules 3944, hexylthiofos, ICIA0858, isopamphos, isovaledione, anthranilamide, mecarbinzid, metazoxolon, furametpyr, methylmercury dicyandiamide, tiadinil, metiram, mucic anhydride, metuli, N-3, 5-dichlorophenyl-succinimide, N-3-nitrophenyl itaconimide, natamycin, N-ethylmercurio-4-toluenesulfonanilide, bis (dimethyldithiocarbamate) nickel, OCH, phenylmercuric dimethyldithiocarbamate, phenylmercuric nitrate, chlophosphate, methiocarb; thiophanate hydrochloride, benomyl, picolonitrile, clomepyridine chloride, pyriftalid and quinacetol; quinacetol sulfate, quinoxalone, quinconazol, rabenzazole, salicylanilide, SSF-109, pentanesulfone, tecoram, thiadifluor, thiabendazole, thiochlororfenthim, thiophanate, dicoform, tioxymid, wifenphos, pyrimethanil, butanetriazole, trichlamide, asomate, XRD-563, and cyanoester, and any mixtures thereof.
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 a compound with an isoxazoline structure and introducing a substituent group on N of an amide group, a series of compounds which are more efficient and can be used for agricultural or forestry insect killing or mite killing and have excellent activity are obtained, and particularly, the compounds have good biological activity on lepidoptera, thysanoptera and other pests.
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.
TABLE 1 Structure of Compounds of formula I
TABLE 21H NMR data
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
Synthesis of (3, 5-dichloro-4-fluorophenyl) boronic acid:
a500 mL three-necked flask was charged with magnesium turnings (3.6g,150mmol,1.5eq.), dried tetrahydrofuran (50mL), and blanketed with nitrogen. 3, 5-dichloro-4-fluorobromobenzene (24.3g,100mmol,1.0eq.) was dissolved in dry tetrahydrofuran (200mL), 20mL of which was added dropwise to the reaction flask via a constant pressure dropping funnel, followed by addition of iodine particles to initiate the Grignard reaction, and the remaining solution was slowly added to the reaction flask. After the addition was complete, the mixture was heated to reflux and stirred for 2 hours. After the reaction is finished, the temperature of the three-necked flask is reduced to-40 ℃, and B (OMe) is slowly added3(150mmol,10.4g,1.5eq.) and reacted at low temperature for 2 hours, followed by stirring at room temperature for another 2 hours. Adding dilute hydrochloric acid into the reaction solution under ice bath, adjusting the pH to about 3, extracting with methyl tert-butyl ether, washing with saturated saline solution, drying with anhydrous sodium sulfate, filtering, and concentrating under reduced pressure to obtain a crude product.
Example 2
Preparation of 1, 3-dichloro-2-fluoro-5- (3,3, 3-trifluoroprop-1-en-2-yl) benzene:
the sealed tube (250mL) was added with (3, 5-dichloro-4-fluorophenyl) boronic acid (26.6g,140mmol,1.0eq.) and PdCl was added2(PPh3)2(1.96g,2.8mmol,0.02eq.), potassium carbonate (38.6g,280mmol,2.0eq.), 2-bromo-3, 3, 3-trifluoropropene (49g,280mmol,2.0eq.), THF/H2O (4:1,100mL) was added, and the mixture was heated at 70 ℃ for 12 hours under sealed conditions. After the reaction, the mixture was diluted with ethyl acetate, washed with saturated brine and then with anhydrous sodium sulfateDrying, filtering, and concentrating under reduced pressure to obtain crude product. The crude product was subjected to silica gel column chromatography (petroleum ether: ethyl acetate 10:1) to give an oil (27g,105mmol) in 75% yield.1H NMR(500MHz,CDCl3):δ7.41(d,J＝6.5Hz,2H),6.05(s,1H),5.80(s,1H)；LC-MS(ESI)[M+H]+＝258.9,[M+Na]+＝280.9,[M+K]+＝296.9。
Example 3
Preparation of 4-bromo-3-methylbenzaldehyde:
