CN115785017B - Substituted benzamide isoxazoline derivative or salt, composition and application thereof as pesticide acceptable - Google Patents

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

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CN115785017B
CN115785017B CN202211554927.0A CN202211554927A CN115785017B CN 115785017 B CN115785017 B CN 115785017B CN 202211554927 A CN202211554927 A CN 202211554927A CN 115785017 B CN115785017 B CN 115785017B
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salt
nematodes
substituted
formula
derivative
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CN115785017A (en
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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 in particular relates to a substituted benzamide isoxazoline derivative or a salt acceptable by pesticides, a composition and application thereof, wherein the compound has a structure shown in a formula (I):

Description

Substituted benzamide isoxazoline derivative or salt, composition and application thereof as pesticide acceptable
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 which are acceptable as pesticides, and application of the compounds or the salt and the composition which are acceptable as pesticides as insecticides or acaricides.
Background
The anilide isoxazolines are a class of compounds that was first discovered and focused by Shiyuan corporation to have insecticidal activity, particularly excellent biological activity against invertebrate pests. With the increasing emphasis of global grain safety, the improvement of agricultural production efficiency is also important. Although the study on the benzil isoxazoline compound has not been interrupted for many years, the benzil 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 phenylamide isoxazoline derivative or a salt, a composition and application thereof which are acceptable by pesticides, have excellent biological activity on lepidoptera, homoptera and thysanoptera pests, and are not easy to generate interactive resistance with the existing bisamide compounds.
Technical solution
The technical scheme adopted by the invention for achieving the purpose is as follows: a substituted anilide isoxazoline derivative or a salt thereof which is acceptable as a pesticide, which is characterized in that the structural formula is shown as formula (I):
in the formula (I), X 1 、X 2 、X 3 Identical or different, each independently selected from F, cl, br, CN or NO 2 ；
R 1 Selected from halogen, CN, C 1 -C 6 Alkyl, halogenated C 1 -C 6 Alkyl, C 2 -C 6 Alkenyl groups;
R 2 selected from H, CN, C 1 -C 6 Alkyl, halogenated C 1 -C 6 Alkyl, C 2 -C 6 Alkenyl, C 1 -C 6 Alkoxy, C 3 -C 6 Cycloalkyl or C 3 -C 6 Cycloalkyl-substituted C 1 -C 6 An alkyl group.
Further, in 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 selected from C 1 -C 6 Alkyl, halogenated C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl or C 3 -C 6 Cycloalkyl-substituted C 1 -C 6 An alkyl group.
Further, in 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 Methyl substituted with cyclopropane, cyclobutane, cyclopentane, cyclohexenyl or cyclopropane groups.
Further, in formula (I), X 1 And X is 3 The same or different is selected from F or Cl respectively;
X 2 f or Cl;
R 1 selected from CH 3 F or CN;
R 2 selected from CH 3 、CH 2 CF 3 Cyclopropane group, CH 2 CH 2 F、CH 2 CH 3 A cyclopentylalkyl group or a cyclohexenyl group. Further, in formula (I), X 1 And X is 3 The same is Cl;
X 2 f is the same as F;
R 1 selected from CH 3 F or CN;
R 2 selected from CH 3 、CH 2 CF 3 Cyclopropane group, CH 2 CH 2 F、CH 2 CH 3 Or a cyclopentylalkyl group.
Further, formula (I) is:
further, formula (I) is:
the pesticide acceptable salt can be a salt prepared by reacting the substituted anilide isoxazoline derivative 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, etc.) or an organic acid (such as oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid or benzoic acid, etc.); the pesticidally acceptable salt may also be a salt obtained by reacting the substituted anilide isoxazoline derivative of the present invention with a chemically acceptable base, wherein the chemically acceptable base may be an inorganic base (e.g. sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate) or an organic base (e.g. trimethylamine, triethylamine, etc.).
Further, the salt which is acceptable as a pesticide may be potassium salt, sodium salt, ammonium salt, calcium salt, pyridinium salt, choline salt, hydrochloride, phosphate, acetate, benzenesulfonate or oxalate.
The invention also discloses an insecticidal or acaricidal composition comprising an insecticidal or acaricidal effective amount of at least one of the substituted benzamide isoxazoline derivatives as described above or their pharmaceutically acceptable salts; further, a formulation carrier or formulation aid is included.
The present invention also discloses a method for controlling plant pests or mites comprising applying to the crop or pest or mite and/or to the habitat thereof a pesticidally or acaricidally effective amount of a substituted anilide isoxazoline derivative as described above or at least one of its pesticidally acceptable salts or a pesticidal or acaricidal composition as described above.
The invention also discloses the use of the substituted anilide isoxazoline derivatives as described above or at least one of their pesticidally acceptable salts or the pesticidal or acaricidal compositions as described above for controlling plant pests in agriculture and other fields.
In the definition of the structural formula of the above compounds, the terms used have the following meanings:
Halogen or halogen: refers to fluorine, chlorine, bromine and iodine.
C 1 -C 6 Alkyl: 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.
Halogenated C 1 -C 6 Alkyl: straight-chain or branched alkyl groups having 1 to 6 carbon atoms, and hydrogen atoms on these alkyl groups may be partially or entirely substituted with halogen, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl and the like.
The synthesis method of the compound shown in the formula I comprises the steps of preparing the compound shown in the formula XI through the compound shown in the formula X, IX and VIII, VII, VI, V, IV, III, II (in the chemical formulas listed below, substituents and symbols have the same meanings as those of the substituents and symbols shown in the formula I as long as the substituents and symbols are not defined otherwise):
further, the reaction may be carried out at normal pressure or high pressure, preferably at 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 are harmful or unwanted insects or mites, especially those which are encountered in agriculture, forestry, in the protection of stored products and in the protection of materials and in the hygiene sector, are active against generally sensitive and resistant species and are effective at all stages of pest or mite development; the invention also relates to a method of inhibiting pests or mites which comprises applying to the locus of the insect, to the locus of the pest, to the area claimed, or directly onto the insect to be controlled a biologically effective amount of a compound of formula (I). The compounds of the invention may also be used to control other invertebrate pests or organisms.
By insect habitat, pest habitat or pest mite habitat is meant the environment in which the insects, pests or pest mites live or their eggs are present, including the air surrounding them, the food consumed or the objects contacted. For example, protection of plants against diseases caused by viruses, fungi or bacteria can be achieved by controlling insects or mites which eat, destroy or contact edible agricultural products, ornamental plants, turf, pasture plants or other plants of economic value by applying the active compounds to the seeds of the plants (before planting), to the seedlings, or to the cuttings, leaves, stems, fruits, grains and/or roots of the plants, or to the soil or other growing medium (before or after planting of the crops), or by controlling sap-feeding pests such as whiteflies, planthoppers, aphids and aphids, etc., or mites such as tetranychus urticae, tetranychus cinnabarinus, etc.; the plants include plants propagated by conventional methods, as well as plants having insect or pest resistance, herbicide resistance, high yield, and/or other beneficial traits by modern biotechnology altering genes. It is contemplated that these compounds can be used to protect fabrics, paper, stored grains, seeds and other food, house, building and other items and/or sites by applying the compounds of the present invention to or near these objects.
By controlling pests or mites, inhibiting pests or mites, it is meant reducing the number of surviving insects, pests or mites, or reducing the number of eggs of surviving insects, pests or mites. The degree of reduction achieved by the compound depends on the application rate of the compound, the particular compound used and the insect, pest or mite species of interest, at least the amount being used to produce the effect.
An insecticide or acaricide comprising the compound represented by the formula (I) or a salt thereof as an active ingredient is suitable for controlling pests or mites in fruit trees, vegetables, other crops and ornamental plants or in the growing environment thereof such as soil.
Examples of pests to which the insecticide of the present invention can be applied include, but are not limited to, lepidopteran insects (Lepidoptera), such as Agrotis ypsilon, agrotis ypsum, kapok (Alabama argillacea), spodoptera littoralis (Angioptera virescens), argyresthia conjugella, spodoptera exigua (Autographa gamma), armyworm (Bupalustris), cacoecia murinana, capua reillulariana, cheimatobia brumata, picea verpa (Choristoneura fumiferana), choristoneura occidentalis, chilo suppressalis (Cirphosum), malus pumila (Cydia pomonella), pine moth (Dendrolimus pini), diahanitides, zea mays (Diatraea grandiosella), egyptian diamond back (Emeria insolana), nanmei corn borer (Elasmopalpus lignosellus), ligustrum lucidum (Eupoecilia ambiguella), evetria bolla, evetzia Feltia subterranea, heliothis armigera (Galleria mellonella), heliothis armigera (Grapholitha funebrana), heliothis armigera (Grapholitha molesta), heliothis armigera (Heliothis armigera), heliothis armigera (Heliothis virescens), heliothis zea (Heliothis zea), heliothis armigera (Heliluundalis), hibernia defoliaria, fangback white moth (Hyphantrichia sanguinea), malus pumila (Hyponomeutamarinlus), solanum lycopersicum (Keiferia lycopersicella), lambdina fiscellaria, spodoptera exigua (Laphygma exigua), phaeda (Leucoptera coffeella), leuconosteroides spinosa (Leucopia), lithocolletis blancardella, callicarpa vinifera (Lobesia botana), begonia (Loxostege sticticalis), lymantria dispar), fabricius (Lymantria monacha), fabricius, peach leaf moths (Lyonetia clerkella), yellow brown cabbage caterpillars (Malacosoma neustria), cabbage loopers (mamestraarassicae), yellow fir moths (Orgyia pseudotsugata), corn borers (Ostrinia nubilalis), small eye moths (panois flagera), cotton red bollworms (Pectinophora gossypiella), black-bone moths (Peridromasaucia), round palm moths (Phalera bucephala), potato moths (Phthorimaea operculella), citrus leaf moths (Phyllocnistis citrella), european butterflies (Pieris brasica), alfalfa noctuid (Plathypena scabra), plutella xylostella (Plutella xylostella), soybean moths (pseudoopsis luncis), rhyacionia frustrana, scrobipalpula absoluta, wheat moths (sitotragacerealela), grape leaf moths (Sparganothis pilleriana), spodoptera litura (spodoptera), sea ash moths (Spodoptera littoralis), prodenia litura (Spodoptera litura), thaumatopoea pityocampa, green oak moths (trichlida), trichosannthes (Zeiraphera canadensi);
Beetles (Coleoptera), for example, the species of Amomum pyriformis (Agrilus sinuatus), amomum straight (Agriotes lineatus), amomum dulcis (Agriotes obscurus), amphimallus solstitialis, anisandrus dispar, amomum mexicam (Anthonomus grandis), amomum apple (Anthonomus pomorum), aphthona euphoridae, athous haemorrhoidalis, amomum betananus (Atomum lineis), amomum longum (Blastophagus piniperda), blitophaga undata, vicia faba (Bruchus rufimanus), pityrospermum peas (Bruchus pisorum), amomum European (Bruchus lentis), amomum apple (Byctiscus betulae), amomum betananum (Casssima) Cerotoma trifurcata, amomum aureobasilicum (Cetonia aureosa), amomum gracilomyces (Ceuthorrhynchus assimilis), withanum genkwa (Ceuthorrhynchus napi), amomum betananensis (Chaetocnema tibialis), amomum fasciatus (Confucus, amomum zetimum (Crioceris asparagi), ctricornutum longhorn beetle (Diabrotica longicornis), amomum longhorn beetle (5268), amomum tsetum roseum (52), leucas, leuca (52, leuca glabra (52) and Leuca (52), leuca glabra (52, leuca glabra (37), leucas well as, leuca (Leucum tsetum, leucum tsetum, leemanum, leucum tsetum, leucum 37) and Leucadenii (52., melanotus communis, oulmeyeriana (Meligethes aeneus), dahurian beetle (Melolontha hippocastani), aureobasidium (Melolontha melolontha), oulemaoryza (Oulmezzae), portugal beak (Ortiorrhynchus sulcatus), fragaria root beetle (Otiorrychusovatus), horseradish beetle (Phaedon cochleariae), phylobius pyri, phyllotretatarinowicepala, pogostemon She Sai (Phyllophaga sp.), fabricius rimonia, phylloperthiatus (Phyllotreta nemorum), soy light foot beetle (Phyllotreta virtuata), japanese beetle (Popillia japonica), pisum sativum (Sitona linetus) and Pogostemon (Sitophilus granaria);
Flies, mosquitoes (Diptera), such as Aedes aegypti (Aedes aegypti), aedes albopictus (Aedes albopictus), aedes Aedes albopictus (Aedes vexans), drosophila mexicana (), anopheles pentadactyla (), anopheles albopictus (), anopheles glabra (), anopheles albopictus (Amylanthus), anopheles parvus (), anopheles suis (Amylanthus), anopheles suis (), anopheles cinematopsis, anopheles cinerea (Amylantha), anopheles (Amylantha sinensis), anopheles (Amylantha), and anopheles anopheles tetranychus (), red head drosophila (), medfly in the middle sea (), myiasis chrysomyia (Chrysomyabezziana), deer fly (), chrysops sibactea, gall midge (), culex pipiens (Culex pipiens), macitermes (), kumquat (), kid's-tail (kid's-tail) and the like anopheles tetranychus (), red head fly (), midge fly (), maggot fly (chrysomyabenzziana), deer fly (), chrysops siplae, gall midge (), culex spinosa (Culex pipiens), mosquito maciter (), schlieren (Hypoderma lineata), leptoconops torrens, vegetable leaf miner (Liriomyza sativae), american leaf miner (Liriomyza trifolii), lucilia camprina, microcephala (Lucilia cuprina), lucilia sericata (Lucilia seriata), lycoria pectoralis, mansonitiatidlanus, eriobotrya sinensis (Mayetiola destructor), autumn fly (Musca austenitalis), musca domestica (Musca omestinica), musca humicola (Muscina stabulans), yangji fly (Oestrus), opomyza florum, european wheat straw fly (Oscinella frat), henbane spring fly (Pegomya hysocyami) Phorbia anti-quat, turnip fly (Phorbia brassicae), phorbia coarctata, phlebotomus argentipes, psorocollumbiae, psila rosae, psorophora discolor, prosimulium mixtum, cherry fruit fly (Rhagoletis cerasi), apple fruit fly (Rhagoletis pomonella), red tail meat fly (Sarcophaga), bot (Sarcophaga), simulium vittatum, stable stings fly (stomoxyscalcitans), tabanus bovines (Tabanus bovines), tabanus atlus, tabanus lineola, tabanus similis, tipula oleracea, and European mosquito (Tipula panudosa);
Thrips (Thysanoptera), such as frankliniella occidentalis (Dichromothrips corbetti), dichromothrips ssp, tabaci (Frankliniella fusca), frankliniella occidentalis (Frankliniella tritici), platycodon grandiflorum (Scirtothrips citri), thrips oryzae (threps oryzae), thrips palmi (threps palmi) and Thrips tabaci (threps tabaci);
termites (Isoptera), such as Calotermes flavicollis, leucotermes flavovipes, heterotermes aureus, yellow limb termites (Reticulitermes flavipes), southern termites (Reticulitermes virginicus), european termites (Reticulitermes lucifugus), black termites (Reticulitermes santonensis), reticulitermes grassei, termes natalensis, and termite termites (Coptotermes formosanus);
cockroaches (Blattaria) -blattadea, such as german cockroaches (Blattella germanica), blattella asahinae, american cockroaches (Periplaneta americana), japanese cockroaches (periplaneta japonica), brown cockroaches (Periplaneta brunnea), periplaneta fuligginosa, australian cockroaches (Periplaneta australasiae), and oriental cockroaches (Blatta orientalis);
Bed bugs, aphids, leafhoppers, whiteflies, scale insects, cicadas (Hemiptera), such as Lygus lucorum (Acrosternum hilare), lygus lucorum (Blissus leucopterus), lygus lucorum (cyrtophyllus) et al, lygus lucorum (Dysdercus cingulatus), dysdercus intermedius, lygus maculatus (Eurygaster integriceps), lygus lucorum (Euschistus impictiventris), lygus lucorum (Leptoglossus phyllopus), lygus lucorum (Lygus lineolaris), lygus lucorum (lygustatensis), lygus lucorum (Nezara virdula), lygus lucorum (Piesma quadat), solubeainsonii, thyanta perditor, acyrthosiphon onobrychis, myzus persicae (Adelslarcis), aphidula nasturtii, myzus persicae (Aphis fasciae), aphis pomis (Aphis pomi), aphis gossypii (Aphis fasyi), aphis hypoyi) North American tea seed aphid (), aphis chneideri, coil (Aphis spirocola), aphis sambuci, pisum sativum (Acyrthosphonplus), potato aphid (), silver leaf whitefly (), , apricot tail aphid (), , cabbage aphid (), , fir cone aphid (), spruce cone aphid (Dreyfusia picea), judge tail aphid (), , dysphisuri, broad bean micro leafhopper (Empoasca fabae), peach tail aphid (), hyperamyzus slacto, wheat long pipe aphid (), big long pipe aphid (), white pipe, rosa tube aphid (Macrosiphon rosae), megoura vicae, aphis nidus Vespae (Melanaphis pyrarius), myzus persicae (Metopolophium dirhodum), allium fistulosum aphid (Myzus ascalonicusDonc), myzuscerasi Li Liuya (Myzus varians), nasonovia rib-nigri, rice planthoppers (Nilaparotalugens), aphis spinosa (Pemphigus bursarius), nilaparvata lugens (Perkinsiella saccharicida), bulletia negundo (Phonodon humuli), phyllon psy (Psyla mali), myzus persicae (Myzus virens), myzus virginiana, nasovia japonica, nitroselis japonica, nilaparvata lupulus, and Orchium spinosum pear psyllium (psylli), allium wintergreen moth aphid (Rhopalomyzus ascalonicus), corn aphid (Rhopalosiphum maidis), cereal spillway aphid (Rhopalosiphum padi), rhopalosiphum insertum, sapphis mala, sapphis mali, wheat binary aphid (Schizaphis graminum), schizoneura lanuginosa, sitobion avena, white fly (Trialeurodes vaporariorum), toxoptera aurantiiand, grape root nodule aphid (viteustifolii), cimex lectularius, cimex hepteus, reduvius senilis, triatoma spp, and Arilus crittatus;
Ants, bees, wasps, phyllostats (Hymenoptera), such as, for example, singapore (athaliarose), phyllostat (Atta cepalotes), atta capiguara, atta cepalotes, atta laevigata, atta robusta, atta sexdens, atta textana, lapa (crematoka), hopanada, holicopaminula, hoplocampa testudinea, black hair ants (Lasius niger), micromonomonomonomonospiralis, tropical fire ants (Solenopsis geminata), red fire ants (Solenopsis invicta), black fire ants (Solenopsis richteri), southern fire ants (Solenopsis xyloni), red ants (pogomyexbaatus), pogonomyrmex californicus, megacephalic ants (Pheidole megacephala), megacaryophyllata (Dasymutilla occidentalis), bumblebee (bumblena), megavesna (Vespa sqsa), paravespula vulgaris, paravespula germanica, 3765, and abrus (Campodontus floridanus), wasp and abrus (Campodontus floridanus);
cricket, grasshopper, locust (Orthoptera), such as living house Ai Xi (Acheta domestica), mole cricket (Gryllotalpa gryllotalpa), migratory locust (Locusta migratoria), black locust bifidus (melanoplus bivittatus), black locust rubrum (Melanoplus femurrubrum), black locust melanoplasmoschus (melanoplospost), black locust migratory (Melanoplus sanguinipes), black locust rubra (Melanoplus spretus), striped red locust (Nomadacris septemfasciata), desert locust america (Schistocerca americana), desert locust africana (Schistocerca gregaria), morgans locust (Dociostaurus maroccanus), court range (Tachycines asynamorus), small locust in caucasia (Oedaleus senegalensis), bologna locust (Zonozerus variegatus), hieroglyphus daganensis, kraussaria angulifera, italian locust (Calliptamus italicus), calamus (Chortoicetes terminifera) and brown locust (Locustana pardalina);
Arachnoidea (Arachnoidea), such as arachnids (Acarina), e.g., soft ticks (Argasidae), hard ticks (Ixodidae) and sarcopticae (Sarcoptidae), such as long star ticks (Amblyomma americanum), tropical flower ticks (Amblyomma variegatum), ambryomma maculatum, bossima sharp ticks (Argas personas), niu Bishi (Boophilus annulatus), boophilus decoloratus, microcow ticks (Boophilus microplus), dermacentor silvarum, anchus angustifous (Dermacentor andersoni), dermata americana (Dermacentor variabilis), hyalomma truncatum, castor hard ticks (Ixodes ribus), ixodes rubicundus, black foot hard ticks (Ixodes scapularis), full ring hard ticks (Ixodes holocyclus), pacific hard ticks (Ixodes), ornithodorus moubata, ornithodorus hermsi, ornithodorus turicata, platycladus fowl spike (Ornithonyssus bacoti), tobinini, gallica, sheep scabies (Psoosis), phalophilus, and Phalophilus, such as Phalocrocis, and Phalocrocis (Rhipicephalus sanguineus, 6342, phalocrocis, and Phalops; the genus Acarina (Tarsonemidae), such as Phytonemus pallidus and Tarsonius paraplectania (Polyphagotarsonemus latus); acarina (Tenuipalpidae), such as Acarina rhodochrous (Brevipalpus phoenicis); tetranychidae, such as Tetranychus cinnabarinus (Tetranychus cinnabarinus), tetranychus (Tetranychus kanzawai), tetranychus urticae (Tetranychus parcificus), tetranychus gossypii (Tetranychus telarius) and Tetranychus urticae (Tetranychus urticae), tetranychus urticae (Pannychus ulmi), tetranychus kangarcinus (Pannychus citri) and Oligonychus pratensis; arachnids (Araneida), such as erythema Kou Zhu (Latrodectus mactans) and brown spider (Loxosceles reclusa);
Fleas (Siphonaptera), such as cat fleas (Ctenocephalides felis), dog fleas (Ctenocephalides canis), rat fleas (Xenopsylla cheopis), itch causing fleas (Pulex iritans), skin penetrating daphnia (tunea penetrans), and fleas with diseases (Nosopsyllus fasciatus);
tuna, tuna (Thysanura), such as western tuna (Lepisma saccharina) and plagiocephalus (Thermobia domestica), polyporus (lippoda (Chilopoda)), such as Scutigera coleoptrata, serratia (bipopoda), such as Narceus spp., [0491] octopus (Dermaptera), such as earwig (forficula auricularia), lice (Mao Shimu (phthopera)), such as human head lice (Pediculus humanus capitis), human lice (Pediculus humanus corporis), pubic lice (Pthirus pubis), bovine blood lice (haemagglutinus), pig blood lice (Haematopinus suis), niu Eshi (Linognathus vituli), bovicobabovievovis, chicken lice (meropon galli), menacanthus stramineus and Solenopotes capillatus;
the order of the Carthamus (Collembola), for example, the genus echinochloa (Onychurus).
They are also suitable for controlling nematodes: plant parasitic nematodes such as root-knot nematodes, northern root-knot nematodes (Meloidogyne), southern root-knot nematodes (Meloidogyne incognita), java root-knot nematodes (Meloidogyne javanica) and other root-knot nematodes (Meloidogyne); cyst-forming nematodes, golden potato nematodes (globodendron stonensis) and other sacculus species (Globodera); grass Gu Bao cyst nematodes (Heterodera avenae), soybean cyst nematodes (Heterodera glycines), beet cyst nematodes (Heterodera schachtii), clover cyst nematodes (Heterodera trifolii) and other cyst nematodes (hetedodera); goiter seed, granatum (Anguina); stem and leaf nematodes, aphelenchoides (Aphelenchoides); spiny nematodes, weed spiny nematodes (belonolausoniudus) and other spiny nematodes (Belonolaimus); pine nematodes, pine wood nematodes (Bursaphelenchus xylophilus) and other Bursaphelenchus species (Bursaphelenchus); the species of the genus strongylus (cricondencma), the species of the genus strongylus (cricondencella), the species of the genus strongylus (cricondenchoides), the species of the genus strongylus (mesocrycronecma); corm nematodes, rotting nematodes (Ditylenchus destructor), sweet potato nematodes (Ditylenchus dipsaci) and other stem nematodes (Ditylenchus); trypanosoma, trypanosoma (dolichorrus); spiraling nematodes, heliocotylenchus multicinctus and other genera helicobacter; sheath and sheath nematodes, sheath and semi-round nematodes (Hemicelliophora) and Hemicentrotus (Hemicinecoat); the genus Trichinella (Hirshmanniella); crown nematodes, gun nematodes (Hoplolaimus); pseudoroot-knot nematodes, pearl nematodes (nacobus); needle nematodes, long-shank nematodes (Longidorus elongatus) and other long-shank nematodes (Longidorus); root rot nematodes, pratylenchus neglectus, piercing root rot nematodes (Pratylenchus), pratylenchus curvitatus, whole body nematodes (Pratylenchus goodeyi) and other root rot nematodes (Pratylenchus); radopholus, radopholus (Radopholus similis) and other Radopholus; reniform nematodes, spiral nematodes (Rotylenchus robustus) and other reniform nematodes (Rotylenchus); scutellonema genus; root-worm, prader (Trichodorus primitivus) and other Bursaphelenchus (Trichodorus); genus quasi-burring (Paratricrodorus); blocking long nematodes, purslane dwarfing nematodes (Tylenchorhynchus claytoni), cis-trans dwarfing nematodes (Tylenchorhynchus dubius) and other dwarfing nematodes (tyrenchonchus); citrus nematodes, hemipiercing nematodes (tyrencchulus); caenorhabditis, the genus caenorhabditis (Xiphinema); and other plant parasitic nematodes.
They can also be used for controlling arachnids (arachnidae), such as acarina (Acarina), for example Soft ticks, hard ticks and scabies, such as Alternaria longifolia (Amblyomma americanum), alternaria tropicalis (Amblyomma variegatum), rhaponticus aculeatus (Argas persicus), niu Bishi (Boophilus annulatus), boophilus decoloratus, rhapontici (Boophilus microplus), dermacentor silvarum, hyalomma truncatum, hard castor bean ticks (Ixodes), ixodes rubicundus, ornithodorus moubata, otobius megnini, dermatophagoides pteronyssinus (Dermanyssus gallinae), sheep scabies (Psorophtes ovis), rhipicephalus appendiculatus, rhipicephalus evertsi, human scabies (Sarcoptes scabiei), and goiter (Eriopyidae), such as Rhizopus apple (Aculus schlechtendali), phyllocoptrata oleivora and Eriophyes sheldoni; the genus Tetranychus (Tarsonemidae), such as Phytonemus pallidus and Tarsonemus lateral (Polyphago tarsonemuslatus); acarina (Tenuipalpidae), such as Acarina rhodochrous (Brevipalpus phoenicis); tetranychidae, such as Tetranychus cinnabarinus (Tetranychus cinnabarinus), tetranychus kanzawai, tetranychus pacificus (Tetranychus pacificus), tetranychus gossypii (Tetranychus telarius) and Tetranychus urticae (Tetranychus urticae), tetranychus urticae (Panonechus ulmi), tetranychus kangari (Panonechus citri) and oligonychus pratensis.
The plant object used for the insecticide of the present invention is not particularly limited; mention may be made, for example, of cereals (e.g., rice, barley, wheat, rye, oat, corn, sorghum, etc.), beans (soybean, bean, broad bean, pea, peanut, etc.), fruit trees/fruits (apple, citrus, pear, grape, peach, japanese apricot, cherry, walnut, apricot, banana, strawberry, etc.), vegetables (cabbage, tomato, spinach, broccoli, lettuce, onion, welsh onion, green pepper, etc.), root vegetables (carrot, potato, sweet potato, radish, lotus root, turnip, etc.), industrial crops (cotton, industrial hemp, paper mulberry, roses, rape, beet, hops, sugarcane, sugar beet, olive, rubber, coffee, tobacco, tea, etc.), berries (pumpkin, cucumber, watermelon, melon, etc.), grasses (grass, milo, timothy, alfalfa, etc.), grasses (lawns, bentgrass, etc.), spices, etc.), crops (lavender, rosemary, pepper, thyme, sweet potato, radish, lotus, turnip, etc.), flowers (chrysanthemum, etc.
Advantageous effects
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
Through chemical modification and molecular design of the compound with the isoxazoline structure, substituent groups are introduced into N of the amide groups, a series of compounds which are more efficient and can be used for agricultural or forestry disinsection or mite killing and have excellent activity are obtained, and particularly, the compounds have excellent biological activity against pests such as lepidoptera, homoptera, thysanoptera and the like, and meanwhile, the compounds have better biological safety.
Embodiments of the invention
The technical solutions in the embodiments of the present invention will be clearly and completely described below in connection with the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
By comprehensively considering the economy, diversity and bioactivity of the synthesized compounds, it is preferred that some of the compounds are listed in the following table. The specific structure of the compounds is shown in Table 1, and the specific structure is shown in Table 2. The compounds of tables 1-2 are only for better illustration of the present invention and are not meant to limit the present invention, and those skilled in the art should not understand that the scope of the above subject matter of the present invention is limited to the following compounds.
The specific structure is shown in table 1:
TABLE 1 Structure of Compounds of formula I
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TABLE 2 1 H NMR data
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The process for preparing the compounds of the present invention is 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. Those skilled in the art will appreciate that other synthetic routes may also be used to synthesize the compounds of the present invention. Although specific starting materials and conditions in the synthetic routes have been described below, they may be readily replaced with other similar starting materials and conditions, and modifications or variations of the preparation methods 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, protection of the appropriate groups during the reaction, and the like.
Example 1
Synthesis of (3, 5-dichloro-4-fluorophenyl) boronic acid:
500mL three-necked flask was charged with magnesium turnings (3.6 g,150mmol,1.5 eq.) and dried tetrahydrofuran (50 mL) was blanketed with nitrogen. 3, 5-dichloro-4-fluorobromobenzene (24.3 g,100mmol,1.0 eq.) was dissolved in dry tetrahydrofuran (200 mL), 20mL was added dropwise to the reaction flask via a constant pressure dropping funnel, the Grignard reaction was initiated by adding iodine granules, and the remaining solution was slowly added to the reaction flask. After the completion of the dropwise addition, the temperature was raised to reflux and stirring was further carried out for 2 hours. After the reaction, the temperature of the three-mouth bottle is reduced to-40 ℃ and B (OMe) is slowly added 3 (150 mmol,10.4g,1.5 eq.) at low temperature for 2 hours and stirring at room temperature for a further 2 hours. Dilute hydrochloric acid is added into the reaction liquid in ice bath, the pH is regulated to about 3, methyl tertiary butyl ether is used for extraction, saturated saline water is used for washing, anhydrous sodium sulfate is used for drying, and crude products are obtained through filtration and reduced pressure concentration.
Example 2
Preparation of 1, 3-dichloro-2-fluoro-5- (3, 3-trifluoroprop-1-en-2-yl) benzene:
a sealed tube (250 mL) was charged with (3, 5-dichloro-4-fluorophenyl) boric acid (26.6 g,140mmol,1.0 eq.) and PdCl was added 2 (PPh 3 ) 2 (1.96 g,2.8mmol,0.02 eq.) potassium carbonate (38.6 g,280mmol,2.0 eq.) 2-bromo-3, 3-trifluoropropene (49 g,280mmol,2.0 eq.) THF/H2O (4:1, 100 ml) was added and heated under closed conditions at 70 ℃ for 12H. After the reaction, ethyl acetate was added to dilute the mixture, and the mixture was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product. The crude product was chromatographed on a column of silica gel (petroleum ether: ethyl acetate=10:1) to give an oil (27 g,105 mmol) 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:
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,1.5eq) was added, TLC monitoring, and after about 2 hours the starting material disappeared. After quenching the excess reducing agent with methanol, saturated potassium sodium tartrate solution was added and stirred until delamination. Separating, washing with saturated saline, drying with anhydrous sodium sulfate, filtering, and concentrating under reduced pressure to obtain crude product. The crude product was chromatographed on a column of silica gel (petroleum ether: ethyl acetate=8:1) to give a white solid (16.9 g,85 mmol) in 85% yield. 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:
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4-bromo-3-methylbenzaldehyde (9.9 g,50mmol,1.0 eq.) was taken, methanol (100 mL), sodium bicarbonate (12.6 g,150mmol,3.0 eq.) and hydroxylamine hydrochloride (3.9 g,55mmol,1.1 eq.) were added, and after about 4 hours the starting material disappeared as monitored by TLC. After the reaction, the methanol was dried by spin-drying, diluted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to give a crude product. The crude product was chromatographed on a column of silica gel (petroleum ether: ethyl acetate=8:1) to give a white solid (9.6 g,45 mmol) in 90% yield. 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:
4-bromo-3-methylbenzaldehyde oxime (4.3 g,20mmol,1.0 eq.) was taken, N-dimethylformamide (10 mL) was added, NCS (4.0 g,30mmol,1.5 eq.) was added, the mixture was stirred for 2 hours at 40℃and then diluted with methyl tert-butyl ether, washed with saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to give a crude chloroxime product. To the crude was added dichloromethane (20 mL), 1, 3-dichloro-2-fluoro-5- (3, 3-trifluoroprop-1-en-2-yl) benzene (5.2 g,20mmol,1.0 eq.) and sodium bicarbonate (5.1 g,60mmol,3.0 eq.) was stirred overnight. The raw materials are eliminated, diluted by adding ethyl acetate, washed by saturated saline solution, dried by anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain crude products. The crude product was chromatographed on a silica gel column (petroleum ether: ethyl acetate=8:1) to give a white solid (6.7 g,14.4 mmol) in 72% yield. 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:
to the autoclave was added 3- (4-bromo-3-methylphenyl) -5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazole (9.4 g,20mmol,1.0 eq.) and triethylamine (20 mL), ethanol (20 mL), 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene (578 mg,1mmol,0.05 eq.), palladium acetate (45 mg,0.2mmol,0.01 eq.) were added, and carbon monoxide gas (0.8 MPa) was introduced for pressure reaction for 12 hours. After the reaction, the solvent was dried by spin-drying, diluted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to give a crude product. The crude product was chromatographed on a column of silica gel (petroleum ether: ethyl acetate=8:1) to give a pale yellow solid (6.5 g,14 mmol) in 70% yield. 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:
to 4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzeneTo ethyl acetate (6.5 g,14mmol,1.0 eq.) was added a 2N NaOH solution (40 mL), and methanol (10 mL) was heated to 50℃for 2 hours. After TLC monitoring the disappearance of starting material, ph=2 was adjusted with dilute hydrochloric acid and a solid precipitated. Suction filtration, filter cake washing with water, drying gave 82% yield of pale yellow solid (5.0 g,11.5 mmol). 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):
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 and dissolved in thionyl chloride (5 ml), followed by stirring under reflux for several hours. LCMS was checked for errors, the solvent was dried, and the residue was dissolved in THF (5 ml) for later use.
1-aminocyclopropane carboxylic acid (200 mg,2mmol,2 eq) is weighed and dissolved in water (10 ml), naOH (80 mg,2mmol,2 eq) is added, stirring is carried out for 0.5h at room temperature, triethylamine (300 mg,3 eq) is added, acyl chloride THF solution is dropwise added in ice water bath, stirring is carried out for 2h at room temperature after the dropwise addition is finished, LCMS detection is correct, ethyl acetate (50 ml.2) is extracted, saturated salt water washing, anhydrous sodium sulfate is dried, and intermediate acid is obtained by concentration and spin drying for standby;
intermediate acid (520 mg,1 mmol) was dissolved in dichloromethane (20 ml), HATU (420 mg,1.1 eq) was added, DIPEA (390 mg,3 eq) was stirred at room temperature for 0.5h, triethylamine hydrochloride (270 mg,2mmol,2 eq) and pyridine (0.5 ml) were added, stirred at room temperature overnight, and LCMS detection gave the product. The reaction solution was washed with dilute hydrochloric acid (1 mol/L,50 ml. Times.2), washed with saturated brine (50 ml. Times.2), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain crude product. Column chromatography (petroleum ether: ethyl acetate=2:1) afforded a pale yellow solid (250 mg,0.42 mmol) in 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):
2-methyl-4- (5- (3, 4, 5-trichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydro-isoxazol-3-yl) benzoic acid (457 mg,1mmol,1.0 eq.) was taken and dissolved in thionyl chloride (5 ml), and stirred under reflux for several hours. LCMS was checked for errors, the solvent was dried, and the residue was dissolved in THF (5 ml) for later use.
1-aminocyclopropane carboxylic acid (200 mg,2mmol,2 eq) is weighed and dissolved in water (10 ml), naOH (80 mg,2mmol,2 eq) is added, stirring is carried out for 0.5h at room temperature, triethylamine (300 mg,3 eq) is added, acyl chloride THF solution is dropwise added in ice water bath, stirring is carried out for 2h at room temperature after the dropwise addition is finished, LCMS detection is correct, ethyl acetate (50 ml.2) is extracted, saturated salt water washing, anhydrous sodium sulfate is dried, and intermediate acid is obtained by concentration and spin drying for standby;
intermediate acid (535 mg,1 mmol) was dissolved in dichloromethane (20 ml), HATU (420 mg,1.1 eq) was added, DIPEA (390 mg,3 eq) was stirred at room temperature for 0.5h, ethylamine (2.0 min thf,1ml,2 eq) and pyridine (0.5 ml) were added, stirred at room temperature overnight, and LCMS detection gave the product. The reaction solution was washed with dilute hydrochloric acid (1 mol/L,50 ml. Times.2), washed with saturated brine (50 ml. Times.2), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain crude product. Column chromatography (petroleum ether: ethyl acetate=2:1) gave a pale yellow solid (200 mg,0.36 mmol) in 36% yield. 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):
2-methyl-4- (5- (3, 4, 5-trichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydro-isoxazol-3-yl) benzoic acid (457 mg,1mmol,1.0 eq.) was taken and dissolved in thionyl chloride (5 ml), and stirred under reflux for several hours. LCMS was checked for errors, the solvent was dried, and the residue was dissolved in THF (5 ml) for later use.
1-aminocyclopropane carboxylic acid (200 mg,2mmol,2 eq) is weighed and dissolved in water (10 ml), naOH (80 mg,2mmol,2 eq) is added, stirring is carried out for 0.5h at room temperature, triethylamine (300 mg,3 eq) is added, acyl chloride THF solution is dropwise added in ice water bath, stirring is carried out for 2h at room temperature after the dropwise addition is finished, LCMS detection is correct, ethyl acetate (50 ml.2) is extracted, saturated salt water washing, anhydrous sodium sulfate is dried, and intermediate acid is obtained by concentration and spin drying for standby;
intermediate acid (535 mg,1 mmol) was dissolved in dichloromethane (20 ml), HATU (420 mg,1.1 eq) was added, DIPEA (390 mg,3 eq) was stirred at room temperature for 0.5h, difluoroethylamine (81 mg,1mmol,1 eq) and pyridine (0.5 ml) were added, stirred at room temperature overnight, and the product was obtained by LCMS detection. The reaction solution was washed with dilute hydrochloric acid (1 mol/L,50 ml. Times.2), washed with saturated brine (50 ml. Times.2), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain crude product. Column chromatography (petroleum ether: ethyl acetate=2:1) gave a white solid (280 mg,0.48 mmol) in 48% yield. 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):
2-methyl-4- (5- (trifluoromethyl) -5- (3, 4, 5-trifluorophenyl) -4, 5-dihydro-isoxazol-3-yl) benzoic acid (403 mg,1mmol,1.0 eq.) was taken, dichloromethane (5 ml) was added to dissolve, HATU (0.380 g,1mmol,1 eq.) was added, DIPEA (0.39 g,3mmol,3 eq.) was stirred at room temperature for 0.5h, then 1-aminocyclopropane carboxylic acid (0.101 g,1mmol,1 eq.) was added in portions and reacted at room temperature overnight, liquid quality was measured to give the productAnd (3) an object. The reaction solution was used directly in the next step. HATU (0.380 g,1mmol,1 eq), DIPEA (0.39 g,3mmol,3 eq) were added to the reaction mixture, stirred at room temperature for 0.5h, catalytic amount of pyridine was added, then methylamine gas was introduced, the reaction was carried out at room temperature overnight, and the liquid quality was detected to give the product. Adding dichloromethane for dilution, washing with dilute hydrochloric acid, 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 a silica gel column (petroleum ether: ethyl acetate=2:1) to give a white solid (340 mg,0.68 mmol) in 68% yield. LC-MS (ESI) [ M+H ]] + ＝500.2,[M+Na] + ＝522.4,[M+K] + ＝538.9。
Example 12
Preparation of the preparation:
1. soluble liquid: 10-50% of the compound of formula (I) and 5-20% of a wetting agent are dissolved in water and/or a water-soluble solvent added to 100% to give the product.
2. Emulsifiable concentrate: 10-70% of the compound of formula (I) and 5-10% of an emulsifier are dissolved in a water-insoluble organic solvent added to 100% to give the product.
3. Aqueous emulsion: 5-30% of a compound of formula (I) and 1-10% of an emulsifier are dissolved in 20-40% of a water-insoluble organic solvent. The mixture was introduced into 100% water by means of an emulsifying machine and made into a homogeneous emulsion to obtain the product.
4. Suspending agent: 10-50% of the compound of formula (I) is crushed in a stirred ball mill in the presence of 2-10% of dispersant and 1-5% of wetting agent, 0.1-5% of thickener and 100% of water to give an active substance suspension.
5. Water dispersible granule: grinding 10-70% of the compound of formula (I) with the addition of dispersant and wetting agent to 100% and preparing it into water dispersible granule by means of industrial production equipment.
All the above are weight percentages.
Evaluation of biological Activity
After dissolving the test compound in N, N-dimethylformamide, it was diluted to a desired concentration with water containing 0.1% Tween-80.
Testing the compounds for insecticidal and acaricidal activity; and the insecticidal and acaricidal activity parallel test is carried out on the compound, and the specific structure of the compound is as follows:
control Compound A (specific Structure is )、
Control Compound B (specific Structure is)、
Control compound C (specific structure is)、
Control compound D (specific structure is)、
Control Compound E (specific Structure is)、
Control Compound F (specific Structure is)、
Control Compound G (specific Structure is)、/>
Control Compound H (specific Structure is)、
Control Compound I (specific Structure is)。
Example 14
Biological activity evaluation: plutella xylostella
The indoor biological measurement adopts a leaf dipping method. Selecting healthy and consistent plutella xylostella 3-instar larvae, immersing fresh cabbage leaves in the liquid medicine for 10 seconds by using tweezers, taking out, naturally airing the liquid medicine, placing the cabbage leaves in a culture dish filled with moisturizing filter paper, and repeating each treatment for 4 times for 20 plutella xylostella 3-instar larvae. The treated test insects are placed in an artificial intelligent culture room with the temperature of 25+/-1 ℃ and the illumination time of L, D=16h and 8h and the relative humidity of 60 percent for feeding. The number of plutella xylostella dead insects was investigated 3 days after the administration, and the mortality (retention of integers) was calculated.
The activity is as follows: at a concentration of 2ppm, greater than 90% of the compounds of the present application have a control effect of 1-24, 29-46, 49-56, 62-68, 81, 89, 92, 101, 109, 129; control compounds a-I had a control effect of greater than 90% of compound A, B, C, G, H, I.
The control compound was assayed for low concentration activity with a portion of the compounds of the application as follows:
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Example 15
Biological activity evaluation: rice planthoppers
The indoor bioassay is carried out by adopting a rice stem dipping method. The rice plants in the tillering stage are washed, sheared into rice stems with roots and about 10cm long, and dried in the air, and 3 rice plants are selected. Soaking rice stem in the prepared medicinal liquid for 30s, taking out, air drying, wrapping root with wet absorbent cotton, placing into culture cup, taking 3-year nymphs of rice planthoppers with standard consistence from potted rice, placing into the culture cup, and repeating each treatment for 4 times with 20 heads per cup. The culture cups after insect inoculation are placed in an artificial intelligent culture room with the relative humidity of 75+/-5% for feeding at the temperature of 26+/-1 ℃ and the illumination time of L, D=16h and 8 h. The number of dead rice planthoppers was investigated 3 days after the drug, and the mortality (retention of integers) was calculated.
The activity is as follows:
at a concentration of 10ppm, the control compounds A-I had compound A, B, C, G with a control effect of greater than 90%.
The control compound was assayed for low concentration activity with a portion of the compounds of the invention as follows:
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the above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention are intended to be included within the scope of the present invention.

Claims (8)

1. A substituted anilide isoxazoline derivative or a salt thereof which is acceptable as a pesticide, which is characterized in that the structural formula is shown as formula (I):
in the formula (I), X 1 And X is 3 The same or different is selected from F or Cl respectively;
X 2 f or Cl;
R 1 selected from CH 3 F or CN;
R 2 selected from CH 3 、CH 2 CF 3 Cyclopropane group, CH 2 CH 2 F、CH 2 CH 3 A cyclopentylalkyl group or a cyclohexenyl group.
2. The substituted benzidine derivative or the salt thereof acceptable as pesticides as claimed in claim 1, wherein the derivative is represented by the formulaI) Wherein X is 1 And X is 3 The same is Cl;
X 2 f is the same as F;
R 1 selected from CH 3 F or CN;
R 2 selected from CH 3 、CH 2 CF 3 Cyclopropane group, CH 2 CH 2 F、CH 2 CH 3 Or a cyclopentylalkyl group.
3. The substituted benzidine derivative or the agriculturally acceptable salt thereof according to claim 2, wherein formula (I) is:
4. a substituted benzidine derivative according to claim 3 or a pesticidally acceptable salt thereof, wherein formula (I) is:
5. an insecticidal or acaricidal composition comprising an insecticidally or acaricidally effective amount of at least one of the substituted anilide isoxazoline derivatives of any one of claims 1 to 4 or a pesticidally acceptable salt thereof.
6. The insecticidal or acaricidal composition according to claim 5, further comprising a formulation carrier or formulation aid.
7. A method for controlling plant pests or mites which comprises applying a pesticidally or acaricidally effective amount of a substituted anilide isoxazoline derivative according to any one of claims 1 to 4 or of a substituted anilide isoxazoline derivative or of a pesticidally acceptable salt thereof as defined in claim 5 or of a pesticidally or acaricidally composition to the crop plants or to the pests or mites and/or their habitat.
8. Use of a substituted anilide isoxazoline derivative according to any one of claims 1 to 4 or as at least one of the pesticidally acceptable salts thereof or of the insecticidal or acaricidal composition according to claim 5 for controlling plant pests or mites in agriculture and other fields.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5206993B2 (en) * 2007-03-07 2013-06-12 日産化学工業株式会社 Isoxazoline-substituted benzamide compounds and pest control agents

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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