CN114957062A - Para-substituted biphenyl thioether compound, composition and application thereof - Google Patents

Para-substituted biphenyl thioether compound, composition and application thereof Download PDF

Info

Publication number
CN114957062A
CN114957062A CN202210783893.6A CN202210783893A CN114957062A CN 114957062 A CN114957062 A CN 114957062A CN 202210783893 A CN202210783893 A CN 202210783893A CN 114957062 A CN114957062 A CN 114957062A
Authority
CN
China
Prior art keywords
para
formula
buo
radical
insecticides
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210783893.6A
Other languages
Chinese (zh)
Other versions
CN114957062B (en
Inventor
葛家成
孙鹏
邢阳阳
胡堂路
刘明东
杨春河
谭兴武
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hailir Pesticides and Chemicals Group Co Ltd
Original Assignee
Hailir Pesticides and Chemicals Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hailir Pesticides and Chemicals Group Co Ltd filed Critical Hailir Pesticides and Chemicals Group Co Ltd
Priority to CN202210783893.6A priority Critical patent/CN114957062B/en
Publication of CN114957062A publication Critical patent/CN114957062A/en
Priority to PCT/CN2023/101703 priority patent/WO2024007862A1/en
Application granted granted Critical
Publication of CN114957062B publication Critical patent/CN114957062B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/01—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton
    • C07C323/09—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton having sulfur atoms of thio groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G13/00—Protecting plants
    • 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
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/14—Ethers
    • 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
    • A01N37/34—Nitriles
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/10—Sulfones; Sulfoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
    • C07C303/08—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with halogenosulfonic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/14—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Agronomy & Crop Science (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention belongs to the field of pesticides, and particularly relates to a para-substituted biphenyl thioether compound, a composition and application thereof, wherein the compound has a structure shown in a formula (I):

