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CN114149433A - Nitrogen-containing spiro derivative or salt thereof acceptable as pesticide, composition and application thereof - Google Patents

Nitrogen-containing spiro derivative or salt thereof acceptable as pesticide, composition and application thereof Download PDF

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Publication number
CN114149433A
CN114149433A CN202010929769.7A CN202010929769A CN114149433A CN 114149433 A CN114149433 A CN 114149433A CN 202010929769 A CN202010929769 A CN 202010929769A CN 114149433 A CN114149433 A CN 114149433A
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radical
alkyl
halo
alkoxy
halogen
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Inventor
葛家成
杨春河
邢阳阳
马娥
刘明东
李丽
胡堂路
白光耀
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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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention belongs to the field of pesticides, and particularly relates to a nitrogenous spiro derivative or a salt acceptable as a pesticide, a composition and an application thereof, wherein the compound has a structure shown in a formula (I):

Description

Nitrogen-containing spiro derivative or salt thereof acceptable as pesticide, composition and application thereof
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a nitrogenous spiro derivative or a salt and a composition thereof acceptable as pesticides, and application of the compound or the salt and the composition acceptable as pesticides.
Background
The present invention provides a novel nitrogen-containing spiro derivative having an insecticide, a process for the preparation thereof, and a use of these compounds in insecticidal, especially excellent insecticidal, acaricidal, molluscicidal and nematicidal activities. Nitrogen-containing spiro derivatives having insecticidal activity are described in patents US6555567, US6479489, EP596298, WO98/05638 and the like, but their insecticidal activity is still insufficient in practical use and also insufficient in safety to crops, and they give rise to varying degrees of resistance after a period of use.
Technical problem
In order to solve the above problems in the prior art, the present invention provides a nitrogen-containing spiro derivative or a salt thereof acceptable as a pesticide, a composition and a use thereof, and surprisingly, the above novel nitrogen-containing spiro derivative having a pyrazole acid structure and an insecticidal activity has excellent biological activity, can effectively kill pests and has sufficient safety to crops, and is not likely to cause resistance.
Technical solution
The technical scheme adopted by the invention for realizing the purpose is as follows: a nitrogenous spiro derivative or a salt thereof which is acceptable as a pesticide has a structural formula shown as a formula (I):
Figure BDA0002669812390000011
in the formula (I), the compound is shown in the specification,
x represents halogen, CN, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl radical, C1-C6Alkoxy radical, C3-C6Cycloalkyl, aryl substituted or unsubstituted with a substituent, and m represents an integer of 0 to 4;
R1to representH. Halogen, CN, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl, halo C2-C6Alkenyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C1-C6Alkylthio, halo C1-C6Alkylthio radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyloxy, nitro, aldehyde, carboxyl, -COOX, -CO-NH2、-CO-NHX、-CO-NX2、-CH2-CO-NH2；
R2Represents H, halogen, CN, C1-C6Alkyl, halo C1-C6Alkyl, cyano-substituted C1-C6Alkyl radical, C2-C6Alkenyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C6Cycloalkyl, phenyl, benzyl;
R3represents H, halogen, CN, C1-C6Alkyl, halo C1-C6Alkyl, cyano-substituted C1-C6Alkyl radical, C2-C6Alkenyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C6Cycloalkyl, phenyl, benzyl;
R4and R5Together form a radical- (CH)2)t-, t represents 2 to 5;
R6represents H, halogen, CN, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C6Cycloalkyl, aryl substituted or unsubstituted with a substituent.
Further, in the formula (I),
x represents halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C2-C4Alkenyl radical, C1-C4Alkoxy radical, C3-C6Cycloalkyl, unsubstituted phenyl or phenyl substituted by CN, m represents an integer of 0 to 3;
R1represents H, halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C2-C4Alkenyl, halo C2-C4Alkenyl radical, C1-C4Alkoxy, halo C1-C4Alkoxy radical, C1-C4Alkylthio, halo C1-C4Alkylthio radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyloxy, nitro, aldehyde, carboxyl, -COOX, -CO-NH2、-CO-NHX、-CO-NX2or-CH2-CO-NH2；
R2Represents H, halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl, cyano-substituted C1-C4Alkyl radical, C2-C4Alkenyl radical, C1-C4Alkoxy or C3-C6A cycloalkyl group;
R3represents H, halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C2-C4Alkenyl radical, C1-C4Alkoxy, halo C1-C4Alkoxy or C3-C6A cycloalkyl group;
R4and R5Together form a radical- (CH)2)t-, t represents 3 to 5;
R6represents H, halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy, halo C1-C4Alkoxy radical, C3-C6Cycloalkyl, aryl unsubstituted or substituted by cyano, or phenyl substituted by cyano.
Further, in the formula (I),
x represents halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C2-C4Alkenyl radical C3-C6Cycloalkyl, m represents an integer of 0 to 3;
R1represents H, halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C2-C4Alkenyl radical, C1-C4Alkoxy radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyloxy, nitro, aldehyde, carboxyl, -COOX, -CO-NH2、-CO-NHX、-CO-NX2or-CH2-CO-NH2；
R2Represents H, halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C2-C4Alkenyl radical, C1-C4Alkoxy or C3-C6A cycloalkyl group;
R3represents H, halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C2-C4Alkenyl radical, C1-C4Alkoxy or C3-C6A cycloalkyl group;
R4and R5Together form a radical- (CH)2)t-, t represents 3 to 5;
R6represents H, halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy radical, C3-C6A cycloalkyl group.
Further, in the formula (I),
x represents H, halogen, CN, C1-C4Alkyl, m represents an integer of 1 to 3;
R1represents halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy radical, C3-C6Cycloalkyl, nitro, aldehyde, carboxyl, -COOX, -CO-NH2、-CO-NHX、-CO-NX2or-CH2-CO-NH2；
R2Represents H, halogen, CN, C1-C4Alkyl radical, C2-C4Alkenyl radical, C1-C4Alkoxy or C3-C6A cycloalkyl group;
R3represents H, halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C2-C4Alkenyl or C3-C6A cycloalkyl group;
R4and R5Together form a radical- (CH)2)t-, t represents 3 to 5;
R6represents H, halogen, CN, C1-C4Alkyl radical, C3-C6A cycloalkyl group.
Further, in the formula (I),
x represents a methyl or ethyl group, m represents 1;
R1represents H, F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3、CH2Br、CHBr2、CBr3、CH2CF3Vinyl, OMe, OEt, n-PrO, i-PrO, n-BuO, i-BuO, s-BuO, t-BuO, cyclopropane, cyclopropaneoxy, nitro, aldehyde, carboxyl, -COOCH3、-COOC2H5、-CO-NH2、-CO-NHCH3or-CO-N (CH)3)2；
R2Represents H, Me or Et;
R3represents H, Me, Et, n-Pr or i-Pr;
R4and R5Together form a radical- (CH)2)t-, t represents 3 or 4;
R6represents H, F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu or t-Bu;
further, in formula (I), X represents a methyl group, m represents 1;
R1represents H, F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH2F、CHF2、CF3OMe, OEt, cyclopropane, -COOCH3、--CO-NH2；
R2Representation H, Me;
R3representation H, Me;
R4and R5Together form a group- (CH2) t-, t represents 3 or 4;
r6 represents H, Me.
Further, the compound of formula (I) is selected from:
Figure BDA0002669812390000031
the salt acceptable as pesticide can be a salt prepared by reacting the nitrogenous spiro derivative with a chemically acceptable acid, wherein the chemically acceptable acid can be an inorganic acid (such as hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid) or an organic acid (such as oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid or benzoic acid); the pesticide acceptable salt can also be a salt prepared by reacting the nitrogen-containing spiro derivative with a chemically acceptable base, wherein the chemically acceptable base can be an inorganic base (such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate) or an organic base (such as trimethylamine, triethylamine and the like).
Further, the pesticidally acceptable salt may be a potassium, sodium, ammonium, calcium, pyridinium or choline salt.
The invention also discloses an insecticidal composition, which comprises an insecticidal effective amount of at least one of the nitrogenous spiro derivatives or the salts thereof acceptable as pesticides.
Preferably, the composition also comprises a preparation carrier or a preparation auxiliary agent.
The present invention also discloses a method for controlling pests, which comprises applying an insecticidally effective amount of at least one of the nitrogen-containing spiro derivatives as described above or a pesticidally acceptable salt thereof or the insecticidal composition as described above to the pests and/or their habitat.
The invention also discloses the application of at least one of the nitrogenous spiro derivatives or the salts thereof acceptable as pesticides or the insecticidal composition on pest control.
In the definitions of the structural formulae of the compounds mentioned above, the terms used have the following meanings:
C1-C6alkyl groups: straight-chain or branched alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like.
Halogen or halogen: refers to fluorine, chlorine, bromine, iodine.
