CN111205223A - Quinoline derivatives, preparation method and application thereof - Google Patents

Quinoline derivatives, preparation method and application thereof Download PDF

Info

Publication number
CN111205223A
CN111205223A CN202010140315.1A CN202010140315A CN111205223A CN 111205223 A CN111205223 A CN 111205223A CN 202010140315 A CN202010140315 A CN 202010140315A CN 111205223 A CN111205223 A CN 111205223A
Authority
CN
China
Prior art keywords
formula
spp
compound
leaf
species
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010140315.1A
Other languages
Chinese (zh)
Other versions
CN111205223B (en
Inventor
许辉
唐剑峰
迟会伟
吴建挺
刘莹
徐龙祥
杨绎
李冬蓉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SHANDONG UNITED PESTICIDE INDUSTRY CO LTD
Original Assignee
SHANDONG UNITED PESTICIDE INDUSTRY CO LTD
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SHANDONG UNITED PESTICIDE INDUSTRY CO LTD filed Critical SHANDONG UNITED PESTICIDE INDUSTRY CO LTD
Priority to CN202010140315.1A priority Critical patent/CN111205223B/en
Publication of CN111205223A publication Critical patent/CN111205223A/en
Priority to PCT/CN2021/078867 priority patent/WO2021175249A1/en
Application granted granted Critical
Publication of CN111205223B publication Critical patent/CN111205223B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