Description

Para-substituted biphenyl thioether compound, composition and application thereof
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a para-substituted biphenyl thioether compound and a composition, and application of the compounds or the salts and the composition which are acceptable as pesticides as insecticides or acaricides.
Background
The trifluoroethyl sulfide (sulfoxide) compound is a novel compound with good acaricidal activity. The first commercial trifluoroethyl sulfide compound, Flupentiofenox, developed in Japanese combinatorial chemistry in 2020 has a good control effect on Tetranychus urticae, and thus, the development of the field is hot. The chemical structural formula of Flupentiofenox is shown as follows:
Figure BDA0003731027890000011
the compound disclosed in patent CN113943238A by Shenyang chemical research and development Limited company has acaricidal activity:
Figure BDA0003731027890000012
wherein R is 1 Selected from nitro, cyano, C 1 -C 4 Alkylthio, trifluoromethanesulfonyl or SCH 2 CF 3 ；R 2 Selected from halogen, cyano or C 1 -C 4 An alkyl group; n is selected from 0, 1 or 2.
The following compounds disclosed in patent WO2017067500 by shenyang chemical pesticide chemical research and development limited company have very good acaricidal activity:
Figure BDA0003731027890000013
it is known that the active compounds described in the above-mentioned documents still have low killing activity in controlling harmful animals, particularly mites, but their acaricidal activity is often unsatisfactory at low concentrations and the control effect on spider mites which have acquired resistance to drugs is inferior, so that there is still an urgent need for new drugs having high efficacy, low toxicity and excellent killing effect on resistant mites in agricultural production.
Disclosure of Invention
Aiming at the defect of insufficient killing activity of a medicament for preventing and controlling mites in the prior art, the invention provides a para-substituted diphenyl sulfide compound and a synthesis method and application thereof, so as to solve the technical problems. In order to develop a pest control agent having the above-described desirable characteristics, the inventors synthesized various aryl sulfide derivatives and conducted intensive studies on the biological activities thereof. As a result, the para-substituted diphenyl sulfide compounds represented by the following general formula show excellent control effects on various pests, particularly on spider mites represented by tetranychus cinnabarinus, tetranychus urticae koch, tetranychus mirabilis, panonychus citri and the like, and the research is continued and the invention is completed.
The technical scheme adopted by the invention for realizing the purpose is as follows: a para-substituted biphenyl thioether compound has a structural formula shown in a formula (I):
Figure BDA0003731027890000021
in the formula (I), the compound is shown in the specification,
R 1 selected from H, CN, halogen, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 2 -C 6 Alkenyl radical, C 2 -C 6 Haloalkenyl, C 2 -C 6 Alkynyl, C 2 -C 6 Halogenated alkynyl, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy radical, C 3 -C 6 Cycloalkyl radical, C 3 -C 6 Alkylene oxide radical or C 3 -C 6 A cycloalkyloxy group;
n is an integer from 0 to 2.
Further, in the formula (I),
R 1 selected from H, CN, halogen, C 1 -C 4 Alkyl, halo C 1 -C 4 Alkyl radical, C 2 -C 4 Alkenyl radical, C 2 -C 4 Haloalkenyl, C 2 -C 4 Alkynyl, C 2 -C 4 Halogenated alkynyl, C 1 -C 4 Alkoxy, halo C 1 -C 4 Alkoxy radical, C 3 -C 6 Cycloalkyl radical, C 3 -C 6 Alkylene oxide radical or C 3 -C 6 A cycloalkyloxy group;
n is an integer from 0 to 2.
Further, in the formula (I),
R 1 selected from H, CN, F, Cl, Br, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CHF 2 、CH 2 F、CF 3 、CCl 3 、CHCl 2 、CH 2 Cl、CBr 3 、CH 2 Br、CHBr 2 、CH 2 CF 3 、CH 2 CFH 2 、CH 2 CHF 2 Vinyl, ethynyl, MeO, EtO, n-PrO, i-PrO, n-BuO, i-BuO, s-BuO, t-BuO, cyclopropane, cyclopentane, cyclohexane, cyclopropaneoxy, cyclopentane oxy, or cyclohexane oxy;
n is 0 or 1.
Further, in the formula (I),
R 1 selected from H, CN, F, Cl, Br, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CHF 2 、CH 2 F、CF 3 、CCl 3 、CHCl 2 、CH 2 Cl、CBr 3 、CH 2 Br、CHBr 2 、CH 2 CF 3 MeO, EtO, n-PrO, i-PrO, n-BuO, i-BuO, s-BuO, t-BuO, cyclopropane, cyclopentane, cyclohexane, cyclopropaneoxy, cyclopentane oxy, or cyclohexane oxy.
Further, in the formula (I),
R 1 selected from CN, F, Cl, Br, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CHF 2 、CH 2 F、CF 3 MeO, EtO, n-PrO, i-PrO, cyclopropane, cyclopentane, cyclohexane, cyclopropaneoxy, cyclopentane oxy, or cyclohexane oxy.
Further, in the formula (I),
R 1 selected from CN, F, Cl, Br, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CHF 2 、CH 2 F、CF 3 MeO, EtO, cyclopropane;
n is 0 or 1.
Further, the compound of formula (I) is selected from:
Figure BDA0003731027890000031
the invention also discloses an insecticidal or acaricidal composition, which comprises an insecticidal or acaricidal effective amount of at least one of the para-substituted biphenyl thioether compounds;
further, the preparation also comprises a preparation carrier or a preparation auxiliary agent.
The invention also discloses a method for controlling pests or mites, which comprises applying an insecticidally or acaricidally effective amount of at least one of the para-substituted diphenyl sulfides as described above or an insecticidally or acaricidally composition as described above to the pests or mites and/or their habitat.