4-bromo-3-methylbenzonitrile (19.6g,100mmol,1.0eq.) was taken, dried dichloromethane (200mL) was added, the temperature was reduced to-5 deg.C, DIBALH (1.0M in toluene,150mL,150mmol,1.5eq.) was added, and TLC monitored, and the starting material disappeared after about 2 hours. After adding methanol to quench excess reducing agent, saturated sodium potassium tartrate solution was added and stirred until the layers separated. Separating, washing with saturated saline solution, drying with anhydrous sodium sulfate, filtering, and concentrating under reduced pressure to obtain crude product. The crude product was chromatographed on silica gel column (petroleum ether: ethyl acetate 8:1) to give a white solid (16.9g,85mmol) in 85% yield.1H NMR(500MHz,CDCl3)δ9.92(s,1H),7.73(d,J＝1.5Hz,1H),7.70(d,J＝8.1Hz,1H),7.52(dd,J＝8.1,2.0Hz,1H),2.45(s,3H)；LC-MS(ESI)[M+H]+＝198.9,[M+Na]+＝221.0,
[M+K]+＝236.9。
Example 4
Preparation of 4-bromo-3-methylbenzaldehyde oxime:
methanol (100mL), sodium bicarbonate (12.6g,150mmol,3.0eq.) and hydroxylamine hydrochloride (3.9g,55mmol,1.1eq.) were added to 4-bromo-3-methylbenzaldehyde (9.9g,50mmol,1.0eq.), monitored by TLC, and the starting material disappeared after about 4 hours. After the reaction, methanol was spin-dried, diluted with ethyl acetate, washed with saturated brine and dried over anhydrous sodium sulfateDrying with sodium sulfate, filtering, and concentrating under reduced pressure to obtain crude product. The crude product was chromatographed on silica gel column (petroleum ether: ethyl acetate 8:1) to give a white solid (9.6g,45mmol) in 90% yield.1H-NMR(500MHz,CDCl3)δ8.05(s,1H),7.55-7.45(m,2H),7.25(d,1H),2.40(s,3H)；LC-MS(ESI)[M+H]+＝214.0,[M+Na]+＝236.0,[M+K]+＝252.0。
Example 5
Preparation of 3- (4-bromo-3-methylphenyl) -5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazole:
adding 4-bromo-3-methylbenzaldehyde oxime (4.3g,20mmol,1.0eq.) into N, N-dimethylformamide (10mL), adding NCS (4.0g,30mmol,1.5eq.) and heating to 40 ℃ and stirring for 2 hours, then adding methyl tert-butyl ether for dilution, washing with saturated saline solution, drying with anhydrous sodium sulfate, filtering, and concentrating under reduced pressure to obtain a chlorooxime crude product. To the crude product was added dichloromethane (20mL), 1, 3-dichloro-2-fluoro-5- (3,3, 3-trifluoroprop-1-en-2-yl) benzene (5.2g,20mmol,1.0eq.), sodium bicarbonate (5.1g,60mmol,3.0eq.) and stirred overnight. Diluting with ethyl acetate, washing with saturated saline solution, drying with anhydrous sodium sulfate, filtering, and concentrating under reduced pressure to obtain crude product. The crude product was chromatographed on silica gel column (petroleum ether: ethyl acetate ═ 8:1) to give a white solid (6.7g,14.4mmol) in 72% yield.1H-NMR(500MHz,CDCl3)δ7.61(dd,J＝8.4,2.0Hz,1H),7.55(d,J＝4.9Hz,2H),7.47(d,J＝8.4Hz,1H),7.24(d,J＝2.2Hz,1H),4.02(d,J＝12.4Hz,1H),3.75(d,J＝12.3Hz,1H),2.35(s,3H)；LC-MS(ESI)[M+H]+＝469.9,[M+Na]+＝491.9,[M+K]+＝507.9。
Example 6
Preparation of ethyl 4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoate:
to the autoclave were added 3- (4-bromo-3-methylphenyl) -5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazole (9.4g,20mmol,1.0eq.), triethylamine (20mL), ethanol (20mL), 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene (578mg,1mmol,0.05eq.), palladium acetate (45mg,0.2mmol,0.01eq.), carbon monoxide gas (0.8MPa) was introduced, and the reaction was pressurized for 12 hours. After the reaction is finished, the solvent is dried by spinning, ethyl acetate is added for dilution, the mixture is washed by saturated saline solution, dried by anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain a crude product. The crude product was subjected to silica gel column chromatography (petroleum ether: ethyl acetate ═ 8:1) to give a pale yellow solid (6.5g,14mmol), yield 70%.1H-NMR(500MHz,CDCl3)δ7.85(d,J＝7.8Hz,1H),7.66(dd,J＝7.8,1.9Hz,1H),7.55(d,J＝4.9Hz,2H),7.40–7.37(m,1H),4.31(q,J＝6.4Hz,2H),4.02(d,J＝12.4Hz,1H),3.75(d,J＝12.3Hz,1H),2.47(s,3H),1.38(t,J＝6.3Hz,3H)；LC-MS(ESI)[M+H]+＝464.0,[M+Na]+＝486.0,[M+K]+＝502.0。
Example 7
