CN108689928B - Quinoline derivative and preparation method and application thereof - Google Patents

Quinoline derivative and preparation method and application thereof Download PDF

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CN108689928B
CN108689928B CN201810798865.5A CN201810798865A CN108689928B CN 108689928 B CN108689928 B CN 108689928B CN 201810798865 A CN201810798865 A CN 201810798865A CN 108689928 B CN108689928 B CN 108689928B
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ethyl
dimethylquinolin
chloro
fluoro
formula
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CN108689928A (en
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唐剑峰
迟会伟
吴建挺
刘莹
李冬蓉
赵恭文
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SHANDONG UNITED PESTICIDE INDUSTRY CO LTD
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/22—Oxygen atoms attached in position 2 or 4
    • C07D215/233—Oxygen atoms attached in position 2 or 4 only one oxygen atom which is attached in position 4
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/60—Quinoline or hydrogenated quinoline ring systems

Abstract

The invention belongs to the technical field of insecticides and acaricides, and particularly relates to quinoline derivatives, and a preparation method and application thereof. Specifically disclosed is a compound represented by the formula (I) below or a salt thereof,

Description

Quinoline derivative and preparation method and application thereof
Technical Field
The invention belongs to the technical field of insecticides and acaricides, and particularly relates to a quinoline derivative and a preparation method and application thereof.
Background
Farmers have attempted to combat pests with insecticides since ancient greek and roman times. In the 20 th century, scientists sought a truly powerful insecticide for large-scale agricultural production. In 1939, swiss scientist paul muller discovered that the potent insecticide DDT (dichlorodiphenyltrichloroethane) became a milestone in the history of insecticide development. An Insecticide (Insecticide) refers to an agent that kills pests, such as beetles, flies, grubs, noseworms, springtails, whiteflies, and nearly ten thousand other pests. The use of the insecticide goes through several stages in sequence: natural pesticides and inorganic compounds were first discovered, but they were single acting, large in dose, and short in duration; organic chlorine, organic phosphorus and other organic synthetic pesticides are characterized by high efficiency and high residue or low residue, and many varieties of the pesticides have high acute toxicity to mammals.
After world war ii, a batch of organochlorine acaricides appeared, but the resistance of harmful mites increased with increasing use time. The type of the current acaricide is greatly developed, the acaricidal activity is greatly improved, and some acaricides which are safe to predatory mites appear. The development trend of acaricides is toward acaricides and insecticides.
Patent document EP0407192 discloses quinoline compounds represented by the following general formula and specific compounds, and the use of the compounds as agricultural insecticides.
Figure BDA0001736615970000011
Patent document US7022855 discloses quinoline compounds represented by the following general formula and specific compounds, and the use of the compounds as agents for controlling ectoparasites.
Figure BDA0001736615970000012
DE2361438 discloses quinoline compounds of the general formula and specific compounds and their use as agricultural pesticides.
Figure BDA0001736615970000021
Patent document EP48437a2 discloses quinoline compounds represented by the following general formula and a specific compound CK1, and the use of the compounds as agricultural pesticides.
Figure BDA0001736615970000022
However, the biological activity of the above compounds is still to be improved, and further development of insecticidal and acaricidal agents having excellent properties is still required.
Disclosure of Invention
In order to improve the above problems, the present invention provides a compound represented by the following formula (I), a stereoisomer, a racemate, a tautomer, an isotopic label, a nitroxide, or a pharmaceutically acceptable salt thereof,
Figure BDA0001736615970000023
r is selected from-COR1、-COOR1、-CONHR1、-CON(R1)2、-CSN(R1)2、-CSNHR1、-PS(OR1)2、-PO(OR1)2；
Each R1Identical or different, independently of one another, selected from the group consisting of unsubstituted or optionally substituted by one or more Rs1Substituted of the following groups: c1-40Alkyl or C3-20A cycloalkyl group;
R2、R3、R4identical or different, independently of one another, from the group consisting of unsubstituted or optionally substituted by one or more Rs2Substituted of the following groups: c1-40Alkyl radical, C3-20Cycloalkyl radical, C1-40An alkoxy group;
each Rs1、Rs2Identical or different, independently of one another, from the group consisting of F, Cl, Br, I, -OH, -SH, -CN, ═ O, -NO2、-NH2、C1-40Alkyl radical, C1-40Alkoxy radical, C1-40Alkylthio radical, C3-20Cycloalkyl or C6-20An aryl group;
X1selected from F, Cl, Br or I.
According to an exemplary embodiment of the invention, R is selected from-COR1、-COOR1、-CONHR1、-CON(R1)2、-CSN(R1)2、-CSNHR1、-PS(OR1)2OR-PO (OR)1)2Wherein each R is1Identical or different, independently of one another, from C1-6An alkyl group; for example, R1Selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.
According to an exemplary embodiment of the invention, R2、R3、R4Identical or different, independently of one another, from C1-6An alkyl group; for example, R2、R3、R4Identical or different, independently of one another, from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.
According to an exemplary embodiment of the invention, R is selected from-COCH3、-COCH2CH3、-COCH2CH2CH3、-COCH(CH3)2、-COCH2CH2CH2CH3、-COCH2CH(CH3)2、-COCH(CH3)CH2CH3、-COC(CH3)3、-COOCH3、-COOCH2CH3、-COOCH2CH2CH3、-COOCH(CH3)2、-COOCH2CH2CH2CH3、-COOCH2CH(CH3)2、-COOCH(CH3)CH2CH3、-COOC(CH3)3、-CONHCH3、-CON(CH3)2、-CSN(CH3)2、-PS(OEt)2、-PS(OMe)2、-PO(OEt)2、-PO(OMe)2。
According to an exemplary embodiment of the invention, X1Selected from F, Cl.
In the present invention, "a pharmaceutically acceptable salt thereof" refers to a salt which can be used in general agricultural and horticultural fields, such as hydrochloride, sulfate, phosphate, acetate, trifluoroacetate, malate, or citrate.
By way of example, the compound of formula (I) is selected from the following compounds,
Figure BDA0001736615970000031
Figure BDA0001736615970000032
Figure BDA0001736615970000041
exemplary groups and/or compounds of the present invention are described in the form of the above tables for the purpose of reducing the space of the specification.
The present invention also provides a process for the preparation of a compound of formula (I) as described above, comprising: reacting the compound shown in the formula (II) with the compound shown in the formula (III) or a compound R-L to obtain the compound shown in the formula (I),
Figure BDA0001736615970000042
r, R therein1、R2、R3、R4、X1Having the definition as described above, L is selected from a leaving group, such as Cl, Br, I or F.
According to the production method of the present invention, the reaction may be carried out in the presence of a base; the base is selected from organic base or inorganic base, and the organic base can be selected from organic amine such as triethylamine, pyridine and the like; the inorganic base may be one, two or more selected from sodium carbonate, potassium carbonate, sodium hydroxide, potassium tert-butoxide, sodium hydride or the like.
According to the production method of the present invention, the reaction may be carried out in a solvent; the solvent may be selected from one, two or more of aromatic hydrocarbon solvents, haloalkane solvents, nitrile solvents, ether solvents, amide solvents, for example, one, two or more selected from toluene, dichloromethane, 1, 2-dichloroethane, acetonitrile, tetrahydrofuran, N-dimethylacetamide, N-dimethylformamide, or dioxane.
According to the preparation method, the reaction temperature can be 0-120 ℃.
According to the production method of the present invention, the reaction can be carried out by a method described in patent document US3244586A or CN1193017A or other similar methods.
The compound represented by the formula (III) or the compound R-L can be synthesized by a method reported in the literature or obtained by purchase.
According to the invention, the preparation process also comprises the preparation of a compound of formula (II) comprising the following steps:
a) reacting a compound shown in a formula (IV) with a compound shown in a formula (V) to obtain a compound shown in a formula (II),
Figure BDA0001736615970000051
wherein R is2、R3、R4、X1Having the definitions as described above.
According to the invention, the reaction can be carried out with reference to the process described in patent document WO 2010007964.
The compounds of formula (V) can be synthesized by methods reported in the literature or obtained by purchase.
According to the invention, the preparation process also comprises the preparation of a compound of formula (IV), comprising the following steps:
b) reducing the compound shown in the formula (VI) to obtain a compound shown in a formula (IV);
Figure BDA0001736615970000052
wherein R is4、X1Having the definitions as described above.
According to the present invention, the reaction can be carried out by referring to the method described in handbook of organic Compound Synthesis 2011 edition.
The compounds of formula (VI) can be synthesized by literature-reported methods or obtained by purchase.
The preparation of the compounds of the formula (I) and their starting materials here can be carried out, depending on the reaction conditions and the choice of starting materials which are suitable in each case, by replacing, for example, in a one-step reaction only one substituent by another substituent according to the invention or by replacing, in the same reaction step, a plurality of substituents by further substituents according to the invention.
If the individual compounds are not obtainable via the above routes, they can be prepared by derivatizing the other compounds or by routinely varying the synthetic routes described.
After completion of the reaction, the reaction mixture can be worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, purifying the crude product by chromatography, for example on alumina or silica gel.
The pharmaceutically acceptable salts of the compounds of formula (I) of the present invention can be prepared by known methods. For example by suitable acid treatment to give an acid addition salt of the compound of formula (I). The preparation method comprises the following steps: the pharmaceutically acceptable salts of the compounds of formula (I) can be conveniently obtained by reacting the compounds of formula (I) with an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, trifluoroacetic acid, malic acid or citric acid in a solvent such as water, diethyl ether or toluene.
The above preparation process can obtain isomer mixture of the compound of formula (I), and if desired, pure isomer can be separated by conventional method such as crystallization or chromatography.
All reactions described above may conveniently be carried out at atmospheric pressure or the autogenous pressure of the particular reaction, unless otherwise indicated.
The present invention also provides a pesticidal composition, such as an insecticidal and/or acaricidal composition, comprising, as an active ingredient, one, two or more of a compound represented by formula (I), a stereoisomer, a racemate, a tautomer, an isotopic label, a nitrogen oxide, or a pharmaceutically acceptable salt thereof.
According to the invention, the active ingredient is present in the composition in a percentage by weight of 0.1 to 99.9%, for example 0.5 to 99%.
According to the invention, the composition also comprises one, two or more agriculturally and/or forestry and/or hygienically acceptable carriers.
According to the invention, the composition may be administered in the form of a formulation.
For example, the compounds of formula (I) as active ingredients are dissolved or dispersed in a carrier or formulated so as to be more easily dispersible for insecticidal and/or acaricidal use.
According to the present invention, the formulation includes, but is not limited to, the following forms: wettable powder, oil suspension, water suspension, aqueous emulsion, aqueous solution, missible oil or microcapsule and the like.
According to the invention, a liquid or solid carrier and optionally a surfactant may also be added to the composition.
The invention also provides application of one, two or more of the compounds shown in the formula (I), stereoisomers, racemates, tautomers, isotopic markers, nitrogen oxides or pharmaceutically acceptable salts thereof as pesticides, such as insecticides and/or acaricides.
The invention also provides application of one, two or more of the compounds shown in the formula (I), stereoisomers, racemates, tautomers, isotopic markers, nitrogen oxides or pharmaceutically acceptable salts thereof in preparing pesticides, such as insecticides and/or acaricides.
The invention also provides a method for controlling pests and/or harmful mites, which comprises applying an effective amount of one, two or more of the compounds shown in the formula (I), stereoisomers, racemates, tautomers, isotopic markers, nitrogen oxides or pharmaceutically acceptable salts thereof or applying the composition to a growth medium of the pests and/or the harmful mites.
According to the invention, the effective amount is from 10 to 1000 grams per hectare, preferably from 20 to 500 grams per hectare.
The active substances according to the invention or the active substances to be used according to the invention are suitable, in view of good plant tolerance, favourable warm-blooded animal toxicity and good environmental compatibility, for protecting plants and plant organs, increasing harvest yields, improving the quality of the harvest and for controlling animal pests, especially pests, mites and the like which occur in agriculture, horticulture, animal husbandry, forestry, gardens and leisure facilities, in the protection of pests and materials in warehouses, and in the hygiene sector. They are preferably used as plant protection compositions. They are active against conventional sensitive and resistant species and against all or individual developmental stages. The pests and mites include but are not limited to:
arthropoda, in particular Arachnida, such as, for example, the genus Amycolatopsis (Acarusssp.), the genus Citrus gall mites (Aceraschedoni), the genus Dermatophagoides (Aculops), the genus Acrophytopyrum (Aculops), the genus Acrophyticus (Acrophytospp), the genus Amblyomma sp, the genus Tetranychus (Amphiyranthus vivinus), the genus Argania (Arganis sp), the genus Boophilus sp, the genus Brevibacterium (Brevipalpus sp), the genus Bryobiageramus, the genus Bryopyrad (Bryopyradiferuptococcus sp), the genus Deuteroptera (Deyrophyllum sp), the genus Dermatophus (Dermatophus sp), the genus Dermatophagoides (Chloromyces sp), the genus Dermatophagoides (Dermatophagoides sp), the genus Dermatophagoides (Hypoglyphosatus sp), the genus Dermatophagoides (Hygrophytes), the genus Dermatophagoides sp), the genus Dermatophagoides (Hygrophytylenchus, the genus Dermatophagoides (Hygrophytin), the genus Dermatophagoides sp, the species Dermatophagoides sp, the genus Dermatophagoides sp, the Ebenaria (Hygrophytylenchus, the genus Dermatophagoides sp, the genus De, Venomous (Latrodectus spp.), Loxosceles spp, Tetranychus (Metatrenchus spp.), Neutratus, Nuphersa spp, Micronychus (Oligonchus spp.), Blastonella (Ornithodorous spp.), Ornithromycotus spp, Ornithronosus spp, Panonychus (Panonychus spp.), Phyllostachys citri (Phytocopterus spp.), Mitragus crenulata (Phytocopterus specvora), Tarsonemus laterosus (Polytarsonemus), Psortus (Psoroptes spp.), Phyllostachys flabellatus (Rhipicephalus spp.), Rhizopus spp., Rhizopus, Tetranychus (Rhynchus spp.), Tetranychus (Tetranychus spp.), Acarus sp., Tetranychus spus (Stepron spp.), Acarus sp., Tetranychus spp.), Tetranychus (Sterculia spyritus spp.), Acarus spp.);
coleoptera (Coleoptera) (beetle): bean species (Acanthoscelides spp.) (elephant), phaseolus vulgaris (Acanthoscelides obtectus) (common pisiform), Ceratoptera alba (Agrilus planipes) and Ceratopteris versicolor (Quadrifolia narrow Germin), Flammulina species (Agrimonia spp.) (wireworm), Anoplophora glabripes (Anopyra glabripennis) (Asian longhorn beetle), Gongosia species (Anthonoma spp.) (Arthrobacter flavidus), Gongosia grandis (Anthonomonus grandis) (Cotton bollworm), Cochloa species (Aphidius spp.), Arthrospora sp.) (Anoloides), Cochloa spp. (Anacardia) and Cochloa sinensis (Aponina spp.) (grub), Cochlothuroptera nigra (Atacnniphyllosporus spilus) (Black beetle) (Pieris), Pieris versicolor (Pieris versicolor) (Pieris indica (Pieris) and Pieris indica (Pieris grandis) and Pieris sinensis (Pieris) species (Pieris sinensis (Pieris) and Pieris variety (Pieris sinensis (Pieris) Pieris variety (Pieris sinensis (Pieris) and Pieris) Pieris (Pieris) such as Pieris (Pieris sinensis (Pieris) and Pieris (Pieris sinensis (Pieris variety (Pieris) and Pistospos) such as, Cacoesia species (Cacoesiaspp.), Callosobruchus maculatus (Callosobruchus macranthus), Callosobruchus maculatus (Callosobruchus chinensis), callosobrucea maculatus (carpopophilius humilis) (stemona), testudinate beetle (Cassida vittata), longifola species (ccroscrna spp.), callosoma species (Ccrotoma spp.), callosomon (chrysomella formosanus), callosobrucea chinensis (Ceromorpha) larva (Ceromorpha), callosophysa (Ceromorpha corpulenta), callosoma turtles (Ceromophycus purpurea), Chinese cabbage tortoiseshell (Ceromophycus purpurea), Brassica chinensis (Ceromophyceae) (callosophyceae), red cabbage beetle (Ceromophycus purpurea), red cabbage beetle (Ceromophycus), red cabbage beetle (Ceratophycus purpurea), red cabbage beetle (Ceromophycus (Ceratophycus), red beetle (Ceratophycus), red beetle (Ceratophysallow), red beetle (Ceromophys (Ceratophyceae), red beetle (Ceromophyceae), red beetle (Ceratophyceae), red beetle (Ceromophys (Ceromophyceae), red beetle (Ceratophyceae), red beetle (Ceratophys (Ceratophyceae), red beetle (Ceratophys (Cerato, Examples of such plants include, but are not limited to, Cryptolepis pusillus (Cryptolepis parvum), Cryptolepis pusillus (Cryptolepis granulosus), Cryptolepis species (Ctenora spp.) (nematodes), elephant species (Curculio spp.) (weevil), Rhinocephalus species (Cycleephora spp.) (Holotrichia dioides), Rhinocephalus pseudoptera (Cyclenophora spp.) (Holotrichia dioides), Rhinocephalus pseudoptera (Apolygus grandis), Rhinocephalus pseudoptera) (Rhinocephalus pseudoptera), Rhinocephalus pseudoptera (Deporus marginatus) (Rhinocephalus pseudoptera) (Mesorula-pectinifera), Rhinocephalus (Rhinocephalus pseudoptera), Rhinocephalus pseudoptera (Rhinocephalus) and Rhinocephalus pseudoptera (Membristylis), Rhinocephalus pseudoptera (Rhinocephalus) Pectinopsis), Rhinocephalus pseudoptera (Rhinocephalus) and Rhinocephalus (Pilus) Pilus chinensis (Membriae) or Rhinocephalus) Pilus (Pilus) Pilus chinensis), Rhinocarpus (Pilus) Pilus chinensis (Pilus) and Rhinocarpus) Pilus chinensis (Pilus) or Pilus chinensis (Pilus) Pilus chinensis) and Pilus chinensis (, Alfalfa leaf weevil (Hypera stictica) (alfalfa weevil), Hyperdos species (Hyperdoss spp.) (argentina stem weevil (Hyperodes weevil)), coffee berry silly (Hypertenemus hamperei) (coffee berry beetle), scolymus species (Ips spp.) (echinacea), tobacco beetle (Lasioderma serricorne) (tobacco beetle), potato beetle (leptotrichu deceleata) (colorado potato beetle), lipogloomys fuscus, lipogynys suturalis, rice water weevil (lissorophiurus oryzophilus) (rice water weevil), silchys species (lycopus sperti), western beetle (Mesorethrus) and Mesorethra tenera (Mesorethephora), Mesorethephora (Mesorrel), Mesorrel beetle (Mesorethephora), Mesorethephora spp Rhinoceros (oryteshoros) (date palm beetle), purchastetree beetle (O ryzaephiulus beetle), rhynchophorus rostratus (merchant grass beetle)), eupolyphaga species (oryphynchus spp) (elephant worm), black horn mud worm (ouema melanocarpus) (orange foot mud worm (cerealeaf beetle)), rice negative mud worm (ouma oryzae), rosewood short-beak elephant species (pandalous spp.) (elephant worm), japanese leafhopper species (phlophyr sephaga), ostrich beetle species (ostrich larva), ostrinia nubilalis (ostrich), ostrinia nubilalis (ostrinia nubilalis), ostrinia parva (ostrinia parva), ostrinia gille (ostrinia gilla), ostrinia gille (ostrinia gille), ostrinia gilla (ostrinia gille, ostrinia gilla (ostrinia gilla), ostrinia gilla (ostrinia fischerie (ostrinia), ostrinia gilla (ostrinia fischerie), ostrinia fischerie (ostrinia fischerie), ostrinia variety (ostrinia fischerie), ostrinia fischerie (ostrinia fischerie), ostrinia gilla variety (ostrinia fischerie), ostrinia fischerie (ostrinia fischerie), ostrinia variety (ostrinia fischerie), ostrinia fischerie (ostrinia fischerie, ostrinia variety (, The plant is selected from the group consisting of cryptorhynchus species (Rhynchophorus spp.) (elephant), silly species (scolytus spp.) (woodchuck moth), shonophorus species (shonophorus spp.) (elephant), pisum sativum leaf elephant (sitonalinus) (pea leaf weevil)), rice elephant species (Sitophilus spp.) (grain weevil), rice elephant (Sitophilus grandis), sessile beetle (steobium panicum) (medicinal material nail), sessile storehouse species (tribulium spp.) (ground beetle), terrestris castaneus (Tribolium grandis), and pseudoflorum purpureum (Tribolium), Tribolium grandis (Tribolium grandis) (Tribolium), Tribolium castaneum (Tribolium grandis) (Tribolium grandis), Tribolium castaneum purpurum (Tribolium castaneum), Tribolium castaneum (Tribolium castaneum), Tribolium castrum (Tribolium castaneum), and Tribolium castaneum (Tribolium carbolium Tribolium), Tribolium carbo.
Dermaptera (Dcrmaptcra) (earwigs).
Vein winged order (Dictyoptera) (cockroach): german cockroach (Blattella germanica) (German cockroach), Blatta orientalis (Blatta orientalis), Blatta palustris (cocitria pennymannica), Periplaneta americana (peri americana) (americana), Blatta australiana (peri australiana), Blatta australiana (australian cockroach), Periplaneta fusca (pcripta rubra) (brown cockroach)), Periplaneta fumosa (peri fuliginosa) (black chest cockroach (cockowbrin), and Periplaneta fuliginosa (brown cockroach)), and Periplaneta fuliginosa (brown cockroach) (Periplaneta rubra) and Periplaneta fuliginosa (brown stripe).
Diptera (Diptera) (flies): mosquito species (Aedes spp.) (mosquito), lucerne fly larvae (agromyzafreontella) (alfa blooms), agromyzis species ((Agromyza spp.) (leaf miner), trypetid species (anastrep spp.) (fruit fly), garlerya persica (anastrepa subsp.) (fruit fly), garlerya persica (garleria persica) (garleria persica (tail fly)), mosquito species (anophes spp.) (mosquito), fruit fly species (batura spp.) (fruit fly), melon fly (bactroceracuse) (melon), citrus fruit fly (bactrocera persicaria) (bactrocera persica), small strip fruit fly species (ceitis spp.) (fruit fly), sea fly larvae (sea fly) (sea fly larvae) (sea fly), sea fly larvae (sea fly larvae) (grub) (sea fly larvae) (sea fly) (mange sp.) (mange spy) (moth, sea fly) (moth larvae) (biles spp.) (fruit fly) (moth) (fruit fly) (mangostera, sea fly) (mangifera), sea fly larvae (sea fly) (mange fly) (mangifera) and sea fly (sea fly) (mange seed variety) (mange fly) (pig larvae) (mange fly) (mange seed) (mange fly) (mange seed variety 6324, sea fly) (moth larvae) (sea fly) (moth larvae) (mange fly) (, Leaf of rape mosquito (Dasineura brassicae) (cabbage mosquito), Dimochi species (Delia spp.), Grapholitha californica (Delia platura) root maggot (seed corn megaglot)), Drosophila species (Drosophila spp.) (vinegar fly), Musca species (Fannia spp.) (housefly), yellow belly fly (Fanniiscaria), summer belly fly (litter fly), Grey belly fly (grey belly fly) (Grey belly fly), Gasterophilus intestinalis (horse stomach), Gracillia persea, Haematobia irrita (Haematobia irris) (blackberry), Black fly species (Hyletia sp.) (root maggot) (root fly), Musca (skin brook.) (cabbage), Musca fly (leaf fly), Musca fly (cabbage fly), Musca fly (cabbage fly) (fly), Musca fly (leaf fly), Haemargia fly (leaf fly (cabbage fly) (fly), Musca fly (leaf fly) (fly, cabbage fly (leaf fly) (fly), Musca fly (leaf fly), Musca fly (leaf fly) (fly) and Mucora fly (leaf fly), Mucora fly (leaf fly), Musca fly (leaf fly) of Musca fly (leaf fly), Musca fly (leaf fly) of Musca fly, Musca fly (leaf fly), Musca fly (fly, The plant includes, but is not limited to, the species fall houseflies (Muscaa utumnalis) (fall flies (face flies)), houseflies (vusca domestica) (house flies)), sheep houseflies (oesterussovies) (sheep nose flies (sheet bot flies)), european houseflies (Oscinella fructis) (sweden houseflies), beet spring flies (Pegomyia beta) (spinach leaf flies (beetrofuminers)), musca spp (P. horbia spp.), carrot stem flies (Psila rosa) (carrot flies (carrotrus fly)), cherry fruit flies (cherry fruit flies), apple fruit flies (rhamnella pomonella (apple maggots)), red mud flies (citrus fruit flies) (yellow flies) (cattle fly (stable), and horse flies (stable flies)).