The invention also discloses the application of at least one of the para-substituted biphenyl thioether compounds or the insecticidal or acaricidal composition in controlling pests or mites in agriculture and other fields.
In the definitions of the above-mentioned structural formulae of the compounds, the terms used in the art have the following meanings:
halogen or halogen: refers to fluorine, chlorine, bromine, iodine.
C 1 -C 6 Alkyl groups: straight-chain or branched alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like.
Halogen substituted C 1 -C 6 Alkyl 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.
C 1 -C 6 Alkoxy groups: a linear or branched alkyl group having 1 to 6 carbon atoms bonded to the structure via an oxygen atom bond.
Halogen substituted C 1 -C 6 Alkoxy group: straight-chain or branched alkoxy groups having 1 to 6 carbon atoms, in which hydrogen atoms may be partially or entirely substituted with halogen, for example, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, etc.
A method for synthesizing the compound shown in the formula I is to prepare the compound shown in the formula VIII through the compounds shown in the formulas VII, VI, V, IV and III (in the chemical formulas listed below, the substituent and the symbol have the same meanings as those of the substituent and the symbol defined in the formula I as long as the substituent and the symbol are not defined otherwise) to obtain the compound shown in the formula II, and then prepare the target product shown in the formula I from the compound shown in the formula II, wherein the compound shown in the formula I can be prepared into the compound I' through an oxidation step.
Figure BDA0003731027890000041
Further, the reaction may be carried out under normal pressure or high pressure, preferably under atmospheric pressure, and the post-treatment may be carried out according to a conventional method.
The active compounds of the formula (I) according to the invention are suitable for controlling pests or mites, i.e. for controlling pests or mites, which mean harmful or unwanted insects or mites, in particular those encountered in agriculture, forestry, in the protection of stores and in the protection of materials and in the hygiene sector, which are active against sensitive and resistant species in general and are effective at all stages of development of the pests or mites; the present invention also relates to a method of inhibiting pests or mites which comprises applying to the locus of the insect, 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 or organisms.
The insect habitat, the pest habitat or the pest mite habitat refers to an environment where insects, pests or pest mites live or eggs of the insects, the pests or the pest mites exist, including air around the environment, food for eating or objects in contact with the environment. For example, by applying the active compounds to the seed of the plant (before planting), to the seedling, or to the planted cuttings, leaves, stems, fruits, grains and/or roots, or to the soil or other growth medium (before or after planting of the crop), it is possible to control insects or pest mites which eat, destroy or come into contact with edible agricultural products, ornamentals, turf, pasture plants or other plants of economic value, it is also possible to achieve protection of these plants against diseases caused by viruses, fungi or bacteria by controlling sap-feeding pests such as whitefly, planthopper, aphid and the like or pest mites such as tetranychus urticae, tetranychus cinnabarinus and the like; such plants include those propagated by conventional means, as well as those plants with insect or pest mite resistance, herbicide resistance, high yield, and/or other beneficial properties resulting from the genetic modification by modern biotechnology. It is contemplated that these compounds will be useful for protecting fabrics, paper, stored grain, seeds and other food, housing, buildings and the like items and/or locations by applying the compounds of the present invention to or near such objects.
The term controlling pests or mites, inhibiting pests or mites refers to reducing the number of live insects, pests or mites, or reducing the number of eggs on which live insects, pests or mites can reside. The degree of reduction achieved by the compound will depend on the rate of application of the compound, the particular compound used and the target insect, pest or pest mite species, at least in amounts that will produce an effect.
By "mortality" is meant an amount sufficient to measurably reduce the number of insects, pests or mites being treated. Typically, 1 to 1000ppm (by weight) of active compound are used. For example, insects or other pests, mites that may be inhibited include, but are not limited to:
lepidoptera: cotton bollworm (Heliothis spp.), cotton bollworm (Helicoverpa spp.), noctuid (Spodoptera spp.), fall armyworm (Mythimna unipicta), black cutworm (Agrotis ipsilon), diamond-pointed diamond-back (Earia spp.), cabbage looper (Trichoplusia ni), velvet armyworm (Antheraea geminata), gray leaf moth (Rachilia nubila), diamond-back moth (Plutella xylostella), Chilo sp, yellow stem borer (Scophularia cephalosporia), borer (Sesamia ferensis), rice leaf roller (Cnhalocrocis medinalis), Ostrinia (Osniella), apple borer (Cytopha persica), cabbage moth (Osricius) and cabbage moth (Osnilla), cabbage moth (Ostrea), apple (Cytopha punctifera), cabbage moth (Plutella xylophila) and cabbage moth (Pionella heterospodoptera), cabbage moth (Plutella xylophila xylostella) and cabbage moth (Plutella xylostella), cabbage moth (Plutella) as well as a xylostella, cabbage moth (Pieris), cabbage moth (Plutella) and cabbage moth (Piropora) as well as a xylostella xylophyta, cabbage moth (Piper) and cabbage moth (Piper) for the same), rice leaf moth (Piper Spodoptera, cabbage moth (Piper Spodoptera), rice leaf moth (Piper Spodoptera) and cabbage moth (Piper Spodoptera) and corn borer, cabbage moth (Piper Spodoptera) for the fruit tree, rice leaf moth (Piper) and cabbage moth (Piper) in the rice leaf moth (Piper Spodoptera) are also, Phyllonorycter spp, Spodoptera frugiperda (Leucoptera maliella), Phyllocnidia (Phyllocnisis citrella), Spodoptera exigua (Podoptera exigua Hubner);
coleoptera order: diabrotica spp, leptinotarsa decemlineata (leptinotarsa decemlineata), phomopsis oryzae (Oulema oryzae), anthurium gossypii (Antonousgrandis), rhynchophorus (lissorophorus oryzae), wireworms (Agriotesspp), Melanotus communis, Coptorhizus japonica (Popilia japonica), Rhinocerocephala spp, Pseudobulbus beetle 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;
from 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);
louse (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);
from the order Acarina: including Tetranychus (Tetranychus), Pediodaceae (Eupodidae), Gephyridae (Eriophyiade), Phytoseiidae (Phytoseiidae), Amycoridae (Acaridae), including but not limited to Tetranychus (Tetranychus spp.), spider mites (Panocyhus spp.), Tetranychus cinnabarinus (Tetranychus cinarinus), Tetranychus orientalis (Eotetranychus carpini), Tetranychus urticae (Tetranychus urticae Koch.), Citrus ruscus (Phyllophorus purpurea), Citrus aurantia (Phylocirus flavus), Aculus pellucorum, Brevibacterium parvus (Brevibacterium flavus), Boophilus (Boophilus), Dermatophagus variabilis (Dermanorvegicus), Amethephora trifoliatus (Amethorum sanguinalis), Tetranychus urticae (Amycophycus mitis mangiferus), Tetranychus urticae (Amycophycus) and Acanthophycus (Amycophyes mangifera);
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 formula I of the present invention shows excellent control activity against various pests or mites when used at low concentrations, has insecticidal or acaricidal activity at every stage of the life cycle of pests or acarids (e.g., eggs, larvae (nymphs), pupae, adults), and shows excellent control activity against those pests or acarids which have developed resistance to conventional insecticides or acaricides. 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 subspecies silurus subspecies (B. thuringiensis subspecies subsp. aizawai), Bacillus thuringiensis subspecies kurstaki (B. thuringiensis subsp. kurstaki), Bacillus thuringiensis subspecies (B. thuringiensis subsp. tenebrisonii), Beauveria bassiana (Beauveria bassiana), Chrysophyte virus (Cydia pomoea grandis virus), Spodoptera litura Nuclear Polyhedrosis Virus (NPV) (Douglas fir potomycosis mortem NPV), Spodoptera gypengii NPV (NPV), Spodoptera litura gypengii NPV (NPV), Spodoptera giva (Spodoptera), Spodoptera litura pholiopsis NPV (P. sp., Spodoptera globosa NPV), Spodoptera litura pholitura coccinella (Novolvularia punctata NPV), Spodoptera rhododendron (Nocardiopsis sp), Spodoptera globosa NPV (Noslopus lutescens sp), Spodoptera rhododendron NPV (Noslopus lutescens sp., Spodoptera purpureus NPV), Spodoptera sp. sp.sp., Spodoptera sp., Spodoptera, 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., chlororazophos and pyrazophos); 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 (phosphoramidothioate) insecticides (e.g., acephate, isocarbophos, isoxathion, methamidophos, and triallate); 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); ketofenamic acid insecticides (e.g., spirodiclofen, spiromesifen); 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, cadmium calcium copper zinc chromate sulfate (cadnium copperzinc chromate sulfate), mycophenolate, CECA, chlorobenthiazone, chlororaniforme, 2- (2-chlorophenyl) -1H-benzimidazole (chlorofenazole), tetrachloroquinoxaline, fenamidone, copper bis (3-phenylsalicylate), copper chromate, thiabendazole, cuprous hydrazine sulfate, cuprobromide, cyamectin, esteramine, fenpropidin, decafosetyl, dichloquinocyl, sclerotium, benzchlorotriazol, dimetachlor, fenaminostrobin, nitrooctyl, nitrobutyl, dipyrithione, sterile, triazophos, doxycycline, EBP, metiram, thiflutriafol, dimethomorph, trifloxystrobin, fludioxonil, flubensultap, fludioxonil, flubensultap, fludioxonil, flubenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbensultap, flubenfurbenfurbensultap, flubenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurben, Benfurathiazole, glyodine, griseofulvin, quinolinylacrylate, Hercules 3944, hexylthiofos, ICIA0858, isopamphos, isovaledione, anthranilamide, mecarbinzid, metazoxolon, furametpyr, methylmercury dicyandiamide, tiadinil, metiram, mucic anhydride, metuli, N-3, 5-dichlorophenyl-succinimide, N-3-nitrophenyl itaconimide, natamycin, N-ethylmercurio-4-toluenesulfonanilide, bis (dimethyldithiocarbamate) nickel, OCH, phenylmercuric dimethyldithiocarbamate, phenylmercuric nitrate, chlophosphate, methiocarb; thiophanate hydrochloride, benomyl, picolonitrile, clomepyridine chloride, pyriftalid and quinacetol; quinacetol sulfate, quinconazole, quinconazol, rabenzazole, salicylanilide, SSF-109, dapsone, tecoram, thiadifluor, thiabendazole, thiochlorofenthim, thiophanate, dicoform, tioxymid, methamphetamine, wifosinate, cyprodinil, butantriazole, trichlamide, arsanilide, XRD-563, and cyanoester, and any mixtures thereof.
Advantageous effects
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
