CN113563322A - 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
- Publication number
- CN113563322A CN113563322A CN202110844912.7A CN202110844912A CN113563322A CN 113563322 A CN113563322 A CN 113563322A CN 202110844912 A CN202110844912 A CN 202110844912A CN 113563322 A CN113563322 A CN 113563322A
- Authority
- CN
- China
- Prior art keywords
- formula
- substituted benzamide
- independently selected
- insecticides
- spp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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 dose.
Technical solution
The technical scheme adopted by the invention for realizing the purpose is as follows: a substituted benzamide isoxazoline derivative or a salt thereof which is acceptable as a pesticide has a structural formula shown as a 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;
G1、G2each independently selected from CH or N, but not both;
n is an integer from 1 to 4.
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, 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;
G1、G2each independently selected from CH or N, but not both;
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；
G1、G2Each independently selected from CH or N, but not both;
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；
G1、G2Each independently selected from CH or N, but not both;
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 or cyclopropane;
R2、R3each independently selected from H or Cl;
G1、G2each independently selected from CH or N, but not both;
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 CH, 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, and the like) or an organic acid (such as oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid or benzoic acid, and the like); the pesticide acceptable salt can also be a salt prepared by reacting the substituted benzamide isoxazoline derivative 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 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 hereinbefore or as a pesticidally acceptable salt thereof or an insecticidal or acaricidal composition as described hereinbefore to the pests or mites and/or to their habitat.
The invention also discloses the use of the substituted benzamide isoxazoline derivatives or at least one of their salts acceptable as pesticides or the insecticidal or acaricidal compositions as described above for 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 or branched alkyl groups having 1 to 6 carbon atoms, the hydrogen atom in such alkyl groups being able toPartially or fully substituted with halogens, e.g., 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 means harmful or unwanted insects or mites, especially those encountered in agriculture, forestry, storage protection and material protection and in the hygiene sector, which compounds are active against sensitive and resistant species in general and are effective at all stages of pest or mite 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 seeds of the plants (before planting), to the seedlings, 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 crops), 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 methods, as well as those plants with insect or pest mite resistance, herbicide resistance, high yield, and/or other beneficial properties resulting from the alteration of genes 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 such as abamectin (abamectin), doramectin, emamectin, eprinomectin, ivermectin, and selamectin; milbemycin insecticides such as lepimectin, cimetidine, miticidin oxime and moxidectin); arsenic-containing insecticides such as calcium arsenate, copper acetoarsenite, copper arsenate, lead arsenate, potassium arsenite and sodium arsenite; biological insecticides such as Bacillus megaterium (Bacillus popilliae), Bacillus sphaericus (B.sphaericus), Bacillus thuringiensis subsp.sp.souriensis (B.thuringiensis subsp.aizawai), Bacillus thuringiensis subsp.kurstaki (B.souring. kurstaki), Bacillus thuringiensis subsp.sp.tenebriensis (B.souring. subsp.sp.tenebrisonii), Beauveria bassiana (Beauveria bassiana), Chrysocomysis japonica (Cydia pomoea grandiosis virus), Spodoptera litura Nuclear Polyhedrosis Virus (NPV) (Douglas grass mortocho NPV), Spodoptera giensis (NPV), Spodoptera litura sythophylyp (NPV), Spodoptera litura cocci (P.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp, Xenorhabdus nematophilus (Xenorhabdus nematophilus), and Xenorhabdus bovienii (xbainienii), plants added protective insecticides such as Cry1Ab, Cry1Ac, Cry1F, cry1a.105, Cry2Ab2, Cry3A, mirCry3A, Cry3Bb1, Cry34, Cry35, and VIP 3A; plant insecticides such as 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 such as 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, Pentachloronitrobenzene, giant knotweed (Reynouria sachalinensis) extract, silthiopham, simeconazole, sodium 2-phenylphenol, sodium bicarbonate, sodium pentachlorophenolate, spiroxamine, sulfur, SYP-Z071, tar oil, tebuconazole, tetrachloronitrobenzene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tolclofos-methyl, tolylfluanide, triadimefon, triadimenol, imidazozine, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, vinclozolin, zineb, ziram, zoxamide, candida rugosa, fusarium oxysporum, gliocladium, Phlebiopsis gigantean, Streptomyces griseoviridus, Trichoderma, (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) phenylthiocyanateme, aminopropylphosphonic acid, trichlofop, Oxidized thiram bactericide, barium polysulfide, Bayer 32394, mexican, quinoxime hydrazone, cyclometaldehyde, benzamacril; benzacril-isobutryl, benzamorf, binapacryl, bis (methylmercury) sulfate, bis (tributyltin) oxide, buthionine, cadimium copper zincate sulfate (cadmiumcalcium copperzinc chromatate sulfate), morcarb, CECA, chlorothiazone, chlororaniformethane, 2- (2-chlorophenyl) -1H-benzimidazole (chlorofenazole), tetrachloroquinoxaline, prochloraz, copper (3-phenylsalicylate), copper chromate, thiabendazole, cuprous hydrazine sulfate, cuprobbam, cyromazine, esteram, fenphostin, dichlornequinone, sclerotium, benzchlorotriazol, dimetachlor, nitrooctyl, nitrobutyl, pirethione, sterile, doxycycline, hydralazine, EBP, metiram, ethirimol, dimethomorph, nitrobenconazole, nitrobensulam, dimethomorph-ethyl, metoclopramide, trifloxystrobin, flutrobin, trifloxystrobin, flutrobin, trifloxystrobin, flutrobin, trifloxystrobin, flutrobin, trifloxystrobin, flutrobin, fludioxonil, glyodine, griseofulvin, quinolinylacrylate, Hercules 3944, hexylthiofos, ICIA0858, isopamphos, isovaledione, o-amide, mecarbizid, metazoxolon, furametpyr, methylmercury dicyandiamide, tiadinil, metiram, muconic anhydride, metiolide, N-3, 5-dichlorophenyl-succinimide, N-3-nitrophenyl itaconimide, natamycin, N-ethylmercurio-4-toluenesulfonanilide, bis (dimethyldithiocarbamate) nickel, OCH, phenylmercuric dimethyldithiocarbamate, phenylmercuric nitrate, chlophosphorus, thiocarb; 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) were added and heated 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 (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:
adding methyl to 4-bromo-3-methylbenzaldehyde (9.9g,50mmol,1.0eq.)Alcohol (100mL), sodium bicarbonate (12.6g,150mmol,3.0eq.) and hydroxylamine hydrochloride (3.9g,55mmol,1.1eq.), monitored by TLC, the starting material disappeared after about 4 hours. After the reaction is finished, methanol 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 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 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- ((6-chloropyridin-3-yl) methyl) -4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -N, 2-dimethylbenzamide (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. 1- (6-chloropyridin-3-yl) -N-methylmethanamine (156mg,1mmol,1.0eq.) was dissolved in dichloromethane (2mL), triethylamine (303mg,3mmol,3eq.) was added, and the acid chloride was added dropwise and 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 (375mg,0.65mmol), yield 65%. LC-MS (ESI) [ M + H]+＝574.0,[M+Na]+＝596.0,[M+K]+＝612.0。
Example 9
Preparation of N- ((6-chloropyridin-3-yl) methyl) -4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -N-isopropyl-2-methylbenzamide (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,and (4) spin-drying the solvent to obtain acyl chloride for later use. 2-chloro-5- (isopropylaminomethyl) pyridine (184mg,1mmol,1.0eq.) was dissolved in dichloromethane (2mL), triethylamine (303mg,3mmol,3eq.) was added, and the mixture was added dropwise to acid chloride and 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 (421mg,0.7mmol), yield 70%. LC-MS (ESI) [ M + H]+＝602.1,[M+Na]+＝659.0,[M+K]+＝640.0。
Example 10
Preparation of N- ((6-chloropyridin-3-yl) methyl) -4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -N-propyl-2-methylbenzamide (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. 2-chloro-5- (n-propylaminomethyl) pyridine (184mg,1mmol,1.0eq.) was dissolved in dichloromethane (2mL), triethylamine (303mg,3mmol,3eq.) was added, and then acid chloride was added dropwise and 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 (441mg,0.72mmol), yield 72%. LC-MS (ESI) [ M + H]+＝602.1,[M+Na]+＝659.0,[M+K]+＝640.0。
Example 11
Preparation of N- ((6-chloropyridin-3-yl) methyl) -4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -N-butyl-2-methylbenzamide (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. 2-chloro-5- (n-butylaminomethyl) pyridine (198mg,1mmol,1.0eq.) was dissolved in dichloromethane (2mL), triethylamine (303mg,3mmol,3eq.) was added, and then acid chloride was added dropwise and 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 (405mg,0.66mmol), yield 66%. LC-MS (ESI) [ M + H]+＝616.1,[M+Na]+＝638.0,[M+K]+＝654.0。