Hemiptera (Hemiptera) (stinkbug): apolygus lucorum (Acrosteronum hieron) (green stink bug), Oryza sativa (Black leucopterus), Oryza sativa (Black stink bug) (giant stink bug), Oryza sativa (sweet stink bug) (potato stink bug), Oryza sativa (sweet stink bug) (stink bug), Daghertussa scabra, Dichelops furcifera, Oryza sativa (brown stink bug), Oryza sativa (rice stink bug), Oryza sativa (brown stink bug) (Eugleus, Oryza sativa (brown stink, Oryza sativa, Oryza sativa (brown stink, Oryza) and Oryza sativa (green stink, Oryza sativa, Oryza variety (green stink, Oryza) and Oryza sativa, Oryza variety (green stink, Oryza variety (green stink, Oryza) and Oryza variety (green stink, Oryza variety (Oryza variety of Oryza variety, Oryza variety of Oryza variety, Oryza variety of Or, Hibiscus syriacus (major poison) neritinus, neuroolpus longirostris, lygus lucorum (Nezara viridula) (southern greestink bug), lygus lucorum (phylocoriss spp.) (lygus), california lygus lucorum (phytosporisorosis), phytoorius repens, Piezodorus guilidingdingi, tetranychius tetragonorrhinus (poecilocussus tetragonorrhinus) (folacinus fertilizer bug), arabius furcifolius vaccicola, pseudoacacia persica, ascoris caseosa and trypanosoma spp (trichomonas spp.) (hematophagus fasciatus)/hunting).
Homoptera (Homoptera) (aphid, scale, whitefly, leafhopper): piper pisum (Acrythosiphopkinsum) (pea aphid)), Coccinum species (Adelges spp.) (adelg ds), Beeurodera brassicae (Aleurodesoprelella) (Beechia cabbages), Aleuroderma sp (Aleuroderma di sposers), Beeurothyrius (Aleurothrix flcosus) (gloomyia whitlow), Begoniothyria albonensis (Aluraria dubia), Begonia biguella (Aluraria), Begonia sp (Aphrophophora sp.), Begonia rhododendron (Begoniothria), Begonia nilapa (Begonia), Begoniothiaca viridae (Begoniothiaspora), Begonia nilapa (Begoniothiaspora), Begoniothiaspora sp (Begoniothiaspora), Begoniothiaspora nilla indica (Begoniothiaca), Begoniothiaca spp. (Begonia), Begonia nilapa spp. (Begonia), Begoniothiaca) Aphis (Begoniothiaca), Begoniothiaca (Begoniothiaca), Begonia (Begoniothiaca), Begoniothiaca) Aphis, Begoniothiaca, Begonia (Begonia), Begoniothiaca) Aphis, Begoniothiaca (Begoniothiaca) Aphis, Begoniothiaca (Begonia (Begoniothiaca) and Begoniothiaca) species (Begoniothiaca) of the genus Begoniothiaca, Begonia (Begoniothiaca, Begonia, Begoniothiaca, Begoni, Asparagus tubular aphid (Brachyryyncria asparagi) (Asparagus aphid), Brevennia rehi, cabbage aphid (Brevicornyne brassiccus), Lecanicillium species (Ceriporiopsis sp.), Lecanicillium species (Ceripospora sp.), Lecanicillium species (Ceriporiopsis), Ceriporiococcus species (Ceriporiopsis rubens) (Red wax scale), Cestrumarium species (Chionaspip sp.), Icelosia species (Chrmophila sp.), Lecanis species (Ceriporiopsis sp.), Lecanis spp (Pyrococcus spp.), Phyllophyceae apple aphid (Phyllophysoporum), Phyllophysalospora indica (Phyllophysalis sp), Phyllophysalospora indica (Phyllophysallow), Phyllophysalospora spp (apple aphid), Phyllophysallow (Phyllophysallow), Phyllophysalospora spp (apple aphid), Phyllophysallow (apple aphid), Phyllo grandis) (Phyllop), Phyllostachydiplophora variety (Phyllophora), Leonii), Leoni grandis (Leoni), Phyllophysallow (Leoni grandis), Leoni (L) (Leoni), Leoni grandis), Leoni (Leoni), Leoni (Malpigeon grandis), Leoni (L. sp), Leoni (Malpigeon grandis (Malpigeon) and Leoni) variety (Malpigeon variety (Malpigeon, Malpigeon) and Leoni variety (L. plusia), Leoni variety (Malpigeon) and Leoni variety (L), C. grandi, Long pipe aphid (Macrosiphum rosae) (rose aphid), Quilamenta quadrangularis (Macrostes quadratus) (purple leaf aphid), Mahanarvafrimbiola, Meopodium graminis (rose grandis), Midis longicornis, Myzus persicae (Myzus persicae) (peach aphid), Nephotedina species (Nephotex spp.) (leafhopper), Nephotex cincticeps (Nephotex nigricans) (green leaf aphid), Nephophora niloticus (Paracoccus), Phosphaera melanosporus (Phosphaera), Phosphaera melanophora (leaf aphid), Phosphaera melanophora (leaf beetle), Phosphaera melanophora (leaf aphid), Phosphaera (Phosphaera), Phosphaera melanophora (leaf), Phosphaera melanophora (leaf), Phosphaera grandis (leaf beetle), Phosphaera (leaf beetle grandis), Phosphaera (Phosphaera) variety (Phosphaera), Phosphaera grandis (Phosphaera), Phosphaera) and Phosphaera (Phosphaera) variety (Phosphaera), Phosphaera (Phosphaera variety (Phosphaera) A sphaericoides, Phosphaera variety (leaf beetle, Phosphaera variety (leaf, Phosphaera) and Phosphaera variety (leaf spot, Phosphaerica melanophora variety (leaf strain, Helicoccus, Phosphaera) and Phosphaera, Helicoccus, Helico, Mealybugs (pseudococcus brcvpcs) (pincalplat mcaly bug), pernicia viridis (Quad raspidiotus perniciosus) (San Jose scale), aphid species (Rhapalosiphum spp.) (aphid) corn leaf aphid (corn leaf aphid)), cervus graminis (rhapalosiphus padi) (opa-cherry aphid), cerulophycus species (issetia spp.) (coccuskummer), cerulophycus elegans (saissetiae kummer) (black aphid), cervus viridis (schapishigella kummerma) (miyawarriophys), cerulophys viridis (singapophycus viridis) (green leaf aphid), cerulophys viridis (green leaf aphid), cerulophys viridis (green leaf aphid), cerulophycus viridis (green leaf aphid), cerulophycus (green leaf aphid), cerulophys (green leaf aphid), cerulophycus viridis (green leaf aphid, green leaf aphid (green leaf aphid, green leaf aphid (green leaf aphid, green leaf aphid, green leaf, The genus Tocopaia (Unaspis spp.) (Lecania), Tocopperas acutus (Unaspis yanonensis) (Arrowhead scale), and Zulia entreriana.
Hymenoptera (Hymenoptera) (ants, wasps and bees): incised leaf ant species (Acromyrmex spp.), Sinkiang leaf beehive (Athalia rosae), leaf ant species (Atta spp.) (Ieafcutting ants), black ant species (Camponotus spp.) (carpenter ant)), pine leaf bee species (Diprion spp.) (Blastus spp.) (Apis spp.)), Formica species (Formica spp.) (Ant), Argentina ant species (Iridogyrmex pollicis) (Argentina), Coccinum subnata (Monorium spp.) (Monochaeta spp.), small termite species (Soliotillum solvellaceae), Solenopsis (Solidaceae) (Pharmata spp.)), new pine leaf bee species (Neomeria spp.) (Melastus spp.)), and Melastus spp.) (Solidanus) (Melastus spp.) (Solidatus, Wasp species (vespela spp.) (yellow jack) and trichogramma species (Xylocopa spp.) (carpenter bee).
Isoptera (Isoptera) (termites): coptotermes spp, Coptotermes curcus, Coptotermes curcuminous, Coptotermes frutus, Coptotermes formosanus, Formosan subcotermena termite, Cornitermesp, Coptotermes terrestris, Coptotermes spp, Coptotermes terrestris, Heterotermes spp, Coptotermes formosanus, Coptotermes formotermes spp, Coptotermes terrestris sp, Coptotermes terrestris indica, Coptotermes terrestris formotermes spp, Coptotermes terrestrus spp, Coptotermes terrestris termes spp, Coptotermes terrestris termes terrestris, Coptotermes terrestrus termes terrestris, Coptotermes termes ter, Reticulitermes banyulensis, Spodoptera grassland (Reticulitermes grassei), Reticulitermes flavipes (Reticulitermes f la vi pes) (eastern soil-dwelling termites), Reticulitermes flavenii (Reticulitermes hagenii), West soil-dwelling termites (Reticulitermes heperus) (West soil-dwelling termites), Moraxella (Reticulitermes santonensis), North-dwelling soil-dwelling termites (Reticulitermes speratus), Reticulitermes nigripes (Reticulitermes tibialis), Reticulitermes virginicus (Reticulitermes virginicus), Reticulitermes formosanus species (Schedorthes spp.) and Zootes spp.