by carrying out chemical modification and molecular design on aryl sulfide with a biphenyl thioether structure and arranging a substituent group at a specific position of a benzene ring, a series of compounds which are more efficient and can be used for agricultural or forestry insecticidal or acaricidal use and have excellent activity are obtained, and particularly, the compounds show excellent control effects on spider mites represented by tetranychus cinnabarinus, tetranychus urticae koch, tetranychus citri and the like, and particularly have better crop safety and target specificity.
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 BDA0003731027890000111
TABLE 1 Structure of Compounds of formula I
Serial number R 1 n Serial number R 1 n
1 CN 0 19 CN 1
2 F 0 20 F 1
3 Cl 0 21 Cl 1
4 Br 0 22 Br 1
5 Me 0 23 Me 1
6 Et 0 24 Et 1
7 n-Pr 0 25 n-Pr 1
8 i-Pr 0 26 i-Pr 1
9 n-Bu 0 27 n-Bu 1
10 i-Bu 0 28 i-Bu 1
11 s-Bu 0 29 s-Bu 1
12 t-Bu 0 30 t-Bu 1
13 CHF 2 0 31 CHF 2 1
14 CH 2 F 0 32 CH 2 F 1
15 CF 3 0 33 CF 3 1
16 MeO 0 34 MeO 1
17 EtO 0 35 EtO 1
18 Cyclopropyl alkyl radical 0 36 Cyclopropyl alkyl radical 1
TABLE 2 1 H NMR data
Figure BDA0003731027890000112
Figure BDA0003731027890000121
Figure BDA0003731027890000131
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 N- (2-fluoro-4-methylphenyl) -acetamide:
Figure BDA0003731027890000141
weighing 2-fluoro-4-methylaniline (10.0g,80mmol,1.0eq.) and sodium bicarbonate (13.4g,160mmol,2.0eq.) in a bottle, adding dichloromethane (200mL) for dissolving, slowly adding acetic anhydride (12.2g,120mmol,1.5eq.) dropwise in an ice-water bath, removing the ice-water bath after dripping, reacting for three hours at room temperature, confirming that the reaction is finished by TLC (PE: EA ═ 5:1), performing suction filtration on the system, leaching the filter cake for multiple times by dichloromethane because the product is easy to solidify, concentrating and desolventizing after leaching to obtain the filter cakeReddish brown needle-like crystals (11.4g,68mmol, 85%). LC-MS (ESI) [ M + H] + ＝168.1,[M+Na] + ＝190.1。
Example 2
Preparation of 5-acetamido-4-fluoro-2-methylbenzenesulfonyl chloride:
Figure BDA0003731027890000142
in a bottle, N- (2-fluoro-4-methylphenyl) -acetamide (10.0g,60mmol,1.0eq.) was weighed, 25mL chlorosulfonic acid was slowly added dropwise, the reaction was heated at 60 ℃ and monitored by TLC after 2 hours (DCM: MeOH ═ 10:1), the reaction was poured into ice water, filtered, the filter cake was rinsed with water and dried to give a yellow solid (9.3g,35mmol, 70%). LC-MS (ESI) [ M + H] + ＝266.1,[M+Na] + ＝288.1。
Example 3
Preparation of N- (2-fluoro-5-mercapto-4-methylphenyl) acetamide:
Figure BDA0003731027890000143
weighing 5-acetamido-4-fluoro-2-methylbenzenesulfonyl chloride (9.3g,35mmol,1.0eq.) in a bottle, adding zinc powder (22.7g,350mmol,10eq.) in glacial acetic acid (100mL), heating to 120 ℃ for reflux reaction, after reacting for about 2 hours, monitoring by TLC (EA: PE ═ 1:1) after raw materials disappear, cooling to room temperature, adding ice water (100mL) and ethyl acetate (100mL), removing excess zinc powder by suction filtration, and leaching a filter cake with ethyl acetate. The combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, filtered with suction, and the solvent was removed by concentration to give a pale yellow solid (5.4g,27mmol, 77%). LC-MS (ESI) [ M + H] + ＝200.1,[M+Na] + ＝222.1。
Example 4
Preparation of N- (2-fluoro-4-methyl-5- ((2,2, 2-trifluoroethyl) thio) phenyl) acetamide:
Figure BDA0003731027890000144
n- (2-fluoro-5-mercapto-4-methylphenyl) acetamide (5.4g,27mmol,1.0eq.) was weighed in a bottle, acetonitrile (100mL), potassium carbonate (5.6g,40.5mmol,1.5eq.) were added, 2,2, 2-trifluoroethyl trifluoromethanesulfonate (9.4g,40.5mmol,1.5eq.) was added dropwise under nitrogen atmosphere, and the mixture was stirred at room temperature overnight. TLC monitoring reaction (PE: EA ═ 2:1), after the material disappeared, adding water to quench, diluting with dichloromethane, washing with saturated brine, combining organic phase, drying with anhydrous sodium sulfate, filtering, concentrating and desolventizing to obtain crude product. Silica gel column chromatography (PE: EA ═ 4:1) afforded a white solid (7g,25mmol, 92%). LC-MS (ESI) [ M + H] + ＝282.1,[M+Na] + ＝304.1。
Example 5
Preparation of 2-fluoro-4-methyl-5- ((2,2, 2-trifluoroethyl) thio) aniline:
Figure BDA0003731027890000151
n- (2-fluoro-4-methyl-5- ((2,2, 2-trifluoroethyl) thio) phenyl) acetamide (7g,25mmol,1.0eq.) was weighed in a bottle and dissolved in ethanol (50mL) and water (10mL), concentrated hydrochloric acid (50mL) was added, heated to 85 ℃ and after about 4 hours of reaction, the reaction was monitored by TLC (PE: EA ═ 5:1), and after disappearance of the starting material, the pH was adjusted to neutral with 1N NaOH solution. Most of the methanol was removed under reduced pressure, diluted with dichloromethane, washed with saturated brine, the organic phases were combined, dried over anhydrous sodium sulfate, filtered with suction, concentrated and desolventized to give a pink liquid (5.3g,22mmol, 88%). LC-MS (ESI) [ M + H] + ＝240.1,[M+Na] + ＝262.1。
Example 6
Preparation of (4-fluoro-5-iodo-2-methylphenyl) (2,2, 2-trifluoroethyl) sulfide:
Figure BDA0003731027890000152
2-fluoro-4-methyl-5- ((2,2, 2-trifluoroethyl) thio) aniline (2.39g,10mmol,1.0eq.) was taken and dissolved in 70% sulfuric acid (2.0 g, 1.0eq.)0mL) is stirred and dissolved, then the temperature is reduced to 0 ℃, aqueous solution of sodium nitrite (1.02g,15mmol,1.5eq.) is slowly dripped, and after the dripping is finished, the mixture is stirred for 30 minutes at 0 ℃ to obtain a diazonium salt intermediate. Subsequently, potassium iodide solid (3.32g,20mmol,2.0eq.) was added, and after stirring at 0 ℃ for 30 minutes, it was further stirred at room temperature for 2 hours. After the reaction, sodium bisulfite solution was added to quench the reaction, and after dilution with ethyl acetate, the reaction mixture was washed with saturated brine, and the organic phases were combined, dried over anhydrous sodium sulfate, filtered with suction, concentrated and desolventized to give a red liquid (2.45g,7mmol, 70%). LC-MS (ESI) [ M + H] + ＝351.0。
Example 7
Preparation of (4', 6-difluoro-4-methyl- [1,1' -biphenyl ] -3-yl) (2,2, 2-trifluoroethyl) sulfide:
Figure BDA0003731027890000153
(4-fluoro-5-iodo-2-methylphenyl) (2,2, 2-trifluoroethyl) sulfide (700mg,2mmol,1.0eq.), triphenylphosphine (50mg,0.2mmol,0.1eq.) and 4-fluorobenzeneboronic acid (420mg,3mmol,1.5eq.), potassium carbonate (828mg,6mmol,3.0eq.), palladium acetate (44mg,0.2mmol,0.1eq.) were dissolved in dioxane (8mL), replaced with nitrogen, and reacted at 80 ℃ for 4 hours. After the reaction was completed, the reaction mixture was diluted with ethyl acetate, washed with saturated brine, and the organic phases were combined, dried over anhydrous sodium sulfate, filtered with suction, and concentrated to remove the solvent to obtain a white solid (540mg,1.7mmol, 85%). LC-MS (ESI) [ M + H] + ＝319.0。
Example 8
Preparation of (4 '-chloro-6-fluoro-4-methyl- [1,1' -biphenyl ] -3-yl) (2,2, 2-trifluoroethyl) sulfide:
Figure BDA0003731027890000161
(4-fluoro-5-iodo-2-methylphenyl) (2,2, 2-trifluoroethyl) sulfide (700mg,2mmol,1.0eq.), triphenylphosphine (50mg,0.2mmol,0.1eq.) and 4-fluorobenzeneboronic acid (468mg,3mmol,1.5eq.), potassium carbonate (828mg,6mmol,3.0eq.), palladium acetate (44mg,0.2mmol,0.1eq.) were added with dioxaneThe ring (8mL) was dissolved, purged with nitrogen, and reacted at 80 ℃ for 4 hours. After the reaction was completed, the reaction mixture was diluted with ethyl acetate, washed with saturated brine, and the organic phases were combined, dried over anhydrous sodium sulfate, filtered with suction, and concentrated to remove the solvent to obtain a white solid (587mg,1.76mmol, 88%). LC-MS (ESI) [ M + H] + ＝335.0。
Example 9
Preparation of 2 '-fluoro-4' -methyl-5 '- ((2,2, 2-trifluoroethyl) thio) - [1,1' -biphenyl ] -4-carbonitrile:
Figure BDA0003731027890000162
(4-fluoro-5-iodo-2-methylphenyl) (2,2, 2-trifluoroethyl) sulfide (700mg,2mmol,1.0eq.), triphenylphosphine (50mg,0.2mmol,0.1eq.) and 4-fluorobenzeneboronic acid (441mg,3mmol,1.5eq.), potassium carbonate (828mg,6mmol,3.0eq.), palladium acetate (44mg,0.2mmol,0.1eq.) were dissolved in dioxane (8mL), replaced with nitrogen, and reacted at 80 ℃ for 4 hours. After the reaction was completed, the reaction mixture was diluted with ethyl acetate, washed with saturated brine, and the organic phases were combined, dried over anhydrous sodium sulfate, filtered with suction, and concentrated to remove the solvent to obtain a white solid (520mg,1.6mmol, 80%). LC-MS (ESI) [ M + H] + ＝326.0。
Example 10
Preparation of 2,4 '-difluoro-4-methyl-5- ((2,2, 2-trifluoroethyl) sulfinyl) -1,1' -biphenyl:
Figure BDA0003731027890000163
taking (4', 6-difluoro-4-methyl- [1,1' -biphenyl)]-3-yl) (2,2, 2-trifluoroethyl) sulfide (318mg,1mmol,1.0eq.) was dissolved in dichloromethane (5mL), stirred at 0 ℃ for 2 hours with the addition of m-chloroperoxybenzoic acid (346mg,2mmol,2.0eq.), monitored by TLC and quenched with sodium bisulfite after disappearance of the starting material. Dilute with dichloromethane, wash with brine, combine the organic phases, dry over anhydrous sodium sulfate, filter with suction, concentrate and exsolve to give a white solid (277mg,0,83mmol, 83%). LC-MS (ESI) [ M + H] + ＝335.0。
Example 11
Preparation of 4 '-chloro-2-fluoro-4-methyl-5- ((2,2, 2-trifluoroethyl) sulfinyl) -1,1' -biphenyl:
Figure BDA0003731027890000171
taking (4 '-chloro-6-fluoro-4-methyl- [1,1' -biphenyl)]-3-yl) (2,2, 2-trifluoroethyl) sulfide (334mg,1mmol,1.0eq.) was dissolved in dichloromethane (5mL), stirred at 0 ℃ for 2 hours with the addition of m-chloroperoxybenzoic acid (346mg,2mmol,2.0eq.), monitored by TLC and quenched with sodium bisulfite after disappearance of the starting material. Dilute with dichloromethane, wash with saturated brine, combine the organic phases, dry over anhydrous sodium sulfate, filter with suction, concentrate and desolventize to give a white solid (288mg,0,82mmol, 82%). LC-MS (ESI) [ M + H] + ＝351.0。
Example 12
Synthesis of 2 '-fluoro-4' -methyl-5 '- ((2,2, 2-trifluoroethyl) sulfinyl) - [1,1' -biphenyl ] -4-carbonitrile:
Figure BDA0003731027890000172
taking 2 '-fluoro-4' -methyl-5 '- ((2,2, 2-trifluoroethyl) thio) - [1,1' -biphenyl]-4-carbonitrile (325mg,1mmol,1.0eq.) was dissolved in dichloromethane (5mL), stirred at 0 deg.C for 2h with the addition of m-chloroperoxybenzoic acid (346mg,2mmol,2.0eq.), monitored by TLC, and quenched with sodium bisulfite after disappearance of starting material. Dilute with dichloromethane, wash with brine, combine the organic phases, dry over anhydrous sodium sulfate, filter with suction, concentrate and desolventize to give a white solid (272mg,0,8mmol, 80%). LC-MS (ESI) [ M + H] + ＝342.0。
Example 13
Preparation of the preparation:
1. suspending agent: weighing 20% of a compound shown in the formula (I), 2% of FS3000 (phosphate type anionic surfactant), 3% of NS-500LQ (nonionic hydroxy polyethylene oxide block copolymer), 0.5% of xanthan gum, 1.5% of magnesium aluminum silicate, 5% of ethylene glycol, 0.5% of organic modified siloxane defoaming agent and deionized water, adding to 100%, preparing into slurry, and sanding to obtain the product.
2. And (3) missible oil: weighing 25% of the compound of the formula (I), 15% of cyclohexanone, 8% of emulsifier and 20% of DMF, adding xylene to 100%, and shearing by a high-shear emulsifying machine to obtain the product.