Preparation of 4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoic acid:
to ethyl 4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoate (6.5g,14mmol,1.0eq.) was added a 2N NaOH solution (40mL) and methanol (10mL) was heated at 50 ℃ for 2 hours. After TLC monitoring the disappearance of starting material, the pH was adjusted to 2 with dilute hydrochloric acid and a solid precipitated. Suction filtration was carried out, the filter cake was washed with water and dried to give a pale yellow solid (5.0g,11.5mmol) in 82% yield.1H NMR(500MHz,CDCl3)δ8.15-8.10(m,1H),7.51-7.65(m,4H),4.17-4.10(m,1H),3.78-2.71(m,1H),2.69(s,3H)；LC-MS(ESI)[M+H]+＝436.0,[M+Na]+＝458.0,[M+K]+＝474.0。
Example 8
Preparation of N- ((2-chlorothiazol-5 yl) methyl) -4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methyl-N-propylbenzamide (compound 50):
4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoic acid (436mg,1mmol,1.0eq.) was taken, dissolved in dichloromethane (3mL), oxalyl chloride (254mg,2mmol,2.0eq.) and one drop of N, N-dimethylformamide were added, and after stirring for 1 hour, the solvent was spin-dried to give the acid chloride for use. N- ((2-chlorothiazol-5-yl) methyl) N-propyl-1-amine (190mg,1mmol,1.0eq.) was dissolved in dichloromethane (2mL), triethylamine (303mg,3mmol,3eq.) was added, then acid chloride was added dropwise, and the mixture was stirred overnight. TLC monitoring, after the reaction is finished, dichloromethane is added for dilution, saturated saline solution is used for washing, anhydrous sodium sulfate is used for drying, filtration and decompression concentration are carried out to obtain a crude product. The crude product was subjected to silica gel column chromatography (petroleum ether: ethyl acetate ═ 2:1) to give a pale yellow solid (394mg,0.65mmol), yield 65%. LC-MS (ESI) [ M + H]+＝608.0,[M+Na]+＝631.8,[M+K]+＝645.9。
Example 9
Preparation of N- ((2-chlorothiazol-5 yl) methyl) -4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methyl-N-ethylbenzamide (compound 52):
4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoic acid (436mg,1mmol,1.0eq.) was taken, dissolved in dichloromethane (3mL), oxalyl chloride (254mg,2mmol,2.0eq.) and one drop of N, N-dimethylformamide were added, and after stirring for 1 hour, the solvent was spin-dried to give the acid chloride for use. N- ((2-chlorothiazol-5-yl) methyl) ethyl-1-amine (176mg,1mmol,1.0eq.) was dissolved in dichloromethane (2mL), triethylamine (303mg,3mmol,3eq.) was added, followed by dropwise addition of acid chloride and stirring overnight.TLC monitoring, after the reaction is finished, dichloromethane is added for dilution, saturated saline solution is used for washing, anhydrous sodium sulfate is used for drying, filtration and decompression concentration are carried out to obtain a crude product. The crude product was subjected to silica gel column chromatography (petroleum ether: ethyl acetate ═ 2:1) to give a pale yellow solid (421mg,0.71mmol), yield 71%. LC-MS (ESI) [ M + H]+＝594.0,[M+Na]+＝616.0,[M+K]+＝631.9。
Example 10
Preparation of N- ((2-chlorothiazol-5 yl) methyl) -4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methyl-N-cyclopropylbenzamide (compound 55):
4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoic acid (436mg,1mmol,1.0eq.) was taken, dissolved in dichloromethane (3mL), oxalyl chloride (254mg,2mmol,2.0eq.) and one drop of N, N-dimethylformamide were added, and after stirring for 1 hour, the solvent was spin-dried to give the acid chloride for use. N- ((2-chlorothiazol-5-yl) methyl) cyclopropyl-1-amine (188mg,1mmol,1.0eq.) was dissolved in dichloromethane (2mL), triethylamine (303mg,3mmol,3eq.) was added, followed by dropwise addition of acid chloride and stirring overnight. TLC monitoring, after the reaction is finished, dichloromethane is added for dilution, saturated saline solution is used for washing, anhydrous sodium sulfate is used for drying, filtration and decompression concentration are carried out to obtain a crude product. The crude product was subjected to silica gel column chromatography (petroleum ether: ethyl acetate ═ 2:1) to give a pale yellow solid (411mg,0.68mmol), yield 68%. LC-MS (ESI) [ M + H]+＝606.0,[M+Na]+＝628.4,[M+K]+＝643.9。
Example 11
Preparation of N- ((2-chlorothiazol-5 yl) methyl) -4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methyl-N-butylbenzamide (compound 60):
4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoic acid (436mg,1mmol,1.0eq.) was taken, dissolved in dichloromethane (3mL), oxalyl chloride (254mg,2mmol,2.0eq.) and one drop of N, N-dimethylformamide were added, and after stirring for 1 hour, the solvent was spin-dried to give the acid chloride for use. N- ((2-chlorothiazol-5-yl) methyl) N-butyl-1-amine (204mg,1mmol,1.0eq.) was dissolved in dichloromethane (2mL), triethylamine (303mg,3mmol,3eq.) was added, then acid chloride was added dropwise, and the mixture was stirred overnight. TLC monitoring, after the reaction is finished, dichloromethane is added for dilution, saturated saline solution is used for washing, anhydrous sodium sulfate is used for drying, filtration and decompression concentration are carried out to obtain a crude product. The crude product was subjected to silica gel column chromatography (petroleum ether: ethyl acetate ═ 2:1) to give a pale yellow solid (391mg,0.63mmol), yield 63%. LC-MS (ESI) [ M + H]+＝622.0,[M+Na]+＝644.1,[M+K]+＝660.0。
Example 12
Preparation of 1,2, 3-trifluoro-5- (3,3, 3-trifluoroprop-1-en-2-yl) benzene:
the sealed tube (250mL) was added with (3,4, 5-trifluorophenyl) boronic acid (24.6g,140mmol,1.0eq.) and PdCl2(PPh3)2(1.96g,2.8mmol,0.02eq.), potassium carbonate (38.6g,280mmol,2.0eq.), 2-bromo-3, 3, 3-trifluoropropene (49g,280mmol,2.0eq.), THF/H was added2O (4:1,100mL), and heating at 70 ℃ for 12h under sealed conditions. After the reaction, ethyl acetate is added for dilution, the mixture is washed by saturated saline solution, dried by anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain a crude product. The crude product was subjected to silica gel column chromatography (petroleum ether: ethyl acetate ═ 10:1) to give an oil (20.5g,91mmol) with a yield of 65%. LC-MS (ESI) [ M + H]+＝227.0,[M+Na]+＝249.0,[M+K]+＝264.9。
Example 13
Preparation of 3- (4-bromo-3-methylphenyl) -5- (3,4, 5-trifluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazole:
adding 4-bromo-3-methylbenzaldehyde oxime (4.3g,20mmol,1.0eq.) into N, N-dimethylformamide (10mL), adding NCS (4.0g,30mmol,1.5eq.) and heating to 40 ℃ and stirring for 2 hours, then adding methyl tert-butyl ether for dilution, washing with saturated saline solution, drying with anhydrous sodium sulfate, filtering, and concentrating under reduced pressure to obtain a chlorooxime crude product. To the crude product was added dichloromethane (20mL), 1,2, 3-trifluoro-5- (3,3, 3-trifluoroprop-1-en-2-yl) benzene (4.5g,20mmol,1.0eq.), sodium bicarbonate (5.1g,60mmol,3.0eq.) and stirred overnight. Diluting with ethyl acetate, washing with saturated saline solution, drying with anhydrous sodium sulfate, filtering, and concentrating under reduced pressure to obtain crude product. The crude product was chromatographed on silica gel column (petroleum ether: ethyl acetate ═ 8:1) to give a white solid (6.2g,14.4mmol) in 72% yield. LC-MS (ESI) [ M + H]+＝437.9,[M+Na]+＝459.9,[M+K]+＝475.9。
Example 14
Preparation of ethyl 4- (5- (3,4, 5-trifluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoate:
to the autoclave were added 3- (4-bromo-3-methylphenyl) -5- (3,4, 5-trifluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazole (8.7g,20mmol,1.0eq.), triethylamine (20mL), ethanol (20mL), 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene (578mg,1mmol,0.05eq.), palladium acetate (45mg,0.2mmol,0.01eq.), carbon monoxide gas (0.8MPa) was introduced, and the reaction was pressurized for 12 hours. After the reaction is finished, the solvent is dried by spinning, ethyl acetate is added for dilution, the mixture is washed by saturated saline solution, dried by anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain a crude product. The crude product was subjected to silica gel column chromatography (petroleum ether: ethyl acetate ═ 8:1) to give a pale yellow solid (5.6g,13mmol), yield 66%. LC-MS (ESI) [ M + H]+＝432.0,[M+Na]+＝454.0,[M+K]+＝470.0。
Example 15
Preparation of 4- (5- (3,4, 5-trifluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoic acid:
to ethyl 4- (5- (3,4, 5-trifluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoate (6.0g,14mmol,1.0eq.) was added 2N NaOH solution (40mL), and methanol (10mL) was heated at 50 ℃ for 2 hours. After TLC monitoring the disappearance of starting material, the pH was adjusted to 2 with dilute hydrochloric acid and a solid precipitated. Suction filtration was carried out, the filter cake was washed with water and dried to give a pale yellow solid (4.8g,11.9mmol) in 85% yield. LC-MS (ESI) [ M + H]+＝404.0,[M+Na]+＝426.0,[M+K]+＝442.0。
Example 16
Preparation of N- ((2-chlorothiazol-5 yl) methyl) -4- (5- (3,4, 5-trifluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methyl-N-propylbenzamide:
4- (5- (3,4, 5-trifluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoic acid (403mg,1mmol,1.0eq.) was taken, dissolved in dichloromethane (3mL), oxalyl chloride (254mg,2mmol,2.0eq.) and one drop of N, N-dimethylformamide were added, and after stirring for 1 hour, the solvent was spin-dried to give the acid chloride for use. N- ((2-chlorothiazol-5-yl) methyl) N-propyl-1-amine (190mg,1mmol,1.0eq.) was dissolved in dichloromethane (2mL), triethylamine (303mg,3mmol,3eq.) was added, then acid chloride was added dropwise, and the mixture was stirred overnight. TLC monitoring, after the reaction is finished, dichloromethane is added for dilution, saturated saline solution is used for washing, anhydrous sodium sulfate is used for drying, filtration and decompression concentration are carried out to obtain a crude product. The crude product was subjected to silica gel column chromatography (petroleum ether: ethyl acetate ═ 2:1) to give a pale yellow solid (373mg,0.65mmol), yield 65%. LC-MS (ESI) [ M + H]+＝576.0,[M+Na]+＝598.0,[M+K]+＝614.0。
Example 17
Preparation of N- ((2-chlorothiazol-5 yl) methyl) -4- (5- (3,4, 5-trifluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methyl-N-methylbenzamide:
4- (5- (3,4, 5-trifluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoic acid (403mg,1mmol,1.0eq.) was taken, dissolved in dichloromethane (3mL), oxalyl chloride (254mg,2mmol,2.0eq.) and one drop of N, N-dimethylformamide were added, and after stirring for 1 hour, the solvent was spin-dried to give the acid chloride for use. N- ((2-chlorothiazol-5-yl) methyl-1-amine (162mg,1mmol,1.0eq.) was dissolved in dichloromethane (2mL), triethylamine (303mg,3mmol,3eq.) was added, followed by dropwise addition of acid chloride and stirring overnight. TLC monitoring, after the reaction is finished, dichloromethane is added for dilution, saturated saline solution is used for washing, anhydrous sodium sulfate is used for drying, filtration and decompression concentration are carried out to obtain a crude product. The crude product was subjected to silica gel column chromatography (petroleum ether: ethyl acetate ═ 2:1) to give a pale yellow solid (399mg,0.73mmol), yield 73%. LC-MS (ESI) [ M + H]+＝548.0,[M+Na]+＝570.0,[M+K]+＝586.0。
Example 18
Preparation of N- ((2-chlorothiazol-5 yl) methyl) -4- (5- (3,4, 5-trifluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methyl-N-methylbenzamide:
4- (5- (3,4, 5-trifluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoic acid (403mg,1mmol,1.0eq.) was taken, dissolved in dichloromethane (3mL), oxalyl chloride (254mg,2mmol,2.0eq.) and one drop of N, N-dimethylformamide were added, and after stirring for 1 hour, the solvent was spin-dried to give the acid chloride for use. Dissolving N- ((2-chlorothiazol-5-yl) methyl) cyclopropyl-1-amine (188mg,1mmol,1.0eq.) in dichloromethane (2mL), adding triethylamine (303mg,3mmol,3eq.), and dropwise adding acylChlorine, stirred overnight. TLC monitoring, after the reaction is finished, dichloromethane is added for dilution, saturated saline solution is used for washing, anhydrous sodium sulfate is used for drying, filtration and decompression concentration are carried out to obtain a crude product. The crude product was subjected to silica gel column chromatography (petroleum ether: ethyl acetate ═ 2:1) to give a pale yellow solid (400mg,0.70mmol), yield 70%. LC-MS (ESI) [ M + H]+＝574.0,[M+Na]+＝596.0,[M+K]+＝612.0。
Example 19
Preparation of N- ((2-chlorothiazol-5 yl) methyl) -4- (5- (3,4, 5-trifluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methyl-N-butylbenzamide:
4- (5- (3,4, 5-trifluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoic acid (403mg,1mmol,1.0eq.) was taken, dissolved in dichloromethane (3mL), oxalyl chloride (254mg,2mmol,2.0eq.) and one drop of N, N-dimethylformamide were added, and after stirring for 1 hour, the solvent was spin-dried to give the acid chloride for use. N- ((2-chlorothiazol-5-yl) methyl) N-butyl-1-amine (204mg,1mmol,1.0eq.) was dissolved in dichloromethane (2mL), triethylamine (303mg,3mmol,3eq.) was added, then acid chloride was added dropwise, and the mixture was stirred overnight. TLC monitoring, after the reaction is finished, dichloromethane is added for dilution, saturated saline solution is used for washing, anhydrous sodium sulfate is used for drying, filtration and decompression concentration are carried out to obtain a crude product. The crude product was subjected to silica gel column chromatography (petroleum ether: ethyl acetate ═ 2:1) to give a pale yellow solid (411mg,0.70mmol), yield 70%. LC-MS (ESI) [ M + H]+＝590.0,[M+Na]+＝612.0,[M+K]+＝628.0。
Example 20
Preparation of N- ((2-chlorothiazol-5 yl) methyl) -4- (5- (3,4, 5-trifluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methyl-N-isopropylbenzamide:
4- (5- (3,4, 5-trifluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoic acid (403mg,1mmol,1.0eq.) was taken, dissolved in dichloromethane (3mL), oxalyl chloride (254mg,2mmol,2.0eq.) and one drop of N, N-dimethylformamide were added, and after stirring for 1 hour, the solvent was spin-dried to give the acid chloride for use. N- ((2-chlorothiazol-5-yl) methyl) isopropyl-1-amine (190mg,1mmol,1.0eq.) was dissolved in dichloromethane (2mL), triethylamine (303mg,3mmol,3eq.) was added, then acid chloride was added dropwise, and the mixture was stirred overnight. TLC monitoring, after the reaction is finished, dichloromethane is added for dilution, saturated saline solution is used for washing, anhydrous sodium sulfate is used for drying, filtration and decompression concentration are carried out to obtain a crude product. The crude product was subjected to silica gel column chromatography (petroleum ether: ethyl acetate ═ 2:1) to give a pale yellow solid (356mg,0.62mmol), yield 62%. LC-MS (ESI) [ M + H]+＝576.0,[M+Na]+＝598.0,[M+K]+＝614.0。
Example 21
Preparation of the preparation:
1. suspending agent: weighing 20% of a compound shown in the formula (I), 4% of FS3000 (phosphate type anionic surfactant), 4% of NS-500LQ (nonionic hydroxy polyethylene oxide block copolymer), 0.5% of xanthan gum, 1.5% of magnesium aluminum silicate, 5% of ethylene glycol, 0.5% of organic modified siloxane defoaming agent and deionized water, adding to 100%, preparing into slurry, and sanding to obtain the product.