Halogen substituted C1-C6Alkyl groups: straight-chain or branched alkyl groups having 1 to 6 carbon atoms, wherein hydrogen atoms in the alkyl groups may be partially or completely substituted with halogen, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl and the like.
C1-C6Alkoxy groups: a linear or branched alkyl group having 1 to 6 carbon atoms bonded to the structure via an oxygen atom bond.
Halogen substituted C1-C6Alkoxy groups: straight or branched alkoxy having 1 to 6 carbon atoms, wherein hydrogen atoms in the alkoxy groups may be partially or wholly replaced by halogen, for example, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, etc.
Aryl: any functional group or substituent derived from a simple aromatic ring.
A process for the synthesis of compounds of formula I, in particular compounds of formula II and compounds of formula III (in the formulae given below, unless otherwise defined, substituents and symbols have the same meaning as those defined in formula I, and Hal in formula III represents halogen such as F, Cl, Br), in the presence of a basic agent, in the presence or absence of a solvent, to give the desired compounds of formula I. The compounds represented by formulae II and III are commercially available:
Figure BDA0002669812390000041
further, the solvent is selected from one or more of acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, benzene, toluene, xylene, dichloroethane and ethyl acetate;
further, the reaction may be carried out under normal pressure or high pressure, preferably under atmospheric pressure, and the post-treatment may be carried out according to a conventional method.
The active compounds according to the invention are suitable for controlling, i.e. controlling, pests, which refer to harmful or unwanted insects, especially those encountered in agriculture, forestry, conservation of stored goods and conservation of materials and in the hygiene sector, are decolleable for sensitive and resistant species in general and are effective at all stages of pest development; the invention also relates to a method of inhibiting pests which comprises applying to the locus of the insect, habitat of the pest, area to be protected, or directly on the insect to be controlled a biologically effective amount of a compound of formula (I). The compounds of the present invention may also be used to control other invertebrate pests.
The insect habitat or the pest habitat refers to an environment where insects or pests live or eggs thereof exist, including air around the environment, food for eating, or objects in contact with the environment. For example, by applying the active compounds to the seeds of the plants (before planting), to the seedlings, or to the planted cuttings, leaves, stems, fruits, grains and/or roots, or to the soil or other growth medium (before or after planting of the crop), it is possible to control insects which eat, destroy or come into contact with edible agricultural products, ornamentals, turf, pasture plants or other plants of economic value, and it is also possible to protect these plants against diseases caused by viruses, fungi or bacteria by controlling sap-feeding pests such as whitefly, planthopper, aphid and the like; such plants include those propagated by conventional methods, as well as those with insect resistance, herbicide resistance, high yield, and/or other beneficial properties resulting from the alteration of genes by modern biotechnology. It is contemplated that these compounds will be useful for protecting fabrics, paper, stored grain, seeds and other food, housing, buildings and the like items and/or locations by applying the compounds of the present invention to or near such objects.
By controlling, or inhibiting pests is meant reducing the number of surviving insects or reducing the number of viable insect eggs. The degree of reduction achieved by the compound will depend on the rate of application of the compound, the particular compound used and the target insect species, at least in amounts that produce an effect.
By "mortality" is meant an amount sufficient to cause a measurable reduction in the number of insects treated. Typically, 1 to 1000ppm (by weight) of active compound are used. For example, insects or other pests that may be inhibited include, but are not limited to:
lepidoptera: heliothis armigera (Heliothis spp.), Heliothis armigera (Helicoverpa spp.), Spodoptera spp.), Mythimna punctatus (Mythimna unipunctata), Agrotis punctatus (Agrotis ipsilon), Diamond-impregnated Diamond (Earias spp.), Trichoplusia (Trichoplusia ni), Heliothis punctatus (Antarctica gemmatalis), Grapholitha californica (Rachipusia nu), Plutella xylostella (Plutella xylostella), Chilo spossia (Chilo spp.), Sclerothiao (Scorphia trifoliata), Sesamia punctiferalis (Sesamia incognita), Sesamia infuena (Sesamia inconensis), Cnaphalocrocis medinalis (Cnaphaloxylophila), Ostrinia Ostrinia (Ostrinia nubilalis), Cydia pomonella (Cydia pomonella), Plutella xylophila xylostella (Plutella xylostellata), Plutella xylostella (Plutella xylostella), Plutella xylostella (Ostrinalis), Plutella xylostella (Ostrinalis), Plutella xylostella (Plutella), Plutella xylostella (Plutella) and Bombycis (Plutella xylostella), Plutella xylostella (Plutella xylostella) Pierca xylostella (Plumbum), Plumbum) Ostrinis (Plumbum) Ostrinis, Sphaea xylostella niponaria) and Plumbum (Plumbum ) No. niponaria) No. Sphaea (Plumbum, Plumbum (Plumbum) No. niponaria) No. Sprens (Plumbum, Plumbum niponaria (Plumbum, Plumbum) No. niponaria (Plumbum, Plumbum niponaria (Plumbum niponaria) No. Sprens (Plumbum ) Pieris (Plumbum) Pierca (Plumbum, Plumbum (Plumbum) No. niponaria (Plumbum ) Pieris (Plumbum, Plumbum niponaria) Pieris (Plumbum, Plumbum niponia (Plumbum niponaria (Plumbum, Plumbum niponia (Plumbum, Plumbum niponaria (Plumbum niponia (Plumbum, Plumbum niponia (Plumbum) Pieris (Plumbum, Plumbum niponia (Plumbum, Plu, Phyllonorycter spp, Spodoptera spirifera (Leucoptera malinella), Phyllocnidae (Phyllocnitia citrella), Spodoptera exigua (Podoptera exigua Hubner);
coleoptera order: diabrotica (Diabrotica spp.), leptinotarsa (leptinotarsa decemlineata), rice weevil (Oulema oryzae), boll beetle (anthomonomgrandis), rice weevil (Lissorhoptrus oryzae), wireworms (agriotespp), melantotus communis, japanese bean beetle (Popillia japonica), cyclephala spp., parfait (Tribolium spp.);
from the order of homoptera: aphids (Aphis spp.), Myzus Persicae (Myzus Persicae), rhopalosiphum spp., plantago asiatica (Dysaphis plantaginea), citrus aphids (toxiptera spp.), alfalfa aphids (Aphis craccivora Koch), euphorbia magna (macrophylla), solanum torvum (auorthum solani), physalis graminis (Sitobion avena), physalis graminis (opodium digerum), trichomonas oryzae (schizophyllum graminum), phoma graminis (branchoides), leafhopper nigra (Nephotettix spp.), brown planthopper (nilavavagaceae), white fly (botrytis furaria), green fly (vegetative louse), red fly (vegetative louse), green fly (grassleaf fly), green fly (grassland fly), green fly (green fly louse aphid), green fly (green grass grus (green grass), green grass grus (green grass);
hemiptera: lygus spp, Eurygaster maura, Lygus lucorum (Nezaravidula), Pizodorum guilidi, Rhagotarda (Leptosporidia varicornis), Cimex lectularius, Tropical bed bug (Cimex eminentius), and Tropical bed bug (Cimex hemipterus);
from the order of thysanoptera: frankliniella occidentalis (Frankliniella occidentalis), Thrips (Thrips spp.), Thrips tabaci (Sciroththrips dorsalis);
from the order of the Isoptera: termites luteinis (termites flavipes), Coptotermes formosanus (Coptotermes formosanus), southern termites vitronectius (reticuliters virginicus), hettotermes saururus, western termites (reticuliters heperuus), Coptotermes freechi, shedperhithermers spp, morindothex sanguinea (reticuliters santonensis), reticuliters graditermes grasse, Reticulitermes batyuensis, xanthophyllitermes bateruptis, Reticulitermes genisis, phyllotentium mellitis, phyllotentium termites (reticuliters tibetalis), phyllitermes speratus (zootermes spp), Coptotermes chinensis (reticuliters spp), termites mellitchirondus (Reticulitermes spp), termites mellitchironella mellea veneris (Reticulitermes spp), termites spectaculeus sper, termites spectaculeus spep (termites spectaculeus sperps, termites specter spruce, termites specter sprues;
the order of Diptera: liriomyza spp, Musca domestica (Musca domestica), Aedes spp, Anopheles spp, commonwia spp, Fannia spp, and disuse fly (Stomoxys spp);
hymenoptera: red ants (Iridomyrmex humilis), fire ants (Solenopsis spp.), old fagopyrum ants (monoomorium pharaonis), Atta spp., harvested ants (pogomomyces spp.), bowlder ants (Camponotus spp.), little family ants (monoomorium spp.), stink family ants (taprooma sessile.), paving ants (Tetramorium spp.), xylococcus spp., xylocarpa spp., xylococcus spp., wasp (vespela spp.), and hornet (Polistes spp.);
trichophaga (feather lice);
lice (sucking lice)): pubic pubis (Pthirus pubis), lice (pediuciruspp.);
orthoptera (locusts, crickets): black locusts (Melanoplus spp.), locusta migratoria (Locustamigratoria), desert locusts (schistoserca gregaria), mole cricket (gryllotalpiade) (mole crickets);
from the order of the blattaria (cockroaches)): blattella orientalis (Blatta orientalis), Blattella germanica (Blattella germanica), Periplaneta americana (Periplaneta americana), Blattella longipedunculata (Supella longipalea), Blattella australis (Periplaneta australiana), Blattella fusca (Periplaneta brunnea), Periplanea pennyana (Parablata pennyvanensis), Blattella fuliginosa (Periplaneta fuliginosa), Blattella henryana (Pycnochelus surriniae);
siphonaptera: fleas (Ctenophilides spp.), human fleas (Pulex irritans);
acarina order: tetranychus (Tetranychus spp.), spider mite (pannychus spp.), Tetranychus cinnabarinus (Tetranychus cinannarinus), Tetranychus orientalis (eotropichus carpini), Tetranychus urticae (Tetranychus urticae Koch.), citrus rust (Phyllocoptruta oleivora), Aculus pelekassi, brevibacterium parvus (brevipupulosus phoeniis), cattle tick (boophilus spp.), variable leather tick (dermatopterus variabilis), red blood head tick (rhynchophyllus sanguineus, american flower tick (Amblyomma densis), true tick (Ixos spp.), cat dust mite (notoepidus), mange spider mite (Sarcophagia mange), spider mite (mange Tetranychus urticae);
nematoda (Nematoda): dirofilaria immitis, root-knot nematode (Meloidogyne spp.), cyst nematode (Heterodera spp.), crown nematode (Hoploima columbus), needlestick nematode (Belololaimus spp.), root-rot nematode (Pratylenchusspp.), reniform nematode (Rotylenchus reniformis), rosette nematode (Criconemaronate), stem nematode (Ditylenchus spp.), leaf bud nematode (Aphelenchus besseyi), and rice field root-knot nematode (Hirschnella spp.).
The compound of the present invention can be applied using a general formulation, and wettable powder, soluble powder, emulsifiable concentrate, aqueous emulsion, suspension, dispersible oil suspension, powder, microcapsule suspension, water dispersible granule, water soluble granule, and the like can be used. Thus the present invention also provides herbicidal compositions comprising compounds of formula I. The compounds of formula I can be formulated in a variety of ways depending on the usual biological and/or chemical physical parameters. Examples of suitable formulation choices are: wettable Powders (WP), wettable liquids (SL), Soluble Powders (SP), dispersible liquids (DC), Aqueous Solutions (AS), Microemulsions (ME), Emulsifiable Concentrates (EC), aqueous Emulsions (EW), sprayable solutions, Suspensions (SC), dispersible oil suspensions (OD), powders (DP), microcapsule suspensions (CS), water dispersible granules (WG), water Soluble Granules (SG), macrogranules (GG), granules for spreading and soil application (GR), Aerosols (AE), ultra low volume agents (ULV) and wax products. Necessary formulation auxiliaries, such as inert substances, surfactants, solvents and other additives.
Suitable active substances which can be mixed with the active substances according to the invention in a compound or tank-mix formulation are, for example, the substances known from the handbook of pesticides (Beijing: chemical industry Press, 1 st edition 5.2015). For example, the insecticidal active substances mentioned below can be mixed with compounds of the formula I (remarks: name of the compound, or common name according to the International organization for standardization (ISO), or chemical name, where appropriate with a reference number): antibiotic insecticides (e.g., allosamidin and thuringiensis); macrolide insecticides (e.g., spinosad, spinoetoram, and other spinosyns including 21-butylspinosyn, and derivatives thereof); avermectin insecticides such as abamectin (abamectin), doramectin, emamectin, eprinomectin, ivermectin, and selamectin; milbemycin insecticides such as lepimectin, cimetidine, miticidin oxime and moxidectin); arsenic-containing insecticides such as calcium arsenate, copper acetoarsenite, copper arsenate, lead arsenate, potassium arsenite and sodium arsenite; biological insecticides such as Bacillus megaterium (Bacillus popilliae), Bacillus sphaericus (B.sphaericus), Bacillus thuringiensis subsp.sp.souriensis (B.thuringiensis subsp.aizawai), Bacillus thuringiensis subsp.kurstaki (B.souring. kurstaki), Bacillus thuringiensis subsp.sp.tenebriensis (B.souring. subsp.sp.tenebrisonii), Beauveria bassiana (Beauveria bassiana), Chrysocomysis japonica (Cydia pomoea grandiosis virus), Spodoptera litura Nuclear Polyhedrosis Virus (NPV) (Douglas grass mortocho NPV), Spodoptera giensis (NPV), Spodoptera litura sythophylyp (NPV), Spodoptera litura cocci (P.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp, Xenorhabdus nematophilus (Xenorhabdus nematophilus), and Xenorhabdus bovienii (xbainienii), plants added protective insecticides such as Cry1Ab, Cry1Ac, Cry1F, cry1a.105, Cry2Ab2, Cry3A, mirCry3A, Cry3Bb1, Cry34, Cry35, and VIP 3A; plant insecticides such as neonicotinoid, azadirachtin, d-limonene, nicotine, pyrethrin, guaethrin I, guaethrin II, heliotropin I, heliotropin II, pyrethrin I, pyrethrin II, amaranth (quassia), rotenone, ryania, and veratrine); carbamate insecticides such as bendiocarb and carbaryl; benzofuranyl methyl carbamate insecticides such as benfuracarb, carbofuran, and furacarb); dimethyl carbamate insecticides (e.g., dimitan, trichlorfon, hyquincarb, and pirimicarb); oxime carbamate insecticides (e.g., cotton boll-carbofuran, aldicarb, butocarbosulfan, methomyl, carbosulfan, oxamyl, carbosulfan, thiodicarb and monocarb); phenyl methyl carbamate insecticides (e.g., carbofuran, methiocarb, oxamyl, dichlorcarb, dicarb, EMPC, ethiofencarb, fentehacarb, fenobucarb, isoprocarb, methiocarb, metolcarb, tebucarb, lufenuron, propoxur, trimethacarb, XMC, and propoxur); dinitrophenol insecticides (e.g., fenaminophen, nitrophenol, pentol, and DNOC); fluorine type insecticides (e.g., barium hexafluorosilicate, cryolite, sodium fluoride, sodium hexafluorosilicate, and sulfluramid); formamidine insecticides (e.g., amitraz, chlordimeform, varacetam and formanate); fumigant type insecticides (e.g., acrylonitrile, carbon disulfide, carbon tetrachloride, chloroform, chloropicrin, p-dichlorobenzene, 1, 2-dichloropropane, ethyl formate, 1, 2-dichloroethane, ethylene oxide, hydrogen cyanide, methyl iodide, methyl bromide, methyl chloroform, dichloromethane, naphthalene, phosphine, sulfuryl fluoride, and tetrachloroethane); inorganic insecticides (e.g., borax, lime sulphur, copper oleate, mercurous chloride, potassium thiocyanate, and sodium thiocyanate); chitin synthesis inhibitors (e.g., bistrifluron, buprofezin, chlorfluazuron, cyromazine, diflubenzuron, flufenoxuron, hexaflumuron, lufenuron, alachlor (novaluron), noviflumuron, chlorfluazuron, teflubenzuron and triflumuron); juvenile mimetics (e.g., juvenile ether (eponenane), fenoxycarb, methoprene, pyriproxyfen, and methoprene); juvenile hormones (e.g., juvenile hormone I, juvenile hormone II, juvenile hormone III); ecdysone agonists (e.g., chromafenozide, flufenozide, methoxyfenozide, and tebufenozide); ecdysone (e.g., alpha-ecdysone and ecdysteroid); molting suppressant formulas (e.g., benchol ether); precocenes (e.g., precocene I, precocene II, precocene III); non-class insect growth regulators (e.g., dicyclanil); nereistoxin analogue (nereistoxin analogue) insecticides (e.g., dimethion, cartap, thiocyclam, and dimehypo (thiosultap)); a nicotinic pesticide (e.g., flonicamid); nitroguanidine insecticides (e.g., clothianidin, dinotefuran, imidacloprid, and thiamethoxam); nitromethylene (nitromethylene) type pesticides (e.g., nitenpyram and nithiazine); pyridylmethylamine insecticides (e.g., acetamiprid, nitenpyram, and thiacloprid); organochlorine insecticides (e.g., bromo-DDT, toxaphene, DDT, pp' -DDT, ethyl-DDD, HCH, γ -HCH, lindane, methoxychlor, pentachlorophenol, and TDE); cyclodiene insecticides (e.g., aldrin, bromoxyrene, bornbuterol, chlordane, galbanum (chloredione), dieldrin, dilor, endosulfan, endrin, HEOD, heptachlor, HHDN, carbachol, isoethan, crimafen and mirex); organophosphate insecticides (e.g., bromfenvinfos, chlorfenvinphos, bafenphos, dichlorvos, chlormephos, chlorfenvinphos, chlormephos, heptenophos, methocrotophos, methamphos, monocrotophos, naloxon, naphthylenephos, phosphamidon, propaphos, TEPP, and sandfenvinphos); organic thiophosphate insecticides (e.g., acephate, fenthion, and phenthoate); aliphatic organic thiophosphate insecticides (e.g., housefly phosphorus, amiton, cadusafos, phosphorus oxychloride, chlormephos, phosphorus Tianle-O, phosphorus Tianle-S, systemic phosphorus-O, systemic phosphorus-S, methyl systemic phosphorus, O-methyl systemic phosphorus, S-methyl systemic phosphorus, phosphorus sulfone (demeton-S-methyl sullphon), disulfoton, ethion, fenamiphos, IPSP, isofenthion, malathion, chlorfenvinphos, sulfoxaflor, isosulfovinphos, phorate, fenitrothion, terbufos and methyl ethosulfan); aliphatic amide organophosphate insecticides (e.g., phosmet, guobao, dimethoate, phoxim, methidathion, omethoate, fenthion, suthion, and aphifenamiphos); oxime organophosphate insecticides (e.g., chlorophoxim, phoxim, and methyl phoxim); heterocyclic organic thiophosphate insecticides (e.g., methylpyrafen, coumaphos, fosthien, dioxaphos, ifop, methidathion, mafenthion, vothion, pyrazothion, pyridaphenthion and quinothion); thiochromane organophosphate insecticides (e.g., dutichlorofos and thiocorofos); benzotriazine organothiophosphate insecticides (e.g., ethyl-valefos and methyl-valefos); isoindoline organophosphate insecticides (e.g., chloroimidan and phoxim); isoxazole organophosphate insecticides (e.g., oxazaphos and zolaprofos); pyrazolopyrimidine organophosphate insecticides (e.g., chlorprazophos and pyraclostrobin); pyridine organic thiophosphate insecticides (e.g., chlorpyrifos and chlorpyrifos-methyl); pyrimidine organothiophosphate insecticides (e.g., butathiofos, diazinon, etrimfos, lirimfos, ethylpyrimidinophos, pirimiphos-methyl, primidophos, pyrithion, and butamiphos); quinoxaline organophosphate insecticides (e.g., quinalphos and methyl quinalphos); thiadiazole organophosphate insecticides (e.g., athidathion, fosthiazate, methidathion, and ethidathion); triazole organic thiophosphate insecticides (e.g., chlortriazophos and triazophos); phenyl organic thiophosphate insecticides (e.g., azophos, bromophos, ethyl bromophos, thiophosphoryl (carbaphenothion), chlorfenapyr, cyanophos, fenamiphos, isochlorophos, fenamiphos, etaphos, vamephos, pyrathiofos, fenthion, dichlorphos, iodophos, dichlofop, parathion, methyl parathion, fenthion, parathion, profenofos, thioprofos, disulfoton, trichlormetaphos-3, and triclopyr); phosphonate insecticides (e.g., butylphosphine and trichlorfon); thiophosphonate (phosphorothioate) insecticides (e.g., tetramethylphosphonium); phenylethylthiophosphonate insecticides (e.g., bendiumothioate and phosphonite); phenylphenylthiophosphonate insecticides (e.g., cyanophosphine, EPN, and bromophenylphosphine); phosphoramidate (phosphamidoate) type pesticides (e.g., foster phosphine, fenamiphos, thiophosphoryl butane, phosphamidon, thiophosphoryl and pirimepiphos); phosphoroamidite (phosphorothioate) insecticides (e.g., acephate, isocarbophos, isoxaphos, methamidophos, and triafamone); phosphoric diamide (phosphorodiamide) insecticides (e.g., methylphosphonium, triazophos, propaphos, and octamethylphosphonium); oxadiazine insecticides (e.g., indoxacarb); phthalimide insecticides (e.g., chlorfenapyr, phosmet, and tetramethrin); pyrazole insecticides (e.g., acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole, tebufenpyrad, tolfenpyrad, and vaniliprole), pyrethroid insecticides (e.g., fluthrin, allethrin, bioallethrin, barthrin, bifenthrin, bioethanolmethrin, cyhalothrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, Zeta-cypermethrin, cyphenothrin, deltamethrin, transfluthrin, permethrin, prallethrin, penfluthrin, cypermethrin, cyhalothrin, esmethrin, esfenvalerate, fenvalerate, fluvalinate, fluthrin, imidacloprofenprin, sumicidin, prallethrin, prallethri, Metofluthrin, permethrin, biothrin, permethrin, phenothrin, prallethrin, pyrethroid allethrin (profluthrin), pyremethrin, resmethrin, bioremethrin, cismethrin, tefluthrin, cyclopentenoprothrin, tetramethrin, tetrabromthrin, and transfluthrin); pyrethroid ether insecticides (e.g., ethofenprox, trifloxystrobin, hexythrox, protifenbute, and silafluofen); pyrimidinamine (pyrimidinamine) insecticides (e.g., flufenarim and pyriminobac-methyl); pyrrole insecticides (e.g., chlorfenapyr); pesticide tetronic acid (e.g., spirodiclofen); thiourea insecticides (e.g., diafenthiuron); urea insecticides (e.g., flucofuron and sulcofuron); and unclassified insecticides (e.g., AKD-3088, closantel, crotonylmethylamine, cyflutenfen (cyflumetofen), E2Y45, EXD, antiacarid, fenazaquin (fenazaquin), fenoxacrim, fenpyroximate (fenpyroximate), FKI-1033, fluendiamide, HGW86, hydramethylnon, IKI-2002, isoprothiolane, terfenapyr, metaflumizone, xanthone, fluformin, NNI-9850, NNI-0101, pymetrozine, pyridaben, pyridalyl, Qcide, iodoether willow, chlorantranilide (ryxypyr), SYJ-159, fenpyrad, and triazamate, and any combination thereof); and any combination thereof.
Some of the fungicides that can be used in combination with the compounds of the present invention include: 2- (thiocyanomethyl-benzothiazole), 2-phenylphenol, 8-hydroxyquinoline sulfate, parasitospora cichoracearum, quisqualis (quisqualis), epoxiconazole, azoxystrobin, bacillus subtilis, benalaxyl, benomyl, benthiavalicarb, benomyl-sulfonate (BABS) salt, bicarbonate, biphenyl, bismerthiazol, bitertanol, rinoconazole, rinderpest, borax, Borax, Bordeaux, boscalid, bromuconazole, bupirimate, lime sulphur, captan, carbendazim, isoprotundine, clidanum, cyclopropamide, carvone, diclometham (Chloroneb), chlorothalonil, ethiprole, Chimomyces, copper hydroxide, copper octoate, copper royal, copper sulfate basic sulfate (coppersulfate (tribasisic)), cuprous oxide, cyazofamid, flufenamid, cyazofamid, cyproconazole, dazomethyl, chlomethyl, chlomethoate, imicarb (tribenuron (tribasic)), cuprous oxide, cyhalonil, cyhalothrin, cyhalonil, cyhalothrin, prochlorvinum, prochlorvini, prochlorvinum, and the use, etc.) Ethylenebis- (dithiocarbamate) diammonium (diammoniumethylenibis- (dithiocarbamate)), benflufenamide, dichlorophen, diclorocyanide, diclofen, dichlorpyran, diethofencarb, difenoconazole, avenacellene (difenoquat ion), fluomepanid, dimethomorph, dimoxystrobin, diniconazole-M, fenaminostrobin, dinocap, diphenylamine, dithianon, dodine free base, dipheny, epoxiconazole, ethaboxam, ethoxyquin, hymexazol, famoxadone, fenamidone, fenamidol, fenbuconazole, methylfuroamide (nfuram), fenhexamid, fenpropathrin, fenpropidin, fenpropimorph, fenpropitin triphenyl acetate, triphenyl tin hydroxide, ferbam, fenflurazon, flufenamidone, flufenflurazone, fludioxonil, fluopicolide, fenflurazole, fenpropimorph, fenflurazole, fluoxastrobin (fluoxastrobin), fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, fol, formaldehyde, fosetyl acid, fosetyl-aluminum, fuberidazole, furalaxyl, iminoctadine acetate, GY-81, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imipram, iminoctadine acetate, iminoctadine tris (albesilate)), ipconazole, iprobenfos, iprodione, iprovalicarb, kasugamycin hydrochloride (kasugamycin hydrochloride), kresoxim-methyl, mansfungstate, mancozeb, maneb, pyrimethanil, metiram, mercuric chloride, mercuric oxide, metalaxyl oxide, mefenoxam, metam-sodium), metam-sodium, metham (sodium-acre), metham-sodium, sodium benzoate, sodium benzoate, sodium benzoate, sodium benzoate, sodium benzoate, sodium benzoate, sodium benzoate, sodium benzoate, sodium, Metconazole, sulbencarb, methyl iodide, methyl isothiocyanate, metiram, metominostrobin, metrafenone, fenaminocycline, myclobutanil, sodium metiram, peptidyl ester, fluoropyrimidinol, octreox, furosemide, oleic acid (fatty acid), orysastrobin, oxadixyl, oxine-copper, oxpoconazole fumarate, carboxin, pefurazoate, penconazole, pencycuron, pentachlorophenol, pentachlorophenyl laurate, penthiopyrad, phenylmercuric acetate, phosphonic acid, isoprothiolane, picoxystrobin, polyoxin-B, polyoxin, potassium bicarbonate, hydroxyquinoline potassium sulfate, probenazole, prochloraz (prochloraz), procymidone, propamocarb hydrochloride, propiconazole, propineb, propoxymidone, prothioconazole, pyraclostrobin, pyrazophos, pyrifos, pyriproxyfen, pyrimethanil, pymetrozine, pyroxim, fluazinam, quinoxalin, quinoxalone, quinoxyfen, fluazid, fluazinam, cloquindox, clorac, and the like, Pentachloronitrobenzene, giant knotweed (Reynouria sachalinensis) extract, silthiopham, simeconazole, sodium 2-phenylphenol, sodium bicarbonate, sodium pentachlorophenolate, spiroxamine, sulfur, SYP-Z071, tar oil, tebuconazole, tetrachloronitrobenzene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tolclofos-methyl, tolylfluanide, triadimefon, triadimenol, imidazozine, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, vinclozolin, zineb, ziram, zoxamide, candida rugosa, fusarium oxysporum, gliocladium, Phlebiopsis gigantean, Streptomyces griseoviridus, Trichoderma, (RS) -N- (3, 5-dichlorophenyl) -2- (methoxymethyl) -succinimide, 1, 2-dichloropropane, 1, 3-dichloro-1, 1,3, 3-tetrafluoroacetone hydrate, 1-chloro-2, 4-dinitronaphthalene, 1-chloro-2-nitrobenzane, 2- (2-heptadecyl-2-imidazolin-1-yl) ethanol, 2, 3-dihydro-5-phenyl-1, 4-dithi-inel,1,4, 4-tetraoxide, 2-methoxyethylmercuric acetate, 2-methoxyethylmercuric chloride, 2-methoxyethylmercuric silicate, 3- (4-chlorophenyl) -5-methylrhodanine, 4- (2-nitroprop-1-enyl) phenylthiocyanateme, aminopropylphosphonic acid, trichlofop, Oxidized thiram bactericide, barium polysulfide, Bayer 32394, mexican, quinoxime hydrazone, cyclometaldehyde, benzamacril; benzacril-isobutryl, benzamorf, binapacryl, bis (methylmercury) sulfate, bis (tributyltin) oxide, buthionine, cadimium copper zincate sulfate (cadmiumcalcium copperzinc chromatate sulfate), morcarb, CECA, chlorothiazone, chlororaniformethane, 2- (2-chlorophenyl) -1H-benzimidazole (chlorofenazole), tetrachloroquinoxaline, prochloraz, copper (3-phenylsalicylate), copper chromate, thiabendazole, cuprous hydrazine sulfate, cuprobbam, cyromazine, esteram, fenphostin, dichlornequinone, sclerotium, benzchlorotriazol, dimetachlor, nitrooctyl, nitrobutyl, pirethione, sterile, doxycycline, hydralazine, EBP, metiram, ethirimol, dimethomorph, nitrobenconazole, nitrobensulam, dimethomorph-ethyl, metoclopramide, trifloxystrobin, flutrobin, trifloxystrobin, flutrobin, trifloxystrobin, flutrobin, trifloxystrobin, flutrobin, trifloxystrobin, flutrobin, fludioxonil, glyodine, griseofulvin, quinolinylacrylate, Hercules 3944, hexylthiofos, ICIA0858, isopamphos, isovaledione, o-amide, mecarbizid, metazoxolon, furametpyr, methylmercury dicyandiamide, tiadinil, metiram, muconic anhydride, metiolide, N-3, 5-dichlorophenyl-succinimide, N-3-nitrophenyl itaconimide, natamycin, N-ethylmercurio-4-toluenesulfonanilide, bis (dimethyldithiocarbamate) nickel, OCH, phenylmercuric dimethyldithiocarbamate, phenylmercuric nitrate, chlophosphorus, thiocarb; thiophanate hydrochloride, benomyl, picolonitrile, clomepyridine chloride, pyriftalid and quinacetol; quinacetol sulfate, quinoxalone, quinconazol, rabenzazole, salicylanilide, SSF-109, pentanesulfone, tecoram, thiadifluor, thiabendazole, thiochlororfenthim, thiophanate, dicoform, tioxymid, wifenphos, pyrimethanil, butanetriazole, trichlamide, asomate, XRD-563, and cyanoester, and any mixtures thereof.
Some of the herbicides that may be used in combination with the compounds of the present invention include: acetochlor, butachlor, alachlor, propisochlor, metolachlor, s-metolachlor, pretilachlor, propyzamide, pretilachlor, napropamide, R-levulinyl-propyzamide, propanil, mefenacet, dibenzamide, diflufenican, flumetsulam, bromobutyrolac, dimethenamid, ethofenoxate, flufenacet, methoxyfenacet, metazachlor, isoxaben, haloxynil, flumethan-butyl, dinafop-propargyl, butachlor, propisochlor, dimethenamid, metamifop, trinitron, chloroformamid, propyzamide, pencycuramide, carprofessin, difloram, diclofenacet, butafenacet, benfluramine, mefenacet, and the, Grazing amine, bensulfuron, quinoxalamine, bensulfuron-methyl, naproxen, acetochlor, naproxen, thiachlor, metazachlor, bensulam, bensulfuron-methyl, prochloraz, chlorophthalimide, butanamide, fluazinam, atrazine, simazine, prometryn, cyanazine, simetryn, ametryn, prometryn, ipratron, flurazin, terbutryn, terbuthylazine, triazineaf-flurazon, ciprofloxacin, cyanazine, prometryn, simatong, azidezin, diuron, isopentetryn, metribuzin, terbuton, metocloprid, cyanazine, bentazon, clonazine, clonorcetryn, atrazine, omethoate, rimsulfuron, thiocyanoton, indoziflam, chlorsulfuron, meturon, bensulfuron, tribenuron, thifensulfuron-methyl, pyrazosulfuron-methyl, sulfosulfuron-methyl ether, sulfometuron, bensulfuron-methyl, Sulfometuron-methyl, nicosulfuron, ethametsulfuron, amidosulfuron, ethoxysulfuron, cyclosulfamuron, rimsulfuron, tetrazolsulfuron, flazasulfuron, monosulfuron-methyl, monosulfuron-ester, flucarbazone-methyl, flupyrsulfuron-methyl, halosulfuron-methyl, imazosulfuron, primisulfuron-methyl, prosulfuron, sulfosulfuron, trifloxysulfuron, triflusulfuron, prosulfuron, triflusulfuron-methyl, metsulfuron-methyl, primisulfuron-methyl, Propyrisulfuron, acifluorfen-methyl, acifluorfen-ethyl, fluoroglycofen-ethyl, oxyfluorfen-ethyl, cumylether, aclonifen, clofenfluroether, fluroxypyr, benfluroxypyr-methyl, trifluoromethoxyfen-methyl, metofen-ethyl, trifluoromethoxyfen-ethyl, trifluofen-ethyl, fluoroglycofen-ethyl, fluromethoxyfen, metofen-ethyl, trifluofen-ethyl, fluromethoxyfen, trifluofen-ethyl, flurometfen, fluromethoxyfen, flurometfen, benfen, flurometfen, benflurometfen, benfluridone, Fluoroglycofen-ester, Halosafen, chlortoluron, isoproturon, linuron, diuron, lufenuron, fluometuron, mefenthiuron, benzuron, sulfosulfuron, isosulfuron, tebuthiuron, clodinuron, chlorsulfuron, metsulfuron, metoxuron, bromuron, metoxuron, chlorsulfuron, mesosulfuron, cyclouron, fensulfuron, meturon, sulfosulfuron, meturon, metoxuron, cyclouron, thifensulfuron-methyl, buthiuron, kuron, cymarone, metoxuron, Chloreturon, tefluron, benuron, phenmedipham, metoron, chlon, tebuthiuron, teflubenzuron, phenmedipham, buthiuron, bensulfuron-ethyl, desmetryn, benazol, benazolin, buthan, benoxa, buthan, bencarb, buthan, benazol, buthan, benazol, buthan, p, buthan, p, buthan, benazol, p, buthan, benazol, p-methyl, p-methyl, benazol, p-methyl, p-methyl, p-methyl, p, Triallate, paraquat, diclofop, pyributicarb, dichlormate, chlometrine, ethiofen, prosulfocarb, clomazone, prosulfocarb, dichlorvos, thiobencarb, promethazine, Isopolinate, Methiobencarb, 2, 4-d butyl ester, 2 methyl 4-sodium chloride, 2, 4-d isooctyl ester, 2 methyl 4-chloroisooctyl ester, 2, 4-d sodium salt, 2, 4-d dimethylamine salt, 2 methyl 4-chloroethyl thioester, 2 methyl 4 chloride, 2, 4-d propionic acid, high 2, 4-d propionate, 2, 4-d butyric acid, 2 methyl 4 chloropropionic acid, 2 methyl 4 chloropropionate, 2 methyl 4 chlorobutyric acid, 2,4, 5-d nasal discharge propionic acid, 2,4, 5-d aldicarb acid, 2 methyl 4-chlomethionate, dicamba, norbenoxanone, valacic acid, triclosanoic acid, triclosan, metoclopramide, triclosan, mechlorvinphos, mechlorvina, dicamba, benoxanil, benazol, benazolin, and so, Diclofop-methyl, fluazifop-p-butyl, haloxyfop-methyl, haloxyfop-ethyl, quizalofop-p-ethyl, fenoxaprop-p-ethyl, propaquizafop-ethyl, fenoxaprop-p-ethyl, clodinafop-ethyl, benfop-p-butyl, benazolin-ethyl, benazolin-p-ethyl, benazolin-ethyl, benfluralin-ethyl, chloroethafloxacin, aminofluanid, benazolin-ethyl, Methalpropalin, propamol, glyphosate, anilofol, glufosinate-ethyl, thiophosphine, piproline, bialaphos, benfop-methyl, bensulide, bialaphos-ethyl, bensulide, dichlorphos, bensulin, fenphos-ethyl, mefenofos, mefenamic acid, me, Mebendazole, imazamethabenz-methyl, fluroxypyr-meptyl, clopyralid, picloram, triclopyr, dithiopyr, haloxydine, triclopyr, thiazopyr, fluridone, aminopyralid, diflufenzopyr, butoxyethyl triclopyr, Clodinate, sethoxydim, clethodim, cycloxydim, dicentrazone, clethodim, tralkoxydim, topramezone, pyroxene, Buthidazole, metribuzin, metamitron, bromoxynil, octanoyl ioxynil, dichlobenil, diphenylacetonitrile, pyraclonil, oxypyr, iobonil, Iodobonil, flumetsulam, florasulam, penoxsulam, flumetsulam, clofenapyr, diclosulam, pyriminobac, pyriftalid, pyriminobac, pyriben, pyribensulbensulbensulben, pyriben, pyribensulam, pyribensulbensulam, pyriben, pyribensulben, clomeben, pyribensulben, pyribensulbensulben, pyriben, clomeben, clomebensulben, clomeben, clofenthi, clomeben, clofenpyr, clofenthi, clofenpyr, clofenthi, clofen, Pyrithiobac-methyl, benzobicyclon, mesotrione, sulcotrione, Tembotrione, Tefuryltrione, Bicyclopyrone, ketodradox, isoxaflutole, fenoxasulfofone, Methiozolin, isopyrafen, pyraflufen, pyraflutole, difenzoquat, pyraflutole, pyroxaflutole, pyroxasulfofone, flumetsul, flumetsulam, metamitron, amicarbazone, oxadiazon, flumetsul, sulfentrazone, Bencarbazone, bisphenoxydim, butafenacil, herbicidal isoxadine, cyclanilazine, terfenadine, flupropyzamide, flupropazabicolol, indoxacarb-ethyl, flumethrin, flumethron, propyzamide, flumethazine, flumethol, carfentrazone, metolachlor, metolachlorfen, metolachlor, Bromopicloram, didafur, pyridaben, Pyridafol, quinclorac, cloquinclorac, bentazon, pyridate, oxaziclomefone, benazolin, cycloxaprop-p-ethyl, cumylfen, propylpyriproxyfen, indanthrone, sodium chlorate, dalapon, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid, mequat, bromophenol oxime, triazasulam, imazazole, flurtamone, ethofumesate, pyrimethanil, clodinafop-clomazone, clodinafop-propargyl, acraldehyde, benfluroxypyr, imazalil, avenae ester, thiadiazolyl, dazomet, hydroxybencotrione, pyroxene, saflufenacil, clofenphos, trichloropropionic acid, aloac, diethammquat, ethnpromid, Iprymidam, ipfenbacazone, thiencarbazone methyl, pyrimisufan, chlorerfluorazole, tripropindin, Sulglycasin, methidathiolin, Campbhichler, aminocyclopyrachlor, halauxifen, fluroxypyr, and any mixture thereof.
Advantageous effects
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
by carrying out chemical modification and molecular design on the compound with the spiro-heterocyclic structure and introducing a pyrazole acid structure, a series of compounds which are more efficient and have better crop safety and can be used for agricultural or forestry insecticidal and have insecticidal activity are obtained, and the compounds have good activity particularly on lepidoptera pests, homoptera pests and mites and have excellent crop safety.
Modes for carrying out the invention
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
By taking into account the economics, diversity and biological activity of the synthesized compounds, it is preferred that some of the compounds are listed in the following table. Specific compound structures are shown in table 1, and specific compound physical property data are shown in table 2. The compounds in tables 1-2 are only for better illustration of the invention and are not intended to be limiting, and those skilled in the art will not understand that the scope of the above subject matter of the invention is limited to the following compounds.
Figure BDA0002669812390000131
TABLE 1 Structure of compound of formula I (wherein a, b, c, d are position marks on benzene ring)
Figure BDA0002669812390000132
Figure BDA0002669812390000141
Figure BDA0002669812390000151
Figure BDA0002669812390000161
TABLE 21H NMR data
Figure BDA0002669812390000162
Figure BDA0002669812390000171
Figure BDA0002669812390000181
Figure BDA0002669812390000191
The methods for preparing the compounds of the present invention are illustrated in the following schemes and examples. The starting materials are commercially available or can be prepared by methods known in the literature or as shown in detail. It will be appreciated by those skilled in the art that other synthetic routes may also be utilized to synthesize the compounds of the present invention. Although specific starting materials and conditions for the synthetic routes are described below, they can be readily substituted with other similar starting materials and conditions, and variations or modifications of the preparation process of the present invention, such as various isomers of the compounds, are included in the scope of the present invention. In addition, the preparation methods described below may be further modified in accordance with the present disclosure using conventional chemical methods well known to those skilled in the art. For example, protecting the appropriate groups during the reaction, and the like.
Example 1
Synthesis of Compound 3:
Figure BDA0002669812390000201
compound intermediate 1(3.02g, 10mmol) and dichloromethane (30ml) were added to a reaction flask, intermediate 2(1.84g, 10mmol) was added with stirring at 20 ℃, triethylamine (2eq) was added with stirring at 20 ℃, TLC tracking reaction (ethyl acetate: petroleum ether ═ 1:1, GF254, UV color development) was followed, after completion of the reaction, solvent was spun off, dried, purified by column chromatography to give compound 1, 3.12g, white solid powder, melting point: 197 ℃ and 202 ℃;1H-NMR(CDCl3-d6,500MHz)δ:7.16-7.13(m,2H),7.03-7.00(m,1H),6.64-6.62(s,1H),4.32-4.29(t,2H),3.78-3.76(s,3H),3.17-3.14(m,4H),2.98-2.95(m,3H),2.55-2.53(s,3H),2.46-2.42(m,5H),1.97-1.94(m,2H),1.66-1.63(m,2H),1.43-1.39(m,6H)ppm.。
example 2
Synthesis of Compound 5:
Figure BDA0002669812390000202
adding compound intermediate 1(3.02g, 10mmol) and dichloromethane (30ml) into a reaction flask, adding intermediate 2(1.98g, 10mmol) at 20 ℃ with stirring, adding triethylamine (2eq) at 20 ℃ with stirring, tracking the reaction by TLC (ethyl acetate: petroleum ether ═ 1:1, GF254, UV color development), after the reaction is completed, removing the solvent by spinning off, drying, purifying by column chromatography to obtain new compound 5, 3.61g, light yellow solid powder, melting point: 178-180 ℃;1H-NMR(CDCl3-d6,500MHz)δ:7.21-7.18(m,1H),7.14-7.11(m,2H),6.71-6.68(s,1H),4.31-4.28(t,2H),3.82-3.79(s,3H),3.18-3.15(m,2H),2.94-2.91(m,2H),2.87-2.84(t,2H),2.52-2.49(s,3H),2.51-2.48(s,3H),2.25-2.23(s,3H),1.80-1.76(m,4H),1.65-1.63(m,2H),1.47-1.44(m,2H)ppm.。
example 3
Synthesis of compound 21:
Figure BDA0002669812390000211
adding compound intermediate 1(3.02g, 10mmol) and dichloromethane (30ml) into a reaction flask, adding intermediate 2(2.26g, 10mmol) at 20 ℃ with stirring, adding triethylamine (2eq) at 20 ℃ with stirring, tracking the reaction by TLC (ethyl acetate: petroleum ether ═ 1:1, GF254, UV color development), after the reaction is completed, removing the solvent by spinning off, drying, purifying by column chromatography to obtain new compound 12, 3.25g, white solid powder, melting point: 220 ℃ and 222 ℃;1H-NMR(CDCl3-d6,500MHz)δ:7.09-7.06(m,1H),6.90-6.87(m,2H),6.92(s,1H),4.25-4.22(t,2H),3.11-3.08(m,2H),2.88-2.85(m,2H),2.65-2.63(t,2H),2.42(s,3H),2.22(s,3H),1.96-1.92(m,4H),1.87-1.84(m,2H),1.55-1.52(m,2H)ppm.。
example 4
Preparation of the preparation:
1. powder preparation: weighing 20% of the compound of the formula (I) and 80% of kaolin, uniformly mixing, and crushing to obtain the product.
2. Wettable powder: weighing 20% of the compound of formula (I), 8% of calcium lignosulfonate, 2% of sodium lauryl sulfate, 3% of white carbon black and kaolin to 100%. Mixing uniformly, and performing jet milling to obtain the product.
3. Water dispersible granules: 60% of the compound of formula (I), 6% of sodium lignosulfonate, 4% of NNO (alkyl naphthalene sulfonate formaldehyde condensate), 2% of nekal BX (sodium dibutylnaphthalene sulfonate), 3% of K-12 (sodium dodecyl sulfate), 5% of carboxymethyl (ethyl) cellulose, 5% of diatomaceous earth, 5% of glucose and kaolin are weighed to 100%. Uniformly mixing, after jet milling, weighing the powder, adding water for mixing, granulating in a granulator, and then drying and screening to obtain granular products.
4. And (3) missible oil: weighing 15% of the compound of the formula (I), 5% of Nongru 700#, 5% of Nongru 500#, 6% of Nongru 1601#, 10% of cyclohexanone, 3% of N-methylpyrrolidone and solvent oil 150, adding to 100%, dissolving completely and mixing uniformly to obtain the product.
5. Suspending agent: weighing 15% of a compound shown in the formula (I), 4% of FS3000 (phosphate type anionic surfactant), 2% of NS-500LQ (nonionic hydroxy polyethylene oxide block copolymer), 0.2% of xanthan gum, 1% of magnesium aluminum silicate, 5% of ethylene glycol, 0.1% of BIT (1, 2-benzisothiazolin-3-one), 0.3% of organic modified siloxane defoamer and adding deionized water to 100%, preparing slurry, and sanding to obtain the product.
The above are all weight percentages.
Examples 5-7 evaluation of biological Activity
Several insects and mites were subjected to insecticidal or sexual determination tests using the above-mentioned compounds according to the method described in NYT 1154.1-2006 indoor bioassay guidelines for agricultural chemicals. The method of measurement is as follows: after the test compound was dissolved in N, N-dimethylformamide, the solution was diluted with water containing 0.1% Tween-80 to the desired concentration.
The insecticidal activity of the compounds is tested by taking alfalfa aphid, diamond back moth, asparagus caterpillar, tetranychus cinnabarinus, tetranychus urticae koch and rice planthopper as targets; and tested in parallel for pesticidal activity with the following compounds, a specific compound having the structure:
spirotetramat (with the specific structure of
Figure BDA0002669812390000221
)、
Control Compound I-1-B-16 (described in CN1232450A, having a specific Structure
Figure BDA0002669812390000222
)、
Control Compound I-1-B-19 (described in CN1232450A, having a specific Structure
Figure BDA0002669812390000223
)、
Control Compound I-1-B-18 (described in CN1232450A, having a specific Structure
Figure BDA0002669812390000224
)、
Control Compound I-1-B-29 (described in CN1232450A, having a specific Structure
Figure BDA0002669812390000225
)。
Example 5
The insecticidal activity of the compound is tested by taking alfalfa aphid, tetranychus cinnabarinus, tetranychus urticae kohlrabi and rice planthopper as targets, and the spraying pressure of a Potter spraying tower is stabilized at 1.47 multiplied by 105Pa, placing the culture dish with the targets in the same physiological state at the bottom of the spraying tower for quantitative spraying, wherein the spraying liquid amount is 1mL, taking out the targets for feeding after the liquid medicine is settled for 5min, repeating the treatment for 4 times, and investigating the mortality of the targets after 48h of treatment.
Some of the test results are as follows:
when the concentration of the liquid medicine is 100ppm, the death rate of the compounds 1-28, 29, 32-41, 44, 46, 48-56, 60-67, 69, 71-74, 76-83 and 86-93 to the aphid of alfalfa is 100 percent, and the death rate of the spirotetramat, the contrast compounds I-1-B-16, I-1-B-19, I-1-B-18 and I-1-B-29 to the aphid of alfalfa is less than 80 percent; the mortality of the compounds 1-32, 35, 37-39, 41, 43, 45-46, 49, 51-55, 57-63, 65, 68-73 and 76-78 to tetranychus cinnabarinus is 100 percent, and the mortality of the spirotetramat, the contrast compounds I-1-B-16, I-1-B-19, I-1-B-18 and I-1-B-29 to tetranychus cinnabarinus is less than 80 percent; the mortality of the compounds 1-32, 35, 37-39, 41, 43, 45-46, 49, 51-55, 57-63, 65, 68-73 and 76-78 to the tetranychus urticae is 100 percent, and the mortality of the spirotetramat, the contrast compounds I-1-B-16, I-1-B-19, I-1-B-18 and I-1-B-29 to the tetranychus urticae is less than 80 percent; the mortality of the compounds 1-16, 18, 21-26, 28, 30-43, 45-49, 51-53, 55, 60-67, 69 and 71-87 to the rice planthopper is 100 percent, and the mortality of the spirotetramat and the comparison compounds I-1-B-16, I-1-B-19, I-1-B-18 and I-1-B-29 to the rice planthopper is less than 80 percent;
when the concentration of the liquid medicine is 20ppm, the death rate of the compounds 1-28, 29, 34, 36, 39, 44, 46, 48, 51, 52, 54, 56, 60-63, 69, 71-74, 76-83 and 86-91 to the aphid of alfalfa is more than 80 percent, and the death rate of the spirotetramat and the contrast compounds I-1-B-16, I-1-B-19, I-1-B-18 and I-1-B-29 to the aphid of alfalfa is less than 60 percent; the mortality of the compounds 1-32, 35, 39, 46, 49, 51-55, 57-63, 65 and 68-71 to tetranychus cinnabarinus is more than 80 percent, and the mortality of the spirotetramat, the contrast compounds I-1-B-16, I-1-B-19, I-1-B-18 and I-1-B-29 to tetranychus cinnabarinus is less than 60 percent; the mortality of the compounds 1-32, 35, 39, 46, 49, 51-55, 57-63 and 68-71 to the tetranychus urticae is more than 80 percent, and the mortality of the spirotetramat, the contrast compounds I-1-B-16, I-1-B-19, I-1-B-18 and I-1-B-29 to the tetranychus urticae is less than 60 percent; the mortality of the compounds 1-16, 18, 21, 23, 25, 28, 30, 33, 35, 45-48, 51-53, 55, 60-65, 69, 71-, 73-75 to the rice planthopper is over 80 percent, and the mortality of the spirotetramat and the control compounds I-1-B-16, I-1-B-19, I-1-B-18 and I-1-B-29 to the rice planthopper is less than 60 percent.
Example 6
The insecticidal activity of the compound is tested by taking diamond back moths and beet armyworms as targets, the targets which are continuously raised indoors and have consistent physiological states (the diamond back moths and the beet armyworms are larvae of 3 years old) are selected, cabbage leaves growing consistently are made into appropriate leaf disks, the leaf disks are soaked in liquid medicine to be tested for 10s, then the leaves are taken out, dried, placed in a culture dish of moisturizing filter paper, the targets are inoculated, 10 times of treatment are repeated every time, 4 times of treatment are repeated every time, and the mortality of the targets is investigated after 48 hours of treatment.
Some of the test results are as follows:
when the concentration of the liquid medicine is 100ppm, the mortality of the compounds 1-30, 34-36, 39-42, 44-46, 48-53, 55, 57-63, 65, 67, 69, 72-75, 77-80 and 83 to the plutella xylostella is 100 percent, and the mortality of the spirotetramat and the contrast compounds I-1-B-16, I-1-B-19, I-1-B-18 and I-1-B-29 to the plutella xylostella is less than 70 percent; the mortality of the compounds 1-30, 33-37, 39, 41-44, 47-50, 52-54, 57-60, 63, 66, 68 and 71-78 to the spodoptera exigua is 100 percent, and the mortality of the spirotetramat and the contrast compounds I-1-B-16, I-1-B-19, I-1-B-18 and I-1-B-29 to the spodoptera exigua is less than 70 percent.
When the concentration of the liquid medicine is 20ppm, the death rate of the compounds 1-18, 20-30, 34, 36, 39, 41-42, 45, 48-51, 55, 58, 61, 65, 67, 69, 72-73, 77, 79 and 83 to the plutella xylostella is 100 percent, and the death rate of the spirotetramat and the comparison compounds I-1-B-16, I-1-B-19, I-1-B-18 and I-1-B-29 to the plutella xylostella is less than 50 percent; the mortality of the compounds 1-3, 5-15, 18-30, 33-36, 39, 41-44, 47-50, 52-54, 57-60, 68, 71, 73 and 77-78 to the spodoptera exigua is 100 percent, and the mortality of the spirotetramat and the contrast compounds I-1-B-16, I-1-B-19, I-1-B-18 and I-1-B-29 to the spodoptera exigua is less than 50 percent.
Example 7
According to the method, the compounds 1, 5 and 7 and the known compound spirotetramat are selected to carry out a diamondback moth insecticidal activity control test, and the experimental results are shown in the following table.
Control test of insecticidal activity of diamondback moth:
compound numbering Concentration (ppm) Mortality (%)
1 20 100
5 20 100
7 20 100
Spirotetramat 20 65
The above embodiments are only for illustrating the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention accordingly, and not to limit the protection scope of the present invention accordingly. All equivalent changes or modifications made in accordance with the spirit of the present disclosure are intended to be covered by the scope of the present disclosure.

Claims (10)

1. A nitrogenous spiro derivative or a salt thereof which is acceptable as a pesticide has a structural formula shown as a formula (I):
Figure FDA0002669812380000011
in the formula (I), the compound is shown in the specification,
x represents halogen, CN, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl radical, C1-C6Alkoxy radical, C3-C6Cycloalkyl radical, is takenAryl substituted or unsubstituted with a substituent, m represents an integer of 0 to 4;
R1represents H, halogen, CN, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl, halo C2-C6Alkenyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C1-C6Alkylthio, halo C1-C6Alkylthio radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyloxy, nitro, aldehyde, carboxyl, -COOX, -CO-NH2、-CO-NHX、-CO-NX2、-CH2-CO-NH2；
R2Represents H, halogen, CN, C1-C6Alkyl, halo C1-C6Alkyl, cyano-substituted C1-C6Alkyl radical, C2-C6Alkenyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C6Cycloalkyl, phenyl, benzyl;
R3represents H, halogen, CN, C1-C6Alkyl, halo C1-C6Alkyl, cyano-substituted C1-C6Alkyl radical, C2-C6Alkenyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C6Cycloalkyl, phenyl, benzyl;
R4and R5Together form a radical- (CH)2)t-, t represents 2 to 5;
R6represents H, halogen, CN, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C6Cycloalkyl, aryl substituted or unsubstituted with a substituent.
2. A nitrogen-containing spiro derivative according to claim 1 or a pesticidally acceptable salt thereof, wherein in formula (I),
x represents halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C2-C4Alkenyl radical, C1-C4Alkoxy radical, C3-C6Cycloalkyl, unsubstituted phenyl or phenyl substituted by CN, m represents an integer of 0 to 3;
R1represents H, halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C2-C4Alkenyl, halo C2-C4Alkenyl radical, C1-C4Alkoxy, halo C1-C4Alkoxy radical, C1-C4Alkylthio, halo C1-C4Alkylthio radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyloxy, nitro, aldehyde, carboxyl, -COOX, -CO-NH2、-CO-NHX、-CO-NX2or-CH2-CO-NH2；
R2Represents H, halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl, cyano-substituted C1-C4Alkyl radical, C2-C4Alkenyl radical, C1-C4Alkoxy or C3-C6A cycloalkyl group;
R3represents H, halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C2-C4Alkenyl radical, C1-C4Alkoxy, halo C1-C4Alkoxy or C3-C6A cycloalkyl group;
R4and R5Together form a radical- (CH)2)t-, t represents 3 to 5;
R6represents H, halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy, halo C1-C4Alkoxy radical, C3-C6Cycloalkyl, aryl unsubstituted or substituted by cyano, or phenyl substituted by cyano.
3. A nitrogen-containing spiro derivative according to claim 1 or a pesticidally acceptable salt thereof, wherein in formula (I),
x represents halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C2-C4Alkenyl radical C3-C6Cycloalkyl, m represents an integer of 0 to 3;
R1represents H, halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C2-C4Alkenyl radical, C1-C4Alkoxy radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyloxy, nitro, aldehyde, carboxyl, -COOX, -CO-NH2、-CO-NHX、-CO-NX2or-CH2-CO-NH2；
R2Represents H, halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C2-C4Alkenyl radical, C1-C4Alkoxy or C3-C6A cycloalkyl group;
R3represents H, halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C2-C4Alkenyl radical, C1-C4Alkoxy or C3-C6A cycloalkyl group;
R4and R5Together form a radical- (CH)2)t-, t represents 3 to 5;
R6represents H, halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy radical, C3-C6A cycloalkyl group.
4. A nitrogen-containing spiro derivative according to any one of claims 1 to 3 or a pesticidally acceptable salt thereof, wherein in formula (I), X represents H, halogen, CN, C1-C4Alkyl, m represents an integer of 1 to 3;
R1represents halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy radical, C3-C6Cycloalkyl, nitro, aldehyde, carboxyl, -COOX, -CO-NH2、-CO-NHX、-CO-NX2or-CH2-CO-NH2；
R2Represents H, halogen, CN, C1-C4Alkyl radical, C2-C4Alkenyl radical, C1-C4Alkoxy or C3-C6A cycloalkyl group;
R3represents H, halogen, CN, C1-C4Alkyl, halo C1-C4Alkyl radical, C2-C4Alkenyl or C3-C6A cycloalkyl group;
R4and R5Together form a radical- (CH)2)t-, t represents 3 to 5;
R6represents H, halogen, CN, C1-C4Alkyl radical, C3-C6A cycloalkyl group.
5. A nitrogen-containing spiro derivative according to claim 1 or a pesticidally acceptable salt thereof, wherein in formula (I), X represents a methyl group or an ethyl group, m represents 1;
R1represents H, F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3、CH2Br、CHBr2、CBr3、CH2CF3Vinyl, OMe, OEt, n-PrO, i-PrO, n-BuO, i-BuO, s-BuO, t-BuO, cyclopropane, cyclopropaneoxy, nitro, aldehyde, carboxyl, -COOCH3、-COOC2H5、-CO-NH2、-CO-NHCH3or-CO-N (CH)3)2；
R2Represents H, Me or Et;
R3represents H, Me, Et, n-Pr or i-Pr;
R4and R5Together form a radical- (CH)2)t-, t represents 3 or 4;
R6represents H, F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu or t-Bu.
6. A nitrogen-containing spiro derivative according to claim 5 or a pesticidally acceptable salt thereof, wherein in formula (I), X represents a methyl group, m represents 1;
R1represents H, F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH2F、CHF2、CF3OMe, OEt, cyclopropane, -COOCH3、--CO-NH2；
R2Representation H, Me;
R3representation H, Me;
R4and R5Together form a radical- (CH)2)t-, t represents 3 or 4;
R6indicating H, Me.
7. A nitrogen-containing spiro derivative according to any one of claims 1 to 6 or a pesticidally acceptable salt thereof, wherein the compound of formula (I) is selected from:
Figure FDA0002669812380000031
8. an insecticidal composition comprising an insecticidally effective amount of at least one of a nitrogen-containing spiro derivative according to any one of claims 1 to 7 or a pesticidally acceptable salt thereof; preferably, the composition also comprises a preparation carrier or a preparation auxiliary agent.
9. A method for controlling pests which comprises applying an insecticidally effective amount of at least one nitrogen-containing spiro derivative according to any one of claims 1 to 7 or a pesticidally acceptable salt thereof or an insecticidal composition according to claim 8 to the pests and/or their habitat.
10. Use of a nitrogen-containing spiro derivative according to any one of claims 1 to 7 or at least one of its salts as a pesticidally acceptable or a pesticidal composition according to claim 8 for controlling pests.
CN202010929769.7A 2020-09-07 2020-09-07 Nitrogen-containing spiro derivative or salt thereof acceptable as pesticide, composition and application thereof Pending CN114149433A (en)

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