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

Abstract

The invention belongs to the 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 derivatives, 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
Pesticides refer to chemical agents used to control pests. Including organic insecticides (organochlorine, organophosphorus, organosulfur preparations and carbamates and pyrethroids), inorganic insecticides (inorganic arsenic, inorganic fluorine, inorganic sulfur preparations), botanical insecticides, mineral oil insecticides, microbial insecticides, and the like.
The pesticide plays an extremely important role in solving the problem of human grain in agricultural production increase. 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 CN1688193A discloses a mixed composition for controlling parasites, which comprises quinoline compounds represented by the following general formula and a specific compound CK1(Compound No. 61) CK2(Compound No. 64):
Figure BDA0002398859190000011
however, the biological activity of the above compounds is still to be further improved.
The inventor of the present invention discloses in the prior application CN108689928ACompounds of the general formula and specific compounds CK3(Compound No. 9) CK4(Compound No. 32).
Figure BDA0002398859190000012
The inventors have further conducted intensive studies to find an insecticidal/acaricidal agent having more excellent properties.
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, a nitrogen oxide thereof, or a pharmaceutically acceptable salt thereof,
Figure BDA0002398859190000021
r is selected from-COR1or-COOR1；
Each R1Identical or different, independently of one another, from C1-12An alkyl group;
R2、R3、R4identical or different, independently of one another, from the group consisting of F, Cl, Br, I, C1-12Alkyl, or C1-12An alkoxy group;
x is selected from F, Cl, Br or I.
According to an embodiment of the present invention, in formula (I),
r is selected from-COR1or-COOR1；
Each R1Identical or different, independently of one another, from C1-4An alkyl group;
R2、R3、R4identical or different, independently of one another, from F, Cl, Br, I or C1-4An alkyl group;
x is selected from F or Cl.
According to an exemplary embodiment of the invention: in the formula (I)
R is selected from-COR1or-COOR1；
R1Is selected from C1-4An alkyl group;
R2、R3、R4identical or different, independently of one another, from C1-4An alkyl group;
x is selected from F or Cl.
By way of example, the compound of formula (I) is selected from the following compounds,
Figure BDA0002398859190000022
Figure BDA0002398859190000023
Figure BDA0002398859190000031
Figure BDA0002398859190000041
the invention also provides a preparation method of the compound shown as the formula (I), which comprises the following steps: reacting the compound shown in the formula (II) with the compound shown in the formula (III) or the compound R-L shown in the formula (III-1) to obtain the compound shown in the formula (I),
Figure BDA0002398859190000042
r, R therein1、R2、R3、R4X has the meaning as defined above and L is selected from leaving groups such as Cl, Br, I or F.
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 of the invention, the reaction temperature can be 0-120 ℃, for example 5-30 ℃.
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 preparation method of the present invention, the reaction can be carried out by a method described in patent documents CN108689928A, US 3244586A or CN1193017A, or other similar methods.
The compound represented by the formula (III) or the compound R-L represented by the formula (III-1) can be synthesized by a method reported in the literature or obtained by purchase.
According to an embodiment of the invention, the preparation process further comprises the preparation of a compound of formula (II) comprising the steps of:
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 BDA0002398859190000051
wherein R is2、R3、R4X has the definition as described above; r5Is C1-4Alkyl groups such as methyl, ethyl, and the like.
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 an embodiment of the invention, the preparation process further comprises 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 BDA0002398859190000052
wherein R is4X has the definition as described above; r5Is C1-4Alkyl groups such as methyl, ethyl, and the like.
According to an embodiment of the present invention, the reaction can be carried out by referring to a method described in handbook of organic compound synthesis 2011 edition, or can be obtained by purchase.
According to an embodiment of the invention, the preparation process further comprises the preparation of a compound of formula (VI) comprising the steps of:
c) nitrifying a compound shown in a formula (VIII) to obtain a compound shown in a formula (VII), and esterifying to obtain a compound shown in a formula (VI);
Figure BDA0002398859190000053
wherein R is4X has the definition as described above; r5Is C1-4Alkyl groups such as methyl, ethyl, and the like.
According to an embodiment of the invention, the reaction can be carried out as described in Tetrahedron Letters 56(2015) 2860-2862.
According to an embodiment of the present invention, the compound of formula (II) may also be prepared by a process comprising the steps of:
Figure BDA0002398859190000054
reacting the compound shown in the formula (IX) with the compound shown in the formula (X) to obtain a mixture shown in the formula (II) and the formula (II-I), and separating and purifying to obtain the compound shown in the formula (II).
Wherein R is2、R3、R4X has the definition as described above; r5Is C1-4Alkyl groups such as methyl, ethyl, and the like.
According to an embodiment of the invention, the reaction can be described in patent documents WO2010151737 or Journal of medicinal Chemistry,49(21), 6351-; 2006.
The compounds represented by the formulae (IX) and (X) can be synthesized by methods reported in the literature 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, a nitrogen oxide, or a pharmaceutically acceptable salt thereof.
According to an embodiment of the invention, the active ingredient is present in the composition in an amount of 0.1 to 99.9% by weight, for example 0.5 to 99% by weight.
According to an embodiment of the invention, one, two or more agriculturally and/or forestry and/or hygienically acceptable carriers are also included in the composition.