3. Wettable powder: weighing 40% of the compound of the formula (I), 7% of sodium dodecyl benzene sulfonate, 10% of sodium lignin sulfonate and the balance of kaolin, and performing jet milling to obtain the product.
The above are all weight percentages.
Example 14
Dissolving the compound to be detected in N, N-dimethylformamide, and preparing the solution containing 0.1% Tween 80 into the solution to be detected with the required concentration for later use. Inoculating Tetranychus cinnabarinus to pea seedlings in the two-leaf period, investigating the cardinality, performing whole-plant spraying treatment by using a spraying tower, repeating the treatment for 3 times, placing the treated pea seedlings in a standard observation room, investigating the number of alive mites after 72 hours, and calculating the mortality.
Testing the compounds of the present application for pesticidal activity; and tested in parallel for acaricidal activity with the following compounds, a specific compound having the structure:
Figure BDA0003731027890000181
some of the test results are as follows:
when the concentration of the liquid medicine is 2ppm,
compounds with target mortality above 80% are: compounds 1-10, 12-16, 18-24, 26, 31-33, 36, control compound CK1-15, CK1, 8, 9, 10.
According to the method, part of compounds and control compounds CK1, 8, 9 and 10 are selected for carrying out parallel determination on tetranychus cinnabarinus killing activity, and the experimental results are shown in the following table:
tetranychus cinnabarinus killing activity control test:
Figure BDA0003731027890000182
Figure BDA0003731027890000191
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 para-substituted biphenyl thioether compound has a structural formula shown in a formula (I):
Figure FDA0003731027880000011
in the formula (I), the compound is shown in the specification,
R 1 selected from H, CN, halogen, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl radical, C 2 -C 6 Alkenyl radical, C 2 -C 6 Haloalkenyl, C 2 -C 6 Alkynyl, C 2 -C 6 Halogenated alkynyl, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy radical, C 3 -C 6 Cycloalkyl radical, C 3 -C 6 Alkylene oxide radical or C 3 -C 6 A cycloalkyloxy group;
n is an integer from 0 to 2.
2. The para-substituted diphenyl sulfide as claimed in claim 1, wherein in the formula (I),
R 1 selected from H, CN, halogen, C 1 -C 4 Alkyl, halo C 1 -C 4 Alkyl radical, C 2 -C 4 Alkenyl radical, C 2 -C 4 Haloalkenyl, C 2 -C 4 Alkynyl, C 2 -C 4 Halogenated alkynyl, C 1 -C 4 Alkoxy, halo C 1 -C 4 Alkoxy radical, C 3 -C 6 Cycloalkyl radical, C 3 -C 6 Alkylene oxide radicals or C 3 -C 6 A cycloalkyloxy group;
n is an integer from 0 to 2.
3. The para-substituted diphenyl sulfide as claimed in claim 2, wherein in the formula (I),
R 1 selected from H, CN, F, Cl, Br, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CHF 2 、CH 2 F、CF 3 、CCl 3 、CHCl 2 、CH 2 Cl、CBr 3 、CH 2 Br、CHBr 2 、CH 2 CF 3 、CH 2 CFH 2 、CH 2 CHF 2 Vinyl, ethynyl, MeO, EtO, n-PrO, i-PrO, n-BuO, i-BuO, s-BuO, t-BuO, cyclopropane, cyclopentane, cyclohexane, cyclopropaneoxy, cyclopentane oxy, or cyclohexane oxy;
n is 0 or 1.
4. The para-substituted diphenyl sulfide as claimed in claim 3, wherein in the formula (I),
R 1 selected from H, CN, F, Cl, Br, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CHF 2 、CH 2 F、CF 3 、CCl 3 、CHCl 2 、CH 2 Cl、CBr 3 、CH 2 Br、CHBr 2 、CH 2 CF 3 MeO, EtO, n-PrO, i-PrO, n-BuO, i-BuO, s-BuO, t-BuO, cyclopropane, cyclopentane, cyclohexane, cyclopropaneoxy, cyclopentane oxy, or cyclohexane oxy.
5. The para-substituted diphenyl sulfide as claimed in any one of claims 1 to 4, wherein in the formula (I),
R 1 is selected from CN、F、Cl、Br、Me、Et、n-Pr、i-Pr、n-Bu、i-Bu、s-Bu、t-Bu、CHF 2 、CH 2 F、CF 3 MeO, EtO, n-PrO, i-PrO, cyclopropane, cyclopentane, cyclohexane, cyclopropaneoxy, cyclopentane oxy, or cyclohexane oxy.
6. The para-substituted biphenyl sulfide compounds of claim 1, wherein in the formula (I),
R 1 selected from CN, F, Cl, Br, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CHF 2 、CH 2 F、CF 3 MeO, EtO, cyclopropane;
n is 0 or 1.
7. A para-substituted diphenyl sulfide as claimed in any one of claims 1 to 6 wherein the compound of formula (I) is selected from the group consisting of:
Figure FDA0003731027880000021
8. an insecticidal or acaricidal composition comprising an insecticidally or acaricidally effective amount of at least one of the para-substituted biphenyl sulfides of any one of claims 1 to 7; preferably, the composition also comprises a preparation carrier or a preparation auxiliary agent.
9. A method for controlling pests or mites which comprises applying an insecticidally or acaricidally effective amount of at least one of the para-substituted biphenylsulfides as claimed in any one of claims 1 to 7 or an insecticidally or acaricidally composition as claimed in claim 8 to the pests or mites and/or their habitat.
10. Use of at least one of the para-substituted diphenyl sulfides according to any one of claims 1 to 7 or the insecticidal or acaricidal composition according to claim 8 for controlling pests or mites in agriculture and other fields.
CN202210783893.6A 2022-07-05 2022-07-05 Para-substituted biphenyl thioether compound, composition and application thereof Active CN114957062B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202210783893.6A CN114957062B (en) 2022-07-05 2022-07-05 Para-substituted biphenyl thioether compound, composition and application thereof
PCT/CN2023/101703 WO2024007862A1 (en) 2022-07-05 2023-06-21 Para-substituted biphenyl thioether compound, composition, and use thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210783893.6A CN114957062B (en) 2022-07-05 2022-07-05 Para-substituted biphenyl thioether compound, composition and application thereof

Publications (2)

Publication Number Publication Date
CN114957062A true CN114957062A (en) 2022-08-30
CN114957062B CN114957062B (en) 2023-12-29

Family

ID=82966776

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210783893.6A Active CN114957062B (en) 2022-07-05 2022-07-05 Para-substituted biphenyl thioether compound, composition and application thereof

Country Status (2)

Country Link
CN (1) CN114957062B (en)
WO (1) WO2024007862A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024007862A1 (en) * 2022-07-05 2024-01-11 海利尔药业集团股份有限公司 Para-substituted biphenyl thioether compound, composition, and use thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999055668A1 (en) * 1998-04-27 1999-11-04 Kumiai Chemical Industry Co., Ltd. 3-arylphenyl sulfide derivatives and insecticides and miticides
WO2007034755A1 (en) * 2005-09-21 2007-03-29 Kumiai Chemical Industry Co., Ltd. Biphenyl sulfide compounds and insecticides and miticides
WO2013027660A1 (en) * 2011-08-23 2013-02-28 Ishihara Sangyo Kaisha, Ltd. Pesticide
CN108602768A (en) * 2014-10-24 2018-09-28 沈阳中化农药化工研发有限公司 A kind of biphenyl compound and its application
CN113943238A (en) * 2020-07-17 2022-01-18 沈阳中化农药化工研发有限公司 Substituted diphenyl sulfide compound and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009023910A (en) * 2007-07-17 2009-02-05 Kumiai Chem Ind Co Ltd Biphenyl sulfide compound and insecticidal or acaricidal agent
CN114957062B (en) * 2022-07-05 2023-12-29 海利尔药业集团股份有限公司 Para-substituted biphenyl thioether compound, composition and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999055668A1 (en) * 1998-04-27 1999-11-04 Kumiai Chemical Industry Co., Ltd. 3-arylphenyl sulfide derivatives and insecticides and miticides
WO2007034755A1 (en) * 2005-09-21 2007-03-29 Kumiai Chemical Industry Co., Ltd. Biphenyl sulfide compounds and insecticides and miticides
WO2013027660A1 (en) * 2011-08-23 2013-02-28 Ishihara Sangyo Kaisha, Ltd. Pesticide
CN108602768A (en) * 2014-10-24 2018-09-28 沈阳中化农药化工研发有限公司 A kind of biphenyl compound and its application
CN113943238A (en) * 2020-07-17 2022-01-18 沈阳中化农药化工研发有限公司 Substituted diphenyl sulfide compound and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024007862A1 (en) * 2022-07-05 2024-01-11 海利尔药业集团股份有限公司 Para-substituted biphenyl thioether compound, composition, and use thereof

Also Published As

Publication number Publication date
CN114957062B (en) 2023-12-29
WO2024007862A1 (en) 2024-01-11

Similar Documents

Publication Publication Date Title
JP4875608B2 (en) Insecticidal N-substituted sulfoximines
CN102264224B (en) Stable sulfoximine-insecticide compositions
KR101344974B1 (en) A method to control insects resistant to common insecticides
KR101364430B1 (en) Insecticidal n-substituted (6-haloalkylpyridin-3-yl)alkyl sulfoximines
KR101364350B1 (en) Insecticidal n-substituted (heteroaryl)cycloalkyl sulfoximines
KR101364355B1 (en) Multi-substituted pyridyl sulfoximines and their use as insecticides
JP5813825B2 (en) Insecticidal substituted azinyl derivatives
JP5248502B2 (en) Insecticidal N-substituted (2-substituted-1,3-thiazole) alkylsulfoximines
JP6469569B2 (en) N-substituted sulfilimines and sulfoximine pyridine N-oxides with insect control action
CN114957062A (en) Para-substituted biphenyl thioether compound, composition and application thereof
JP5781579B2 (en) Insecticidal (1,3,5) -triazinylphenylhydrazone
CN114605297B (en) Aryl sulfide containing substituted benzylamine structure, composition and application thereof
CN113563322B (en) Substituted benzamide isoxazoline derivative or salt acceptable as pesticide, composition and application thereof
CN113582987B (en) Substituted benzamide isoxazoline derivative or salt acceptable as pesticide, composition and application thereof
CN114516869A (en) Spirocyclic tetronic acid compound or salt and composition thereof acceptable as pesticide and application thereof
CN114149433A (en) Nitrogen-containing spiro derivative or salt thereof acceptable as pesticide, composition and application thereof
CN115433182A (en) Spiromesifen derivative or salt and composition thereof acceptable as pesticide and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant