CN115785017A - Substituted benzamide isoxazoline derivative or salt thereof acceptable as pesticide, composition and application thereof - Google Patents

Substituted benzamide isoxazoline derivative or salt thereof acceptable as pesticide, composition and application thereof Download PDF

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Publication number
CN115785017A
CN115785017A CN202211554927.0A CN202211554927A CN115785017A CN 115785017 A CN115785017 A CN 115785017A CN 202211554927 A CN202211554927 A CN 202211554927A CN 115785017 A CN115785017 A CN 115785017A
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formula
salt
substituted benzamide
substituted
isoxazoline derivative
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CN115785017B (en
Inventor
葛家成
邢阳阳
马娥
刘明东
孙鹏
胡堂路
张亚弢
孙毅轩
孟维康
谢勇
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Hailir Pesticides and Chemicals Group Co Ltd
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Hailir Pesticides and Chemicals Group Co Ltd
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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

Substituted benzamide isoxazoline derivative or salt thereof acceptable as pesticide, composition and application thereof
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a substituted benzamide isoxazoline derivative or a salt and a composition thereof acceptable as pesticides, and application of the compound or the salt and the composition as pesticides or acaricides.
Background
Benzamide isoxazolines are compounds which have insecticidal activity, and particularly have excellent biological activity against invertebrate pests, which were first discovered and noted by stone shoji. With the increasing emphasis on global food safety, it is important to improve the agricultural production efficiency. Although researches on benzamide isoxazoline compounds have not been interrupted for many years, a benzamide isoxazoline compound which has good quick-acting property, broad insecticidal spectrum and safety to crops cannot be obtained.
Technical problem
In order to solve the problems in the prior art, the invention provides a substituted benzamide isoxazoline derivative or a salt thereof acceptable as a pesticide, a composition and application thereof, wherein the substituted benzamide isoxazoline derivative has excellent biological activity on lepidoptera, homoptera and thysanoptera pests, and is not easy to generate cross resistance with the existing bisamide compounds.
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 is characterized in that the structural formula is shown as the formula (I):
Figure SMS_1
in the formula (I), X 1 、X 2 、X 3 The same or different, are respectively and independently selected from F, cl, br, CN or NO 2 ；
R 1 Selected from halogen, CN, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 2 -C 6 An alkenyl group;
R 2 selected from H, CN, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 2 -C 6 Alkenyl radical, C 1 -C 6 Alkoxy radical, C 3 -C 6 Cycloalkyl or C 3 -C 6 Cycloalkyl-substituted C 1 -C 6 An alkyl group.
Further, in the formula (I), X 1 、X 2 、X 3 Identical or different, each independently selected from F, cl, br or CN;
R 1 selected from halogen, CN or C 1 -C 6 An alkyl group;
R 2 is selected from C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 3 -C 6 Cycloalkyl or C 3 -C 6 Cycloalkyl-substituted C 1 -C 6 An alkyl group.
Further, in the formula (I), X 1 、X 2 、X 3 The same or different, are respectively and independently selected from F, cl or Br;
R 1 selected from F, cl, br, methyl, ethyl, propyl or butyl;
R 2 selected from methyl, ethyl, propyl, butyl, CH 2 Cl、CHCl 2 、CCl 3 、CH 2 F、CHF 2 、CF 3 、CH 2 CF 3 、CH 2 CH 2 F、CH 2 CHF 2 Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cyclopropyl substituted methyl.
Further, in the formula (I), X 1 And X 3 The same or different, are respectively selected from F or Cl;
X 2 is F or Cl;
R 1 is selected from CH 3 F orCN；
R 2 Is selected from CH 3 、CH 2 CF 3 Cyclopropane, CH 2 CH 2 F、CH 2 CH 3 A cyclopentyl group or a cyclohexyl group. Further, in the formula (I), X 1 And X 3 Same, all are Cl;
X 2 is F;
R 1 is selected from CH 3 F or CN;
R 2 is selected from CH 3 、CH 2 CF 3 Cyclopropane, CH 2 CH 2 F、CH 2 CH 3 Or a cyclopentyl group.
Further, formula (I) is:
Figure SMS_2
further, formula (I) is:
Figure SMS_3
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 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 or their salts acceptable as pesticides; further, the composition also comprises a preparation carrier or a preparation auxiliary agent.
Also disclosed is a method for controlling plant pests or mites which comprises applying an insecticidally or acaricidally effective amount of at least one of the substituted benzamide isoxazoline derivatives or as described above or as a pesticidally acceptable salt thereof or an insecticidal or acaricidal composition as described above to the crops or pests or mites and/or their habitat.
The invention also discloses the use of the substituted benzamide isoxazoline derivatives as described above or at least one of their salts acceptable as pesticides or the insecticidal or acaricidal compositions as described previously for controlling plant pests 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.
C 1 -C 6 Alkyl groups: straight-chain or branched alkyl groups having 1 to 6 carbon atoms such as methyl Me, ethyl Et, n-propyl n-Pr, isopropyl i-Pr, or n-butyl n-Bu, isobutyl i-Bu, sec-butyl s-Bu, tert-butyl t-Bu, etc.
Halogen substituted C 1 -C 6 Alkyl groups: straight-chain or branched alkyl groups having 1 to 6 carbon atoms, in which hydrogen atoms may be partially or completely substituted with halogen, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl and the like.
A process for the synthesis of compounds of formula I, in particular compounds of formula XI which are prepared by reacting compounds of formula XI of formula I via compounds of formulae X, IX, VIII, VII, VI, V, IV, III, II (in the formulae given below, where substituents and symbols have the same meaning as those defined in formula I, unless otherwise specified):
Figure SMS_4
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 stores 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 development of the pests or mites; the present invention also relates to a method of inhibiting pests or mites which comprises applying to the locus of the insect, the insect habitat, the pest habitat, the area claimed, 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, houses, buildings and the like items and/or locations by applying the compounds of the 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 are effective.
An insecticide or acaricide comprising the compound represented by the formula (I) or a salt thereof as an active ingredient is useful for controlling pests or mites in the fields of fruit trees, vegetables, other crops and ornamental plants or their growing environments such as soil.
<xnotran> , , ( (Lepidoptera)), (Agrotis ypsilon), (Agrotis segetum), (Alabama argillacea), (Anticarsiagemmatalis), argyresthia conjugella, (Autographa gamma), (Bupaluspiniarius), cacoecia murinana, capua reticulana, cheimatobia brumata, (Choristoneura fumiferana), choristoneura occidentalis, (Cirphisunipuncta), (Cydia pomonella), (Dendrolimus pini), diaphanianitidalis, (Diatraea grandiosella), (Earias insulana), (Elasmopalpus lignosellus), (Eupoecilia ambiguella), evetria bouliana, feltia subterranea, (Galleria mellonella), (Grapholitha funebrana), (Grapholitha molesta), (Heliothisarmigera), (Heliothis virescens), (Heliothis zea), (Hellulaundalis), hibernia defoliaria, (Hyphantria cunea), (Hyponomeutamalinellus), (Keiferia lycopersicella), lambdina fiscellaria, (Laphygma exigua), (Leucoptera coffeella), (Leucopterascitella), lithocolletis blancardella, (Lobesia botrana), (Loxostege sticticalis), (Lymantria dispar), (Lymantria monacha), </xnotran> Peach latent moth (Lyonetia clerkella), pholiota fulvescens (Malacosoma neusteria), cabbage looper (Mamestraabarassicae), yellow fir moth (Orgyia pseudotsugata), corn borer (Ostrinia nubilalis), small eye moth (Panoliis flammera), red bollworm of cotton (Pectinophora gossypiella), oriental armyworm (Peridomauca), round palm moth (Phalera bucephala), potato wheat moth (Phorimaea operculella), citrus leaf miner (Phylochia citrifolia), european butterfly (Pieriis brasilia), alfalfa green armyworm (Plastyla abscura), cabbage moth (Pluylostella xylostella), soybean looper (Hypoxylus), european looper (Spodoptera), spodoptera frugiperda (Spodopteria fructicola), spodoptera fructicola (Spodoptera fructicola), spodoptera litura (Spodoptera fructicola), spodoptera fructicola (Spodoptera fructicola), spodoptera (Spodoptera fructicola (Spodoptera);
<xnotran> ( (Coleoptera)), (Agrilus sinuatus), (Agriotes lineatus), (Agriotes obscurus), amphimallus solstitialis, anisandrus dispar, (Anthonomus grandis), (Anthonomuspomorum), aphthona euphoridae, athous haemorrhoidalis, (Atomarialinearis), (Blastophagus piniperda), blitophaga undata, (Bruchus rufimanus), (Bruchus pisorum), (Bruchus lentis), (Byctiscus betulae), (Cassida nebulosa), cerotoma trifurcata, (Cetonia aurata), (Ceuthorrhynchus assimilis), (Ceuthorrhynchus napi), (Chaetocnema tibialis), conoderusvespertinus, (Crioceris asparagi), ctenicera ssp., (Diabrotica longicornis), diabrotica semipunctata, diabrotica 12-punctata, (Diabrotica speciosa), (Diabrotica virgifera), (Epilachna varivestis), (Epitrix hirtipennis), (Eutinobothrus brasiliensis), (Hylobius abietis), (Hypera brunneipennis), (Hypera postica), (Ipstypographus), (Lema bilineata), (Lema melanopus), (Leptinotarsa decemlineata), limonius californicus, (Lissorhoptrusoryzophilus), </xnotran> Melanotus communis, rape dewetters (Meligethes aeneus), chestnut gill beetles (Melolontha hippopastani), five-month gill beetles (Melolontha mellona), mud worm of rice (Oulemaryzae), grape black ear beak (Oritronchus sulcataus), strawberry root weevil (Oitrorhynchus), horse radish leaf beetle (Phaedon cochleariae), phyllobium pyriformis, phyllotretophyceae, phyllostachys nigra (Phylloga. Sp), phyllotreta trichocarpa (Phyllotreta), phyllotreta somnifera (Phyllotreta nigra), phyllotreta indica (Phyllotrematopsis), phyllotreta indica (Phyllotreta nigra), and Japanese pea (Pholiota);
<xnotran> , ( (Diptera)), (Aedes aegypti), (Aedesalbopictus), (Aedes vexans), (Anastrepha ludens), (Anopheles maculipennis), anopheles crucians, (Anopheles albimanus), (Anopheles gambiae), anopheles freeborni, (Anopheles leucosphyrus), (Anopheles minimus), (Anopheles quadrimaculatus), (Calliphora vicina), (Ceratitis capitata), (Chrysomyabezziana), chrysomya hominivorax, chrysomya macellaria, (Chrysops discalis), chrysops silacea, chrysops atlanticus, cochliomyia hominivorax, (Contarinia sorghicola), cordylobia anthropophaga, culicoides furens, (Culex pipiens), (Culex nigripalpus), (Culex quinquefasciatus), (Culex tarsalis), culiseta inornata, culiseta melanura, (Dacuscucurbitae), (Dacus oleae), (Dasineura brassicae), (Delia antique), (Delia coarctata), (Delia platura), (Delia radicum), (Dermatobia hominis), (Fannia canicularis), geomyza Tripunctata, (Gasterophilus intestinalis), (Glossinamorsitans), (Glossina palpalis), glossina fuscipes, glossina tachinoides, haematobia irritans, haplodiplosis equestris, hippelates spp., (Hylemyia platura), </xnotran> Leaf miner (Hypoderma linearis), leptoconis torrens, vegetable leaf miner (Liriomyza sativae), american leaf miner (Liriomyza trifolii), lucilia caprina, lucilia cuprina (Lucilia cuprina), lucilia sericata (Lucilia sericata), lycoriia petiolis, mansonitia numus, lucilia cuprina, lucilia sericata, lucilia pelaria, and Mansoniella midge gall (Mayeriola destructor), autumn house fly (Musca autunnalis), house fly (Musca domestica), stable fly (Musca stabulans), sheep fly (Oestrus ovis), opomyza florum, european house fly (Oscinella frat), ficus erecta (Pegomyc hysocy), phorbia antia squa radish fly (Phorbia brassicae), phorbia coarctata, phorbotomus argentipes, psorophoracolumbiae, psila rosae, psorophora discolor, prosimulium mixum, cherry fruit fly (Rhagoletis cerasi), apple fruit fly (Rhagoletis pomonella), sarcophaga rubra (Sarcophaga emerrholidis), sarcophaga (Sarcophaga), simulium vitatum, stable fly (Stomoxystans), tabanus bovis (Tabanus bovinus), tabanus atratus, tabanus rubra (Tabanus lineola), tabanus similis, tipula oleracea, and European mosquito (Tipula paludo sativa);
thrips (Thysanoptera), such as Thrips orchid (dichlorthrips corbeti), dichlorthrips ssp, thrips tabaci (Frankliniella fusca), thrips medicaginis (Frankliniella occidentalis), thrips orientalis (Frankliniella tritici), thrips platycodonis (Scirtothrips citri), thrips oryzae (Thrips oryzae), thrips palmi (Thrips palmi), and Thrips tabaci (Thrips tabaci);
termites (Isoptera), such as Calotermes flaviolis, leucotermes flavipes, hetotermes aureus, reticulitermes flavipes, reticulitermes virginicus, eurotiames lucifugus, blastoma virginica, termite gradsei, termes natalensis and Coptotermes formosanus;
cockroaches (Blattaria) -Blattodea, such as Blattaria germanica (Blattaria germanica), blattaria asahinae, american cockroach (Periplaneta americana), japanese cockroach (Periplaneta japonica), brown cockroach (Periplaneta brunnea), periplaneta fuligginosa, australis Blatta (Periplaneta australiana), and Blattaria orientalis (Blatta orientalis);
<xnotran> , , , , , ( (Hemiptera)), (Acrosternum hilare), (Blissus leucopterus), (Cyrtopeltisnotatus), (Dysdercus cingulatus), dysdercus intermedius, (Eurygaster integriceps), (Euschistus impictiventris), (Leptoglossus phyllopus), (Lygus lineolaris), (Lyguspratensis), (Nezara viridula), (Piesma quadrata), solubeainsularis, thyanta perditor, acyrthosiphon onobrychis, (Adelgeslaricis), aphidula nasturtii, (Aphis fabae), (Aphis forbesi), (Aphis pomi), (Aphis gossypii), (Aphis grossulariae), aphisschneideri, (Aphis spiraecola), aphis sambuci, (Acyrthosiphonpisum), (Aulacorthum solani), (Bemisia argentifolii), brachycaudus cardui, (Brachycaudus helichrysi), brachycaudus persicae, brachycaudus prunicola, (Brevicoryne brassicae), capitophorus horni, cerosipha gossypii, chaetosiphon fragaefolii, cryptomyzus ribis, (Dreyfusia nordmannianae), (Dreyfusia piceae), (Dysaphis radicola), dysaulacorthum pseudosolani, dysaphis plantaginea, dysaphispyri, (Empoasca fabae), (Hyalopterus pruni), hyperomyzuslactucae, (Macrosiphum avenae), (Macrosiphum euphorbiae), </xnotran> Rosa multiflora (Macrosipon rosae), megoura viride, negleia sida (Melanaphila pyrarius), meadowra mairei (Methopolophium dirhodium), myzus persicae, chophysodiumson (Myzus ascalonicious donc), myzuscacis, prunus persicae (Myzus varians), nasonovialis-nigri, nilaparvata lugens (Nilaparvata), pemphigus gorius (Pemphigus bursararius), tagetes canus (Perkinsia sacchara), homopsis verrucosa (Phoodon humus), malaysia prurus (Pslama malis), pyricularia piricola (Psylopsis), pimpinella pyrum (Psyllia), and Malaysia punctata (Psoralis) (ii) the species Phosphaerella viridis (Rhopalomyces ascalonicius), zea mays (Rhopalosiphum maidis), aphis graminicola (Rhopalosiphum padi), rhopalosiphum insertum, sappaaphis mala, sappaaphis mali, schizaphis graminum, schizoneura lanuginosa, aphis graminis (Sitobion avenae), trialeurodes vaporariorum, toxoptera aurantia nd, rhizopus viticola (Viteusvitifolii), cimex tulalemma, cimex hemipterus, reduvius sensis, triatoma spp. And Arilus citritus;
ants, bees, wasps, and leaf bees (Hymenoptera), such as Sinkiang apis mellifera (Athaliarosae), ant incisa (Atta cephalotes), atta capiguara, atta cephalolites, atta laevigata, atta robusta, atta sexdens, atta texana, ant belladonna (Crematographer), hoplocapamina, hoplocapa testininea, black Terra (Lasius nigra), solenopsis radiata (Monomorpharonia), solenopsis invicta (Solenopsis geminata), solenopsis invicta (Solenopsis virica), solenopsis radiata (Solenopsis xylotonia), solenopsis invicta (Solenopsis rey), solenopsis quince red ants (Pogonomycexbarus), pogonomycex californica, spotted ants (Pheidole megacephala), velvet ants (Dasymusella occidentalis), bumble species (Bombus), hornets (Vespela squarosa), paravessula vularis, paravessula pennyvanica, paravessula germarica, brazilian bee (Dolichovella maculolata), vespela crassa (Vespera crabrogro), wasps (Polistes rubiginosa), camptontus floridanus and Argentina ant (Linitema huma);
cricket, grasshopper, locusts (Orthoptera), such as cricket (Acheta domestica), mole cricket (grylotalpa), migratory Locusta (Locusta miglatoria), hemifusus maculates (Melanoplus bivattus), erythropodus nigra (melanopodus femorubrum), mezoplus nigra (melanopodus nigricans), melanopodus nigra (melanopodus nigricans), hemimorpha americana (melanopodus sanguinipes), hemimorpha migratoria nigra (melanopodus sanguipes), hemiphyte melanophyte melanophytes (melanopodus spruce), striatus red locust (melanocortis maculata), hemifusca americana (schizophysalica), schanosoma americana (schistolocustca), schoecium maculata (schanosarcina), schoecium maculata (trichophyceae grassland), locusta (hypopharyophylla), locustus (hypopharyophyllus), locustus maculata (hypopharyophyllus maculata), locustus maculatus (hypopharyophyllus) and locustus (hypopharyophyllus);
<xnotran> (Arachnoidea), ( (Acarina)), (Argasidae), (Ixodidae) (Sarcoptidae), (Amblyomma americanum), (Amblyomma variegatum), ambryomma maculatum, (Argas persicus), (Boophilus annulatus), boophilus decoloratus, (Boophilus microplus), dermacentor silvarum, (Dermacentor andersoni), (Dermacentorvariabilis), hyalomma truncatum, (Ixodes ricinus), ixodes rubicundus, (Ixodes scapularis), (Ixodes holocyclus), (Ixodespacificus), ornithodorus moubata, ornithodorus hermsi, ornithodorus turicata, (Ornithonyssus bacoti), otobius megnini, (Dermanyssusgallinae), (Psoroptes ovis), (Rhipicephalus sanguineus), rhipicephalus appendiculatus, rhipicephalus evertsi, (Sarcoptes scabiei), (Eriophyidae), (Aculus schlechtendali), phyllocoptrataoleivora Eriophyes sheldoni; </xnotran> Dermatophagoides (Tarsonemidae), such as Phytonemus pallidus and Tarsonemus laterosus (Polyphagotarsonemus latus); spider mites (tenuipiladae), such as red spider mite (brevipus phoenicis); tetranychus (Tetranyhidae), such as Tetranychus cinnabarinus (Tetranychus cinnabarinus), tetranychus cinnabarinus (Tetranychus kanzawai), tetranychus pacificus (Tetranychus pacificus), tetranychus gossypii (Tetranychus Tetranychus tetranyicus) and Tetranychus urticae (Tetranychus urticae), tetranychus pomi (Pannychus ulmi), tetranychus ulmi (Pannychus citri) and Oligonychus pratenses; araneida (Araneida), such as the Amaranthus roseus (Latrodectus macrants) and the Brownia spider (Loxosceles reclusia);
fleas (Siphonaptera), such as cat fleas (Ctenococcus felis), dog fleas (Ctenococcus canis), xenopsylla cheopis (Xenopsylla cheopis), prurigo (Pulex irutans), dermabrasion fleas (Tunga pierrans) and nospherd fleas (Nosopsyllus fasciatus);
chlamydomonas, cheilfish (Thysanura), such as chlamydomonas occidentalis (Lepisma saccharana) and chlamydomonas maculata (Thermobia domestica), copepods (Chilopoda), such as scutiger colortrata, millipedes (Diplopoda), such as narcoleus spp., [0491] earoca (Dermaptera), such as compactula auricularia, louse (Phthiraptera), such as trichum auricularia, louse (Phthiraptera), such as Pediculus humanus capitis (pediococcus), pediculus humanus (pediluus gorius), pubis (pthorusus), blood louse (haemapulirus), cattle blood louse (trichoderma), pig trichoderma (trichoderma), cattle trichoderma, cattle trichoderma and cattle trichoderma;
from the order of the Collelmbola (springtail), for example, the genus Onychiurus (Onychiurus).
They are also suitable for controlling nematodes: plant parasitic nematodes such as root-knot nematodes, northern root-knot nematodes (melodogyne hapla), southern root-knot nematodes (melodogyne incognita), meloidogyne javanica (melodogyne japonica) and other root-knot nematodes (melodogyne); cyst-forming nematodes, potato gold thread (Globodera) and other globulospora species (Globodera); heterodera avenae (Heterodera avenae), heterodera glycines (Heterodera glycines), heterodera betanae (Heterodera schachtii), trefoil cyst nematode (Heterodera trifolii) and other cyst nematodes (Heterodera); seed gall nematode, granulomatosis (Anguina); nematode stem and leaf, aphelenchoides (Aphelenchoides); nematoda, weed nematoda (belonolaima longicaudatus) and other nematoda (belonolaimas); pine nematodes, pine wood nematodes (Bursaphelenchus xylophilus) and other Euglena species (Bursaphelenchus); roundworm, trichinella circinata (Criconema), trichinella ringonidis (Criconemella), strongyloides (Criconemoides), cyclotella (Mesocriconema); globodera, putrescent stem nematode (Ditylenchus destructor), sweet potato stem nematode (Ditylenchus dipsaci) and other phylogenetic species (Ditylenchus); conus, conus spp (Dolichodorus); helicoid nematodes, heliocentenchus multicinctus and other genera of Helicotylenchus; coleoptera and coleoptera, coleoptera (Hemicliophora) and Hemicconoides (Hemicconemoides); latent root nematodes (Hirshmanniella); coronaria, rifle nematode (hopolaimaus); pseudorhizomatoid, phyllanthus (Nacobbus); nematodes, longilineans transversa (Longidorus elengatus) and other longetidae (Longidorus); root-rot nematodes, pratylenchus negectus, root-rot nematodes (Pratylenchus penetrrans), pratylenchus curvatus, pratylenchus goodeyi and other species of root-rot nematodes (Pratylenchus); periploca, radopholus similis (Radopholus simlis) and other species of Periploca (Radopholus); reniform nematodes, discoid nematodes (Rotylenchus robustus) and other species of reniform nematodes (Rotylenchus); scutellonema; residual root nematodes, primitive ragworms (Trichodorus primativus) and other trichodera species (Trichodorus); genus pseudospiders (parathichodours); the species of nematodes include, for example, portulaca oleracea (Tylenochlornchus claytoni), coprinus brevicus (Tylenochlornchus dubius), and other species of Brevibacterium (Tylenochlornchus); citrus nematodes, heminematoda (Tylenchulus); sword nematode, sword nematode (xiphilinema); and other plant parasitic nematodes.
They can also be used for controlling arachnids (arachnids), such as acarids (order acarina), for example the families of the soft, hard and sarcoptic acaridae, such as the long-star-shaped ticks (Amblyomma americanum), the tropical flower ticks (Amblyomma variegatum), the Persian tick (Argas persicus), the cowlice (Boophilus annuatus), the Boophilus decorticatus, the Boophilus microplus (Boophilus microplus), the German silverareum, the Hyalomma truncatum, the Ricinum hard tick (Ixodesricinus), the Ixodes rubicundus, the Ornithiodorus mouubulus, the Otobius megrini, the Dermanyssus gallina, the sheep scabies (Psoropteris), the Rhiocephalus pendula, the aphidicola, the Epicoccus apercha, the Rhynchophyllus purpureus phaea, the Rhynchophyllus mange (Acacia), and the acarina, such as mange (Acanthopanax mange, and Acacia; dermatophagoides (Tarsonemidae), such as Phytonemus pallidus and Tarsonemus laterosus (Polyphagotarsonemulatus); spider mites (tenuipiladae), such as red spider mite (brevipus phoenicis); tetranychus (Tetranyhidae), such as Tetranychus cinnabarinus (Tetranychus cinabarinus), tetranychus cinnabarinus (Tetranychus kanzawai), tetranychus pacificus (Tetranychus pacificus), tetranychus gossypii (Tetranychus Tetranychus), and Tetranychus urticae (Tetranychus urticae), tetranychus pomi (Pannychus ulmi), tetranychus ulmi (Pannychus urtri), phyllostachys citroensis (Pannychus urtri), and oligoychus pratensis.
The plant object used for the pesticide of the present invention is not particularly limited; mention may be made, for example, of cereals (e.g., examples of the plants include rice, barley, wheat, rye, oat, corn, sorghum, etc.), beans (soybean, adzuki bean, broad bean, pea, groundnut, etc.), fruit trees/fruits (apple, citrus, pear, grape, peach, japanese apricot tree, cherry, walnut, apricot tree, banana, strawberry, etc.), vegetables (cabbage, tomato, spinach, broccoli, lettuce, onion, welsh onion, green pepper, etc.), root vegetables (carrot, potato, sweet potato, radish, lotus root, turnip, etc.), industrial crops (cotton, industrial hemp, paper mulberry, kohlrabi, rape, beet, hops, sugarcane, sugar beet, olive, rubber, coffee, tobacco, tea, etc.), berry fruits (pumpkin, cucumber, melon, etc.), grasses (orchard grass, hollyhock, terra, alfalfa, etc.), turfgrass (korean chickweed, bentgrass, etc.), spices, rosemary, thyme, parsley, chrysanthemum, rose, etc., and flowers.
Advantageous effects
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
through chemical modification and molecular design of a compound with an isoxazoline structure and introduction of 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 the compounds particularly have good biological activity on lepidoptera, homoptera, thysanoptera and other pests and have better biological safety.
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 obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to 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. The specific structure of the compound is shown in table 1, and the specific structure confirmation is shown in table 2. The compounds in tables 1-2 are only for better illustration of the invention and are not intended to be limiting, and those skilled in the art will not understand that the scope of the above subject matter of the invention is limited to the following compounds.
Figure SMS_5
The specific structure is shown in table 1:
TABLE 1 Structure of Compounds of formula I
Figure SMS_6
Figure SMS_7
Figure SMS_8
Figure SMS_9
Figure SMS_10
TABLE 2 1 H NMR data
Figure SMS_11
Figure SMS_12
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 used to synthesize the compounds of the present invention. Although specific starting materials and conditions for the synthetic routes are described below, they may be readily substituted for 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 within 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:
Figure SMS_13
a500 mL three-necked flask was charged with magnesium chips (3.6 g,150mmol, 1.5eq.), dried tetrahydrofuran (50 mL), and protected with nitrogen. 3, 5-dichloro-4-fluorobromobenzene (24.3 g,100mmol,1.0 eq.) was dissolved in dry tetrahydrofuran (200 mL), 20mL of the solution 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, the temperature of the three-necked flask was lowered to-40 ℃ and B (OMe) was slowly added 3 (150mmol, 10.4g,1.5 eq.) and reacted at low temperature for 2 hours and stirred 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-trifluoroprop-1-en-2-yl) benzene:
Figure SMS_14
the sealed tube (250 mL) was charged with (3, 5-dichloro-4-fluorophenyl) boronic acid (26.6g, 140mmol,1.0 eq.) and PdCl was added 2 (PPh 3 ) 2 (1.96g, 2.8mmol, 0.02eq.), potassium carbonate (38.6g, 280mmol, 2.0eq.), 2-bromo-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 a closed condition. 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) to give an oil (27g, 105mmol) in 75% yield. 1 H NMR(400MHz,CDCl 3 ):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:
Figure SMS_15
4-bromo-3-methylbenzonitrile (19.6 g,100mmol,1.0 eq.) was taken, dried dichloromethane (200 mL) was added, the temperature was reduced to-5 ℃, DIBALH (1.0M in toluene,150mL,150mmol,1.5 eq.) 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 subjected to silica gel column chromatography (petroleum ether: ethyl acetate = 8) to give a white solid (16.9g, 85mmol) with a yield of 85%. 1 H NMR(400MHz,CDCl 3 )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:
Figure SMS_16
4-bromo-3-methylbenzaldehyde (9.9g, 50mmol, 1.0eq.) was taken, methanol (100 mL), sodium bicarbonate (12.6 g,150mmol, 3.0eq.) and hydroxylamine hydrochloride (3.9g, 55mmol, 1.1eq.) were added, and the starting material disappeared after about 4 hours, monitored by TLC. After the reaction is finished, methanol is dried by spinning, ethyl acetate is added for dilution, the mixture is washed by saturated salt 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 H-NMR(400MHz,CDCl 3 )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:
Figure SMS_17
adding N, N-dimethylformamide (10 mL) into 4-bromo-3-methylbenzaldehyde oxime (4.3 g,20mmol and 1.0eq.), adding NCS (4.0 g,30mmol and 1.5eq.) and heating to 40 ℃, stirring for 2 hours, adding methyl tert-butyl ether for dilution, washing with saturated salt 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 (20 mL), 1, 3-dichloro-2-fluoro-5- (3, 3-trifluoroprop-1-en-2-yl) benzene (5.2g, 20mmol, 1.0eq.), and sodium bicarbonate (5.1g, 60mmol, 3.0eq.) and stirred overnight. When the raw materials disappear, 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 H-NMR(400MHz,CDCl 3 )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:
Figure SMS_18
3- (4-bromo-3-methylphenyl) -5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazole (9.4g, 20mmol, 1.0eq.), triethylamine (20 mL), ethanol (20 mL), 4, 5-bis (diphenylphosphine) -9, 9-dimethylxanthene (578mg, 1mmol, 0.05eq.), palladium acetate (45mg, 0.2mmol, 0.01eq.), carbon monoxide gas (0.8 MPa) and pressure reaction were carried out 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 is chromatographed by silica gel column (petroleum)Ether: ethyl acetate = 8) gave a pale yellow solid (6.5g, 14mmol) with a yield of 70%. 1 H-NMR(400MHz,CDCl 3 )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:
Figure SMS_19
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 (40 mL), and methanol (10 mL) was heated at 50 ℃ for 2 hours. After TLC monitoring disappearance of the starting material, pH =2 was adjusted with dilute hydrochloric acid and a solid precipitated. Suction filtration was carried out, and the filter cake was washed with water and dried to obtain a pale yellow solid (5.0 g,11.5 mmol) in 82% yield. 1 H NMR(400MHz,CDCl 3 )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 4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methyl-N- (1- (2, 2-trifluoroethyl) carbamoyl) cyclopropyl) benzamide (9):
Figure SMS_20
4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoic acid (436 mg,1mmol,1.0 eq.) was taken, dissolved in thionyl chloride (5 ml), and stirred under reflux for several hours. LCMS check correct, spin dry solvent, and dissolve residue in THF (5 ml) for use.
Weighing 1-aminocyclopropanecarboxylic acid (200mg, 2mmol, 2eq) and dissolving in water (10 ml), adding NaOH (80mg, 2mmol, 2eq) and stirring at room temperature for 0.5h, adding triethylamine (300mg, 3eq), dropwise adding an acyl chloride THF solution in an ice-water bath, stirring at room temperature for 2h after dropwise adding, performing LCMS detection, extracting with ethyl acetate (50ml, 2), washing with saturated salt water, drying with anhydrous sodium sulfate, concentrating and spin-drying to obtain an intermediate acid for later use;
the intermediate acid (520mg, 1mmol) was dissolved in dichloromethane (20 ml), HATU (420mg, 1.1eq) and DIPEA (390mg, 3eq) were added and stirred at room temperature for 0.5h, trifluoroethylamine hydrochloride (270mg, 2mmol, 2eq) and pyridine (0.5 ml) were added and stirred at room temperature overnight, and the product was detected by LCMS. The reaction mixture was washed with diluted hydrochloric acid (1 mol/L, 50ml. Times.2), with saturated brine (50ml. Times.2), dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product. Column chromatography (petroleum ether: ethyl acetate = 2) gave a pale yellow solid (250mg, 0.42mmol), 42% yield. LC-MS (ESI) [ M + H ]] + ＝600.0,[M+Na] + ＝622.4,[M+K] + ＝637.9。
Example 9
Preparation of N- (1- (ethylcarbamoyl) cyclopropyl) -2-methyl-4- (5- (3, 4, 5-trichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) benzamide (82):
Figure SMS_21
2-methyl-4- (5- (3, 4, 5-trichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) benzoic acid (451mg, 1mmol,1.0 eq.) was dissolved in thionyl chloride (5 ml) and stirred under reflux for several hours. LCMS check right, spin dry solvent, residue dissolved in THF (5 ml) for use.
Weighing 1-aminocyclopropanecarboxylic acid (200mg, 2mmol, 2eq) and dissolving in water (10 ml), adding NaOH (80mg, 2mmol, 2eq) and stirring at room temperature for 0.5h, adding triethylamine (300mg, 3eq), dropwise adding an acyl chloride THF solution in an ice-water bath, stirring at room temperature for 2h after dropwise adding, performing LCMS detection, extracting with ethyl acetate (50ml, 2), washing with saturated salt water, drying with anhydrous sodium sulfate, concentrating and spin-drying to obtain an intermediate acid for later use;
the intermediate acid (535mg, 1mmol) was dissolved in dichloromethane (20 ml), HATU (420mg, 1.1eq), DIPEA (390mg, 3eq) were added and stirred at room temperature for 0.5h, ethylamine (2.0 MinTHF,1ml, 2eq) and pyridine (0.5 ml) were added and stirred at room temperature overnight and checked by LCMS to give the product. The reaction mixture was washed with diluted hydrochloric acid (1 mol/L,50ml × 2), washed with saturated brine (50ml × 2), dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product. Column chromatography (petroleum ether: ethyl acetate = 2) gave a pale yellow solid (200mg, 0.36mmol) with a yield of 36%. LC-MS (ESI) [ M + H ]] + ＝561.3,[M+Na] + ＝584.4,[M+K] + ＝600.2。
Example 10
Preparation of N- (1- (2, 2-difluoroethyl) carbamoyl) cyclopropyl) -2-methyl-4- (5- (3, 4, 5-trichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) benzamide (93):
Figure SMS_22
2-methyl-4- (5- (3, 4, 5-trichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) benzoic acid (451mg, 1mmol,1.0 eq.) was dissolved in thionyl chloride (5 ml) and stirred under reflux for several hours. LCMS check correct, spin dry solvent, and dissolve residue in THF (5 ml) for use.
Weighing 1-aminocyclopropanecarboxylic acid (200mg, 2mmol, 2eq) and dissolving in water (10 ml), adding NaOH (80mg, 2mmol, 2eq) and stirring at room temperature for 0.5h, adding triethylamine (300mg, 3eq), dropwise adding an acyl chloride THF solution in an ice-water bath, stirring at room temperature for 2h after dropwise adding, performing LCMS detection, extracting with ethyl acetate (50ml, 2), washing with saturated salt water, drying with anhydrous sodium sulfate, concentrating and spin-drying to obtain an intermediate acid for later use;
the intermediate acid (535mg, 1mmol) was dissolved in dichloromethane (20 ml), HATU (420mg, 1.1eq), DIPEA (390mg, 3eq) were added and stirred at room temperature for 0.5h, difluoroethylamine (81mg, 1mmol, 1eq) and pyridine (0.5 ml) were added and stirred at room temperature overnight, and the product was detected by LCMS. The reaction mixture was washed with diluted hydrochloric acid (1 mol/L, 50ml. Times.2), with saturated brine (50ml. Times.2), dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product. Column chromatography (Petroleum ether: acetic acid ethyl ester)Ester = 2) to give a white solid (280mg, 0.48mmol), yield 48%. LC-MS (ESI) [ M + H ]] + ＝598.2,[M+Na] + ＝620.4,[M+K] + ＝636.1。
Example 11
Preparation of 2-methyl-N- (1- (methylcarbamoyl) cyclopropyl) -4- (5- (trifluoromethyl) -5- (3, 4, 5-trifluorophenyl) -4, 5-dihydroisoxazol-3-yl) benzamide (101):
Figure SMS_23
2-methyl-4- (5- (trifluoromethyl) -5- (3, 4, 5-trifluorophenyl) -4, 5-dihydroisoxazol-3-yl) benzoic acid (403mg, 1mmol, 1.0eq.) was taken, dichloromethane (5 ml) was added to dissolve, HATU (0.380g, 1mmol, 1eq.) and DIPEA (0.39g, 3mmol, 3eq.) were added, stirring was carried out at room temperature for 0.5h, then 1-aminocyclopropanecarboxylic acid (0.101g, 1mmol, 1eq.) was added in portions, the reaction was carried out at room temperature overnight, and the product was detected in liquid form. The reaction solution was used directly in the next step. HATU (0.380g, 1mmol, 1eq) and DIPEA (0.39g, 3mmol, 3eq) are added into the reaction solution, stirred for 0.5h at room temperature, a catalytic amount of pyridine is added, methylamine gas is introduced, the reaction is carried out overnight at room temperature, and the product is obtained by liquid chromatography. Adding dichloromethane for dilution, washing with dilute hydrochloric acid, washing with saturated brine, drying with anhydrous sodium sulfate, filtering, and concentrating under reduced pressure to obtain crude product. The crude product was subjected to silica gel column chromatography (petroleum ether: ethyl acetate = 2) to give a white solid (340mg, 0.68mmol) with a yield of 68%. LC-MS (ESI) [ M + H ]] + ＝500.2,[M+Na] + ＝522.4,[M+K] + ＝538.9。
Example 12
Preparation of the preparation:
1. soluble liquid agent: dissolving 10-50% of the compound of formula (I) and 5-20% of wetting agent in water and/or water-soluble solvent added to 100% to obtain the product.
2. Missible oil: dissolving 10-70% of compound of formula (I) and 5-10% of emulsifier in 100% of water-insoluble organic solvent to obtain the product.
3. Emulsion in water: dissolving 5-30% of the compound of formula (I) and 1-10% of an emulsifier in 20-40% of a water-insoluble organic solvent. The mixture was introduced into water added to 100% by means of an emulsifying machine and made into a homogeneous emulsion to obtain the product.
4. Suspending agent: in a stirred ball mill, 10-50% of the compound of formula (I) is ground in the presence of 2-10% of a dispersant, 1-5% of a wetting agent, 0.1-5% of a thickener and 100% of water to form an active substance suspension.
5. Water dispersible granules: grinding 10-70% of the compound of formula (I) with the addition of 100% of dispersing and wetting agents and shaping it into water-dispersible granules with the aid of industrial production equipment to give the product.
The above are all weight percentages.
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 insecticidal and acaricidal 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 (specific Structure
Figure SMS_24
)、
Control Compound B (specific Structure
Figure SMS_25
)、
Control Compound C (specific Structure
Figure SMS_26
)、
Control Compound D (specific Structure
Figure SMS_27
)、
Control Compound E (specific Structure
Figure SMS_28
)、
Control Compound F (specific Structure
Figure SMS_29
)、
Control Compound G (specific Structure is
Figure SMS_30
)、
Reference Compound H (having the particular Structure
Figure SMS_31
)、
Reference Compound I (detailed Structure
Figure SMS_32
)。
Example 14
And (3) evaluating the biological activity: diamondback moth
The indoor bioassay adopts a leaf soaking method. Selecting healthy and consistent 3-instar plutella xylostella larvae, putting fresh cabbage leaves into the liquid medicine by using tweezers, soaking for 10 seconds, taking out, naturally airing the liquid medicine, putting the cabbage leaves into a culture dish padded with moisturizing filter paper, and repeating the treatment for 4 times for 20 3-instar plutella xylostella larvae in each dish. The treated test insects are cultured in an artificial intelligent culture room with the temperature of 25 +/-1 ℃, the illumination time L: D = 1697 h, and the relative humidity of 60 percent. The number of dead diamondback moth insects was investigated 3 days after the application, and the mortality rate was calculated (integer retained).
The activity was as follows: at a concentration of 2ppm, more than 90% of the compounds of the present application have a controlling effect of 1-24, 29-46, 49-56, 62-68, 81, 89, 92, 101, 109, 129; in the control compound A-I, the control compounds A, B, C, G, H and I have the control effect of more than 90 percent.
The control compound and a portion of the compound of the invention were subjected to low concentration activity assays, with the following results:
Figure SMS_33
Figure SMS_34
Figure SMS_35
example 15
Evaluation of biological Activity: rice planthopper
The indoor biological assay adopts a rice stem soaking method. The rice plants at the tillering stage are cleaned, cut into rice stems with roots of about 10cm in length, and dried in the air, and 3 rice plants are combined into one group. Soaking rice stem in the prepared liquid medicine for 30s, taking out, slightly drying, wrapping the root with wet absorbent cotton, placing into a culture cup, taking 3-year-old nymphs of rice planthopper with consistent standard from potted rice, placing into the culture cup, and repeating the treatment for 4 times for 20 heads each cup. And (3) placing the culture cup after inoculation in an artificial intelligent culture room with the temperature of 26 +/-1 ℃, the illumination time L: D = 1693 h and the relative humidity of 75 +/-5% for feeding. The number of dead insects of rice planthoppers was investigated 3 days after the application, and the mortality (retention of whole number) was calculated.
The activity was as follows:
at a concentration of 10ppm, compounds A, B, C, G were present in control compound A-I with a control effect of greater than 90%.
The control compound and a portion of the compound of the invention were subjected to low concentration activity assays, with the following results:
Figure SMS_36
Figure SMS_37
the above embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention by this. 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 is characterized in that the structural formula is shown as the formula (I):
Figure FDA0003982889940000011
in the formula (I), the compound is shown in the specification,
X 1 、X 2 、X 3 the same or different, are respectively and independently selected from F, cl, br, CN or NO 2 ；
R 1 Selected from halogen, CN, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 2 -C 6 An alkenyl group;
R 2 selected from H, CN, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 2 -C 6 Alkenyl radical, C 1 -C 6 Alkoxy radical, C 3 -C 6 Cycloalkyl or C 3 -C 6 Cycloalkyl-substituted C 1 -C 6 An alkyl group.
2. The substituted benzamide isoxazoline derivative or a pesticidally acceptable salt thereof according to claim 1, characterized in that, in the formula (I),
X 1 、X 2 、X 3 the same or different, are respectively and independently selected from F, cl, br or CN;
R 1 selected from halogen, CN or C 1 -C 6 An alkyl group;
R 2 is selected from C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 3 -C 6 Cycloalkyl or C 3 -C 6 Cycloalkyl-substituted C 1 -C 6 An alkyl group.
3. The substituted benzamide isoxazoline derivative or a pesticidally acceptable salt thereof according to claim 1 or 2, characterized in that, in the formula (I),
X 1 、X 2 、X 3 identical or different, each independently selected from F, cl or Br;
R 1 selected from F, cl, br, methyl, ethyl, propyl or butyl;
R 2 selected from methyl, ethyl, propyl, butyl, CH 2 Cl、CHCl 2 、CCl 3 、CH 2 F、CHF 2 、CF 3 、CH 2 CF 3 、CH 2 CH 2 F、CH 2 CHF 2 Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cyclopropyl substituted methyl.
4. Substituted benzamide isoxazoline derivative or its pesticidally acceptable salt according to any one of claims 1 to 3, characterized in that in formula (I), X 1 And X 3 Identical or different, respectively selected from F or Cl;
X 2 is F or Cl;
R 1 is selected from CH 3 F or CN;
R 2 is selected from CH 3 、CH 2 CF 3 Cyclopropane, CH 2 CH 2 F、CH 2 CH 3 Cyclopentyl or cyclohexyl.
5. The substituted benzamide isoxazoline derivative or a pesticidally acceptable salt thereof according to any one of claims 1 to 4, characterized in that, in the formula (I), X 1 And X 3 Same, all are Cl;
X 2 is F;
R 1 is selected from CH 3 F or CN;
R 2 is selected from CH 3 、CH 2 CF 3 Cyclopropyl, CH 2 CH 2 F、CH 2 CH 3 Or a cyclopentyl group.
6. The substituted benzamide isoxazoline derivative or its salt as a pesticidal acceptable salt according to any one of claims 1 to 4, which is represented by the formula (I):
Figure FDA0003982889940000021
。
7. the substituted benzamide isoxazoline derivative or its salt as a pesticidal acceptable salt according to any one of claims 1 to 6, which is represented by the formula (I):
Figure FDA0003982889940000022
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 salt thereof as a pesticidally acceptable salt; preferably, the composition also comprises a preparation carrier or a preparation auxiliary agent.
9. A method for controlling plant pests or mites which comprises applying an insecticidally or acaricidally effective amount of at least one of the substituted benzamide isoxazoline derivatives or their salts as claimed in any one of claims 1 to 7 or an insecticidal or acaricidal composition as claimed in claim 8 to crops or 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 plant pests or mites in agriculture and other fields.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100144797A1 (en) * 2007-03-07 2010-06-10 Takeshi Mita Isoxazoline-substituted benzamide compound and pest control agent
CN101778566A (en) * 2007-08-17 2010-07-14 英特威国际有限公司 Isoxazoline compositions and as the purposes of antiparasitic agent
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
CN111936492A (en) * 2018-02-12 2020-11-13 Fmc公司 Naphthalene isoxazoline compounds for controlling invertebrate pests
CN112174904A (en) * 2019-07-01 2021-01-05 沈阳化工大学 Isoxazoline compound and application thereof
CN114605324A (en) * 2022-03-28 2022-06-10 山东省联合农药工业有限公司 Isoxazoline substituted benzamide derivative and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100144797A1 (en) * 2007-03-07 2010-06-10 Takeshi Mita Isoxazoline-substituted benzamide compound and pest control agent
CN101778566A (en) * 2007-08-17 2010-07-14 英特威国际有限公司 Isoxazoline compositions and as the purposes of antiparasitic agent
CN111936492A (en) * 2018-02-12 2020-11-13 Fmc公司 Naphthalene isoxazoline compounds for controlling invertebrate pests
CN112174904A (en) * 2019-07-01 2021-01-05 沈阳化工大学 Isoxazoline compound and application thereof
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
CN114605324A (en) * 2022-03-28 2022-06-10 山东省联合农药工业有限公司 Isoxazoline substituted benzamide derivative and preparation method and application thereof

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