Lepidoptera (Lepidoptera) (moths and butterflies): achoea janata, Trichoides fusca (Adoxophyesspp.), Trichoides gossypii (Adoxophyceae orana), Gekko sp (Agrotis spp.), cutworm (Agrotis ipsilon) (Black cutworm), Trichoides gossypii (Alabama arginae) (Cotton leaf worm (cottonleaf worm), Amorbia cuneata, Amylosis tradiatricella (Na orange), Anacoptida defectecta, Spodoptera punctata (Na orange), Trichoides trichogramma (Anthriella), Trichoides kummer (Anarsia Lineata) (peach twigs borrer), Cochloa erecta (Anomorpha), Trichoides (Boiloptera), Trichoides punctata (Boiloptera), Trichoides (Bombycina) and leaf (leaf), Trichoides punctifera punctata (leaf), Pseudoptera punctata (Ostrinia) and leaf fall (leaf), Pseudoptera punctifera (leaf), Spodopterocarpus punctifera (Bodinaria), Spodoptera (Boyloptera), Spodopterocarpus punctifera (leaf), Spodoptera (Bodinifera), Spodoptera (Ostrinia) and Spodopterocarpus punctifera (Bodinifera), Spodoptera), Spyrifera (leaf), Sporicrocea) and Sporina (leaf, Spyrila) and Spodoptera (Bodinifera) and Spyrifera (leaf Capua reticulana, peach moth (Carposina niponensis) (peach fruit moth)), Phlebia species (Chilo spp.), mango lateral tail moth (Chuumetraversars) (mango shot bor), Choristoneura rosea (Choristoneura rosea) (Choristoneura roseola), Orthosiphon rosella (obliquus leaf roller), Spodoptera species (Chrysodeeixis spp.), Phlebia punctata (Cnaphalodendron punctatus) (Cnapellus (grass), Phaneria pulata (Colias spp.), Pleurotus litura (Graafflekura)), Sporidia sp., Choristoneura litura heteroclita (cabbage), Spodoptera litura (apple moth), Spodoptera litura heteroclita (apple stem moth) (apple stem moth (apple stem borer), Spodoptera litura heteroclita (moth), Spodoptera frugiperda (apple stem borer), Spodoptera frugiperda (moth (apple stem borer), Spodoptera (moth), Spodoptera frugiperda (moth (apple stem borer), Spodoptera (moth), Spodoptera frugiperda (moth), Spodoptera) and Spodoptera) species (Plutella) Sporidonnaea) and Sporina litura), Sporina (moth (Plutella) insect (Plutella) Sporigana) of Plutella) species (Plutella) and Plutella) Plutella frugiperda (Plutella) of Plutell, borer species (Diatraeassp.) (stem borer (staged borer)), sugarcane borer (Diatraea saccharalis) (sugaranee borer), southwestern corn stem borer (Diatraea grandiosella) (southwestern corn borer), diamond-back seed species (eariaspp.) (cotton bollworm), diamond-like diamond-back (Earias) and (eariao) diamond-back (eariao natula) (egyptianbornem), diamond-back (eariao) diamond-back (eariao. ella) (rougheri. bud), Ectopophaarrangement self-alumina, southern corn borer (easmopalpus lignosporus) (messenger corn borer), phomopsis lata (ostrinia), European pink moth (ostrinia (ostrinia), European pink moth (ostrinia nubila), European pink moth (ostrinia), ostrinia (ostrinia variety (ostrinia), ostrinia variety (ostrinia variety) (ostrinia), ostrinia variety (ostrinia variety) (ostrinia), ostrinia variety (ostrinia variety) (ostrinia), cne), ostrinia variety (ostrinia variety) (, The plant may be selected from the group consisting of primary cutworms (Euxoa auricularis) (armychus), cutworm species (felia spp.) (cutworms), hornworm species (Gortyna spp.) (stem borers), oriental moth (Grapholita molesta) (peach (apricot) fruit borer (original fruit moth)), trilobia (hedylella indica) (bean leaf borer (bean leaf webber)), cyan worm species (heliotropia spp.) (night moth), cotton bollworm (Helicoverpa armigera) (cottonbollworm), cotton bollworm (Helicoverpa armyworm) (helicoptera), cotton bollworm (Helicoverpa armyworm) (helicopterocarpa punctifera), cabbage looper (helicopterocarpa punctifera), seedling moth (helicopterocarpa punctifera) (corn borer/cotton worm)), solid moth species (helicopterocarpa sp.) (helicoptera), cabbage moth (cabbage looper), cabbage loopers (cabbage loopers) (cabbage loopers ) (cabbage loopers, loopers (cabbage loopers), and corn borers) (cabbage loopers, loopers, grape leaf borer (Lobesia botana) (grapple fruit moth), Loxagrotis species (Loxagrotissp.), noctuid (noctuid), soybean leaf beetle (Loxagrotis albocosta) (western bean crop), gypsy moth (Lymantria dispar) (gypsy moly), peach leaf miner (Lyonetherkella) (apple leaf moth (apple leaf miner)), oil palm bag moth (mahasencia acearum) (oil palm bat), broad leaf beetle (mangosteria spongia), leaf beetle (ostrinia), cabbage leaf moth (Mamestrauba indica) (cabbage leaf moth (cabbage armyworm) (tomato leaf moth (cabbage armyworm)), soybean leaf borer (Maruca), soybean leaf borer (diaphania), cabbage leaf borer (ostrinia), European cabbage leaf borer (ostrinia), European cabbage moth (ostrinia nubila (ostrinia), European cabbage moth (ostrinia nubila (ostrinia), European cabbage moth (ostrinia nubila (ostrinia) and ostrinia nubila (ostrinia nubila) or ostrinia (ostrinia nubila), European rice stem borer (ostrinia nubila) or ostrinia (ostrinia nubila) or ostrinia (ostrinia nubila), ostrinia nubila (ostrinia nubila) or ostrinia, Apple leaf rollers (Pandemis heparama) (brown apple tortrix), african reach (Papilio demodulcus), red bell moth (Pectinophora gossypiella) (pink bollworm (pinkborolmum)), oriental armyworm species (Peridroma spp.) (root cutting), mottled tiger (Peridroma saucia) (variegated cutworm), coffee leaf miner (Perilurella coffea) (white coffee leaf miner), potato leaf miner (Phorimaea operculella) (potato leaf miner), citrus leaf miner (Phyllanthus flavus), cabbage leaf miner (Phyllanthus nigra), cabbage leaf miner (Pieris grandiflora) (cabbage apple leaf moth) (cabbage looper), cabbage leaf moth (cabbage leaf moth) (cabbage looper), cabbage leaf miner (cabbage leaf moth) (cabbage looper), cabbage leaf moth (cabbage leaf moth) (cabbage leaf moth), cabbage leaf moth (cabbage leaf moth) (cabbage leaf, Pseudoplusia unipunctata (Spodoptera), Spodoptera frugiperda (Spodoptera), Spodoptera exigua (Spodoptera), Ectropicalis gigantea (Rachiplusia nu), Chilo supressalis (Chilo supressalis), Scopolia triforida (Scrphaga incertulas), Anthriscus sylvestris (Sesamia spp.), Sporidia punctata (Stemona), Spodoptera oryzae (Sesamiaifenestrans) (Pink rice stemona), Sesamina punctiferalis (Sesamia nigrella), Spodoptera punctata (Sesamina nigra), Spodoptera punctata (Sesamia nigra), Spodoptera litura (Spodoptera spongiosa), Spodoptera litura heterosporum (Spodoptera), Spodoptera frugiperda Spodoptera (Spodoptera), Spodoptera frugiperda (Spodoptera), Spodoptera) and Spodoptera (Spodoptera) A frugiperda (Spodoptera), Spodoptera (Spodoptera) are, The species of the genus Neplusia (Yponomeuta spp.), the dull coffee leopard moth (Zeuzeconffeae) (red branchborer), Zeuzerapyrina (leopard moth) and Spodoptera litura (Fabricius).
Mallophaga ((Mallophaga) feather louse (chewing lice)): ovine feather louse (Bovicola ovis) (sheeppbiting louse), turkey short horn feather louse (menacantheus stramineus) (chick feather louse) and chicken feather louse (Menopon gallinea) (common hen house).
Orthoptera (Orthoptera) (grasshopper, locust and cricket): arana nigra (anacrus simplex) (Mormon horns (Mormon cricket)), mole cricket (Gryllotalpidae) (mole cricket)), eastern asia migratory locust (Locusta migratoria), grasshopper species (Melanoplus spp.) (grasshopper), acephala wing spurs (microcentrumretrierve) (angular winged katydia (grasshopper)), pterophora species (pterophora spp.) (pterophora, steleophaga egr, pterygrosaurus (scuddita) (forked tail bush (fork tailed butydia)), and tuberous ridge (vanilloida).
Phthiraptera (Phthiraptera) (sucking lice): the blood sucking lice species (haemattopinnus spp.) (bovine lice and swine lice), sheep jaw lice (linogluchus ovilus) (sheep lice), head lice (pediluus humanus capitis) (body lice), human body lice (pediluus humanus (body lice) and crab lice (Pthirus pubis) (crab lice).
Siphonaptera (daphnaptera) (fleas): ctenocephalides canis (dog flea), Ctenocephalides felis (cat flea) and human flea (Pulex irutans) (human flea).
Thysanoptera (thrips): frankliniella fusca (Frankliniella fusca) (tobaco third), Frankliniella occidentalis (western flower) Frankliniella hultrias (western flower), Frankliniella shultzii (Frankliniella williamsii) (corn Thrips), Frankliniella glasshouse Thrips (IIelothrips hamoralidis) (greenhous third), Riphisprothrips cruentus, Scirpus sp (Sciroththrips spp), Platycodon grandiflorum (Scirthricirris) (citrus trough), Frankliniella tabacum (Scirthrips spp), Talothriparia (yellow Thrips spp), and Throughthrips (Thripus spp).
Thysanoptera (Thysanura) (bristletail): chlamydomonas species (Lepisma spp.) (silverfish) and locusta species (Thermobia spp.) (locusta spp.).
From the order of Acarina (Acarina) (mites (mite) and cicadas (tick)): woodbee shield mite (Acarapsis woodi) (parasitic mites in the trachea of bees), dermatophagoides farinae (Acarus spp.), dermatophagoides farinae (food mites), Acarus macrorhizus (Acarus sroro) (rice mite), mango bud mite (acaeriana mangifera) (mango bud mite), acanthophyceae (Acarus spp.), tomato sepedophytes (Acarus lycopersici) (tomato septemite), acanthophyceae (Acarus pellucida), Acarus procumbens (Acarus pellucekassia), acanthophyceae (Acarus pellucida), bovine sporus schaticus (acarpinophagus), apple septorius (apple septorius durus), american cottus (amymmalia mange), acarina (mangium fasciatus) (mangifer, mangium spp.), red mite (mangiferus spossilus spp), and mangrove sporus flavus sporus sp (mangiferus spp) Tetranychus species (Eottranus spp.), hornbeam Tetranychus (Eottranchus carpini) (yellow spider mite), Tetranychus sp. (Eriophylus spp.), hard tick species (I.; odes sp.) (tick), Tetranychus sp. (Metatrox spp.), Catharynus (Notoedres cati), Pediculus microplus species (Oligonychus spp.), Calonychus coffee mites (Oligonychus coffeeus), Pectilus graciliatus (Oligonychus coides), Tetranychus tarda (Oligonus callorus) (southern mite), Tetranychus urticae (Tetranychus urticae), Tetranychus urticae (Tetranychus urticae) (Tetranychus), Tetranychus urticae (Tetranychus urticae) (Rhynchus (Tetranychus), Tetranychus) (Tetranychus (Tetrastictus) and Tetrastictus (Tetrastictus) species (Tetrastictus), Tetrastictus) and Tetrastictus (Tetrasticus (Tetrastictus) as well as a) as a (Tetrastictus) as well as a) as a (Tetrasticus (Tetrastictus) as a (Tetrasticus) and Tetrasticus (Tetrastic, Scabies (Sarcoptes scabies) (itch mite), crocodile crown gall mite (tetragophthora perseafarae), Tetranychus species (Tetranychus spp.), Tetranychus urticae (Tetranychus urticae) (two spider mites (twospotter mite)) and Varroa destructor (Varroa destructor) (honey bee mite).
Nematoda (nematodes): the species Aphelenchoides (Aphelenchoides spp.) (bud and leaf and pine wood nematodes (budand leaf & pine wood nematodes)), the species nematodiasis (Belonolaevis spp.) (sting nematodies), the species Cyclotella minor (Criconema spp.) (ring nematodies), the species Dirofilaria immitis (Dirofilaria immitis) (dog heartword), the species Ditylenchus spp. (stem and bulb nematodes), the species Brachypoda (Heterodera spp.) (Cystodina), the species Heterocladia (Heterodera zeyla) (coenostylenchus nematodies), the species Heterocladia (Heterocladia zeyla) (coenospora nematodies), the species Heterophyllia (Hirsoniella spp.) (root knot nematode), the species Neurophylla spp. (Meloidogyne spp.) (root and Meloidogyne spp. (Meloidogyne spp.) (Meloidogyne) and Meloidogyne (Meloidogyne spp. (Meloidogyne) can) (Meloidogyne spp.) (root knot, the species (Meloidogyne incognita), the species (Meloidogyne spp.) (Meloidogyne) can), the species (Meloidogyne spp. (Meloidog -shaped neuron).
General class (general classes of insects): white pine worm (Scutigerella immaculata).
Owing to their positive properties, the compounds of the formula (I) can be used advantageously for protecting crops, domestic animals and livestock animals of agricultural and horticultural importance, as well as the environment customary for humans, against pests and/or mites.
The amount of the compound of formula (I) to be used to obtain the desired effect will vary depending on various factors such as the compound used, the crop to be protected, the type of pest, the extent of infection, the climatic conditions, the method of application and the dosage form employed.
The ingredients of the dosage forms or compositions described herein are selected in accordance with the physical properties of the active ingredient, the mode of application and environmental factors such as soil type, moisture and temperature.
Useful dosage forms include solutions such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspensions), and the like, which may optionally be viscous jellies. Useful dosage forms also include solids such as powders, granules, tablets, pills, films, and the like, which may be water dispersible ("wettable") or water soluble. The effective components can be microencapsulated and made into suspension or solid dosage form; in addition, the whole dosage form of the effective components can be encapsulated. The capsule can control or delay the release of the effective components. Sprayable formulations can be diluted in a suitable medium using spray volumes of about one to several hundred liters per hectare. The compositions in high concentrations are mainly used as intermediates for further processing.
Typical solid diluents are described in Watkins et al, Handbook of Instrument Dust Diluendsand Cariers, 2nd Ed., Dorland Books, Caldwell, N.J.. Typical liquid diluents are described in Marsden, Solventsguide, 2nd Ed., Interscience, New York, 1950. McCutcheon's Detergents and Emulsifiers annular, Allured pub. Corp., Ridgewood, New Jersey, and Sisely and Wood, Encyclopedia of Surface Active Agents, chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended applications. All formulations may contain small amounts of additives to reduce foaming, coalescence, corrosion, microbial growth, etc., or thickeners to increase viscosity.
Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, sulfonated dialkyl succinates, alkyl sulfates, alkyl benzene sulfonates, organosilanes, N, N-dialkyl taurates, lignosulfonates, aldehyde condensates for naphthalenesulfonates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers.
Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starches, sugars, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate, liquid diluents include, for example, water, N-dimethylformamide, dimethylsulfone, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffin, alkylbenzene, alkylnaphthalene, olive oil, castor oil, linseed oil, tung oil, sesame oil, corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil and cocoa oil, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, dodecanol and tetrahydrofurfuryl alcohol.
Solutions, including emulsifiable concentrates, can be prepared by simply mixing the components. Powders and fines can be prepared by mixing and the suspending agents are generally prepared by wet milling, usually by grinding in a hammer mill or liquid energy mill; see, for example, U.S. Pat. No. 3060,084, granules and pellets are prepared by spraying the active substance onto freshly prepared granular carriers or by granulation techniques. SeeBrowning, "Agglomerization", Chemical Engineering, Decumber 4, 1967, pp147-48, Perry's Chemical Engineering's Handbook, 4TH Ed., McGraw-Hill, New York, 1963, Pages 8-57and following, and WO 91/13546. The preparation of pellets is described in U.S.4172714, water dispersible and water soluble granules are described in U.S.4144050, U.S.3920442 and DE 3246493 to prepare tablets as described in US 5180587, U.S.5232701 and U.S. 5208030. Films may be prepared by the methods described in GB2095558 and u.s.3299566.
More information on processing can be found in U.S.3,235,361, Col.6, line 16through Chol.7, line19and EXAMPLES 10-41; U.S. Pat. No. 3,309,192, Col.5, line 43through Col.7, line 62and applications 8, 12, 15, 39, 41, 52, 53, 58, 132, 138, 140, 162, 164, 166, 167and 169-182; U.S.2,891,855, col.3, line 66through col.5, line 17and Examples 1-4; klingman, WeedControl as a Science, John Wiley and Sons, Inc., New York 1961, pp 81-96; andHandce et al, Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.
Herein, for certain applications of the composition, for example in agriculture, one, two or more other bactericides, acaricides, herbicides, plant growth regulators or fertilizers and the like may be added to the insecticidal and/or acaricidal composition of the invention, whereby additional advantages and effects may be produced.
Definition and description of terms
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the claimed subject matter belongs. All patents, patent applications, and publications cited herein are incorporated by reference in their entirety unless otherwise indicated. If there are multiple definitions of terms herein, the definition in this section controls.
It is understood that reference may be made to (including Carey and Sundberg "ADVANCED ORGANICCHEMISTRY 4THED. "Vols.A (2000) and B (2001), Plenum Press, New York). Unless otherwise indicated, conventional methods within the skill of the art are employed, such as mass spectrometry, NMR, IR and UV/Vis spectroscopy, and pharmacological methods. Unless a specific definition is set forth, the terms used herein in the context of analytical chemistry, organic synthetic chemistry, and the relevant description of pharmaceutical and pharmaceutical chemistry are known in the artIn (1). Standard techniques can be used in chemical synthesis, chemical analysis, pharmaceutical preparation, formulation and delivery, and treatment of patients. For example, the reaction and purification can be carried out using the manufacturer's instructions for use of the kit, or in a manner known in the art or as described herein. The techniques and methods described above can generally be practiced according to conventional methods well known in the art, as described in various general and more specific documents referred to and discussed in this specification. In the present specification, groups and substituents thereof may be selected by one skilled in the art to provide stable moieties and compounds. When a substituent is described by a general formula written from left to right, the substituent also includes chemically equivalent substituents obtained when a formula is written from right to left, as long as it complies with the valence rules. For example, CH2O is equivalent to OCH2The substitution position may be bonded with an oxygen atom or a carbon atom of a methylene group.
The term "C1-40Alkyl is understood to preferably mean a straight-chain or branched saturated monovalent hydrocarbon radical having from 1 to 40 carbon atoms, preferably C1-10An alkyl group. "C1-10Alkyl "is understood to preferably mean a straight-chain or branched, saturated monovalent hydrocarbon radical having 1,2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. The alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a 2-methylbutyl group, a 1-ethylpropyl group, a 1, 2-dimethylpropyl group, a neopentyl group, a 1, 1-dimethylpropyl group, a 4-methylpentyl group, a 3-methylpentyl group, a 2-ethylbutyl group, a 1-ethylbutyl group, a 3, 3-dimethylbutyl group, a2, 2-dimethylbutyl group, a 1, 1-dimethylbutyl group, a2, 3-dimethylbutyl group, a 1, 3-dimethylbutyl group or a 1, 2-dimethylbutyl group. In particular, the radicals have 1,2, 3, 4, 5, 6 carbon atoms ("C)1-6Alkyl groups) such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, more particularly groups having 1,2 or 3 carbon atoms ("C)1-3Alkyl groups) such as methyl, ethyl, n-propyl or isopropyl.
The term "C3-20Cycloalkyl is understood to mean a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3 to 20 carbon atoms, preferably "C3-10Cycloalkyl groups ". The term "C3-10Cycloalkyl "is understood to mean a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. Said C is3-10Cycloalkyl groups may be monocyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or bicyclic hydrocarbon groups such as decalin rings.
The term "C6-20Aryl "is understood to preferably mean a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6 to 20 carbon atoms, preferably" C6-14Aryl ". The term "C6-14Aryl "is to be understood as preferably meaning a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms (" C6-14Aryl group "), in particular a ring having 6 carbon atoms (" C6Aryl "), such as phenyl; or biphenyl, or is a ring having 9 carbon atoms ("C9Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C10Aryl radicals), such as tetralinyl, dihydronaphthyl or naphthyl, or rings having 13 carbon atoms ("C13Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C)14Aryl), such as anthracenyl.
The above for the term "alkyl", e.g. "C1-40The definition of alkyl "applies equally to compounds containing" C1-40Other terms for alkyl radicals, e.g. the term "C1-40Alkoxy group "," C1-40Alkylthio groups ", and the like.
The term "pharmaceutically acceptable salt" as used herein refers to salts that retain the biological potency of the free acid and free base of the specified compound, and that are biologically or otherwise non-adverse. The compounds of the present application also include pharmaceutically acceptable salts, such as nitrates, hydrochlorides, sulfates, phosphates, or the like. Pharmaceutically acceptableSalts refer to the form in which the base group in the parent compound is converted to a salt. Pharmaceutically acceptable salts include, but are not limited to, inorganic or organic acid salts of basic groups such as amine (amino) groups. Pharmaceutically acceptable salts of the present application can be synthesized from the parent compound by reacting a basic group in the parent compound with 1-4 equivalents of an acid in a solvent system. Suitable salts are listed in Remingtong's pharmaceutical sciences, 17thed., Mack Publishing Company, Easton, Pa.,1985, p.1418 and Journal of Pharmaceutical Science,66,2(1977), for example the hydrochloride salt.
The term "isotopic label" as used herein refers to isotopically labeled compounds of the present application.
"stereoisomers" as used herein refers to isomers resulting from the different arrangement of atoms in a molecule in space. The compounds of formula (I) contain asymmetric or chiral centers and, therefore, exist in different stereoisomeric forms. All stereostructures and mixtures of formula (I) are as such, including racemic mixtures, as part of the present application. Diastereomeric mixtures can be separated into the individual diastereomers, based on their different physicochemical properties, by well-known means, e.g., resolution of the enantiomers can be converted into the diastereomers by reaction with a suitable optically active substance (e.g., a chiral alcohol or Mosher's moylchloride), which can be separated and converted (e.g., hydrolyzed) into the corresponding individual isomers. Some of the compounds of formula (I) may be atropisomers (e.g., substituted aryl) are also part of this application. Enantiomers can also be separated using a chiral chromatography column. The compounds of formula (I) may exist in different tautomeric forms, which forms are included within the scope of the present application. For example, keto-enol and imine-enamine forms of the compounds.
Advantageous effects
The compound of formula (I) shows good activity to various pests and mites in agriculture or other fields. Furthermore, these compounds can be used for the preparation of insecticides and/or acaricides because of their excellent control effect at very low doses.
In addition, the compound has simple preparation steps and high yield, thereby having good application prospect.
The inventors of the present invention have also found that the X substituent at the 6-position and the substituent at the 7-position on the quinoline ring in the compound of formula (I) have a large influence on the activity of the compound, and thus the compound of the present invention exhibits an excellent controlling effect on bemisia tabaci, thrips occidentalis, and the like.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. The following examples are merely illustrative and explanatory of the present invention and should not be construed as limiting the scope of the invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The following chromatographic conditions were used for the LC-MS detection analysis in the examples below:
a chromatographic column: agilent ZORBAX SB-C18150 mm X4.6 mm, 5 μm (i.d);
detection wavelength: 254 nm; flow rate: 0.8 mL/min; column temperature: 30 ℃;
gradient elution conditions:
time (min) Acetonitrile (%) 0.1 aqueous formic acid solution (% by volume)
0.00 50 50
5.00 50 50
15.00 90 10
20.00 90 10
Synthetic examples
Example 1: preparation of 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-yl acetate (Compound 1)
Figure BDA0001736615970000181
The first step of reaction: preparation of isopropyl 2-amino-5-chloro-4-methylbenzoate: 33.6g (0.6mol) of iron powder, 0.048g of ammonium chloride, 60ml of ethanol and 12ml of water were added to a three-necked flask at room temperature, and a solution of 20.6g (0.08mol) of isopropyl 5-chloro-4-methyl-2-nitrobenzoate in 35ml of ethanol was added dropwise to the above mixture. Heated to reflux for 5 hours. Heating was stopped, filtration was carried out, ethanol was distilled off under reduced pressure, the pH was adjusted to alkalinity, and extraction was carried out with ethyl acetate (3X 25 ml). Recrystallization with methanol gave 12.7g of product with a yield of 70%.
The second step of reaction: preparation of 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ol: 11.37g (0.05mol) of isopropyl 2-amino-5-chloro-4-methylbenzoate, 8.6g (0.1mol) of 3-pentanone and 6.8g (0.05mol) of zinc chloride were dissolved in 120ml of xylene in this order at room temperature. The temperature was raised to reflux, and 4.5g (0.033mol) of zinc chloride was added to the reaction system and reacted for 30 hours. The reaction mixture was cooled to room temperature, 40ml of 15% dilute hydrochloric acid was added, filtration was carried out, the filter cake was washed with 100ml of methanol/water (1/1), and the product was obtained after drying in 60% yield. LC-MS [ M + H ]]+＝236.09、[M+Na]+＝258.07、[M+K]+＝274.04。
The third step of reaction: preparation of 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-yl acetate: 2.35g (0.01mol) of 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ol and 2.24g (0.02mol) of potassium tert-butoxide were dissolved in 30ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a cold bath. To the mixture was added 0.95g (0.012mol) of acetyl chloride in portions, the temperature was maintained below 20 ℃. After the addition, the reaction was carried out at room temperature for 4 hours. To the reaction system, 30ml of water was added, and extracted with ethyl acetate (3 × 30 ml). The organic layers were combined, washed with saturated brine (30ml), and dried over anhydrous magnesium sulfate. Decompression desolventizing, column chromatography to obtain 2.1g of product with 75% yield. LC-MS [ M + H ]]+＝278.10、[M+Na]+＝300.08、[M+K]+＝316.05。
Example 2: preparation of 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ylpropionate (Compound 2)
Figure BDA0001736615970000191
2.35g (0.01mol) of 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ol and 2.24g (0.02mol) of potassium tert-butoxide were dissolved in 30ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a cold bath. To the above mixture was added 1.1g (0.012mol) of propionyl chloride in portions, the temperature was maintained below 20 ℃. After the addition, the reaction was carried out at room temperature for 5 hours. To the reaction system, 30ml of water was added, and extracted with ethyl acetate (3 × 30 ml). The organic layers were combined, washed with saturated brine (30ml), and dried over anhydrous magnesium sulfate. Decompression desolventizing, column chromatography to obtain 1.9g of product with 65% yield. LC-MS [ M + H ]]+＝292.11、[M+Na]+＝314.09、[M+K]+＝330.06。
Example 3: preparation of 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ylbutyrate (Compound 3)
Figure BDA0001736615970000192
2.35g (0.01mol) of 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ol and 2.24g (0.02mol) of potassium tert-butoxide were dissolved in 30ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a cold bath. Adding 1.2 portions of the mixture8g (0.012mol) of butyryl chloride, the temperature being maintained below 20 ℃. After the addition, the reaction was carried out at room temperature for 5 hours. To the reaction system, 30ml of water was added, and extracted with ethyl acetate (3 × 30 ml). The organic layers were combined, washed with saturated brine (30ml), and dried over anhydrous magnesium sulfate. Decompression desolventizing, column chromatography to obtain 1.98g of product with 65% yield. LC-MS [ M + H ]]+＝306.13、[M+Na]+＝328.11、[M+K]+＝344.08。
Example 4: preparation of methyl 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ylcarbonate (Compound 9)
Figure BDA0001736615970000193
2.35g (0.01mol) of 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ol and 2.24g (0.02mol) of potassium tert-butoxide were dissolved in 30ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a cold bath. To the mixture was added 1.13g (0.012mol) of methyl chloroformate in portions, the temperature being maintained below 20 ℃. After the addition, the reaction was carried out at room temperature for 5 hours. To the reaction system, 30ml of water was added, and extracted with ethyl acetate (3 × 30 ml). The organic layers were combined, washed with saturated brine (30ml), and dried over anhydrous magnesium sulfate. Decompression desolventizing, column chromatography to obtain 2.2g of product with 75% yield. LC-MS [ M + H ]]+＝294.09、[M+Na]+＝316.07、[M+K]+＝332.04。
Example 5: preparation of 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ylcarbonate ethyl ester (Compound 10):
Figure BDA0001736615970000201
2.35g (0.01mol) of 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ol and 2.24g (0.02mol) of potassium tert-butoxide were dissolved in 30ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a cold bath. To the mixture was added 1.3g (0.012mol) of ethyl chloroformate in portions, the temperature was maintained below 20 ℃. After the addition, the reaction was carried out at room temperature for 5 hours. To the reaction system, 30ml of water was added, and extracted with ethyl acetate (3 × 30 ml). The organic layers were combined, washed with saturated brine (30ml), and dried over anhydrous magnesium sulfate. Decompression desolventizing, column chromatography to obtain 2.3g of product with 78% yield. LC-MS [ alpha ], [ alphaM+H]+＝308.11、[M+Na]+＝330.09、[M+K]+＝346.06。
Example 6: preparation of 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ylcarbonate isopropyl ester (Compound 12)
Figure BDA0001736615970000202
2.35g (0.01mol) of 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ol and 2.24g (0.02mol) of potassium tert-butoxide were dissolved in 30ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a cold bath. To the mixture was added 1.48g (0.012mol) of isopropyl chloride in portions, the temperature was maintained below 20 ℃. After the addition, the reaction was carried out at room temperature for 5 hours. To the reaction system, 30ml of water was added, and extracted with ethyl acetate (3 × 30 ml). The organic layers were combined, washed with saturated brine (30ml), and dried over anhydrous magnesium sulfate. Decompression desolventizing, column chromatography to obtain 2.2g of product with 70% yield. LC-MS [ M + H ]]+＝322.12、[M+Na]+＝344.1、[M+K]+＝360.07。
Example 7: preparation of 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ylmethyl carbamate (Compound 17)
Figure BDA0001736615970000203
2.35g (0.01mol) of 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ol and 2.24g (0.02mol) of potassium tert-butoxide were dissolved in 30ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a cold bath. To the mixture was added 1.12g (0.012mol) of methylcarbamoyl chloride in portions, the temperature was maintained below 20 ℃. After the addition, the reaction was carried out at 50 ℃ for 8 hours. To the reaction system, 30ml of water was added, and extracted with ethyl acetate (3 × 30 ml). The organic layers were combined, washed with saturated brine (30ml), and dried over anhydrous magnesium sulfate. Decompression desolventizing, column chromatography to obtain 1.6g of product with 55% yield. LC-MS [ M + H ]]+＝293.11、[M+Na]+＝315.09、[M+K]+＝331.06。
Example 8: preparation of 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-yldimethylcarbamate (Compound 18)
Figure BDA0001736615970000204
2.35g (0.01mol) of 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ol and 2.24g (0.02mol) of potassium tert-butoxide were dissolved in 30ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a cold bath. To the mixture was added 1.29g (0.012mol) of dimethylcarbamyl chloride in portions, the temperature being maintained below 20 ℃. After the addition, the reaction was carried out at 50 ℃ for 8 hours. To the reaction system, 30ml of water was added, and extracted with ethyl acetate (3 × 30 ml). The organic layers were combined, washed with saturated brine (30ml), and dried over anhydrous magnesium sulfate. Decompression desolventizing, column chromatography to obtain 1.53g of product with 50% yield. LC-MS [ M + H ]]+＝307.12、[M+Na]+＝329.1、[M+K]+＝345.07。
Example 9: preparation of oxy-6-chloro-2-ethyl-3, 7-dimethylquinolin-4-yldimethylaminothiocarbamate (Compound 19)
Figure BDA0001736615970000211
2.35g (0.01mol) of 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ol and 2.24g (0.02mol) of potassium tert-butoxide were dissolved in 30ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a cold bath. To the mixture was added 1.48g (0.012mol) of dimethylaminothiocarbonyl chloride in portions, the temperature being kept below 20 ℃. After the addition, the reaction was carried out at 50 ℃ for 8 hours. To the reaction system, 30ml of water was added, and extracted with ethyl acetate (3 × 30 ml). The organic layers were combined, washed with saturated brine (30ml), and dried over anhydrous magnesium sulfate. Decompression desolventizing, column chromatography to obtain 1.81g of product with the yield of 56%. LC-MS [ M + H ]]+＝323.10、[M+Na]+＝345.08、[M+K]+＝361.05。
Example 10: preparation of O-6-chloro-2-ethyl-3, 7-dimethylquinolin-4-yloxy, O-diethylthiophosphate (Compound 20)
Figure BDA0001736615970000212
2.35g (0.01mol) of 6-chloro-2-ethyl-3, 7-dimethylQuinoline-4-hydroxy, 2.24g (0.02mol) potassium tert-butoxide were dissolved in 30ml of N, N-dimethylacetamide in that order and cooled to 10 ℃ in a low temperature bath. To the above mixture was added 2.26g (0.012mol) of diethylthiophosphoryl chloride in portions, and the temperature was maintained below 20 ℃. After the addition, the reaction was carried out at 50 ℃ for 8 hours. To the reaction system, 30ml of water was added, and extracted with ethyl acetate (3 × 30 ml). The organic layers were combined, washed with saturated brine (30ml), and dried over anhydrous magnesium sulfate. Decompression desolventizing, column chromatography to obtain 1.93g, yield 50%. LC-MS [ M + H ]]+＝388.09、[M+Na]+＝410.07、[M+K]+＝426.04。
Example 11: preparation of 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-yl diethyl phosphate (Compound 22)
Figure BDA0001736615970000213
2.35g (0.01mol) of 6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ol and 2.24g (0.02mol) of potassium tert-butoxide were dissolved in 30ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a cold bath. To the above mixture was added 2.07g (0.012mol) of diethylphosphoryl chloride in portions, the temperature was maintained below 20 ℃. After the addition, the reaction was carried out at 55 ℃ for 6 hours. To the reaction system, 30ml of water was added, and extracted with ethyl acetate (3 × 30 ml). The organic layers were combined, washed with saturated brine (30ml), and dried over anhydrous magnesium sulfate. Decompression desolventizing, column chromatography to obtain 1.86g of product with 50% yield. LC-MS [ M + H ]]+＝372.12、[M+Na]+＝394.10、[M+K]+＝410.07。
Example 12: preparation of 2-Ethyl-6-fluoro-3, 7-dimethylquinolin-4-yl acetate (Compound 24)
Figure BDA0001736615970000221
The first step of reaction: preparation of isopropyl 2-amino-5-fluoro-4-methylbenzoate: 33.6g (0.6mol) of iron powder, 0.048g of ammonium chloride, 60ml of ethanol and 12ml of water were put into a three-necked flask at room temperature, and a solution of 19.3g (0.08mol) of isopropyl 5-fluoro-4-methyl-2-nitrobenzoate in 35ml of ethanol was added dropwise to the above mixture. Heated to reflux for 5 hours. Heating was stopped, filtration was carried out, ethanol was distilled off under reduced pressure, the pH was adjusted to alkalinity, and extraction was carried out with ethyl acetate (3X 25 ml). Recrystallization with methanol gave 12.6g of product with 75% yield.
The second step of reaction: preparation of 2-ethyl-6-fluoro-3, 7-dimethylquinolin-4-ol: 11.37g (0.05mol) of isopropyl 2-amino-5-fluoro-4-methylbenzoate, 8.6g (0.1mol) of 3-pentanone and 6.8g (0.05mol) of zinc chloride were dissolved in 120ml of xylene in this order at room temperature. The temperature was raised to reflux, and 4.5g (0.033mol) of zinc chloride was added to the reaction system and reacted for 30 hours. The reaction mixture was cooled to room temperature, 40ml of 15% dilute hydrochloric acid was added, filtration was carried out, the filter cake was washed with 100ml of methanol/water (1/1), and the product was obtained after drying in 66% yield. LC-MS [ M + H ]]+＝220.12、[M+Na]+＝242.10、[M+K]+＝258.07。
The third step of reaction: preparation of 2-ethyl-6-fluoro-3, 7-dimethylquinolin-4-yl acetate: 2.22g (0.01mol) of 2-ethyl-6-fluoro-3, 7-dimethylquinolin-4-ol and 2.24g (0.02mol) of potassium tert-butoxide were dissolved in 30ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a cold bath. To the mixture was added 0.95g (0.012mol) of acetyl chloride in portions, the temperature was maintained below 20 ℃. After the addition, the reaction was carried out at room temperature for 4 hours. To the reaction system, 30ml of water was added, and extracted with ethyl acetate (3 × 30 ml). The organic layers were combined, washed with saturated brine (30ml), and dried over anhydrous magnesium sulfate. Decompression desolventizing, column chromatography to obtain 1.8g of product with 72% yield. LC-MS [ M + H ]]+＝262.13、[M+Na]+＝284.11、[M+K]+＝300.08。
Example 13: preparation of methyl 2-ethyl-6-fluoro-3, 7-dimethylquinolin-4-ylcarbonate (Compound 32)
Figure BDA0001736615970000222
2.22g (0.01mol) of 2-ethyl-6-fluoro-3, 7-dimethylquinolin-4-ol and 2.24g (0.02mol) of potassium tert-butoxide were dissolved in 30ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a cold bath. To the mixture was added 1.13g (0.012mol) of methyl chloroformate in portions, the temperature being maintained below 20 ℃. After the addition, the reaction was carried out at room temperature for 5 hours. 30ml of water and ethyl acetate were added to the reaction system(3 x 30ml) extraction. The organic layers were combined, washed with saturated brine (30ml), and dried over anhydrous magnesium sulfate. Decompression desolventizing, column chromatography to obtain 1.9g of product with 70% yield. LC-MS [ M + H ]]+＝278.12、[M+Na]+＝300.10、[M+K]+＝316.07。
Example 14: preparation of 2-Ethyl-6-fluoro-3, 7-dimethylquinolin-4-ylmethyl carbamate (Compound 40)
Figure BDA0001736615970000231
2.22g (0.01mol) of 2-ethyl-6-fluoro-3, 7-dimethylquinolin-4-ol and 2.24g (0.02mol) of potassium tert-butoxide were dissolved in 30ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a cold bath. To the mixture was added 1.12g (0.012mol) of methylcarbamoyl chloride in portions, the temperature was maintained below 20 ℃. After the addition, the reaction was carried out at 50 ℃ for 8 hours. To the reaction system, 30ml of water was added, and extracted with ethyl acetate (3 × 30 ml). The organic layers were combined, washed with saturated brine (30ml), and dried over anhydrous magnesium sulfate. Decompression desolventizing, column chromatography to obtain 1.3g of product with 50% yield. LC-MS [ M + H ]]+＝277.14、[M+Na]+＝299.12、[M+K]+＝315.09。
Example 15: preparation of oxy-2-ethyl-6-fluoro-3, 7-dimethylquinolin-4-yl dimethylthiocarbamate (Compound 42)
Figure BDA0001736615970000232
2.22g (0.01mol) of 2-ethyl-6-fluoro-3, 7-dimethylquinolin-4-ol and 2.24g (0.02mol) of potassium tert-butoxide were dissolved in 30ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a cold bath. To the mixture was added 1.48g (0.012mol) of dimethylaminothiocarbonyl chloride in portions, the temperature being kept below 20 ℃. After the addition, the reaction was carried out at 50 ℃ for 8 hours. To the reaction system, 30ml of water was added, and extracted with ethyl acetate (3 × 30 ml). The organic layers were combined, washed with saturated brine (30ml), and dried over anhydrous magnesium sulfate. Decompression desolventizing, column chromatography to obtain 1.68g of product with 55% yield. LC-MS [ M + H ]]+＝307.13、[M+Na]+＝329.11、[M+K]+＝345.08。
The present invention also synthesizes the compounds in the following tables, with reference to the methods in the above examples, and the compounds and characterization results are shown in the following tables:
Figure BDA0001736615970000233
Figure BDA0001736615970000241
Figure BDA0001736615970000251
Figure BDA0001736615970000261
Figure BDA0001736615970000271
formulation examples
In the following examples, all percentages are by weight and all dosage forms are prepared using conventional methods.
Example 16:
in this example, the compound obtained in the above example is used to prepare a wettable powder, which is specifically prepared by using the following raw material compositions in proportion:
165.0% of compound, 2.0% of dodecylphenol polyethoxy glycol ether, 4.0% of sodium lignosulfonate, 6.0% of sodium aluminosilicate and 23.0% of montmorillonite (calcined).
Example 17:
in this example, granules were prepared using the compounds obtained in the above examples, specifically using the following raw material compositions:
210.0% of compound, 2% of sodium dodecyl sulfate as other components, 6% of calcium lignosulfonate, 10% of potassium chloride, 1% of polydimethylsiloxane and 100% of soluble starch.
Example 18:
in this example, the compound obtained in the above example is used to prepare an extruded pellet, specifically using the following raw material composition:
925.0% of compound, 10.0% of anhydrous calcium sulfate, 5.0% of crude calcium lignosulfonate, 1.0% of sodium alkyl naphthalene sulfonate and 59.0% of calcium/magnesium bentonite.
Example 19:
in this example, the compound obtained in the above example is used to prepare emulsifiable concentrate, and specifically, the emulsifiable concentrate is prepared by using the following raw material compositions:
1725.0% of compound, 15060% of solvent, PEG 4005% of Rhodacal 70/B3% of RhodameenRAM/77%.
Example 20:
in this example, the compound obtained in the above example is used to prepare an aqueous suspension, specifically, the following raw material composition is used to prepare the aqueous suspension:
1830.0%, POE polystyrene phenyl ether sulfate 5.0%, xanthan gum 0.5%, polyethylene glycol 5%, triethanolamine 1%, sorbitol 0.5% and water to 100.0%.
Biological activity assay
Example 21:
1. determination of insecticidal Activity
In this example, several insects were tested for insecticidal activity using the compounds prepared in the above examples.
And (3) testing the insecticidal activity: the test method is that a test compound sample is dissolved by a suitable solvent (the kind of the solvent is acetone, methanol, DMSO, etc., and is selected according to the dissolving capacity of the solvent on the sample) to prepare a test solution with a required concentration. The test cell consisted of a small open container containing 12-15 day old radish plants. The plants were pre-infested by placing 30-40 pests on a leaf of the test plant that was cut from a cultivated plant (leaf cutting method). As the leaves dehydrate, the pests move on the test plants. After pre-dip dyeing, the soil of the test cell was covered with a layer of sand.
The test method is as follows: the test was repeated three times, and after spraying the formulated test compound, each test unit was allowed to dry for 1 hour, and then a black mesh cap was placed on top. The test cells were kept in a growth chamber at 25 ℃ and 70% relative humidity for 6 days. Insect mortality was then visually assessed for each test unit.
(1) Test results for the control of myzus persicae by exemplary example Compounds
At a dose of 600ppm, the compounds with the lethality rate of more than 80% to the green peach aphids comprise: 1.2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46;
at a dose of 100ppm, the compounds with the lethality rate of more than 80% to the green peach aphids comprise: 1.2, 3, 4, 9, 10, 11, 12, 16, 17, 18, 19, 20, 24, 25, 26, 27, 32, 33, 34, 35, 40, 42;
at a dose of 50ppm, the compounds with the lethality rate of more than 80% to the green peach aphids comprise: 1.2, 9, 10, 12, 17, 18, 19, 24, 25, 32, 33, 40.
(2) Test results for exemplary example Compounds against Bemisia tabaci
At a dose of 600ppm, the compounds with the fatality rate of more than 80% to bemisia tabaci are as follows: 1.2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46;
at a dose of 100ppm, the compounds with the fatality rate of more than 80% to bemisia tabaci are as follows: 1.2, 3, 4, 5, 6, 9, 10, 11, 12, 13, 16, 17, 18, 19, 20, 21, 24, 25, 26, 27, 32, 33, 34, 35,36, 37, 38, 39, 40, 42, 44;
at a dose of 50ppm, the compounds with the fatality rate of more than 80% to bemisia tabaci are: 1.2, 3, 9, 10, 12, 17, 18, 19, 24, 25, 26, 27, 32, 33, 35, 40, 42.
(3) Test results for the control of Aphis gossypii by exemplary example Compounds
At a dose of 600ppm, the compounds with the lethality rate of more than 80% to cotton aphid comprise: 1.2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 24, 25, 26, 27, 28, 30, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46;
at a dose of 100ppm, the compounds with the lethality rate of more than 80% to cotton aphid comprise: 1.2, 3, 4, 9, 10, 11, 12, 16, 17, 18, 19, 24, 25, 26, 27, 32, 33, 34, 35, 40, 42;
at a dose of 50ppm, the compounds with a lethality rate of more than 80% to Aphis gossypii have the following characteristics: 1.2, 9, 10, 17, 18, 24, 25, 32, 33, 40.
(4) Test results for controlling frankliniella occidentalis by exemplary example Compounds
At a dose of 600ppm, the compounds with the fatality rate of more than 80 percent to frankliniella occidentalis have the following characteristics: 1.2, 3, 4, 9, 10, 11, 12, 13, 16, 17, 18, 19, 20, 21, 24, 25, 26, 27, 32, 33, 34, 35,36, 39, 40, 41, 42, 43, 44;
at a dose of 100ppm, the compounds with the fatality rate of more than 80 percent to frankliniella occidentalis have the following characteristics: 1.2, 4, 9, 10, 12, 17, 18, 19, 24, 25, 27, 32, 33, 35, 40, 41, 42;
at a dose of 50ppm, the compounds with the fatality rate of more than 80 percent to frankliniella occidentalis have the following characteristics: 1.2, 9, 10, 12, 17, 18, 19, 24, 25, 32, 33, 35, 40, 41, 42.
(5) Test results for exemplary example Compounds against Plutella xylostella
At a dose of 600ppm, the compounds with the fatality rate to plutella xylostella of more than 80 percent are: 1.2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46;
at a dose of 100ppm, the compounds with the fatality rate to plutella xylostella of more than 80 percent are: 1.2, 3, 4, 9, 10, 11, 12, 16, 17, 18, 19, 20, 21, 24, 25, 26, 27, 28, 29, 32, 33, 34, 35,36, 39, 40, 42, 44;
at a dose of 50ppm, the compounds with a mortality rate of more than 80% to plutella xylostella comprise: 1.2, 9, 10, 17, 18, 19, 24, 25, 26, 29, 32, 33, 35,36, 39, 42, 44.
(6) Test results of the exemplary embodiment Compounds for controlling Pieris rapae
At a dose of 600ppm, the compounds with a fatality rate of more than 80% to pieris rapae are: 1.2, 3, 4, 9, 10, 11, 12, 16, 17, 18, 19, 20, 21, 24, 25, 26, 27, 32, 33, 34, 35,36, 39, 40, 41, 42, 43, 44;
at a dose of 100ppm, the compounds with a fatality rate of more than 80% to pieris rapae are: 1.2, 9, 10, 11, 12, 17, 18, 19, 24, 25, 26, 32, 33, 34, 35,36, 39, 40, 42, 43;
at a dose of 50ppm, the compounds with a fatality rate of more than 80% to pieris rapae are: 1.2, 9, 17, 18, 19, 24, 25, 26, 32, 33, 35, 40, 42.
(7) Exemplary example Compounds control armyworm test results
At a dose of 600ppm, the compounds with a lethality of more than 80% to armyworm are: 1.2, 3, 4, 9, 10, 11, 12, 16, 17, 18, 19, 20, 24, 25, 26, 27, 32, 33, 34, 35,36, 39, 40, 41, 42, 43, 44;
at a dose of 100ppm, the compounds with a lethality rate of more than 80% to armyworm are: 1.2, 9, 10, 12, 17, 18, 19, 24, 25, 26, 27, 32, 33, 34, 35, 39, 40, 41, 42, 43, 44;
at a dose of 50ppm, the compounds with a lethality rate of more than 80% to armyworm are: 1.2, 9, 17, 19, 24, 25, 26, 32, 33, 35, 40, 42.
(8) Exemplary example Compounds control Prodenia litura test results
At a dose of 600ppm, the compounds with a mortality rate of more than 80% to prodenia litura comprise: 1.2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46;
at a dose of 100ppm, the compounds with a mortality rate of more than 80% to prodenia litura comprise: 1.2, 3, 4, 9, 10, 11, 12, 16, 17, 18, 19, 20, 21, 24, 25, 26, 27, 28, 29, 32, 33, 34, 35,36, 39, 40, 42, 44;
at a dose of 50ppm, the compounds with a mortality rate of more than 80% to prodenia litura comprise: 1.2, 9, 10, 17, 18, 19, 20, 24, 25, 26, 29, 32, 33, 35,36, 39, 42, 44.
(9) Test results for exemplary example Compounds to control Chilo suppressalis
At a dose of 600ppm, the compounds with the lethality rate of more than 80 percent to chilo suppressalis comprise: 1.2, 3, 4, 9, 10, 11, 12, 13, 17, 18, 19, 20, 21, 24, 25, 26, 27, 32, 33, 34, 35, 39, 40, 41, 42, 43, 44;
at a dose of 100ppm, the compounds with the lethality rate of more than 80 percent to chilo suppressalis comprise: 1.2, 3, 4, 9, 10, 12, 17, 19, 20, 24, 25, 26, 27, 32, 33, 34, 35, 40, 42, 43;
at a dose of 50ppm, the compounds with the lethality rate of more than 80 percent to chilo suppressalis comprise: 1.2, 3, 4, 9, 10, 12, 17, 24, 25, 26, 27, 32, 33, 34, 35, 40, 42.
(10) Test results for the control of rice leaf rollers by exemplary example Compounds
At a dose of 600ppm, the compounds with the lethality rate of more than 80 percent to rice leaf roller comprise: 1.2, 3, 4, 9, 10, 11, 12, 13, 16, 17, 18, 19, 20, 21, 24, 25, 26, 27, 32, 33, 34, 35,36, 39, 40, 41, 42, 43, 44;
at a dose of 100ppm, the compounds with the lethality rate of more than 80 percent to rice leaf roller comprise: 1.2, 4, 9, 10, 12, 17, 18, 19, 24, 25, 27, 32, 33, 35, 40, 41, 42;
at a dose of 50ppm, the compounds with the lethality rate of more than 80 percent to rice leaf roller comprise: 1.2, 9, 10, 12, 17, 18, 19, 24, 25, 32, 33, 40, 41, 42.
(11) Test results for controlling brown planthopper with exemplary example compounds
At a dose of 600ppm, the compounds with the fatality rate of more than 80% to brown planthopper comprise: 1.2, 3, 4, 9, 10, 12, 17, 18, 19, 20, 21, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46;
at a dose of 100ppm, the compounds with the fatality rate of more than 80 percent to brown planthopper comprise: 1.2, 3, 9, 10, 12, 17, 18, 19, 20, 21, 24, 25, 26, 27, 32, 33, 34, 35, 40, 42, 44;
at a dose of 50ppm, the compounds with the fatality rate of more than 80% to brown planthopper comprise: 1.2, 3, 9, 10, 12, 17, 18, 19, 24, 25, 26, 27, 32, 33, 35, 40.
2. Acaricidal Activity assay
In this example, several mite-killing activity tests were carried out using the compounds prepared in the above examples.
The test method is as follows: dissolving a compound sample to be detected with a suitable solvent (the kind of the solvent is acetone, methanol, DMSO, etc., and is selected according to the dissolving capacity of the solvent on the sample), and preparing the solution to be detected with the required concentration. The double-sided adhesive tape is cut into 2-3 cm long pieces, the pieces are attached to one end of a microscope slide, paper pieces on the adhesive tape are removed by tweezers, female adult mites which are consistent in size, bright in body color and lively in action are selected by a zero-number brush pen, the backs of the female adult mites are adhered to the double-sided adhesive tape (paying attention to the fact that the female adult mites do not stick to the mite feet, the mite beards and a mouth tool), 4 lines of the double-sided adhesive tape are adhered to each piece, and 10 heads of the double.
The test method is as follows: the test was repeated three times, and after 4 hours in a biochemical incubator at a temperature of (25+1) ° c and a relative humidity of about 85%, the dead or inactive individuals were removed by binocular observation. Soaking one end of the glass sheet with the mites into the liquid medicine, slightly shaking for 5s, taking out, and quickly sucking away the mites and the redundant liquid medicine around the mites with absorbent paper. Placing in the biochemical incubator, examining the result with binoculars after 24h, and touching mite body with writing brush to kill people with sufficient mites. The obtained data is used for solving a toxicity regression equation, LC50, a 95% confidence limit and a correlation coefficient by using DPS statistical software.
The following results were obtained for the Tetranychus cinnabarinus part:
at a dose of 600ppm, the compounds with the lethality rate of more than 80 percent to tetranychus cinnabarinus have the following components: 1.2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46;
at a dose of 100ppm, the compounds with the lethality rate of more than 80 percent to tetranychus cinnabarinus have the following components: 1.2, 3, 4, 9, 10, 11, 12, 16, 17, 18, 19, 24, 25, 26, 27, 32, 33, 34, 35, 39, 40, 41, 42;
at a dose of 50ppm, the compounds with the lethality rate of more than 80 percent to tetranychus cinnabarinus have the following components: 1.2, 9, 10, 17, 19, 24, 25, 26, 27, 32, 33, 35, 40, 42.
3. Test results for exemplary example compounds and control agents
This example performs a comparative test of the activity of exemplary compounds of the examples versus control agents (control agents CK-1, CK-2, CK-3, CK-4 and CK-5 were prepared by themselves according to the methods described in the literature). The test results are shown in the following table.
Figure BDA0001736615970000311
Figure BDA0001736615970000321
In addition to the compounds listed in the above table, other exemplary compounds of the present invention have better control activity against pests and mites than the control agents. Therefore, the compound shown as the formula (I) shows good activity to various pests and mites in the agricultural field.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (13)

1. A compound represented by the following formula (I) or a pharmaceutically acceptable salt thereof,
Figure FDA0002391981340000011
r is selected from-COR1、-COOR1、-CONHR1、-CON(R1)2、-CSN(R1)2、-CSNHR1、-PS(OR1)2、-PO(OR1)2；
Each R1Identical or different, independently of one another, from C1-4An alkyl group;
R2、R3identical or different, independently of one another, from C1-4An alkyl group;
R4identical or different, independently of one another, from methyl or ethyl;
X1selected from F, Cl, Br or I.
2. The compound of claim 1, wherein R is selected from the group consisting of-COR1、-COOR1、-CONHR1、-CON(R1)2、-CSN(R1)2、-CSNHR1、-PS(OR1)2OR-PO (OR)1)2Wherein each R is1Identical or different, independently of one another, from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl;
R2、R3identical or different, independently of one another, from C1-4An alkyl group; r4Is selected from methyl;
X1selected from F, Cl.
3. The compound according to claim 1 or 2, wherein the compound of formula (I) is selected from the following compounds:
6-chloro-2-ethyl-3, 7-dimethylquinolin-4-yl acetate
6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ylpropionate
6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ylbutanoate
6-chloro-2-ethyl-3, 7-dimethylquinolin-4-yl isobutyrate
6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ylvalerate
6-chloro-2-ethyl-3, 7-dimethylquinolin-4-yl 3-methylbutyrate
6-chloro-2-ethyl-3, 7-dimethylquinolin-4-yl 2-methylbutyrate
6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ylpivalate
6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ylcarbonate methyl ester
6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ylcarbonate ethyl ester
6-chloro-2-ethyl-3, 7-dimethylquinolin-4-yl-carbonate propyl ester
6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ylcarbonate isopropyl ester
6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ylcarbonate butyl ester
6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ylcarboic acid isobutyl ester
6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ylcarbonate sec-butyl ester
6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ylcarbonate tert-butyl ester
6-chloro-2-ethyl-3, 7-dimethylquinolin-4-ylmethyl carbamate
6-chloro-2-ethyl-3, 7-dimethylquinolin-4-yl dimethylcarbamate
Oxy-6-chloro-2-ethyl-3, 7-dimethylquinolin-4-yl dimethylthiocarbamate
Oxy-6-chloro-2-ethyl-3, 7-dimethylquinolin-4-yloxy, oxy-diethylthiophosphate
Oxy-6-chloro-2-ethyl-3, 7-dimethylquinolin-4-yloxy, oxy-dimethyl phosphorothioate
6-chloro-2-ethyl-3, 7-dimethylquinolin-4-yl diethylphosphate
6-chloro-2-ethyl-3, 7-dimethylquinolin-4-yl dimethylphosphate
2-Ethyl-6-fluoro-3, 7-dimethylquinolin-4-yl acetate
2-Ethyl-6-fluoro-3, 7-dimethylquinolin-4-ylpropionate
2-ethyl-6-fluoro-3, 7-dimethylquinolin-4-ylbutanoate
2-Ethyl-6-fluoro-3, 7-dimethylquinolin-4-yl isobutyrate
2-Ethyl-6-fluoro-3, 7-dimethylquinolin-4-ylvalerate
2-ethyl-6-fluoro-3, 7-dimethylquinolin-4-yl 3-methylbutyrate
2-Ethyl-6-fluoro-3, 7-dimethylquinolin-4-yl 2-methylbutyrate
2-Ethyl-6-fluoro-3, 7-dimethylquinolin-4-ylpivalate
2-Ethyl-6-fluoro-3, 7-dimethylquinolin-4-ylcarbonate methyl ester
2-Ethyl-6-fluoro-3, 7-dimethylquinolin-4-ylcarbonate ethyl ester
2-Ethyl-6-fluoro-3, 7-dimethylquinolin-4-yl-carbonate propyl ester
2-Ethyl-6-fluoro-3, 7-dimethylquinolin-4-ylcarbonate isopropyl ester
2-Ethyl-6-fluoro-3, 7-dimethylquinolin-4-yl-carboxylic acid butyl ester
2-Ethyl-6-fluoro-3, 7-dimethylquinolin-4-ylcarboic acid isobutyl ester
2-Ethyl-6-fluoro-3, 7-dimethylquinolin-4-ylcarbonate sec-butyl ester
2-Ethyl-6-fluoro-3, 7-dimethylquinolin-4-ylcarbonate tert-butyl ester
2-Ethyl-6-fluoro-3, 7-dimethylquinolin-4-ylmethyl carbamate
2-Ethyl-6-fluoro-3, 7-dimethylquinolin-4-yl dimethylcarbamate
Oxy-2-ethyl-6-fluoro-3, 7-dimethylquinolin-4-yl dimethylthiocarbamate
Oxy-2-ethyl-6-fluoro-3, 7-dimethylquinolin-4-yloxy, oxy-diethylthiophosphate
Oxy-2-ethyl-6-fluoro-3, 7-dimethylquinolin-4-yloxy, oxy-dimethyl phosphorothioate
2-Ethyl-6-fluoro-3, 7-dimethylquinolin-4-yl diethylphosphate
2-ethyl-6-fluoro-3, 7-dimethylquinolin-4-yl dimethylphosphate.
4. A process for the preparation of a compound of formula (I) as claimed in any one of claims 1 to 3, comprising: reacting the compound shown in the formula (II) with the compound shown in the formula (III) or a compound R-L to obtain the compound shown in the formula (I),
Figure FDA0002391981340000031
r, R therein1、R2、R3、R4、X1Having the definition as claimed in any of claims 1 to 3, L is selected from Cl, Br or I.
5. The process of claim 4, further comprising the step of preparing a compound of formula (II) comprising:
a) reacting a compound shown in a formula (IV) with a compound shown in a formula (V) to obtain a compound shown in a formula (II),
Figure FDA0002391981340000032
wherein R is2、R3、R4、X1Having the definition as set forth in any one of claims 1 to 3.
6. The process according to claim 4 or 5, further comprising the preparation of a compound of formula (IV) comprising the steps of:
b) reducing the compound shown in the formula (VI) to obtain a compound shown in a formula (IV);
Figure FDA0002391981340000033
wherein R is4、X1Having the claims1-3, as defined in any one of claims.
7. A pesticidal composition comprising, as an active ingredient, one or both of a compound represented by the formula (I) as described in any one of claims 1 to 3, or a pharmaceutically acceptable salt thereof.
8. The pesticidal composition according to claim 7, characterized in that it is an insecticidal and/or acaricidal composition.
9. Use of one or both of the compounds of formula (I) or a pharmaceutically acceptable salt thereof as claimed in any one of claims 1 to 3 as a pesticide, wherein the use is for diagnostic or therapeutic purposes other than disease.
10. Use according to claim 9, characterized in that the pesticide is an insecticide and/or acaricide.
11. Use of one or both of the compounds of formula (I) or a pharmaceutically acceptable salt thereof as claimed in any one of claims 1 to 3 in the preparation of a pesticide.
12. Use according to claim 11, characterized in that the pesticide is an insecticide and/or acaricide.
13. A method for controlling pests and/or mites which comprises applying an effective amount of one, two or more of the compounds of formula (I) or pharmaceutically acceptable salts thereof as claimed in any one of claims 1 to 3, or a composition as claimed in claim 7 or 8 to the growth medium of pests and/or mites, wherein said method is for non-disease diagnostic or therapeutic purposes.
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