2. And (3) missible oil: weighing 20% of the compound of the formula (I), 10% of cyclohexanone, 12% of emulsifier, 15% of DMF, adding xylene to 100%, and shearing by a high-shear emulsifying machine to obtain the product.
3. Wettable powder: 30% of the compound of the formula (I), 8% of sodium dodecyl benzene sulfonate, 8% of sodium lignin sulfonate and the balance of kaolin are weighed and subjected to airflow crushing to obtain the product.
The above are all weight percentages.
Evaluation of biological Activity
After dissolving the test compound in N, N-dimethylformamide, the solution was diluted with water containing 0.1% Tween-80 to the desired concentration.
Testing the pesticidal activity of these compounds; and tested in parallel with the insecticidal and acaricidal activity of the following compounds, a particular compound having the structure:
control Compound A (Compound 5-047 of patent WO2007026965A, having the specific Structure
Control Compound B (Compound 5-042 of patent WO2007026965A, having the specific Structure
Control Compound C (Compounds 2-73 in patent CN104169278A, having the specific Structure
Control Compound D (Compounds 2-65 of patent CN104169278A, having the specific Structure
A control compound E (compounds 3-116 in patent CN1930136A, the specific structure is
A control compound F (compounds 3-113 in patent CN1930136A, with a specific structure
Example 22
The activity of the compound on the beet armyworms is tested by taking the beet armyworm third-instar larvae as targets, the insecticidal activity is determined by adopting an insect-soaking method, and the mortality of the targets is investigated 2-3 days after treatment.
Some of the test results are as follows:
when the concentration of the liquid medicine is 1ppm,
compounds with a fatality rate above 85% to the target are: compounds 27-32, 49, 51, 58-64, 66-68.
According to the method, part of compounds and control compounds A-F are selected to carry out the activity parallel determination of killing the beet armyworm, and the experimental results are shown in the following table:
control test for killing beet armyworm activity:
example 23
The aphid with the same age is used as a target to test the activity of the compound on the aphid, the insecticidal activity is determined by adopting a dropping method, and the mortality of the target is investigated 24 hours after treatment.
Some of the test results are as follows:
when the concentration of the liquid medicine is 5ppm,
compounds with a fatality rate above 85% to the target are: compounds 7-16, 27, 48-49, 51-54, 58-59, 63-68, 70-73.
According to the method, part of compounds and control compounds A-F are selected for carrying out parallel determination on aphid killing activity, and the experimental results are shown in the following table:
aphid-killing activity control test:
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 substituted benzamide isoxazoline derivative or a pesticidally acceptable salt thereof, having the structural formula shown in formula (I):
in the formula (I), the compound is shown in the specification,
X1、X2、X3the same or different, are respectively selected from F or Cl;
R1selected from halogen, CN, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl radical, C1-C6Alkoxy or C3-C6A cycloalkyl group;
R2、R3each independently selected from H, halogen, CN, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl radical, C1-C6Alkoxy or C3-C6A cycloalkyl group;
G1is S, G2Is N;
n is an integer from 1 to 5.
2. A substituted benzamide isoxazoline derivative or a pesticidally acceptable salt thereof according to claim 1, characterized in that, in formula (I),
X1、X3the same or different, are respectively selected from F or Cl;
X2is F;
R1is selected from C1-C4Alkyl, halo C1-C4Alkyl radical, C2-C4Alkenyl radical, C1-C4Alkoxy or C3-C6A cycloalkyl group;
R2、R3each independently selected from H, halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl or C3-C6A cycloalkyl group;
G1is S, G2Is N;
n represents 1,2 or 3.
3. A substituted benzamide isoxazoline derivative or a pesticidally acceptable salt thereof according to claim 1, characterized in that, in formula (I),
X1、X3the same or different, are respectively selected from F or Cl;
X2is F;
R1selected from Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3、CH2Br、CHBr2、CBr3、CH2CF3、CH2CH2Cl, OMe, OEt, n-PrO, i-PrO, n-BuO, i-BuO, s-BuO, t-BuO, cyclopropane, cyclobutane, cyclopentane or cyclohexane;
R2、R3are respectively and independently selected from H, F, Cl, Br, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu and CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3、CH2Br、CHBr2、CBr3、CH2CF3、CH2CH2Cl；
G1Is S, G2Is N;
n represents 1,2 or 3.
4. A substituted benzamide isoxazoline derivative or a pesticidally acceptable salt thereof according to any one of claims 1 to 3, characterized in that in formula (I),
X1、X3the same or different, are respectively selected from F or Cl;
X2is F;
R1selected from Me, Et, n-Pr,i-Pr、n-Bu、i-Bu、s-Bu、t-Bu、CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3A cyclopropyl, cyclopentyl or cyclohexyl group;
R2、R3each independently selected from H, F, Cl, Br, CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3；
G1Is S, G2Is N;
n represents 1 or 2.
5. A substituted benzamide isoxazoline derivative or a pesticidally acceptable salt thereof according to claim 1, characterized in that, in formula (I),
X1、X2、X3is also F, or X1、X3X when both are Cl2Is F;
R1selected from Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, cyclopropane or cyclopentane;
R2、R3each independently selected from H or Cl;
G1is S, G2Is N;
n is 1 or 2.
6. A substituted benzamide isoxazoline derivative or a pesticidally acceptable salt thereof according to claim 5, characterized in that in formula (I),
X1、X2、X3is also F, or X1、X3X when both are Cl2Is F;
R1selected from Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu or cyclopropane;
R2is Cl;
R3is H;
G1is S, G2Is N;
n is 1.
7. A substituted benzamide isoxazoline derivative or its salt as a pesticidally acceptable salt according to any of claims 1 to 6, characterized in that the compound of the formula (I) is selected from:
8. an insecticidal or acaricidal composition comprising an insecticidally or acaricidally effective amount of at least one of the substituted benzamide isoxazoline derivatives or as a pesticidally acceptable salt thereof according to any one of claims 1 to 7; preferably, the composition also comprises a preparation carrier or a preparation auxiliary agent.
9. A method for controlling pests or mites which comprises applying an insecticidally or acaricidally effective amount of at least one of the substituted benzamide isoxazoline derivatives or as pesticidally acceptable salts thereof as claimed in any one of claims 1 to 7 or an insecticidal or acaricidal composition as claimed in claim 8 to the pests or mites and/or their habitat.
10. Use of a substituted benzamide isoxazoline derivative or at least one of its salts as a pesticide acceptable according to any one of claims 1 to 7 or an insecticidal or acaricidal composition according to claim 8 for controlling pests or mites in agriculture and other fields.
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| WO2007026965A1 (en) * | 2005-09-02 | 2007-03-08 | Nissan Chemical Industries, Ltd. | Isoxazoline-substituted benzamide compound and harmful organism-controlling agent |
| CN1930136A (en) * | 2004-03-05 | 2007-03-14 | 日产化学工业株式会社 | Isoxazoline-substituted benzamide compound and noxious organism control agent |
| CN104169278A (en) * | 2011-12-23 | 2014-11-26 | 巴斯夫欧洲公司 | Isothiazoline compounds for combating invertebrate pests |
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2021
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1930136A (en) * | 2004-03-05 | 2007-03-14 | 日产化学工业株式会社 | Isoxazoline-substituted benzamide compound and noxious organism control agent |
| WO2007026965A1 (en) * | 2005-09-02 | 2007-03-08 | Nissan Chemical Industries, Ltd. | Isoxazoline-substituted benzamide compound and harmful organism-controlling agent |
| CN104169278A (en) * | 2011-12-23 | 2014-11-26 | 巴斯夫欧洲公司 | Isothiazoline compounds for combating invertebrate pests |
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| CN113582987B (en) | 2023-06-30 |
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