Example 12
Synthesis of N- ((6-chloropyridin-3-yl) methyl) -4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -N-ethyl-2-methylbenzamide (compound 62):
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. 2-chloro-5- (ethylaminomethyl) pyridine (170mg,1mmol,1.0eq.) was dissolved in dichloromethane (2mL), triethylamine (303mg,3mmol,3eq.) was added, and then acid chloride was added dropwise and 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 is chromatographed by silica gel column (petroleum)Ether: ethyl acetate 2:1) gave a pale yellow solid (457mg,0.78mmol) in 78% yield. LC-MS (ESI) [ M + H]+＝588.1,[M+Na]+＝610.0,[M+K]+＝626.0。
Example 13
Synthesis of N- ((6-chloropyridin-3-yl) methyl) -4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -N-cyclopropyl-2-methylbenzamide (compound 65):
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. 2-chloro-5- (cyclopropylaminomethyl) pyridine (182mg,1mmol,1.0eq.) was dissolved in dichloromethane (2mL), triethylamine (303mg,3mmol,3eq.) was added, and the mixture was added dropwise to the acid chloride and 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 (450mg,0.7758mmol), yield 75%. LC-MS (ESI) [ M + H]+＝600.1,[M+Na]+＝622.0,[M+K]+＝638.0。
Example 14
Preparation of the preparation:
1. suspending agent: weighing 20% of a compound shown in the formula (I), 3% of FS3000 (phosphate type anionic surfactant), 3% of NS-500LQ (nonionic hydroxy polyethylene oxide block copolymer), 0.5% of xanthan gum, 1.5% of magnesium aluminum silicate, 5% of ethylene glycol, 0.3% 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 25% of the compound of the formula (I), 20% of cyclohexanone, 10% of emulsifier and 20% of DMF, adding xylene to 100%, and shearing by a high-shear emulsifying machine to obtain the product.
3. Wettable powder: weighing 40% of the compound of the formula (I), 5% of sodium dodecyl benzene sulfonate, 10% of sodium lignin sulfonate and the balance of kaolin, and performing jet milling 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 1 in patent CN111909143A, the specific structure is
Control Compound B (Compound 2 of patent CN111909143A, the detailed structure is
Control Compound C (Compound 9 of patent CN111909143A, the detailed structure is
Control Compound D (Compound 10 of patent CN111909143A, the detailed structure is
Control Compound E (Compound of patent JP2008239611A, having the specific Structure
The reference compound F (compound 6-054 in patent CN1930136A, the specific structure is
Example 15
The activity of the compound on beet armyworms is tested by taking beet armyworm larvae of 2-3 years old 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 80% to the target are: compounds 4, 6, 12-27, 34-74, 82-87.
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 16
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 80% to the target are: 3-25 parts of compound, 32-75 parts of compound and 82-87 parts of compound.
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:
| compound numbering | Concentration (ppm) | Mortality (%) |
| 53 | 2.5 | 95 |
| 55 | 2.5 | 95 |
| 56 | 2.5 | 90 |
| 57 | 2.5 | 95 |
| 60 | 2.5 | 90 |
| 61 | 2.5 | 100 |
| 62 | 2.5 | 100 |
| 65 | 2.5 | 100 |
| 69 | 2.5 | 95 |
| A | 2.5 | 35 |
| B | 2.5 | 20 |
| C | 2.5 | 25 |
| D | 2.5 | 25 |
| E | 2.5 | 0 |
| F | 2.5 | 0 |
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 salt thereof which is acceptable as a pesticide has a structural formula shown as a 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;
G1、G2each independently selected from CH or N, but not both;
n is an integer from 1 to 4.
2. The substituted benzamide isoxazoline derivative or a pesticidally acceptable salt thereof according to claim 1, wherein 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, 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;
G1、G2each independently selected from CH or N, but not both;
n represents 1,2 or 3.
3. The substituted benzamide isoxazoline derivative or a pesticidally acceptable salt thereof according to claim 1, wherein 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；
G1、G2Each independently selected from CH or N, but not both;
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 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；
G1、G2Each independently selected from CH or N, but not both;
n represents 1 or 2.
5. The substituted benzamide isoxazoline derivative or a pesticidally acceptable salt thereof according to claim 1, wherein 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;
R2、R3each independently selected from H or Cl;
G1、G2each independently selected from CH or N, but not both;
n is 1 or 2.
6. The substituted benzamide isoxazoline derivative or a pesticidally acceptable salt thereof according to claim 5, wherein 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 CH, 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 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 of 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 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 substituted benzamide isoxazoline derivatives or at least one of their salts as defined in any one of claims 1 to 7 or as pesticidally acceptable salts or of the insecticidal or acaricidal composition according to claim 8 for controlling pests or mites in agriculture and other fields.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110844912.7A CN113563322B (en) | 2021-07-26 | 2021-07-26 | Substituted benzamide isoxazoline derivative or salt acceptable as pesticide, composition and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110844912.7A CN113563322B (en) | 2021-07-26 | 2021-07-26 | Substituted benzamide isoxazoline derivative or salt acceptable as pesticide, composition and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113563322A true CN113563322A (en) | 2021-10-29 |
| CN113563322B CN113563322B (en) | 2023-07-07 |
Family
ID=78167461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110844912.7A Active CN113563322B (en) | 2021-07-26 | 2021-07-26 | Substituted benzamide isoxazoline derivative or salt acceptable as pesticide, composition and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113563322B (en) |
Citations (6)
| 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 |
| JP2008239611A (en) * | 2007-02-27 | 2008-10-09 | Nissan Chem Ind Ltd | Isoxazoline-substituted benzamide compound and pesticide |
| WO2013092943A1 (en) * | 2011-12-23 | 2013-06-27 | Basf Se | Isothiazoline compounds for combating invertebrate pests |
| CN103705509A (en) * | 2007-08-17 | 2014-04-09 | 英特威国际有限公司 | Isoxazoline compositions and their use as antiparasitics |
| CN108026090A (en) * | 2015-09-23 | 2018-05-11 | 先正达参股股份有限公司 | Benzamide and analog as the substitution of insecticide isoxazolines |
| CN111909143A (en) * | 2020-07-30 | 2020-11-10 | 山东省联合农药工业有限公司 | Isoxazoline substituted benzamide derivative and preparation method and application thereof |
-
2021
- 2021-07-26 CN CN202110844912.7A patent/CN113563322B/en active Active
Patent Citations (7)
| 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 |
| CN102532048A (en) * | 2004-03-05 | 2012-07-04 | 日产化学工业株式会社 | Isoxazoline-substituted benzamide compound and pesticide |
| JP2008239611A (en) * | 2007-02-27 | 2008-10-09 | Nissan Chem Ind Ltd | Isoxazoline-substituted benzamide compound and pesticide |
| CN103705509A (en) * | 2007-08-17 | 2014-04-09 | 英特威国际有限公司 | Isoxazoline compositions and their use as antiparasitics |
| WO2013092943A1 (en) * | 2011-12-23 | 2013-06-27 | Basf Se | Isothiazoline compounds for combating invertebrate pests |
| CN108026090A (en) * | 2015-09-23 | 2018-05-11 | 先正达参股股份有限公司 | Benzamide and analog as the substitution of insecticide isoxazolines |
| CN111909143A (en) * | 2020-07-30 | 2020-11-10 | 山东省联合农药工业有限公司 | Isoxazoline substituted benzamide derivative and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113563322B (en) | 2023-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4875608B2 (en) | Insecticidal N-substituted sulfoximines | |
| JP6464109B2 (en) | Stable sulfoximine insecticide composition | |
| KR101344974B1 (en) | A method to control insects resistant to common insecticides | |
| JP5180966B2 (en) | Heteroaryl (substituted) alkyl N-substituted sulfoximines as insecticides | |
| KR101364430B1 (en) | Insecticidal n-substituted (6-haloalkylpyridin-3-yl)alkyl sulfoximines | |
| KR101364355B1 (en) | Multi-substituted pyridyl sulfoximines and their use as insecticides | |
| KR101364350B1 (en) | Insecticidal n-substituted (heteroaryl)cycloalkyl sulfoximines | |
| JP5248502B2 (en) | Insecticidal N-substituted (2-substituted-1,3-thiazole) alkylsulfoximines | |
| JP5813825B2 (en) | Insecticidal substituted azinyl derivatives | |
| JP2014097991A (en) | Insecticidal isoxazolines | |
| JP2009526074A5 (en) | ||
| JP6469569B2 (en) | N-substituted sulfilimines and sulfoximine pyridine N-oxides with insect control action | |
| CN114957062A (en) | Para-substituted biphenyl thioether compound, composition and application thereof | |
| JP5781579B2 (en) | Insecticidal (1,3,5) -triazinylphenylhydrazone | |
| CN113563322A (en) | Substituted benzamide isoxazoline derivative or salt and composition thereof acceptable as pesticide and application thereof | |
| CN113582987A (en) | Substituted benzamide isoxazoline derivative or salt and composition thereof acceptable as pesticide and application thereof | |
| CN114516869A (en) | Spirocyclic tetronic acid compound or salt and composition thereof acceptable as pesticide and application thereof | |
| CN114605297B (en) | Aryl sulfide containing substituted benzylamine structure, composition and application thereof | |
| CN115433182A (en) | Spiromesifen derivative or salt and composition thereof acceptable as pesticide and application thereof | |
| CN114149433A (en) | Nitrogen-containing spiro derivative or salt thereof acceptable as pesticide, composition and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |