A substituted benzamide derivative or its acceptable salt as pesticide, composition and use thereof

Abstract

The present invention belongs to the field of pesticides, and specifically relates to a substituted benzamide derivative or a salt thereof acceptable as a pesticide, a composition and use thereof, wherein the compound has a structure of formula (I): wherein the definitions of the groups in the formula are as shown in the specification. The substituted benzamide derivative of the present invention has highly effective insecticidal or acaricidal activity, is particularly suitable for the prevention and treatment of pests such as Lepidoptera and Thysanoptera, and has ideal safety for crops, and has good application prospects.

Description

Technical Field

[0001] The present invention belongs to the technical field of pesticides, and specifically relates to a substituted benzamide compound or its salt or composition acceptable as a pesticide, and to the use of the compound or its salt or composition acceptable as a pesticide as an insecticide. Background Art

[0002] Benzamide compounds are a class of compounds with good insecticidal activity and have always been the preferred direction for the creation and research of new pesticides; fluorinated derivatives, especially fluorinated organic compounds, are also the preferred direction for the creation and research of new pesticides due to their better fat solubility, stability and permeability. In 2014, Bayer CropScience AG developed the first phenylpyrazole nicotinamide fluorinated insecticide, which has a good preventive effect on Lepidoptera and some Homoptera pests, and has since triggered a wave of research and development in this field. Its chemical structure is shown below:

[0003]

[0004] However, the above active compounds only have good control effects on Lepidoptera and some Homoptera pests, while there is still much room for improvement in their activity against Thysanoptera and other Homoptera pests. Therefore, in order to achieve pesticide reduction and increase in efficiency, it is urgent to further broaden the insecticidal spectrum of phenylpyrazole nicotinamide insecticides and improve their biological activity.

[0005] Technical issues

[0006] In order to solve the above problems existing in the prior art, the present invention provides a substituted benzamide derivative or its salt acceptable as a pesticide, a composition and its use, which has excellent biological activity against Lepidoptera, Homoptera and Thysanoptera pests and is not easy to produce cross-resistance with existing diamide compounds.

[0007] Technical Solutions

[0008] The technical solution adopted by the present invention to achieve the above-mentioned purpose is: a substituted benzamide derivative or a salt thereof acceptable as a pesticide, whose structural formula is shown in formula (I):

[0009]

[0010] In formula (I), R1 and R2 are independently selected from H, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkyl substituted with C1-C6 alkoxy, C3-C6 cycloalkyl or C1-C6 alkyl substituted with C3-C6 cycloalkyl;

[0011] R3 is selected from H, halogen, CN, C1-C6 alkyl or halogenated C1-C6 alkyl;

[0012] n is an integer selected from 1-6.

[0013] Further, in formula (I), R1 is selected from H, C1-C6 alkyl, C3-C6 cycloalkyl or C1-C6 alkyl substituted with C3-C6 cycloalkyl;

[0014] R2 is selected from H, C1-C6 alkyl, halogenated C1-C6 alkyl or C1-C6 alkoxy-substituted C1-C6 alkyl;

[0015] R3 is selected from halogen, CN or halogenated C1-C6 alkyl;

[0016] n is an integer selected from 1-5.

[0017] Further, in formula (I), R1 is a C1-C4 alkyl group, a C3-C6 cycloalkyl group, or a C1-C6 alkyl group substituted with a C3-C6 cycloalkyl group;

[0018] R2 is H or C1-C4 alkyl;

[0019] R3 is selected from halogen or CN;

[0020] n is an integer selected from 1-4.

[0021] Further, in formula (I), R1 is Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, cyclopropanyl, cyclobutanyl, cyclopentanyl, cyclohexanyl or methyl substituted by cyclopropanyl;

[0022] R2 is selected from H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu or t-Bu;

[0023] R3 is selected from F, Cl, Br or CN;

[0024] n is an integer selected from 1-4.

[0025] Further, in formula (I), in formula (I), R1 is selected from methyl, ethyl, n-propyl, isopropyl, cyclopropane or cyclobutane;

[0026] R2 is selected from H, methyl or ethyl;

[0027] R3 is selected from F, Cl or Br;

[0028] n is 1, 2 or 3.

[0029] Further, in formula (I), R1 is selected from methyl or cyclopropane;

[0030] R2 is selected from H or methyl;

[0031] R3 is selected from F, Cl or Br;

[0032] n is 1, 2 or 3.

[0033] Further, formula (I) is specifically:

[0034]

[0035] The pesticide-acceptable salt may be a salt obtained by reacting the substituted benzamide derivative of the present invention with a chemically acceptable acid, wherein the chemically acceptable acid may 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 pesticide-acceptable salt may also be a salt obtained by reacting the substituted benzamide derivative of the present invention with a chemically acceptable base, wherein the chemically acceptable base may be an inorganic base (such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate) or an organic base (such as trimethylamine, triethylamine, etc.).

[0036] Furthermore, 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, a phosphate, an acetate, a benzenesulfonate or an oxalate.

[0037] The present invention also discloses an insecticidal composition, comprising an insecticidal effective amount of the substituted benzamide derivatives as described above or at least one of their pesticide-acceptable salts; further comprising a formulation carrier or a formulation adjuvant.

[0038] The present invention also discloses a method for controlling plant pests, comprising applying an insecticidal effective amount of the substituted benzamide derivatives as described above or at least one of their pesticide-acceptable salts or the insecticidal composition as described above to crops or pests and / or their habitats.

[0039] The present invention also discloses the use of the substituted benzamide derivatives or at least one of their pesticide-acceptable salts or the insecticidal composition described above in controlling plant pests in agriculture and other fields.

[0040] In the definition of the above compound structural formula, the professional terms used have the following meanings:

[0041] Halogen or halogen: refers to fluorine, chlorine, bromine and iodine.

[0042] C1-C6 alkyl: a straight chain or branched chain alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl or n-butyl, isobutyl, sec-butyl, tert-butyl, etc.

[0043] Halogenated C1-C6 alkyl: a straight or branched alkyl group having 1 to 6 carbon atoms, in which the hydrogen atoms may be partially or completely replaced by halogen, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, etc.

[0044] The method for synthesizing the compound of formula I is specifically to prepare the compound of formula I by reacting the compound of formula XI with the compound of formula X, IX, VIII, VII, VI, V, IV, III, or II (in the chemical formulas listed below, unless otherwise defined, the substituents and symbols have the same meanings as the substituents and symbols defined in formula I):

[0045]

[0046] The insecticide comprising the compound represented by formula (I) or a salt thereof as an active ingredient is suitable for controlling pests in the soil in the fields of fruit trees, vegetables, other crops and ornamental plants.

[0047] Examples of pests to which the insecticide of the present invention can be applied include, but are not limited to, lepidoptera, such as Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsiagemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capuareticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphaniani idalis, Diatraea grandiosella, Earias sutchuenensis, and the like. insulana), Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetriabouliana, Feltia subterranea, Galleria mellonella, Grapholithafunebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellulaundalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeutamalinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella), Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostegesticticalis), Lymantria dispar, Lymantria monacha, Lyonetiaclerkella, Malacosoma neustria, Mamestrabrassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolisflammea, Pectinophora gossypiella, Peridromasaucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypenascabra, Plutella xylostella), soybean armyworm (Pseudoplusiaincludens), Rhyacioniafrustrana, Scrobipalpula absoluta, wheat moth (Sitotrogacerealella), grape leaf roller (Sparganothis pilleriana), fall armyworm (Spodopterafrugiperda), sea armyworm (Spodoptera littoralis), cutworm (Spodoptera litura), Thaumatopoea pityocampa, green oak moth (Tortrix viridana), powder looper (Trichoplusiani), and Zeirapheracana densi;

[0048] Beetles (Coleoptera), for example, Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia scabra aurata), Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp.、Diabrotica longicornis、Diabrotica semipunctata、Diabrotica 12-punctata、Diabrotica speciosa、Diabroticavirgifera、Epilachna varivestis、Epitrix hirtipennis、Eutinobothrus brasiliensis、Hylobius abietis、Hypera brunneipennis、Hypera postica、Ipstypographus、Lema bilineata、Lema melanopus、Leptinotarsa ​​decemlineata、Limonius californicus、Lissorhoptrusoryzophilus、Melanotus communis, Meligithes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulemaoryzae, Ortiorrhynchus sulcatus, Otiorrhynchusovatus, Phaedon cochleariae, Phyllobius pyri, Phyllotretachrysocephala, Phyllophaga sp., Phylloperthahorticola, Phyllotreta nemorum, Phyllotretastriolata, Popillia japonica, Sitonalineatus, and Sitophilus granaria.

[0049] flies, mosquitoes (order Diptera), for example, Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles salbimanus, 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, Culisetamelanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gasterophilus intestinalis), Glossina morsitans, Glossina palpalis, Glossinafuscipes, Glossinatachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansoniatitillanus, Mayetiola destructor, Musca autumnalis, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami), Phorbiaantiqua, Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis, Sarcophaga, Simulium vittatum, Stomoxyscalcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, Tabanus similis, Tipula oleracea and Tipula paludosa;

[0050] Thrips (Thysanoptera), for example Dichromothrips corbetti, Dichromothrips ssp, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci;

[0051] Termites (Isoptera), for example, Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Reticulitermes santonensis, Reticulitermes grassei, Termes natalensis and Coptotermes formosanus;

[0052] Cockroaches (Blattaria-Blattodea), for example, Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae and Blatta orientalis;

[0053] Bugs, aphids, leafhoppers, whiteflies, scale insects, cicadas (Hemiptera), for example Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis, Thyanta perditor, Acyrthosiphon onobrychis, larch aphid (Adelgeslaricis), Aphidula nasturtii, beet aphid (Aphis fabae), strawberry root aphid (Aphis forbesi), apple aphid (Aphis pomi), cotton aphid (Aphis gossypii), North American tea aphid (Aphis grossulariae), Aphis schneideri, leaf roller aphid (Aphis spiraecola), Aphis sambuci, pea aphid (Acyrthosiphonpisum), potato aphid (Aulacorthum solani), silver leaf whitefly (Bemisia argentifolii), Brachycaudus cardui, apricot round tail aphid (Brachycaudus helichrysi), Brachycaudus persicae, Brachycaudus prunicola, cabbage aphid (Brevicoryne brassicae), Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzusribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthumpseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzus persicae, Myzus ascalonicus Donc, Myzus cerasi, Myzus varians, Nasonoviaribis-nigri, Nilaparvatalugens, Pemphigus bursarius, Perkinsiella saccharicida), Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphummaidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, Viteus vitifolii, Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., and Arilus critatus;

[0054] Ants, bees, wasps, sawflies (Hymenoptera), for example Athaliarosae, Atta cephalotes, Atta capiguara, Atta cephalotes, Attalaevigata, Atta robusta, Atta sexdens, Atta texana, Crematogaster, Hoplocampaminuta, Hoplocampa testudinea, Lasius niger, Monomoriumpharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidolemegacephala, Dasymutilla occidentalis), Bombus, Vespula squamosa, Paravespula vulgaris, Paravespula pennsylvanica, Paravespula germanica, Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Campodontus floridanus, and Argentine ant Linepithema humile;

[0055] Crickets, grasshoppers, locusts (Orthoptera), for example, Acheta domestica, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus), Hieroglyphus daganensis, Kraussaria angulifera, Italian locust (Calliptamus italicus), Australian plague locust (Chortoicetes terminifera), and brown migratory locust (Locustana pardalina);

[0056] Arachnoidea, such as spiders (Acarina), for example, Argasidae, Ixodidae and Sarcoptidae, such as 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 holobiont holocyclus), Ixodespacificus, Ornithodorus moubata, Ornithodorus hermsi, Ornithodorusturicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssusgallinae, Psoroptes ovis, Rhipicephalussanguineus, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae, such as Aculusschlechtendali, Phyllocoptrataoleivora and Eriophyes sheldoni; Tarsonemidae, such as Phytonemus pallidus and Polyphagotarsonemuslatus; Tenuipalpidae, such as Brevipalpus phoenicis;From the genus Tetranychidae, for example, Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri and Oligonychus pratensis; From the order Araneida, for example, Latrodectus mactans and Loxosceles reclusa;

[0057] Fleas (Siphonaptera), for example, Ctenocephalides felis (cat flea), Ctenocephalides canis (dog flea), Xenopsylla cheopis (chinese flea), Pulex irritans (itch flea), Tunga penetrans (skin flea) and Nosopsyllus fasciatus (skin flea);

[0058] Silverfish, domestic silverfish (Thysanura), for example, Lepisma saccharina and Thermobia domestica, centipedes (Chilopoda), for example, Scutigera coleoptrata, millipedes (Diplopoda), for example, Narceus spp., earwigs (Dermaptera), for example, forficula auricularia, lice (Phthiraptera), for example, Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus usurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae), Menacanthus stramineus and Solenopotes capillatus;

[0059] From the order of the Collembola (Springtails), for example, Onychiurus.

[0060] They are also suitable for controlling nematodes: plant-parasitic nematodes such as the root-knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica and other Meloidogyne species; the cyst-forming nematodes, Globodera arostochiensis and other Globodera species; the cereal cyst nematodes, Heterodera glycines, Heterodera schachtii, Heterodera clover trifolii and other cyst nematodes of the genera Heterodera; seed gall nematodes, Anguina; stem and leaf nematodes, Aphelenchoides; sting nematodes, Belonolaimus longicaudatus and other Belonolaimus; pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus; ring nematodes, Criconema, Criconemella, Criconemoides, Mesocriconema; bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other stem nematodes of the genera Ditylenchus; cone nematodes, Dolichodorus; spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus; sheath and sheath nematodes, Hemicycliophora and Hemicriconemoides; root nematodes of the genera Hirshmanniella; crown nematodes, Hoplolaimus; pseudo-root-knot nematodes, Nacobbus; needle nematodes, Longidoruse longatus and other Longidorus;Root-rot nematodes, Pratylenchus neglectus, Pratylenchuspenetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Boring nematodes, Radopholus similis and other Radopholus species; Renal-shaped nematodes, Rotylenchus robustus and other Rotylenchus species; Scutellonema species; Stump root nematodes, Trichodorus primitivus and other Trichodorus species; Paratrichodorus species; Growth-blocking nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius) and other dwarf nematodes of the genus Tylenchorhynchus; citrus nematodes, of the genus Tylenchulus; sword nematodes, of the genus Xiphinema; and other plant-parasitic nematodes.

[0061] They can also be used to control spiders (Arachnids), such as ticks (Acarina), for example the families of Aspleniidae, Ixodidae and Sarcoptes, such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabies, scabiei, as well as Eriophyidae, such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae, such as Phytonemus pallidus and Polyphagotarsonemuslatus; Tenuipalpidae, such as Brevipalpus phoenicis; Tetranychidae, such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus stellaris and Tetranychus urticae; Panonychus spp. ulmi), citrus spider mite (Panonychus citri) and oligonychus pratensis.

[0062] The plant objects to which the pesticide of the present invention is applied are not particularly limited; for example, cereals (e.g., rice, barley, wheat, rye, oats, corn, sorghum, etc.), legumes (soybeans, adzuki beans, broad beans, peas, peanuts, etc.), fruit trees / fruits (apples, citrus, pears, grapes, peaches, Japanese apricots, cherries, walnuts, apricots, bananas, strawberries, etc.), vegetables (cabbage, tomatoes, spinach, cabbage, lettuce, onions, green onions, green peppers, etc.), root vegetables (carrots, potatoes, sweet potatoes, radishes, etc.), , lotus root, turnip, etc.), industrial crops (cotton, hemp, mulberry, balsam pear, rapeseed, sugar beet, hops, sugar cane, sugar beet, olive, rubber, coffee, tobacco, tea, etc.), berries (pumpkin, cucumber, watermelon, melon, etc.), forage (orchard grass, milo, timothy, alfalfa, purple lucerne, etc.), lawn grass (Korean zoysia, bentgrass, etc.), spices (lavender, rosemary, thyme, parsley, pepper, ginger, etc.), and flowers (chrysanthemum, rose, orchid, etc.).

[0063] Beneficial Effects

[0064] Due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0065] By chemically modifying and molecularly designing compounds with a phenylpyrazolonic acid amide structure, a cyano-substituted structure was introduced on the N of the amide group, thereby obtaining a series of compounds with broad-spectrum insecticidal properties and excellent activity for use in agricultural or forestry pest control, especially having unexpected biological activity against most homopteran pests and thysanoptera pests.

[0066] Embodiments of the present invention

[0067] The technical solutions in the embodiments of the present invention will be described clearly and completely below in combination with the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0068] By comprehensively considering the economic efficiency, diversity and biological activity of the synthesized compounds, some compounds are selected and listed in the following table. The specific compound structures are shown in Table 1, and the specific structural confirmation is shown in Table 2. The compounds in Tables 1-2 are only for better illustrating the present invention and do not limit the present invention. Those skilled in the art should not understand this as the scope of the above subject matter of the present invention is limited to the following compounds.

[0069]

[0070] The specific structure is shown in Table 1:

[0071] Table 1 Structure of compounds of formula I

[0072] Serial number <![CDATA[R1]]> <![CDATA[R2]]> <![CDATA[R3]]> n Serial number <![CDATA[R1]]> <![CDATA[R2]]> <![CDATA[R3]]> n 1 Cyclopropane H Cl 1 21 Cyclopropane H F 1 2 Cyclopropane H Cl 2 22 Cyclopropane H F 2 3 Cyclopropane Me Cl 1 23 Cyclopropane Me F 1 4 i-Pr H Cl 1 24 i-Pr H F 1 5 i-Pr H Cl 2 25 i-Pr H F 2 6 i-Pr Me Cl 1 26 i-Pr Me F 1 7 n-Pr H Cl 1 27 n-Pr H F 1 8 n-Pr H Cl 2 28 n-Pr H F 2 9 n-Pr Me Cl 1 29 n-Pr Me F 1 10 Cyclopentyl H Cl 1 30 Cyclopentyl H F 1 11 Cyclopentyl H Cl 2 31 Cyclopentyl H F 2 12 Cyclopentyl Me Cl 1 32 Cyclopentyl Me F 1 13 Cyclohexane H Cl 1 33 Cyclohexane H F 1 14 Cyclohexane H Cl 2 34 Cyclohexane H F 2 15 Cyclohexane Me Cl 1 35 Cyclopropane Me F 3 16 MeO OMeO Cl 0 36 Cyclopropane E Cl 2 17 E E Cl 0 37 Cyclopropane E F 2 18 Cyclopropane Cyclopropane Cl 0 38 Cyclopropane H Cl 3 19 Cyclopropane Me Cl 2 39 Cyclopropane H F 3 20 Cyclopropane Me F 2 40 Cyclopropane Me Cl 3

[0073] Table 2 1 H NMR data

[0074]

[0075]

[0076] The method for preparing the compounds of the present invention is described in the following technical schemes and examples. The raw materials can be purchased from the market or can be prepared by methods known in the literature or as shown in the detailed description. It should be understood by those skilled in the art that other synthetic routes can also be used to synthesize the compounds of the present invention. Although the specific raw materials and conditions in the synthetic route have been described below, it can be easily replaced with other similar raw materials and conditions, and these modifications or variations of the preparation method of the present invention such as various isomers of the compound are included within the scope of the present invention. In addition, the preparation method described below can be further modified according to the disclosure of the present invention using conventional chemical methods well known to those skilled in the art. For example, appropriate groups are protected during the reaction, etc.

[0077] Example 1

[0078] Synthesis of 4-(heptafluoroisopropane)-aniline:

[0079]

[0080] Aniline (46.55 g, 500 mmol), 600 ml methyl tert-butyl ether, and 600 ml water were added to a 2L three-necked flask. Under mechanical stirring, hydrosulfite (109 g, 625 mmol) and tetrabutylammonium hydrogen sulfate (8.5 g, 25 mmol) were added. Sodium bicarbonate (88.5 g, 875 mmol) was slowly added in batches. Heptafluoroisopropane (185 g, 625 mmol) was slowly added dropwise. The mixture was stirred at room temperature overnight. The reaction was completely stopped by TLC (PE / EA=50 / 1). The reaction solution was separated and the organic phase was collected. The remaining aqueous phase was extracted with ethyl acetate. The organic phases were combined, washed three times with saturated brine, dried over anhydrous sodium sulfate, and concentrated to obtain a reddish brown liquid (115 g, yield 88%). GC-MS[M]=261.2.

[0081] Example 2

[0082] Synthesis of 2,6-dichloro-4-(perfluoropropane-2-yl)aniline:

[0083]

[0084] Under ice water bath, add 4-(heptafluoroisopropane)-phenylaniline (26.1g, 100mmol), acetic acid (500ml), and N-chlorosuccinimide (NCS) (29.3g, 220mmol) in batches to a 1L single-mouth bottle, slowly raise the temperature to reflux, and stir for several hours. TLC (PE / EA=50 / 1) detection shows that the reaction is completely stopped, washed with water, extracted with ethyl acetate, the organic phase is washed with saturated brine 3 times, dried over anhydrous sodium sulfate, the solvent is evaporated under reduced pressure, and purified by column chromatography to obtain a brown-red needle-shaped crystal product (24.75g, yield 75%). GC-MS [M] = 329.7.

[0085] Example 3

[0086] Synthesis of 2,6-dichloro-4-(perfluoropropane-2-yl)phenylhydrazine:

[0087]

[0088] Add 2,6-dichloro-4-(perfluoropropane-2-yl)aniline (16.45g, 50mmol), acetic acid (20ml), water (20ml), and sulfuric acid (160ml) to a 500ml single-mouth bottle. Heat to 80°C and stir for 1 hour. Then slowly drop to 0°C and slowly add sodium nitrite (3.79g, 55mmol) aqueous solution. After the addition is complete, stir for 30 minutes. Add the above-prepared diazonium salt to the dilute hydrochloric acid solution of stannous chloride (22.56g, 100mmol). After the addition is complete, transfer the reaction bottle to room temperature and stir for 2 hours. Filter by suction, transfer the filter cake to dilute alkali solution, extract with ethyl acetate, wash three times with saturated brine, dry over anhydrous sodium sulfate, concentrate and spin-dry to obtain a reddish-brown solid (10.3g, yield 60%). LC-MS (ESI) [M+H] + =345.2,[M+Na] + =367.2.

[0089] Example 4

[0090] Synthesis of 1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-1H-pyrazole:

[0091]

[0092] Add 2,6-dichloro-4-(perfluoropropane-2-yl)phenylhydrazine (34.4 g, 100 mmol), ethanol (100 ml), sulfuric acid (9.8 g, 100 mmol) and 1,1,3,3-tetramethoxypropane (18 g, 110 mmol) to a 250 ml single-mouth bottle. Heat to 80 °C and stir for 3 hours. TLC (PE / EA = 50 / 1) detected that the reaction was completely stopped, washed with water, extracted with ethyl acetate, the organic phase was washed with saturated brine 3 times, dried over anhydrous sodium sulfate, the solvent was evaporated under reduced pressure, and purified by column chromatography to obtain a brown-red oily product (30.4 g, yield 80%). LC-MS (ESI) [M+H] + =380.7,[M+Na] + =403.2.

[0093] Example 5

[0094] Synthesis of 1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-4-iodo-1H-pyrazole:

[0095]

[0096] Add 1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-1H-pyrazole (19 g, 50 mmol), acetonitrile (280 ml), and NIS (45 g, 200 mmol) to a 500 ml single-mouth bottle. Heat to reflux temperature and stir overnight. TLC (PE / EA=50 / 1) detection shows that the reaction is completely stopped, washed with water, extracted with ethyl acetate, the organic phase is washed with saturated brine three times, dried over anhydrous sodium sulfate, distilled under reduced pressure to save some solvent, filtered, and the remaining organic phase is purified by column chromatography to obtain a white solid product (11.4 g, yield 45%). LC-MS (ESI) [M+H] + =506.7,[M+Na] + =528.7.

[0097] Example 6

[0098] Synthesis of 1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-1H-pyrazole:

[0099]

[0100] Add 1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-4-iodo-1H-pyrazole (10g, 20mmol), DMSO (120ml), biboric acid pinacol ester (6g, 24mmol), potassium acetate (3.9g, 40mmol), bistriphenylphosphine palladium dichloride (0.7g, 1mmol) to a 250ml single-mouth bottle. Blow the mixture with nitrogen for 1min. Heat to 80°C and stir for 8 hours. TLC (PE / EA=50 / 1) detected that the reaction was completely stopped, the reaction mixture was diluted with ethyl acetate, filtered through a diatomaceous earth pad, and the filtrate was washed 3 times with saturated ammonium chloride aqueous solution and saturated brine. Dry the organic phase over anhydrous sodium sulfate, filter, concentrate and spin dry. The obtained brown solid was used directly in the next step without purification.

[0101] Example 7

[0102] Synthesis of 2-chloro-5-(1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-1H-pyrazol-4-yl)nicotinate:

[0103]

[0104] Add 1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-1H-pyrazole (10g, 20mmol), 1,4-dioxane (100ml), water (20ml), 5-bromo-2-chloronicotinic acid methyl ester (6g, 24mmol), potassium carbonate (5.5g, 40mmol), bistriphenylphosphine palladium dichloride (0.7g, 1mmol) to a 250ml single-mouth bottle. Blow the mixture with nitrogen for 1min. Heat to 80°C and stir for 8 hours. TLC (PE / EA=10 / 1) detected that the reaction was completely stopped, the reaction mixture was diluted with ethyl acetate, filtered through a diatomaceous earth pad, and the filtrate was washed 3 times with saturated ammonium chloride aqueous solution and saturated brine. Dry the organic phase over anhydrous sodium sulfate, filter, concentrate and spin dry. The remaining organic phase was purified by column chromatography to obtain a light yellow transparent oily product (4.4 g, yield 40%). LC-MS (ESI) [M+H] + =549.8,[M+Na] + =571.7.

[0105] Example 8

[0106] Synthesis of 2-fluoro-5-(1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-1H-pyrazol-4-yl)nicotinate:

[0107]

[0108] Add 1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-1H-pyrazole (10g, 20mmol), 1,4-dioxane (100ml), water (20ml), 5-bromo-2-fluoronicotinate (5.6g, 24mmol), potassium carbonate (5.5g, 40mmol), bistriphenylphosphine palladium dichloride (0.7g, 1mmol) to a 250ml single-mouth bottle. Blow the mixture with nitrogen for 1min. Heat to 90°C and stir for 8 hours. TLC (PE / EA=10 / 1) detected that the reaction was completely stopped, the reaction mixture was diluted with ethyl acetate, filtered through a diatomaceous earth pad, and the filtrate was washed 3 times with saturated aqueous ammonium chloride solution and saturated brine. Dry the organic phase over anhydrous sodium sulfate, filter, concentrate and spin dry. The remaining organic phase was purified by column chromatography to obtain a light yellow transparent oily product (3.8 g, yield 36%). LC-MS (ESI) [M+H] + =533.8,[M+Na] + =555.9.

[0109] Example 9

[0110] Synthesis of 2-chloro-5-(1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-1H-pyrazol-4-yl)nicotinic acid:

[0111]

[0112] Add 2-chloro-5-(1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-1H-pyrazol-4-yl)nicotinate (5.5g, 10mmol), lithium hydroxide monohydrate (0.84g, 20mmol), and water (20ml) to a 100ml single-mouth bottle. Stir the mixture at 40°C for 4 hours. TLC (PE / EA=5 / 1) detected that the reaction was completely stopped, concentrated the reaction solution, washed the residue with water, extracted with ethyl acetate, collected the aqueous phase, adjusted to Ph=4 with dilute hydrochloric acid, precipitated solid, filtered, and dried to obtain a white solid product (2.35g, yield 44%). LC-MS (ESI) [M+H] + =535.6,[M+Na] + =558.4.

[0113] Example 10

[0114] Synthesis of 2-chloro-5-(1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-1H-pyrazol-4-yl)nicotinyl chloride:

[0115]

[0116] Add 2-chloro-5-(1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-1H-pyrazol-4-yl)nicotinic acid (535mg, 1mmol), oxalyl chloride (151mg, 1.2mmol), dichloromethane (10ml), N,N-dimethylformamide (10mg) to a 100ml single-mouth bottle. A large amount of gas emerges from the reaction system. After the system stabilizes, continue stirring at room temperature for 2 hours. The solvent is spin-dried and the residue is directly used in the next step.

[0117] Embodiment 11

[0118] Synthesis of 2-chloro-N-(cyanomethyl)-N-cyclopropyl-5-(1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-1H-pyrazol-4-yl)nicotinamide:

[0119]

[0120] At room temperature, add 2-chloro-5-(1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-1H-pyrazol-4-yl)nicotinyl chloride (550mg, 1mmol), dipea (260mg, 2mmol), 2-(cyclopropylamino)acetonitrile (140mg, 1.4mmol), and DCM (10ml) to a 100ml single-mouth bottle. Stir for 2 hours. TLC (PE / EA=3 / 1) detected that the reaction was completely stopped, washed with water, extracted with dichloromethane, collected the organic phase and concentrated, and the remaining crude product was subjected to column chromatography to obtain a white solid powder reaction solution. The residue was washed with water, extracted with ethyl acetate, and the aqueous phase was collected and adjusted to acidity with dilute hydrochloric acid. The solid was precipitated, filtered, and dried to obtain a white solid product (275mg, yield 45%). LC-MS (ESI) [M+H] + =413.9,[M+Na] + =636.4.

[0121] Example 12

[0122] Synthesis of N-(cyanomethyl)-5-(1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-1H-pyrazol-4-yl)-2-fluoro-N-isopropylnicotinamide:

[0123]

[0124] At room temperature, add 5-(1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-1H-pyrazol-4-yl)-2-fluoronicotinyl chloride (535mg, 1mmol), dipea (260mg, 2mmol), 2-(isopropylamino)acetonitrile (130mg, 1.3mmol), and DCM (10ml) to a 100ml single-mouth bottle. Stir for 2 hours. TLC (PE / EA=3 / 1) detected that the reaction was completely stopped, washed with water, extracted with dichloromethane, collected the organic phase and concentrated, and the remaining crude product was subjected to column chromatography to obtain a white solid powder reaction solution. The residue was washed with water, extracted with ethyl acetate, and the aqueous phase was collected and adjusted to acidity with dilute hydrochloric acid. The solid was precipitated, filtered, and dried to obtain a white solid product (275mg, yield 45%). LC-MS (ESI) [M+H] + =600.2,[M+Na] + =622.1.

[0125] Example 13

[0126] Preparation of the preparation:

[0127] 1. Soluble liquid: Dissolve 10-50% of the compound of formula (I) and 5-20% of a wetting agent in 100% water and / or a water-soluble solvent to obtain the product.

[0128] 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 obtain the product.

[0129] 3. Water emulsion: Dissolve 5-30% of the compound of formula (I) and 1-10% of an emulsifier in 20-40% of a water-insoluble organic solvent. Use an emulsifier to introduce the mixture into 100% water and make a homogeneous emulsion to obtain the product.

[0130] 4. Suspension: 10-50% of the compound of formula (I) is ground in a stirred ball mill with 2-10% of a dispersant, 1-5% of a wetting agent, 0.1-5% of a thickener and water up to 100% to prepare an active substance suspension to obtain the product.

[0131] 5. Water dispersible granules: Grind 10-70% of the compound of formula (I) under the condition of adding up to 100% of dispersant and wetting agent and make it into water dispersible granules with the aid of industrial production equipment to obtain the product.

[0132] All the above are weight percentages.

[0133] Embodiment 14

[0134] Evaluation of biological activity: Plutella xylostella

[0135] After the test compound is dissolved in N,N-dimethylformamide, it is diluted to the required concentration with water containing 0.1% Tween-80. The leaf immersion method is used for indoor bioassay. Select healthy and consistent 3rd-instar larvae of diamondback moth, use tweezers to place fresh cabbage leaves in the drug solution and immerse them for 10 seconds, then take them out. After the drug solution is naturally dried, place the cabbage leaves in a culture dish lined with moisturizing filter paper, with 20 3rd-instar larvae of diamondback moth in each dish, and each treatment is repeated 4 times. A blank treatment without the solvent of the test compound is used as a control. The treated test insects are placed in an artificial intelligence culture room at 25±1℃, a light period of L:D=16h:8h, and a relative humidity of 60% for breeding. The number of dead diamondback moths is investigated 3 days after the drug is applied, and the mortality rate is calculated (retain integers).

[0136] The activities are as follows: At a concentration of 2 ppm, the protective efficacy of the compounds of the present application is greater than 90% for 1-9, 12, 14-15, 18-29, and 35-40.

[0137] The control compound and some of the compounds of the present invention were tested for low concentration activity, and the results are as follows:

[0138]

[0139]

[0140] Embodiment 15

[0141] Evaluation of biological activity: Flower Thrips

[0142] After the test compound was dissolved in N,N-dimethylformamide, it was diluted to the required concentration with water containing 0.1% Tween-80. The test tube film method was used for indoor bioassay. Flower thrips were collected from corn plants in the greenhouse without any pesticides, and healthy and active individuals were selected for the test. Fill 1.5mL centrifuge tubes with each concentration of solution, pour out the solution after 5 hours, and dry it for use; use a hole puncher to punch fresh cabbage leaves into discs with a diameter of 1cm, soak the leaves in each concentration of solution for 10s, take them out and place them on absorbent paper to dry, and then use tweezers to clamp them into centrifuge tubes with corresponding concentrations of solution, one piece per tube; repeat 3 times for each concentration, and use the treatment of soaking tubes and leaves with solvents without the test compound as blank controls; use a sucker to suck the test flower thrips into the centrifuge tube, and repeat 20 heads per time. After covering the tube mouth with a 200-mesh gauze, the fish were placed in an artificial intelligence culture room at 25±1°C, with a light duration of L:D=16h:8h and a relative humidity of 75±5% for breeding. The number of dead flower thrips was investigated 2 days after the drug administration, and the mortality rate was calculated (retaining integers).

[0143] The control compound and some of the compounds of the present invention were tested for low concentration activity, and the results are as follows:

[0144]

[0145]

[0146] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable ordinary technicians in the field to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made based on the essence of the content of the present invention should be included in the protection scope of the present invention.

Claims

1. A substituted benzamide derivative or a pesticide-acceptable salt thereof, the structural formula of which is shown in formula (I): In formula (I), R1 is a C3-C6 cycloalkyl group, and R2 is independently selected from H or a C1-C6 alkyl group; R3 is halogen; n is an integer selected from 1-4.

2. A substituted benzamide derivative or a pesticide-acceptable salt thereof as claimed in claim 1, characterized in that: In formula (I), R2 is H or C1-C4 alkyl.

3. A substituted benzamide derivative or a pesticide-acceptable salt thereof as claimed in claim 2, characterized in that: In formula (I), R1 is cyclopropane, cyclobutane or cyclopentane; R2 is selected from H, Me, Et, n-Pr or i-Pr; R3 is selected from F or Cl; n is an integer selected from 1-3.

4. A substituted benzamide derivative or a pesticide-acceptable salt thereof as claimed in claim 3, characterized in that: In formula (I), R1 is selected from cyclopropane or cyclobutane; R2 is selected from H, methyl or ethyl; R3 is selected from F or Cl; n is 1, 2 or 3.

5. A substituted benzamide derivative or a pesticide-acceptable salt thereof as claimed in claim 4, characterized in that: In formula (I), R1 is selected from cyclopropane; R2 is selected from H or methyl; R3 is selected from F or Cl; n is 1, 2 or 3.

6. A substituted benzamide derivative or a pesticide-acceptable salt thereof as claimed in claim 5, characterized in that: Formula (I) is:

7. An insecticidal composition, characterized in that: The invention comprises an insecticidally effective amount of at least one of the substituted benzamide derivatives according to any one of claims 1 to 6 or a pesticide-acceptable salt thereof, and also comprises a formulation carrier or a formulation adjuvant.

8. A method for controlling plant pests, characterized in that: The method comprises applying an insecticidal effective amount of at least one of the substituted benzamide derivatives according to any one of claims 1 to 6 or a pesticide-acceptable salt thereof, or the insecticidal composition according to claim 7 on crops or pests and / or their habitats.

9. Use of at least one of the substituted benzamide derivatives according to any one of claims 1 to 6 or their pesticide-acceptable salts or the insecticidal composition according to claim 7 for controlling plant pests in agriculture and other fields.

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