CN114394912B - Meta-diamide compound or salt and composition acceptable by pesticide and application thereof - Google Patents

Meta-diamide compound or salt and composition acceptable by pesticide and application thereof Download PDF

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Publication number
CN114394912B
CN114394912B CN202210081326.6A CN202210081326A CN114394912B CN 114394912 B CN114394912 B CN 114394912B CN 202210081326 A CN202210081326 A CN 202210081326A CN 114394912 B CN114394912 B CN 114394912B
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compound
nematodes
reaction
salt
mol
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CN114394912A (en
Inventor
葛家成
胡堂路
李丽
邢阳阳
孙鹏
吕心童
邱佳鹏
杨春河
张永芳
王均竹
董成武
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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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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/66—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides

Abstract

The invention belongs to the field of pesticides, and in particular relates to a metadiamide compound or a salt acceptable by the metadiamide compound serving as a pesticide, a composition and application thereof, wherein the compound has a structure shown in a formula (I):

Description

Meta-diamide compound or salt and composition acceptable by pesticide and application thereof
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a metadiamide compound or a salt and a composition thereof which are acceptable as pesticides, and application of the compound or the salt and the composition thereof which are acceptable as pesticides.
Background
The metadiamide compound is concerned worldwide for its insecticidal activity, and is becoming a new focus of attention in the pesticide market following the neonicotinoid compound and the diamide compound. The metadiamide compounds belong to IRAC 30 group, and the mechanism is gamma-aminobutyric acid (GABA) receptor antagonists, which are different from the diamide compounds which are widely used at present and have obvious resistance problem.
The insecticidal activity of the metadiamides has been reported, for example, CN102119143B reports a series of metadiamides and their insecticidal activities, disclosing compounds CK1 (compound number: 7-1596), CK2 (compound number: 7-1597), CK3 (compound number: 6-1126), CK4 (compound number: 7-1574), and disclosing the insecticidal activities of these compounds, wherein CK4 (ISO generic name brofilolide, chinese generic name bromofluorobenzene bisamide) has been commercialized; in addition, other metadiamide compounds are also disclosed in the prior art, and the specific structure is as follows:
although the problem of resistance of bisamide compounds is solved by the current commercial metadiamide compounds, development of more efficient pesticides is still a urgent problem as the use requirements of pesticides are continuously improved in reality.
Technical problem
In order to solve the problems in the prior art, the invention provides a metadiamide compound or a salt, a composition and application thereof which are acceptable as pesticides, can effectively kill pests, has better safety to crops, and has excellent lasting effect and quick acting performance.
Technical solution
The technical scheme adopted by the invention for achieving the purpose is as follows: a compound of the metadiamide class or the salt which is acceptable by pesticides, the structural formula is shown in the formula (I):
In the formula (I) of the present invention,
X 1 、X 2 、X 3 、X 4 are independently selected from H, halogen, CN, C 1 -C 6 Alkyl, halogenated C 1 -C 6 Alkyl or C 3 -C 6 Cycloalkyl, X 1 、X 2 、X 3 、X 4 Not simultaneously H;
R 1 、R 2 are independently selected from H, halogen, CN, C 1 -C 6 Alkyl, halogenated C 1 -C 6 Alkyl or C 3 -C 6 Cycloalkyl;
R 3 selected from H, C 1 -C 6 Alkyl, halogenated C 1 -C 6 Alkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy, C 3 -C 6 Cycloalkyl or C 3 -C 6 Cycloalkyl-substituted C 1 -C 6 An alkyl group;
Y 1 selected from halogen, CN, C 1 -C 6 Alkyl, halogenated C 1 -C 6 Alkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, C 1 -C 6 Alkoxy, halo 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), R 1 、R 2 Each independently selected from H, F, cl, br, CN; still further, R 1 、R 2 F, cl or Br at the same time; still further, R 1 、R 2 And F.
Further, in formula (I), Y 1 Selected from halogen or halogenated C 1 -C 4 An alkyl group.
Further, in formula (I), R 3 Selected from H, C 1 -C 4 Alkyl, C 2 -C 4 Alkenyl, C 2 -C 4 Alkynyl, C 3 -C 6 Cycloalkyl or C 3 -C 6 Cycloalkyl-substituted C 1 -C 4 An alkyl group;
further, R 3 Selected from H, me, et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, vinyl, allyl, ethynyl, propargyl, cyclopropanyl, cyclobutylalkyl, cyclopentanyl, cyclohexenyl, cyclopropylmethyl, or cyclobutanemethyl;
Still more preferably, R 3 Selected from H, me or Et.
Further, in formula (I), X 1 、X 2 、X 3 、X 4 Are respectively and independently selected from H, F, cl, CF 3 And X is 1 、X 2 、X 3 、X 4 Not simultaneously H;
still further, X 1 、X 2 At the same time F and X 3 、X 4 At the same time H, or X 1 、X 2 At the same time H and X 3 、X 4 At the same time F, or X 1 、X 2 H and F and X respectively 3 、X 4 H and F, respectively, or X 1 、X 2 At the same time H and X 3 、X 4 H and CF respectively 3 Or X 1 、X 2 At the same time H and X 3 、X 4 H and F, respectively, or X 1 、X 2 At the same time is Cl and X 3 、X 4 At the same time H, or X 1 、X 2 、X 3 、X 4 And F is divided into two parts.
Further, in formula (I), X 1 、X 2 、X 3 、X 4 Are respectively and independently selected from H, F, cl, CF 3 And X is 1 、X 2 、X 3 、X 4 Not simultaneously H;
R 1 、R 2 and F is the same time;
R 3 selected from H, me, et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, vinyl,Ethynyl, cyclopropanyl, cyclobutylalkyl, cyclopentanyl, cyclohexenyl, cyclopropanemethyl or cyclobutanemethyl;
Y 1 selected from Br or CF 3 。
Still further, the structure of formula (I) is specifically as follows,
the salt which is acceptable as pesticide can be a salt prepared by reacting the metadiamide compound of the invention with a chemically acceptable acid, wherein the chemically acceptable acid can be an inorganic acid (such as hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid, 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 can also be a salt prepared by reacting the metadiamide compound of the invention with a chemically acceptable base, wherein the chemically acceptable base can be an inorganic base (such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate) or an organic base (such as trimethylamine, triethylamine and the like).
Further, the salt 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 composition, which comprises an insecticidal effective amount of at least one of the metadiamide compounds or the salts thereof which are acceptable by pesticides; further, a formulation carrier or formulation aid is included.
The present invention also discloses a method for controlling plant pests, which comprises applying a pesticidally effective amount of at least one of the metadiamides as described above or as pesticidally acceptable salts thereof or of the pesticidal composition as described above to the crop or the pest and/or its habitat.
The invention also discloses the use of the metadiamide compound or at least one of the salts thereof which can be accepted as pesticides or the insecticidal composition in agriculture and other fields for controlling plant pests.
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 or branched alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl or n-butyl, isobutyl, sec-butyl, tert-butyl and the like.
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.
C 1 -C 6 An alkoxy group: a straight or branched alkyl group having 1 to 6 carbon atoms is bonded to the structure through an oxygen atom bond.
The compounds of formula I of the present invention may be prepared by the following process, wherein the groups are as defined above, unless otherwise noted.
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.
Further, the synthesis method of II is exemplified as follows:
further, II' is at R 3 In the case of H, the same applies to II, and II' can be omitted.
Further, the synthesis method of II "is exemplified as follows:
further, the synthesis method of II' "is exemplified as follows:
further, III is commercially available.
An insecticide comprising a compound represented by the formula (I) or a salt thereof as an active ingredient is suitable for controlling pests in soil in the fields of fruit trees, vegetables, other crops and ornamental plants.
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, cuvettes (Meligethes aeneus), megacephalum (Melolontha hippocastani), holotrichum (Melolontha melolontha), yellow mud beetles (oulema oryzae), red beak (Ortiorrhynchus sulcatus), strawberry root beetles (Otiorrychusotus), horseradish beetles (Phaedon cochleariae), phyllobius pyri, phyllotretatarinowicepala, phyllophaga (She Sai) feeding, garden tortoise (Phylloperthiavirtuca), soybean light foot beetles (Phyllotreta nemorum), yellow leaf beetles (Phyllotreta striolata), japanese beetles (Popillia japonica), pea leaf beetles (Sitona lineups) and rice beetles (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 ascalonicus Donc), 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, the plant species of the order of the Sinkiage (Athaliarosia), the plant species of the order of the leaf of the Sinkiage (Atta cepalotes), the plant species of the Atta capiguara, the plant species of the Atta cepalotes, the plant species of the Atta laevigata, the plant species of the Atta robusta, the Atta sexdens, the Atta textana, the genus of the Formica (Cremastraste), the plant species of the Hoplocalpaminula, hoplocampa testudinea, the plant species of the black currant (Lasius niger), the plant species of the yellow ant (Monomorium pharaonis), the tropical fire species (Solenopsis geminata), the red fire species (Solenopsis invicta), the black fire species (Solenopsis richteri), the south fire species of the ant (Solenopsis xyloni), the red ants (Pogomyrmba) Pogonomyrmex californicus, the head species of the plant species of the Solanum (Pheidole megacephala), the plant species of the velvet species of the Cynanc (Dasymutilla occidentalis), the plant species of the Fluber (Bombius), the plant species of the Vespera, paravespula vulgaris, paravespula pennsylvanica, paravespula germanica, 3724, and the plant species of the Vecrassi (Polistes rubiginosa), and the plant species of the wasp (463).
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);
clothes fish, household fish (Thysanura), such as western clothes fish (Lepisma saccharina) and plagiocephalus (Thermobia domestica), carpopodium (cheilopoda), such as Scutigera coleoptrata, serratia (bipopoda), such as Narceus spp, octopus (Dermaptera), such as earwig (forficula auricularia), lice (Mao Shimu (phthamirapra)), such as human head lice (Pediculus humanus capitis), human lice (Pediculus humanus corporis), pubic lice (Pthirus pubis), bovine blood lice (haemaboleuseuresters), pig blood lice (Haematopinus suis), niu Eshi (Linognathus vituli), bovicollabosis, chicken lice (meropon gallinae), 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 of, for example, 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, hemp, paper mulberry, roses, rape, beet, hops, sugarcane, sugar beet, olive, rubber, coffee, tobacco, tea, etc.), berries (pumpkin, cucumber, watermelon, melon, etc.), pastures (grasses, milo, alfalfa, grass, bentgrass, etc.), spices, etc., crops (lavender, rosemary, thyme, pepper, thyme, celery, flowers, chrysanthemum, etc.), flowers, roses, etc.
Advantageous effects
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
By chemical modification and molecular design of the compound with the metadiamide structure, a substituent is introduced into N of an amide group and/or at least one substituent which is not H is additionally arranged on a fluorine substituted phenyl group, so that a series of compounds which are more efficient and can be used for agricultural or forestry disinsection and have excellent activity are obtained, and particularly, the compounds have quick-acting and lasting disinsection activity at low dosage.
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. Specific compound structures are shown in table 1, and specific compound physical property data are 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.
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
Preparation of Compound I-1:
(1) Preparation of 2-bromo-4- (heptafluoropropane-2-yl) -6- (trifluoromethyl) aniline:
FeSO was added to a dry 500mL single-necked flask 4 ·7H 2 O (9.73 g,0.035 mol) was dissolved in 20mL of water, 200mL of DMSO, O-trifluoromethylaniline (16.11 g,0.1 mol), 2-heptafluoroiodopropane (44.39 g,0.15 mol) were added in this order, and hydrogen peroxide (20 mL) was slowly added dropwise under ice-water bath, stirred at room temperature, LC-MS Monitoring the reaction, after the reaction is finished, adding 50mL of 5% hydrochloric acid aqueous solution and 200mL of ethyl acetate for extraction once, collecting an organic phase, washing 150mL of saturated brine for 3 times, drying by anhydrous sodium sulfate, filtering, concentrating under reduced pressure, dissolving in 200mL of DMF, adding NBS (19.58 g,0.11 mol), stirring for 1h at 60 ℃, monitoring the reaction by LC-MS, adding 100mL of saturated sodium chloride aqueous solution after the reaction is finished, extracting three times by 150mL of dichloromethane, merging the organic phases, drying by anhydrous sodium sulfate, concentrating under reduced pressure, and separating the product by column chromatography (eluting with petroleum ether: ethyl acetate=50:1), thereby obtaining a target product (32.23 g, yield is 79.2%) as yellow oily liquid.