According to an embodiment of 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 an embodiment of the 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 embodiments of 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, 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, nitrogen oxides or pharmaceutically acceptable salts thereof in preparation of 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, 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 an embodiment of 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.) (wasp (sawfly)), ant species (Formica spp.) (Ant), Argentina ant species (Iridogyrmex pollicis) (Argentineant), Coccinum subspecies (Monorium spp.) (Monoformica spp.), little ant species (Solidarium Solenopsis (Solidaceae) (Pharmata Solenopsis (Solidaceae)), new pine leaf bee species (Neomeria spp.) (Melastus spp.)), family bee species (Solidago spp.) (Melastus spp.) (Solidago spp.) (Solidago), and species (Solidago spp.) (Solidago) 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.), Heliothis virescens (Stemona), Heliothis oryzae (Sesamia infrens) (Pink rice stembopogonis), Heliothis virescens (Sesamia nigrella), Spodoptera virescens (Sesamina nigrella), Spodoptera punctata (Sesamia nigeri), Spodoptera virescens (Spodoptera), Spodoptera armyworm (Spodoptera), Spodoptera frugiella armyworm (Spodoptera), Spodoptera frugiperda (Spodoptera), Spodoptera spp., Spodoptera), Spodoptera frugiperda (Spodoptera) and Spodoptera (Spodoptera) variety (Spodoptera) including Spodoptera variety (Spodoptera) and Spodoptera variety (Spodoptera) including Spodoptera variety (Spodoptera) such as, 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 forthThe terminology used herein in the pertinent description of analytical chemistry, organic synthetic chemistry, and pharmaceutical chemistry is known in the art. 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 "C1-12Alkyl is understood to mean a straight-chain or branched saturated monovalent hydrocarbon radical having from 1 to 12 carbon atoms. Preferably "C1-6Alkyl group and C1-6Alkyl "denotes straight and branched chain alkyl groups having 1,2, 3, 4, 5, or 6 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, a 2, 2-dimethylbutyl group, a 1, 1-dimethylbutyl group, a 2, 3-dimethylbutyl group, a 1, 3-dimethylbutyl group or a 1, 2-dimethylbutyl group.
The term "C1-12Alkoxy "denotes-O-C1-12Alkyl radical, wherein C1-12Alkyl groups have the above definitions.
The term "pharmaceutically acceptable salt" as used herein means that the designation is retainedSalts of the compounds which are biologically or otherwise not adversely affected by the biological potency of the free acid and free base. The compound of the present application also includes pharmaceutically acceptable salts, such as nitrate, hydrochloride, sulfate, phosphate, acetate, trifluoroacetate, malate, citrate and the like, which can be generally used in the field of agriculture and horticulture. Pharmaceutically acceptable salts 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.
"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 substituent at the 5-position and the X-substituent at the 6-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) Methanol (%) 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, 5-dimethylquinolin-4-yl acetate (Compound 1)
Figure BDA0002398859190000171
The first step of reaction: preparation of 3-chloro-2-methyl-6-nitrobenzoic acid: 17.1g (0.1mol) of 3-chloro-2-methylbenzoic acid and 130g (1.3mol) of concentrated sulfuric acid were added to a three-necked flask at room temperature, stirred, and cooled to 0 ℃ in an ice bath. 7.7g (0.12mol) of fuming nitric acid is dripped into the mixture, and the temperature is maintained at 0-5 ℃. After 30min, the reaction was continued at 0 ℃ for 5 h. The reaction solution was added dropwise to 230ml of water at 0 ℃ and 20 min. White solid is separated out, filtered and dried in vacuum to obtain 18g of product with the yield of 83.7 percent. LC-MS [ M + H ]]+＝216.01、[M+Na]+＝237.99、[M+K]+＝253.96。
The second step of reaction: preparation of isopropyl 3-chloro-2-methyl-6-nitrobenzoate: 13g (0.06mol) of 3-chloro-2-methyl-6-nitrobenzoic acid, 10g (0.072mol) of potassium carbonate and 50ml of N, N-dimethylformamide are stirred at room temperature in a three-necked flask. To the above mixture was added in portions 12.5g (0.072mol) of iodoisopropane. After the addition, the reaction was continued for 3 hours at room temperature with stirring. 200ml of water was added to the above reaction solution. Ethyl acetate (3 × 80ml) was extracted and the organic phases combined. Washed with saturated saline (80 ml). Dried over anhydrous sodium sulfate. And (5) filtering. Vacuum concentrating to obtain 8.1g product with yield of 52%.
LC-MS[M+H]+＝258.06、[M+Na]+＝280.04、[M+K]+＝296.01。
The third step of reaction: preparation of isopropyl 6-amino-3-chloro-2-methylbenzoate: 16.8g (0.3mol) of iron powder, 0.024g of ammonium chloride, 40ml of ethanol and 8ml of water were put into a three-necked flask at room temperature, and a 20ml ethanol solution of 7.8g (0.03mol) of isopropyl 3-chloro-2-methyl-6-nitrobenzoate was added dropwise to the above mixture. Heated to reflux for 5 hours. The heating was stopped, the filtration was carried out, the ethanol was distilled off under reduced pressure, and 50ml of ethyl acetate and 20ml of water were added to the residue and washed once. The organic phase was dried over anhydrous sodium sulfate. Filtering, and concentrating the filtrate under reduced pressure. The methanol is recrystallized to obtain 4.3g of product with the yield of 62 percent.
LC-MS[M+H]+＝228.08、[M+Na]+＝250.06、[M+K]+＝266.03。
And a fourth step of reaction: preparation of 6-chloro-2-ethyl-3, 5-dimethylquinolin-4-ol: 3.5g (0.015mol) of isopropyl 6-amino-3-chloro-2-methylbenzoate, 2.8g (0.03mol) of 3-pentanone and 2.2g (0.015mol) of zinc chloride were dissolved in 40ml of xylene in this order at room temperature. The temperature is raised to reflux, 1.5g (0.01mol) of zinc chloride is added into the reaction system, and the reaction is carried out for 30 hours. The reaction mixture was cooled to room temperature, 15ml of 15% dilute hydrochloric acid was added, suction filtration was carried out, the filter cake was washed with 35ml of methanol/water (1/1), and after drying, 2.1g of the product was obtained, yield 58%. LC-MS [ M + H ]]+＝236.09、[M+Na]+＝258.07、[M+K]+＝274.04。
The fifth step of reaction: preparation of 6-chloro-2-ethyl-3, 5-dimethylquinolin-4-yl acetate: 1.18g (0.005mol) of 6-chloro-2-ethyl-3, 5-dimethylquinolin-4-ol and 1.12g (0.01mol) of potassium tert-butoxide were dissolved in 15ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a low-temperature bath. To the above mixture was added 0.48g (0.006mol) 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 was added 20ml of water, and extracted with ethyl acetate (3 × 10 ml). The organic layers were combined, washed with saturated brine (15ml), and dried over anhydrous magnesium sulfate. The organic phase is decompressed and desolventized, and the product is obtained by column chromatography (eluent: ethyl acetate: petroleum ether (1:6)) with the yield of 68 percent, wherein the weight of the product is 0.95 g.
LC-MS[M+H]+＝278.10、[M+Na]+＝300.08、[M+K]+＝316.05。
1H-NMR (400MHz, solvent CDCl)3)δ(ppm):7.92(1H,m),7.46(1H,dd),3.02(2H,q),2.67(3H,s),2.56(3H,s),2.52(3H,s),1.36(3H,t)。
Example 2: preparation of 6-chloro-2-ethyl-3, 5-dimethylquinolin-4-ylpropionate (Compound 2)
Figure BDA0002398859190000181
1.18g (0.005mol) of 6-chloro-2-ethyl-3, 5-dimethylquinolin-4-ol and 1.12g (0.01mol) of potassium tert-butoxide were dissolved in 15ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a low-temperature bath. To the above mixture was added in portions 0.6g (0.006mol) of propionyl 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 was added 20ml of water, and extracted with ethyl acetate (3 × 15 ml). The organic layers were combined, washed with saturated brine (20ml), and dried over anhydrous sodium sulfate. Filtering, desolventizing the filtrate under reduced pressure, and performing column chromatography (eluent: ethyl acetate: petroleum ether (1:5)) to obtain 0.9g of a product with the yield of 62%.
LC-MS[M+H]+＝292.11、[M+Na]+＝314.09、[M+K]+＝330.06。
1H-NMR (400MHz, solvent CDCl)3)δ(ppm):7.91(1H,m),7.47(1H,dd),3.02(2H,q),2.67(3H,s),2.56(3H,s),2.52(2H,q),1.36(3H,t),1.12(3H,t)。
Example 3: preparation of methyl 6-chloro-2-ethyl-3, 5-dimethylquinolin-4-ylcarbonate (Compound 9)
Figure BDA0002398859190000182
1.18g (0.005mol) of 6-chloro-2-Ethyl-3, 5-dimethylquinolin-4-ol and 1.12g (0.01mol) of potassium tert-butoxide are dissolved in succession in 15ml of N, N-dimethylacetamide and cooled to 10 ℃ in a low-temperature bath. To the above mixture was added 0.58g (0.006mol) 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 was added 20ml of water, and extracted with ethyl acetate (3 × 15 ml). The organic layers were combined, washed with saturated brine (20ml), and dried over anhydrous sodium sulfate. Filtering, desolventizing the filtrate under reduced pressure, and performing column chromatography (eluent: ethyl acetate: petroleum ether (1:6)) to obtain 1.1g of a product with the yield of 72 percent. LC-MS [ M + H ]]+＝294.09、[M+Na]+＝316.07、[M+K]+＝332.04。
1H-NMR (400MHz, solvent CDCl)3)δ(ppm):7.98(1H,m),7.46(1H,t),3.98(3H,s),3.00(2H,q),2.67(3H,s),2.56(3H,s),1.36(3H,t)。
Example 4: preparation of 6-chloro-2-ethyl-3, 5-dimethylquinolin-4-ylcarbonate ethyl ester (Compound 10)
Figure BDA0002398859190000191
1.18g (0.005mol) of 6-chloro-2-ethyl-3, 5-dimethylquinolin-4-ol and 1.12g (0.01mol) of potassium tert-butoxide were dissolved in 15ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a low-temperature bath. To the above mixture was added 0.65g (0.006mol) of ethyl 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 was added 20ml of water, and extracted with ethyl acetate (3 × 15 ml). The organic layers were combined, washed with saturated brine (20ml), and dried over anhydrous sodium sulfate. Filtering, desolventizing the filtrate under reduced pressure, and performing column chromatography (eluent: ethyl acetate: petroleum ether (1:6)) to obtain 1.05g of a product with the yield of 68 percent. LC-MS [ M + H ]]+＝308.11、[M+Na]+＝330.09、[M+K]+＝346.06。
1H-NMR (400MHz, solvent CDCl)3)δ(ppm):7.97(1H,m),7.46(1H,t),4.38(2H,q),3.00(2H,q),2.67(3H,s),2.56(3H,s),1.43(3H,t),1.36(3H,t)。
Example 5: preparation of methyl 2-ethyl-6-fluoro-3, 5-dimethylquinolin-4-ylcarbonate (Compound 35):
Figure BDA0002398859190000192
the first step of reaction: preparation of 3-fluoro-2-methyl-6-nitrobenzoic acid: 15.8g (0.1mol) of 3-fluoro-2-methylbenzoic acid and 130g (1.3mol) of concentrated sulfuric acid were added to a three-necked flask at room temperature, stirred, and cooled to 0 ℃ in an ice bath. 7.7g (0.12mol) of fuming nitric acid is dripped into the mixture, and the temperature is maintained at 0-5 ℃. After 30min, the reaction was continued at 0 ℃ for 5 h. The reaction solution was added dropwise to 220ml of water at 0 ℃ for 30 min. White solid is separated out, filtered and dried in vacuum to obtain 17.1g of product with yield of 86%. LC-MS [ M + H ]]+＝200.04、[M+Na]+＝222.02、[M+K]+＝237.99。
The second step of reaction: preparation of isopropyl 3-fluoro-2-methyl-6-nitrobenzoate: 12g (0.06mol) of 3-fluoro-2-methyl-6-nitrobenzoic acid, 10g (0.072mol) of potassium carbonate and 50ml of N, N-dimethylformamide are stirred at room temperature in a three-necked flask. To the above mixture was added in portions 12.5g (0.072mol) of iodoisopropane. After the addition, the reaction was continued for 3 hours at room temperature with stirring. 200ml of water was added to the above reaction solution. Ethyl acetate (3 × 80ml) was extracted and the organic phases combined. Washed with saturated saline (80 ml). Dried over anhydrous sodium sulfate. Filtering, decompressing and concentrating the filtrate to obtain 8.6g of the product with the yield of 60 percent.
LC-MS[M+H]+＝242.09、[M+Na]+＝264.07、[M+K]+＝280.04。
The third step of reaction: preparation of isopropyl 6-amino-3-fluoro-2-methylbenzoate: 16.8g (0.3mol) of iron powder, 0.024g of ammonium chloride, 40ml of ethanol and 8ml of water were put into a three-necked flask at room temperature, and a solution of 7.2g (0.03mol) of 3-fluoro-2-methyl-6-nitrobenzoic acid isopropyl ester in 20ml of ethanol was added dropwise to the above mixture. Heated to reflux for 5 hours. The heating was stopped, the filtration was carried out, the ethanol was distilled off under reduced pressure, and 50ml of ethyl acetate and 20ml of water were added to the residue and washed once. The organic phase was dried over anhydrous sodium sulfate. Filtering, and concentrating the filtrate under reduced pressure. The methanol is recrystallized to obtain 4.3g of product with the yield of 68 percent.
LC-MS[M+H]+＝212.11、[M+Na]+＝234.09、[M+K]+＝250.06。
And a fourth step of reaction: preparation of 2-ethyl-6-fluoro-3, 5-dimethylquinolin-4-ol: 3.2g (0.015mol) of isopropyl 6-amino-3-fluoro-2-methylbenzoate, 2.8g (0.03mol) of 3-pentanone and 2.2g (0.015mol) of zinc chloride were dissolved in 40ml of xylene in this order at room temperature. The temperature is raised to reflux, 1.5g (0.01mol) of zinc chloride is added into the reaction system, and the reaction is carried out for 30 hours. The reaction mixture was cooled to room temperature, 15ml of 15% dilute hydrochloric acid was added, suction filtration was carried out, the filter cake was washed with 35ml of methanol/water (1/1), and the product was obtained after drying in 56% yield. LC-MS [ M + H ]]+＝220.12、[M+Na]+＝242.1、[M+K]+＝258.07。
The fifth step of reaction: preparation of methyl 2-ethyl-6-fluoro-3, 5-dimethylquinolin-4-ylcarbonate: 1.1g (0.005mol) of 2-ethyl-6-fluoro-3, 5-dimethylquinolin-4-ol and 1.12g (0.01mol) of potassium tert-butoxide were dissolved in 15ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a low-temperature bath. To the above mixture was added 0.58g (0.006mol) of methyl chloroformate in portions, the temperature being maintained below 20 ℃. After the addition, the reaction was carried out at room temperature for 4 hours. To the reaction system was added 20ml of water, and extracted with ethyl acetate (3 × 12 ml). The organic layers were combined, washed with saturated brine (15ml), and dried over anhydrous sodium sulfate. Filtering, and removing the solution from the filtrate under reduced pressure. Column chromatography (eluent: ethyl acetate: petroleum ether (1:6)) gave 1.06g, 76% yield.
LC-MS[M+H]+＝278.12、[M+Na]+＝300.1、[M+K]+＝316.07。
1H-NMR (400MHz, solvent CDCl)3)δ(ppm):7.83(1H,m),7.16(1H,t),3.97(3H,s),3.00(2H,q),2.65(3H,s),2.56(3H,s),1.36(3H,t)。
Example 6: preparation of ethyl 2-ethyl-6-fluoro-3, 5-dimethylquinolin-4-ylcarbonate (Compound 36):
Figure BDA0002398859190000201
1.1g (0.005mol) of 2-ethyl-6-fluoro-3, 5-dimethylquinolin-4-ol and 1.12g (0.01mol) of potassium tert-butoxide were dissolved in 15ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a low-temperature bath. To the above mixture was added 0.68g (0.006mol) of ethyl chloroformate in portions, the temperature being maintained below 20 ℃. After the addition, the reaction was carried out at room temperature for 4 hours. To the reaction system was added 20ml of water, and extracted with ethyl acetate (3 × 12 ml). The organic layers were combined, washed with saturated brine (15ml), and dried over anhydrous sodium sulfate. Filtering, and removing the solution from the filtrate under reduced pressure. Column chromatography (eluent: ethyl acetate: petroleum ether (1:6)) gave 1.1g, 75% yield.
LC-MS[M+H]+＝292.14、[M+Na]+＝314.12、[M+K]+＝330.09。
1H-NMR (400MHz, solvent CDCl)3)δ(ppm):7.82(1H,m),7.15(1H,t),4.36(2H,q),3.00(2H,q),2.65(3H,s),2.56(3H,s),1.43(3H,t),1.36(3H,t)。
Example 7: preparation of methyl 6-fluoro-2, 3, 5-trimethylquinolin-4-ylcarbonate (Compound 43)
Figure BDA0002398859190000202
The first step of reaction: preparation of 6-fluoro-2, 3, 5-trimethylquinolin-4-ol: 3.2g (0.015mol) of isopropyl 6-amino-3-fluoro-2-methylbenzoate, 4.4g (0.03mol) of ethyl 2-methylacetoacetate and 6g of polyphosphoric acid were successively charged into a three-necked flask at room temperature. The temperature is increased to 150 ℃ and the reaction is carried out for 2 h. The reaction solution is cooled to 60 ℃, poured into 75ml of saturated sodium carbonate solution, fully and uniformly mixed, and solid is separated out. And (5) carrying out suction filtration, and carrying out vacuum drying on a filter cake. Column chromatography (eluent: ethyl acetate: petroleum ether (1: 4)) gave 1.4g, 46% yield.
LC-MS[M+H]+＝206.1、[M+Na]+＝228.08、[M+K]+＝244.05。
The second step of reaction: preparation of methyl 6-fluoro-2, 3, 5-trimethylquinolin-4-ylcarbonate: 1.05g (0.005mol) of 6-fluoro-2, 3, 5-trimethylquinolin-4-hydroxy and 1.12g (0.01mol) of potassium tert-butoxide were dissolved in 15ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ by a cold bath. To the above mixture was added 0.58g (0.006mol) of methyl chloroformate in portions, the temperature being maintained below 20 ℃. After the addition, the reaction was carried out at room temperature for 4 hours. To the reaction system was added 20ml of water, and extracted with ethyl acetate (3 × 12 ml). The organic layers were combined, washed with saturated brine (15ml), and dried over anhydrous sodium sulfate. Filtering, and removing the solution from the filtrate under reduced pressure. Column chromatography (eluent: ethyl acetate: petroleum ether (1:5)) gave 1.05g, 80% yield.
LC-MS[M+H]+＝264.11、[M+Na]+＝286.09、[M+K]+＝302.06。
1H-NMR (400MHz, solvent CDCl)3)δ(ppm):7.85(1H,m),7.17(1H,t),3.97(3H,s),2.91(3H,s),2.65(3H,s),2.56(3H,s)。
Example 8: preparation of 6-fluoro-2, 3, 5-trimethylquinolin-4-yl carboxylic acid ethyl ester (Compound 44)
Figure BDA0002398859190000211
1.05g (0.005mol) of 6-fluoro-2, 3, 5-trimethylquinolin-4-ol and 1.12g (0.01mol) of potassium tert-butoxide were dissolved in 15ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ with a low-temperature bath. To the above mixture was added 0.65g (0.006mol) of ethyl chloroformate in portions, the temperature being maintained below 20 ℃. After the addition, the reaction was carried out at room temperature for 4 hours. To the reaction system was added 20ml of water, and extracted with ethyl acetate (3 × 12 ml). The organic layers were combined, washed with saturated brine (15ml), and dried over anhydrous sodium sulfate. Filtering, and removing the solution from the filtrate under reduced pressure. Column chromatography (eluent: ethyl acetate: petroleum ether (1:6)) gave 1.08g, 78% yield.
LC-MS[M+H]+＝278.12、[M+Na]+＝300.1、[M+K]+＝316.07。
1H-NMR (400MHz, solvent CDCl)3)δ(ppm):7.81(1H,m),7.16(1H,t),4.36(2H,q),2.92(3H,s),2.65(3H,s),2.57(3H,s),1.44(3H,t)。
The present invention also synthesizes the following compounds by reference to the methods in the above examples:
Figure BDA0002398859190000212
Figure BDA0002398859190000221
Figure BDA0002398859190000231
Figure BDA0002398859190000241
Figure BDA0002398859190000251
formulation examples
In the following examples, all percentages are by weight and all dosage forms are prepared using conventional methods.
Example 9:
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:
950.0% of compound, 4.0% of dodecylphenol polyethoxy glycol ether, 6.0% of sodium lignosulfonate, 8.0% of sodium aluminosilicate and 32.0% of montmorillonite (calcined).
Example 10:
in this example, granules were prepared using the compounds obtained in the above examples, specifically using the following raw material compositions:
3520.0% of compound, 2.0% of sodium dodecyl sulfate as other components, 6.0% of calcium lignosulfonate, 10.0% of potassium chloride, 1.0% of polydimethylsiloxane and soluble starch to make up to 100%.
Example 11:
in this example, the compound obtained in the above example is used to prepare an extruded pellet, specifically using the following raw material composition:
3630.0% of compound, 9.0% of anhydrous calcium sulfate, 4.0% of crude calcium lignosulfonate, 1.0% of sodium alkyl naphthalene sulfonate and 56.0% of calcium/magnesium bentonite.
Example 12:
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:
4425.0% of compound, 15060% of solvent, PEG 4005% of Rhodacal 70/B3% of RhodameenRAM/77%.
Example 13:
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:
6630.0%, 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 14:
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. The mortality rate (mortality) of the insects was then visually evaluated for each test unit, by calculating,
Figure BDA0002398859190000261
(1) test results for the control of myzus persicae by exemplary example Compounds
At a dose of 400ppm, the compounds with the lethality rate of more than 80% to the green peach aphids comprise: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 100ppm, the compounds with the lethality rate of more than 80% to the green peach aphids comprise: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 25ppm, the compounds with the lethality rate of more than 80% to the green peach aphids comprise: 9. 10, 11, 12, 13, 14, 15, 16, 19, 35,36, 37, 38, 39, 40, 41, 42, 43, 57, 66, 69.
(2) Test results for exemplary example Compounds against Bemisia tabaci
At a dose of 400ppm, the compounds with the fatality rate of more than 80% to bemisia tabaci are as follows: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 100ppm, the compounds with the fatality rate of more than 80% to bemisia tabaci are as follows: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 25ppm, the compounds with a mortality rate of more than 80% to bemisia tabaci are: 9. 10, 11, 12, 13, 14, 15, 16, 19, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 57, 66, 69, 77, 79.
(3) Test results for the control of Aphis gossypii by exemplary example Compounds
At a dose of 400ppm, the compounds with the lethality rate of more than 80% to cotton aphid comprise: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 100ppm, the compounds with the lethality rate of more than 80% to cotton aphid comprise: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 25ppm, the compounds with a lethality rate of more than 80% to Aphis gossypii have the following characteristics: 9. 10, 11, 12, 13, 14, 15, 16, 19, 35,36, 37, 38, 39, 40, 41, 42, 43, 57, 66, 69.
(4) Test results for controlling frankliniella occidentalis by exemplary example Compounds
At a dose of 400ppm, the compounds with the fatality rate of more than 80 percent to frankliniella occidentalis have the following characteristics: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;
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, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 25ppm, the compounds with the fatality rate of more than 80 percent to frankliniella occidentalis have the following characteristics: 9. 10, 11, 12, 13, 14, 15, 16, 19, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 57, 59, 66, 69, 77, 79.
(5) Test results for exemplary example Compounds against Plutella xylostella
At a dose of 400ppm, the compounds with the lethality rate of more than 80 percent to the plutella xylostella comprise: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 100ppm, the compounds with the fatality rate to plutella xylostella of more than 80 percent are: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 25ppm, the compounds with a mortality rate of more than 80% to plutella xylostella are: 9. 10, 11, 12, 13, 14, 15, 16, 17, 35,36, 37, 38, 39, 40, 41, 42, 66, 69, 77, 79.
(6) Test results of the exemplary embodiment Compounds for controlling Pieris rapae
At a dose of 400ppm, the compounds with a fatality rate of more than 80% to pieris rapae are: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 100ppm, the compounds with a fatality rate of more than 80% to pieris rapae are: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 25ppm, the compounds with a fatality rate of more than 80% to pieris rapae are: 9. 10, 11, 12, 13, 14, 15, 16, 17, 19, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 57, 59, 66, 69.
(7) Exemplary example Compounds control armyworm test results
At a dose of 400ppm, the compounds with a lethality rate of more than 80% to armyworm are: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 100ppm, the compounds with a lethality rate of more than 80% to armyworm are: 1.8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 25ppm, the compounds with a lethality of more than 80% to armyworm are: 9. 10, 11, 12, 13, 16, 35,36, 37, 38, 39, 40, 41, 42, 66, 69, 77, 79.
(8) Exemplary example Compounds control Prodenia litura test results
At a dose of 400ppm, the compounds with the mortality rate of prodenia litura of more than 80 percent comprise: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 100ppm, the compounds with a mortality rate of more than 80% to prodenia litura comprise: 9. 10, 11, 12, 13, 14, 15, 16, 19, 20, 26, 27, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 25ppm, the compounds with a mortality rate of more than 80% to prodenia litura comprise: 9. 10, 11, 12, 13, 16, 35,36, 37, 38, 39, 40, 41, 42.
(9) Test results for exemplary example Compounds to control Chilo suppressalis
At a dose of 400ppm, the compounds with the lethality rate of more than 80 percent to chilo suppressalis comprise: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 100ppm, the compounds with the lethality rate of more than 80 percent to chilo suppressalis comprise: 9. 10, 11, 12, 13, 14, 15, 16, 35,36, 37, 38, 39, 40, 41, 42, 66, 69, 77, 79;
at a dose of 25ppm, the compounds with the lethality rate of more than 80 percent to chilo suppressalis comprise: 9. 10, 11, 12, 16, 35,36, 37, 38, 39, 40, 42.
(10) Test results for the control of rice leaf rollers by exemplary example Compounds
At a dose of 400ppm, the compounds with the lethality rate of more than 80 percent to rice leaf roller comprise: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 100ppm, the compounds with the lethality rate of more than 80 percent to rice leaf roller comprise: 1.4, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 25ppm, the compounds with the lethality rate of more than 80 percent to rice leaf roller comprise: 9. 10, 11, 12, 13, 14, 15, 16, 17, 35,36, 37, 38, 39, 40, 41, 42, 66, 69, 77, 79.
(11) Test results for controlling brown planthopper with exemplary example compounds
At a dose of 400ppm, the compounds with the fatality rate of more than 80% to brown planthopper comprise: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 100ppm, the compounds with the fatality rate of more than 80 percent to brown planthopper comprise: 1. 2,8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 51, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 25ppm, the compounds with the fatality rate of more than 80% to brown planthopper comprise: 9. 10, 11, 12, 13, 14, 15, 16, 19, 35,36, 37, 38, 39, 40, 41, 42, 43, 66, 69, 77, 79.
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 by using binoculars after 24h, touching the mite body by using a writing brush, and calculating the mortality rate by taking the mite with enough immobility as death. The mortality rate was calculated as follows:
Figure BDA0002398859190000291
the following results were obtained for the Tetranychus cinnabarinus part:
at a dose of 400ppm, the compounds with the lethality rate of more than 80 percent to tetranychus cinnabarinus have the following components: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;
at a dose of 100ppm, the compounds with the lethality rate of more than 80 percent to tetranychus cinnabarinus have the following components: 1. 9, 10, 11, 12, 13, 15, 16, 35,36, 37, 38, 39, 40, 41, 42, 43, 66, 69, 77, 79;
at a dose of 25ppm, the compounds with the lethality rate of more than 80 percent to tetranychus cinnabarinus have the following components: 9. 11, 12, 16, 35,36, 37, 38, 39, 42, 43.
3. Test results for exemplary example compounds and control agents
This example illustrates the preparation of exemplary example Compounds with a control agentComparative test for Activity (control CK prepared by itself according to the methods described in the literature1、CK2、CK3And CK4). The test results are shown in the following table.
Figure BDA0002398859190000292
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 (10)

1. A compound represented by the following formula (I), a stereoisomer, a racemate, a tautomer, a nitrogen oxide or a pharmaceutically acceptable salt thereof,
Figure FDA0002398859180000011
r is selected from-COR1or-COOR1；
Each R1Identical or different, independently of one another, from C1-12An alkyl group;
R2、R3、R4identical or different, independently of one another, from C1-12Alkyl, or C1-12An alkoxy group;
x is selected from F, Cl, Br or I.
2. The compound of claim 1, wherein in formula (I)
R is selected from-COR1or-COOR1；
Each R1Are the same or different and are selected independently of one anotherFrom C1-4An alkyl group;
R2、R3、R4identical or different, independently of one another, from F, Cl, Br, I or C1-4An alkyl group;
x is selected from F or Cl.
3. A compound according to claim 1 or 2, characterized in that in formula (I)
R is selected from-COR1or-COOR1；
R1Independently selected from C1-4An alkyl group;
R2、R3、R4identical or different, independently of one another, from C1-4An alkyl group;
x is selected from F or Cl.
4. A compound according to any one of claims 1 to 3, wherein the compound of formula (I) is selected from the group consisting of,
Figure FDA0002398859180000012
Figure FDA0002398859180000013
Figure FDA0002398859180000021
Figure FDA0002398859180000031
5. a process for the preparation of a compound of formula (I) as claimed in any one of claims 1 to 4, comprising the steps of: reacting the compound shown in the formula (II) with the compound shown in the formula (III) or the compound R-L shown in the formula (III-1) to obtain the compound shown in the formula (I),
Figure FDA0002398859180000041
r, R therein1、R2、R3、R4X has the definition as claimed in any of claims 1 to 4, L is selected from a leaving group, such as Cl, Br, I or F.
6. The process of claim 5, further comprising the step of preparing a compound of formula (II) comprising:
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 FDA0002398859180000042
wherein R is2、R3、R4X has the definition as set forth in any one of claims 1 to 4; r5Is C1-4Alkyl groups such as methyl, ethyl, and the like.
7. 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 the formula (I) as claimed in any one of claims 1 to 4, a stereoisomer, a racemate, a tautomer, a nitrogen oxide or a pharmaceutically acceptable salt thereof.
8. Use of one, two or more of the compounds of formula (I), their stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof according to any one of claims 1 to 4 as pesticides, such as insecticides and/or acaricides.
9. Use of one, two or more of the compounds of formula (I), their stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof as claimed in any one of claims 1 to 4 for the preparation of a pesticide, e.g. an insecticide and/or an acaricide.
10. A method for controlling pests and/or harmful mites comprising applying an effective amount of one, two or more of the compounds of formula (I), its stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof as described in any one of claims 1-4, or said composition to a growth medium for pests and/or harmful mites.
CN202010140315.1A 2020-03-03 2020-03-03 Quinoline derivatives, preparation method and application thereof Active CN111205223B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202010140315.1A CN111205223B (en) 2020-03-03 2020-03-03 Quinoline derivatives, preparation method and application thereof
PCT/CN2021/078867 WO2021175249A1 (en) 2020-03-03 2021-03-03 Quinoline derivative, preparation method therefor and use thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010140315.1A CN111205223B (en) 2020-03-03 2020-03-03 Quinoline derivatives, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN111205223A true CN111205223A (en) 2020-05-29
CN111205223B CN111205223B (en) 2021-06-22

Family

ID=70786149

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010140315.1A Active CN111205223B (en) 2020-03-03 2020-03-03 Quinoline derivatives, preparation method and application thereof

Country Status (2)

Country Link
CN (1) CN111205223B (en)
WO (1) WO2021175249A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021175249A1 (en) * 2020-03-03 2021-09-10 山东省联合农药工业有限公司 Quinoline derivative, preparation method therefor and use thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5190952A (en) * 1989-07-07 1993-03-02 Meiji Seika Kabushiki Kaisha 4-acyloxyquinoline derivatives and insecticidal or acaricidal compositions containing same
CN1688193A (en) * 2002-10-11 2005-10-26 明治制果株式会社 Mixed compositions for controlling parasitic insects
CN1310889C (en) * 2001-04-12 2007-04-18 明治制果株式会社 Halogen-substituted quinoline derivatives and ectoparasite control agent
CN108689928A (en) * 2018-07-19 2018-10-23 山东省联合农药工业有限公司 A kind of quinoline derivatives and preparation method thereof and purposes

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040077602A1 (en) * 2002-10-11 2004-04-22 Meiji Seika Kaisha, Ltd. Mixture composition for controlling ectoparasites
MX2019010886A (en) * 2017-03-17 2019-10-15 Meiji Seika Pharma Co Ltd Mesostigmata mite control agent.
JP7389750B2 (en) * 2018-09-14 2023-11-30 Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 Composition for controlling mites of the suborder Mesospirata
CN111205223B (en) * 2020-03-03 2021-06-22 山东省联合农药工业有限公司 Quinoline derivatives, preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5190952A (en) * 1989-07-07 1993-03-02 Meiji Seika Kabushiki Kaisha 4-acyloxyquinoline derivatives and insecticidal or acaricidal compositions containing same
CN1310889C (en) * 2001-04-12 2007-04-18 明治制果株式会社 Halogen-substituted quinoline derivatives and ectoparasite control agent
CN1688193A (en) * 2002-10-11 2005-10-26 明治制果株式会社 Mixed compositions for controlling parasitic insects
CN108689928A (en) * 2018-07-19 2018-10-23 山东省联合农药工业有限公司 A kind of quinoline derivatives and preparation method thereof and purposes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021175249A1 (en) * 2020-03-03 2021-09-10 山东省联合农药工业有限公司 Quinoline derivative, preparation method therefor and use thereof

Also Published As

Publication number Publication date
CN111205223B (en) 2021-06-22
WO2021175249A1 (en) 2021-09-10

Similar Documents

Publication Publication Date Title
CN111909143B (en) Isoxazoline substituted benzamide derivative and preparation method and application thereof
CN106167484B (en) Pyrimidine-containing substituted pyrazole compound and preparation method and application thereof
JPH085859B2 (en) New alkylenediamines
CN114605324A (en) Isoxazoline substituted benzamide derivative and preparation method and application thereof
CN112430210A (en) Bisamide compound and application thereof
CN109689644B (en) Pyridazinone compound and application thereof
CN112174904A (en) Isoxazoline compound and application thereof
CN109776427B (en) Pyrimidine diamine compound and application thereof
CN111163638A (en) Pesticidal compositions and methods
CN111205223B (en) Quinoline derivatives, preparation method and application thereof
CN108689928B (en) Quinoline derivative and preparation method and application thereof
CN108069973B (en) Substituted six-membered heterocyclic compound containing pyrimido ring and preparation method and application thereof
JPS62281807A (en) Insecticide
CN111004218A (en) Piperidine-containing pyrimidine compound and application thereof
CN109485644B (en) Substituted benzisothiazole compound and preparation method and application thereof
CN110272452B (en) Quinoline derivatives, preparation method and application thereof
CN113149900A (en) Amide compound and application thereof
CN114621280A (en) Silicon acrylonitrile compound and preparation method and application thereof
CN113264924A (en) Dioxane pyrimidine derivative and preparation method and application thereof
JPH04234874A (en) Substituted 2-(6-(pyrimidinyl)-indol-yl) acrylic ester and process for producing same
CN113347883A (en) Pesticidal compositions and methods
US5141939A (en) Pesticidal chromen-6-yl-methyl-oxy-and-thiapyrizinones
CN106279040B (en) Pyrimidine compound containing oximino and application thereof
CN113912495A (en) Fluorine-containing butylene ester derivative and preparation method and application thereof
CN109320505B (en) Preparation and application of halogenated butenolide compound with insecticidal activity

Legal Events

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