(2) Preparation of N- (2-bromo-4- (heptafluoropropane-2-yl) -6- (trifluoromethyl) phenyl) -2-fluoro-3-nitrobenzamide:
in a dry 500mL single-neck flask was added 2-fluoro-3-nitrobenzoic acid (18.5 g,0.1 mol), dissolved in 200mL dichloromethane, and 4 drops of DMF were added dropwise, oxalyl chloride (14.22 g,0.112 mol) was slowly added dropwise under ice-water bath, stirred at room temperature for 3h, LC-MS monitored reaction, after the reaction was completed, concentrated under reduced pressure, and dissolved in 20mL acetonitrile for use. The product of the first step was added to a dry 500mL single-neck flask, dissolved with 200mL acetonitrile, KI (3.98 g,0.024 mol) was added, a 2-fluoro-3-nitrobenzoyl chloride acetonitrile solution was slowly added dropwise to the reaction system under stirring at room temperature, stirring was performed for 20h at 85 ℃, the reaction was monitored by lc-MS, after the reaction was completed, the reaction was concentrated under reduced pressure, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate=5:1) to obtain the objective product (31.50 g, yield 69.3%) as a yellow oily liquid.
(3) Preparation of 3-amino-N- (2-bromo-4- (heptafluoropropane-2-yl) -6- (trifluoromethyl) phenyl) -2-fluorobenzamide:
stannous chloride dihydrate (37.53 g,0.166 mol) was added to a dry 500mL single-neck flask, dissolved in concentrated hydrochloric acid, and the second step product was dissolved in 80mL methanol and added dropwise to the reaction system. The reaction mixture was heated to 60 ℃ and reacted for 3h, the reaction was monitored by lc-MS, after the reaction was completed, the PH was adjusted to 8-9 with aqueous sodium hydroxide solution, a large amount of solids were precipitated, filtered off with suction, concentrated under reduced pressure, extracted with ethyl acetate, dried, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate=4:1) to give the desired product (27.02 g, yield 90.5%) as a yellow solid.
(4) Preparation of Compound I-1:
compound intermediate III-1 (2.13 g,0.01 mol), toluene (30 mL) were added to a dry 100mL single-necked flask, compound intermediate II-1 (5.44 g,0.01 mol) was added with stirring at room temperature, the reaction mixture was heated to 90 ℃, the reaction was monitored by lc-MS, after the reaction was completed, concentrated under reduced pressure, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate=5:1) to give the objective product I-1 (2.82 g, yield 40.2%).
Example 2
Preparation of Compound I-4:
(1) Preparation of 2, 6-dibromo-4- (heptafluoropropane-2-yl) aniline:
FeSO was added to a dry 500mL single-necked flask 4 ·7H 2 O (9.73 g,0.035 mol) was dissolved in 20mL of water, 200mL of DMSO,2, 6-dibromoaniline (25.09 g,0.1 mol), 2-heptafluoroiodopropane (44.39 g,0.15 mol) were added in sequence, 20mL of hydrogen peroxide was slowly added dropwise under ice water bath, stirring was performed at room temperature, LC-MS was monitored for reaction, after the reaction was completed, 50mL of 5% aqueous hydrochloric acid solution and 200mL of ethyl acetate were added for extraction once, the organic phase was collected, 150mL of saturated salt water was washed 3 times, anhydrous sodium sulfate was addedDrying, filtering, concentrating under reduced pressure, and separating the product by column chromatography (petroleum ether: ethyl acetate=50:1) to obtain the target product (35.53 g, yield 85.2%) as yellow solid.
(2) Preparation of N- (2, 6-dibromo-4- (heptafluoropropyl-2-yl) phenyl) -2-fluoro-3-nitrobenzamide
In a dry 500mL single-neck flask was added 2-fluoro-3-nitrobenzoic acid (19.70 g,0.106 mol), dissolved in 200mL dichloromethane, and 4 drops of DMF were added dropwise, oxalyl chloride (15.15 g,0.119 mol) was slowly added dropwise under ice-water bath, stirred at room temperature for 3h, LC-MS monitored reaction, after the reaction was completed, concentrated under reduced pressure, and dissolved in 20mL acetonitrile for use. The product of the first step was added to a dry 500mL single-neck flask, dissolved with 200mL acetonitrile, KI (4.24 g,0.026 mol) was added, a 2-fluoro-3-nitrobenzoyl chloride acetonitrile solution was slowly added dropwise to the reaction system under stirring at room temperature, stirring was carried out for 20h at 85 ℃, the reaction was monitored by lc-MS, after the reaction was completed, the reaction was concentrated under reduced pressure, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate=5:1) to obtain the objective product (45.97 g, yield 92.4%) as a yellow solid.
(3) Preparation of 3-amino-N- (2, 6-dibromo-4- (heptafluoropropane-2-yl) phenyl) -2-fluorobenzamide:
stannous chloride dihydrate (53.28 g,0.236 mol) was added to a dry 500mL single-necked flask, dissolved in concentrated hydrochloric acid, and the second-step product was dissolved in 80mL methanol and added dropwise to the reaction system. The reaction mixture was heated to 60 ℃ and reacted for 3h, the reaction was monitored by lc-MS, after the reaction was completed, the PH was adjusted to 8-9 with aqueous sodium hydroxide solution, a large amount of solids were precipitated, filtered off with suction, concentrated under reduced pressure, extracted with ethyl acetate, dried, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate=4:1) to give the desired product (40.16 g, yield 92.1%) as a yellow solid.
(4) Preparation of N- (2, 6-dibromo-4- (heptafluoropropane-2-yl) phenyl) -2-fluoro-3- (methylamino) benzamide:
150mL of tetrahydrofuran and NaH (9.68 g,60%,0.242 mol) were sequentially added into a dry 500mL single-neck flask, 3-amino-N- (2, 6-dibromo-4- (heptafluoropropane-2-yl) phenyl) -2-fluorobenzamide, methyl iodide (15.43 g,0.108 mol) was added dropwise under stirring at room temperature, the mixture was heated to 60 ℃ after the completion of the dropwise addition, the reaction was monitored by LC-MS, cooled to room temperature after the completion of the reaction, quenched by adding 5mL of water, concentrated under reduced pressure, extracted by ethyl acetate, dried, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate=5:1) to obtain the target product (28.91 g, yield: 70.2%).
(5) Preparation of Compound I-4:
compound intermediate III-1 (2.13 g,0.01 mol), toluene (30 mL) were added to a dry 100mL single-necked flask, compound intermediate II-4 (5.68 g,0.01 mol) was added with stirring at room temperature, the reaction mixture was heated to 90 ℃, the reaction was monitored by lc-MS, after the reaction was completed, concentrated under reduced pressure, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate=5:1) to give the objective product I-4 (2.74 g, yield: 37.7%).
Example 3
Preparation of Compound I-23:
(1) Preparation of 2, 6-dibromo-4- (heptafluoropropane-2-yl) aniline:
in a dry 500mL single portFeSO was added to the flask 4 ·7H 2 O (9.73 g,0.035 mol) was dissolved in 20mL of water, 200mL of DMSO,2, 6-dibromoaniline (25.09 g,0.1 mol) and 2-heptafluoroiodopropane (44.39 g,0.15 mol) were added in sequence, 20mL of hydrogen peroxide was slowly added dropwise under ice water bath, stirring was performed at room temperature, LC-MS was monitored for reaction, after the reaction was completed, 50mL of 5% aqueous hydrochloric acid solution and 200mL of ethyl acetate were added to extract once, the organic phase was collected, 150mL of saturated brine was washed 3 times, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate=50:1) to obtain the objective product (35.53 g, yield 85.2%) as yellow solid.
(2) Preparation of N- (2, 6-dibromo-4- (heptafluoropropyl-2-yl) phenyl) -2-fluoro-3-nitrobenzamide:
in a dry 500mL single-neck flask was added 2-fluoro-3-nitrobenzoic acid (19.70 g,0.106 mol), dissolved in 200mL dichloromethane, and 4 drops of DMF were added dropwise, oxalyl chloride (15.15 g,0.119 mol) was slowly added dropwise under ice-water bath, stirred at room temperature for 3h, LC-MS monitored reaction, after the reaction was completed, concentrated under reduced pressure, and dissolved in 20mL acetonitrile for use. The product of the first step was added to a dry 500mL single-neck flask, dissolved with 200mL acetonitrile, KI (4.24 g,0.026 mol) was added, a 2-fluoro-3-nitrobenzoyl chloride acetonitrile solution was slowly added dropwise to the reaction system under stirring at room temperature, stirring was carried out for 20h at 85 ℃, the reaction was monitored by lc-MS, after the reaction was completed, the reaction was concentrated under reduced pressure, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate=5:1) to obtain the objective product (45.97 g, yield 92.4%) as a yellow solid.
(3) Preparation of 3-amino-N- (2, 6-dibromo-4- (heptafluoropropane-2-yl) phenyl) -2-fluorobenzamide:
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stannous chloride dihydrate (53.29 g,0.236 mol) was added to a dry 500mL single-necked flask, dissolved in concentrated hydrochloric acid, and the second-step product was dissolved in 80mL methanol and added dropwise to the reaction system. The reaction mixture was heated to 60 ℃ and reacted for 3h, the reaction was monitored by lc-MS, after the reaction was completed, the PH was adjusted to 8-9 with aqueous sodium hydroxide solution, a large amount of solids were precipitated, filtered off with suction, concentrated under reduced pressure, extracted with ethyl acetate, dried, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate=4:1) to give the desired product (40.16 g, yield 92.1%) as a yellow solid.
(4) Preparation of Compound I-23:
compound intermediate III-6 (2.48 g,0.01 mol), toluene (30 mL) was added to a dry 100mL single-necked flask, compound intermediate II-3 (5.54, 0.01 mol) was added with stirring at room temperature, the reaction mixture was heated to 90 ℃, the reaction was monitored by lc-MS, after the reaction was completed, the reaction was concentrated under reduced pressure, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate=5:1) to give the objective product I-23 (3.23 g, yield 43.4%).
Example 4
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: 15-70% 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: 5-40% 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: crushing 20-60% of the compound of formula (I) in a stirred ball mill in the presence of 2-10% of dispersant and 1-5% of wetting agent, 0.1-2% of thickener and 100% of water to obtain an active substance suspension.
5. Water dispersible granule: grinding 50-80% 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.
Example 5
Biological activity evaluation: plutella xylostella (Plutella xylostella)
After dissolving the test compound in N, N-dimethylformamide, it was diluted to a desired concentration with water containing 0.1% Tween-80.
The indoor bioassay adopts a leaf dipping method. And (3) selecting 3-instar larvae of plutella xylostella with uniform and consistent health sizes for testing, placing cabbage leaves in the liquid medicine to be tested for 10 seconds, taking out, naturally airing the cabbage leaves, placing the cabbage leaves in a culture dish, inoculating 30 larvae into each dish, repeating the treatment for 4 times for each concentration, and setting solvent treatment with the same content without the liquid medicine as a blank control. Placing in a climatic chamber with a light period of 16h:8h (light: dark) at the temperature of (25+/-1) DEG C for feeding. The number of plutella xylostella dead insects was investigated 2 days after the administration, and the mortality (retention of integers) was calculated.
The activity is as follows:
at a concentration of 10ppm, the control effect in compounds 1-36 and CK1-16 is greater than 90%: compounds 1-33, CK4, CK5.
The above compounds were subjected to low concentration activity assay with the following results:
Example 6
Biological activity evaluation: chilo suppressalis (Chilo suppressalis)
After dissolving the test compound in N, N-dimethylformamide, it was diluted to a desired concentration with water containing 0.1% Tween-80. The indoor biological measurement adopts a leaf dipping method. Selecting healthy and consistent Chilo suppressalis 3-instar larvae, immersing fresh cane shoot slices in the liquid medicine for 10 seconds by using tweezers, taking out, naturally airing the liquid medicine, placing the cane shoot slices in culture dishes filled with moisturizing filter paper, repeating each treatment for 4 times for 20-head Chilo suppressalis 3-instar larvae, and taking blank treatment as a control. 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 death rate (integer reserved) was calculated by investigating the number of dead chilo suppressalis 2 days after the drug.
The activity is as follows:
at 20ppm concentration, the control effect in the compounds 1-36 and CK1-16 is greater than 90 percent: compounds 1-33, CK2, CK4.
The above compounds were subjected to low concentration activity assay with the following results:
example 7
Biological activity evaluation: beet armyworm (Laphygma exigua)
After dissolving the test compound in N, N-dimethylformamide, it was diluted to a desired concentration with water containing 0.1% Tween-80.
The indoor bioassay adopts a leaf dipping method. And (3) selecting healthy and uniform asparagus caterpillar 3-instar larvae for testing, placing cabbage leaves in the liquid medicine to be tested for 10 seconds, taking out, naturally airing the cabbage leaves, placing the cabbage leaves in a culture dish, inoculating 30 larvae into each dish, repeating the treatment for 4 times, and setting solvent treatment without the same content of the liquid medicine as a blank control. Placing in a climatic chamber with a light period of 16h:8h (light: dark) at the temperature of (25+/-1) DEG C for feeding. The dead number of asparagus caterpillar was investigated 2 days after the drug, and the mortality (retention of the integer) was calculated.
The activity is as follows:
at 20ppm concentration, the control effect in the compounds 1-36 and CK1-16 is greater than 90 percent: compounds 1-33, CK4, CK5.
The above compounds were subjected to low concentration activity assay with the following results:
example 8
Biological activity evaluation: prodenia litura (Spodoptera litura)
After dissolving the test compound in N, N-dimethylformamide, it was diluted to a desired concentration with water containing 0.1% Tween-80.
The indoor bioassay adopts a leaf dipping method. And (3) selecting 3-instar larvae of prodenia litura with uniform and consistent health sizes for testing, placing cabbage leaves in the liquid medicine to be tested for 10 seconds, taking out, naturally airing the cabbage leaves, placing the cabbage leaves in a culture dish, inoculating 30 larvae into each dish, repeating the treatment for 4 times, and setting solvent treatment with the same content without the liquid medicine as a blank control. Placing at (25+/-1) DEG C, and the photoperiod is 16h:8h (illumination: darkness) of artificial climate chamber. The number of dead prodenia litura was investigated 3 days after the drug and the mortality (integer retention) was calculated.
The activity is as follows:
at 20ppm concentration, the control effect in the compounds 1-36 and CK1-16 is greater than 90 percent: compounds 1-33, CK4.
The above compounds were subjected to low concentration activity assay with the following results:
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 (5)

1. A metadiamide compound or a pesticidally acceptable salt thereof, selected from any one of the following:
2. an insecticidal composition comprising an insecticidally effective amount of at least one of the metadiamides of claim 1 or a pesticidally acceptable salt thereof.
3. The insecticidal composition of claim 2, further comprising a formulation carrier or formulation aid.
4. A method for controlling plant pests, which comprises applying a pesticidally effective amount of at least one of the metadiamides of claim 1 or a pesticidally acceptable salt thereof or the pesticidal composition of claim 2 or 3 to crops or pests and/or habitats thereof, said pests being plutella xylostella, chilo suppressalis, asparagus caterpillar or prodenia litura.
5. Use of the metadiamides of claim 1 or at least one of their pesticidally acceptable salts or the pesticidal compositions of claim 2 or 3 for controlling plant pests in agriculture and other fields, said pests being plutella xylostella, striped rice borer, asparagus caterpillar or prodenia litura.
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CN112661665A (en) * 2019-10-15 2021-04-16 南通泰禾化工股份有限公司 Amide compound and preparation method and application thereof
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CN114573547A (en) * 2020-12-01 2022-06-03 东莞市东阳光农药研发有限公司 Amide derivative, preparation method and application thereof

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